Nordic Wood Biorefinery Conference 2012

NWBC 2012
The 4th Nordic Wood Biorefnery

Conference
Helsinki, Finland
2325 October, 2012
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53

VTT TECHNOLOGY 53
NWBC 2012
The 4th Nordc Wood Borefnery
Conference
Hesnk, Fnand, 23-25 October, 2012

2
ISBN 978-951-38-7880-1 (soft back ed.)
ISSN 2242-1211 (soft back ed.)
ISBN 978-951-38-7881-8 (URL: http://www.vtt.f/pubcatons/ndex.|sp)
ISSN 2242-122X (URL: http://www.vtt.f/pubcatons/ndex.|sp)
Copyrght VTT 2012

| ULKAISI| A - UTGIVARE - PUBLISHER
VTT
PL 1000 (Teknkante 4 A, Espoo)
02044 VTT
Puh. 020 722 111, faks 020 722 7001
VTT
PB 1000 (Teknkvgen 4 A, Esbo)
FI-02044 VTT
Tfn +358 20 722 111, teefax +358 20 722 7001
VTT Technca Research Centre of Fnand
P.O. Box 1000 (Teknkante 4 A, Espoo)
FI-02044 VTT, Fnand
Te. +358 20 722 111, fax +358 20 722 7001
Technca edtng Tar|a Haapaanen
Kop|yv Oy, Kuopo 2012

3
Preface
Klaus Niemel
Chairman of the Organising Committee, VTT, Finland

"An attempt to discuss fully the influence of chemistry on the utilization of waste wood leads so
deeply into practically all fields of chemistry that a paper of this kind must necessarily be limited to a
small number of topics." Ths s how S.F. Acree (from Forest Products Laboratory and Unversty of
Wsconsn) started hs revew paper, neary 100 years ago, on the chemca utsaton of wood, and
Acree contnued by statng that "attention is given, therefore, to those phases of this subject which
are of most importance commercially and which seem to show greatest promise for the future.
Snce the days of Acree, enormous advances n chemca, enzymatc, mechanca and therma
utsaton of wood and a other parts of trees have taken pace. Therefore, n our modern borefn-
ery era Acrees "this subject" needs to be understood to cover much more than |ust the "chemistry
on the utilization of waste wood". Takng ths nto account, the organsers of the NWBC 2012 event
sncerey hope that the seected presentatons cover "those phases of this subject which are of
most importance commercially and which seem to show greatest promise for the future".
Today, the "greatest promise for the future" s apparenty shown by hghy ntegrated forest n-
dustry systems wth optmsed tota energy baances and maxmsed output of dfferent vaue-added
products; athough more robust and smpe stand-aone systems aso show a ot of potenta. Ths
book of proceedngs contans numerous exampes of ndustra and academc vews on these ap-
proaches for wood-based borefnng. The organsers of the NWBC 2012 wsh to warmy thank a
the sesson chars, speakers, poster presenters and ther co-authors for ther vauabe contrbutons.
Ths event has benefted from the knd support from the sponsors sted esewhere n ths book.
Ther support has enabed many young researchers to partcpate n ths conference and to present
ther studes. Last but not east the organsers wsh to gve speca thanks to Tar|a Haapaanen, the
technca edtor of ths book of proceedngs.
It has been cted above how Acree started hs paper n 1915. Ths reference s made even more
meanngfu by endng ths short preface by repeatng Acrees fna sentence of that pubcaton:
".the future will probably show that the application of chemistry to the utilization of forest products
extends into nearly every field of human endeavor."
The organsers wsh a conference partcpants an exctng and stmuatng conference.
Reference
Acree, S.F. 1915. What chemstry has done to ad the utzaton of wood. | . Ind. Eng. Chem. 7,
pp. 913-915.

4
Contents
Preface ........................................................................................................................................ 3
Tuesday, 23 October: Bi orefi nery strategy and i nnovation .................................................... 9
Intatng a Pubc-Prvate Partnershp for borefneres ........................................................... 11
Reguatory and ega frameworks for wood borefneres n EU and Russa ............................. 15
Forest borefneres - sustanabe busness opportuntes n Scandnava and North Amerca ..... 20
Roadmap for advanced bo-based materas ......................................................................... 26
Bo-based chemcas - success by maxmzng vaue and beng resource effcent ................. 28
Roe of COST n European forest and forest products research ............................................. 30
Understandng wood ce wa structure, bopoymer nteracton and composton:
mpcatons for current products and new matera nnovaton ................................................ 36
Genetcay engneered (GE) forest trees as borefnery raw materas - egsatve
and scentfc status .............................................................................................................. 40
Used wood sortng, utzaton and recycng n dfferent vaue chans ..................................... 45
The Forest Refne pro|ect - deveopment of effcent forest bomass suppy chans for
borefneres ......................................................................................................................... 51
ForestSpeCs fndngs on byproducts of forest ndustry: coud bark be more vauabe
than tmber?......................................................................................................................... 56
Supportng processes n borefneres by correct water treatment ........................................... 60
Wednesday, 24 October: ndustri al devel opments .................................................................. 69
Actua and future trends n dssovng pup manufacture ........................................................ 71
Andrtzs new technoogy apped to dssovng pup grades - a dfferent approach ................. 82
Forest borefnery custer - a possbe path to bobased products ........................................... 87
Producton of surface actve agents from hemceuoses extracted from wood chps .............. 93
The Forest Borefnery: Canadan drvers and ongong actvtes ............................................ 98
Economc and ecoogca assessment of borefneres - fndngs of the German
borefnery roadmap process .............................................................................................. 104
New pot-pant facty of the "German Lgnoceuose Feedstock Borefnery Pro|ect"
n Leuna - experences wth frst tme operatons................................................................. 109
The LgnoRef pro|ect: A natona research ntatve to enhance borefnery process
deveopments n Norway .................................................................................................... 112
Fnnsh BoRefne - new bomass products programme - RD&D on bofues and
borefneres n Fnand ....................................................................................................... 118
The Doms| borefnery - how to make more from the tree .................................................. 119
UPM - producng fues of the future from wood-based raw materas ................................... 121

5
Scang up Borregaards BALI borefnery concept............................................................ 125
New Swedsh programme Ethano Processes - status and chaenges ................................ 126
Borefnery ntatves mpemented by Nppon Paper - torrefacton of wood bomass
for co-frng n a puverzed coa boer ................................................................................. 129
Pressurzed entraned fow gasfcaton of bomass powder - nta resuts from pot
pant experments............................................................................................................... 136
Green Fue Nordc - The Smart Way: Utsng RTP technoogy to produce
sustanabe 2nd generaton bo-o from oca feedstocks...................................................... 142
Towards ndustra producton of mcroba o for hgh quaty traffc fues .............................. 147
CHP-ntegrated bo-o producton demonstraton pant, pro|ect deveopment and current status ...... 151
Thursday, 25 October: R&D hi ghli ghts .................................................................................. 157
Utzaton of hydroyss gnn n the Sovet Unon and Russa: What s appcabe n
the wood borefnery era? ................................................................................................... 159
The Lgnoworks strategc network - a Canadan approach to vaue-added gnn products .... 169
Lgnn-based sustanabe packagng soutons ..................................................................... 174
Lgnn based carbon fbres - recent progress ...................................................................... 180
Rapd refnng of gnoceuoscs to carbohydrates and gnn-based new materas
(gnophenos) and desgn of sustanabe ndustra network connectng forests
and chemca ndustres ...................................................................................................... 186
Sugars and gnn from ceuosc source - hgh quaty, hgh vaue products -
the "wet wood mng" approach ......................................................................................... 194
Ionc quds n wood and bomass dssouton and fractonaton ........................................... 196
Ethano-based organosov borefneres: feedstock-fexbty & economc evauaton ............. 199
Bobutano from forest resdues - a process utzng SO
2
-ethano-water fractonaton
and ABE fermentaton ........................................................................................................ 205
Upgradng pup m waste streams for ntegraton wth fsh farmng ...................................... 211
FPInnovatons nove fractonaton process for gnoceuosc bomass ................................. 214
Co-producton of renewabe poymers and ethano from eucayptus-based pup ms ........... 221
Lgnn remova from dfferent back quors .......................................................................... 227
Recovery of bobased ght carboxyc acds from dute aqueous soutons ........................... 239
Some xyan ethers for coatng appcatons ......................................................................... 246
Posters ................................................................................................................................... 253
Actvtes of IEA boenergy task 42 "borefnery" on wood based boenergy drven
borefneres - cassfcaton, sustanabty assessment, compexty ndex and
nternatona perspectves unt 2025 ................................................................................... 255
Immobzaton of ceuases on magnetc partces enabes enzyme re-use durng
hydroyss of pretreated spruce ........................................................................................... 258

6
Contrast of Escherichia coli KO11 and Saccharomyces cerevisiae ATCC96581 n
fermentng Pinus patula hydroysate pretreated at severe steam exposon condtons ................ 260
Smutaneous producton of ethano and softwood kraft pup: pretreatments and effects
of nhbtors on fermentatons .............................................................................................. 262
Sustanabe bofue: nnovatons n boethano producton technooges (SusBoFue) ............ 265
Oxdatve pretreatment of CCA-treated wood for boethano producton ................................ 267
Improvement of enzymatc hydroyss condtons of Salix viminalis poysacchardes .............. 269
Producton of fermentabe sugars by enzymatc hydroyss of pretreated waste texte .......... 271
Monosaccharde producton from gnoceuosc bomasses va concentrated acd hydroyss ...... 273
Process schemes for chromatographc fractonaton of gnoceuosc concentrated
acd hydroysates ............................................................................................................... 275
Potenta expanson of second generaton Fscher Tropsch bodese producton n Fnand ......... 277
Bofues and chemcas from gnoceuosc materas - a scheme for condtonng
SO
2
-ethano-water spent quor for ABE fermentaton .......................................................... 279
Opportuntes and chaenges n emergng boenergy busness: Case of Fnnsh
sawmng ndustry ............................................................................................................. 281
Premnary spectra characterzaton of the caorfc vaue of pyrotc products from
wood bomass .................................................................................................................... 285
An ndustra pant (25,000 m
3
/yr) for wood utraoxypyroyss by the formed ayer process ..... 287
Measurement methods for physca propertes of the pyroyss o components ..................... 289
Effect of pastcs on the co-quefacton of ceuosc bomass and pastcs to qud fue ......... 291
AFORE - Forest Borefneres: Added-vaue from chemcas and poymers by new,
ntegrated separaton, fractonaton and upgradng methods ................................................ 293
Boconverson of prmary sudge from Portuguese pup and paper ms to fermentabe sugars ........ 294
Investgatng anaerobc dgeston of pup washng effuent usng bench-scae UASB reactors .......... 296
From brch to soda-AO pups, pure xyan and fractons thereof - HemEx pro|ect overvew .............. 298
Impementaton of gnn-based borefnery wthn a Canadan kraft m: Impact on
utty system and soutons toward optma operaton ........................................................... 301
Opportuntes for energy upgradng by means of an absorpton heat pump n an
ntegrated forest borefnery ................................................................................................ 304
The LgnoForce System for the recovery of gnn from back quor................................... 306
Infuence of the use of hgh shear rate modue n membrane ftraton performance
n utraftraton of back quor ............................................................................................. 309
Impact of gnn extracton on the recovery oop of the Kraft process: Measures to
mnmze the consumpton of chemcas .............................................................................. 311
Bo-methano producton from kraft pup m condensates ................................................... 313
Utzaton of byproduct streams treated by wet oxdaton ..................................................... 315
Borefnery and energy savngs ........................................................................................... 318

7
Towards optma treatment procedure upon fractonaton of Nordc gnoceuoses
usng nove akano amne - superbase onc qud system .................................................. 320
Sustanabe Resource Technoogy (SuReTech) .................................................................. 323
Identfcaton of degradaton products from brch wood n water extracts ............................... 325
Akane oxdaton pretreatment of wood materas to produce ethano .................................. 327
Enzymes - toos to upgrade bomass to hgh-vaue products ............................................... 329
Enzyme technooges for the producton of hgh-vaue poymers and chemcas from
forest resources ................................................................................................................. 331
Thermostabzng mutatons mproved the stabty of Trichoderma reesei GH11
xyanase n hgh pressure ................................................................................................... 333
Some aspects of the changes n the brch wood morphoogca structure and ts
components composton n the acdc hydroyss process ................................................... 335
Low temperature sufonaton of gnoceuose for effectve bomass deconstructon
and converson .................................................................................................................. 337
Lqud phase acetoxyaton of -pnene ............................................................................... 339
Bocompostes based on brch subern ................................................................................ 342
Isoaton of trterpene rch extracts from outer brch bark ...................................................... 344
Fractonaton and structura charactersaton of softwood kraft gnns................................... 346
Funaoka gnn factatng sustanabe and recycabe bocompostes for transportaton......... 349
Compostes of kraft gnn ................................................................................................... 353
Seectve enzymatc degradaton of aka extracted gnn for the producton of
hgh-vaue aromatc components ........................................................................................ 356
From gnns to aromatc synthons by base cataysed degradaton n contnuous
reactors - a tentatve revew ............................................................................................... 358
Optmzaton of the kraft gnn copoymerzaton wth -caproactone for hgher
vaue gnn-adhesves ........................................................................................................ 361
Fast cataytc pyroyss of gnn ........................................................................................... 363
Anaytca toos to study the chemstry of hydrotherma gnn depoymersaton .................... 365
Pused corona dscharge oxdaton n gnn modfcaton ...................................................... 366
Synthetc humc materas from gneous waste materas of the South-Afrcan pupng
and sugar ndustres. Synthess and propertes ................................................................... 368
Effect of back quor type and gnn fractonaton on the poymersaton of a Kraft
gnn by accase. Optmsaton of the operaton condtons ................................................... 371
Recovery strateges contro the wood hydroysate barrer performance ................................ 375
Desgn of new boresource packagng from wood hydroysates ............................................ 378
Spray appcaton of bopoymers and taored refnng as toos n the producton of
formabe paper matera for nove appcatons .................................................................... 380
Renewabe barrer fms from wood hydroysates ................................................................. 382

8
Functonazng of ceuosc fbres through patented modfcaton reactons to ncrease
hydrophobcty ................................................................................................................... 384
Nanoceuose as a toughenng agent ................................................................................. 387
Ceuose regeneraton from soutons of eucayptus wood n 1-ay-3-methymdazoum
chorde.............................................................................................................................. 389
Producton and separaton of water soube ceo-ogomers by supercrtca water
treatment and membrane ftraton ...................................................................................... 391
Comparson of oxygen degnfcaton of hgh-kappa pne Kraft pup n throughfow
and batch mode ................................................................................................................. 393
Hemceuose precptaton n methano-water soutons and ts effect wth soubty
parameters ........................................................................................................................ 395
Recovery of hgh moar mass hemceuoses from brch saw dust........................................ 398
Scae-up of pressursed hot fow-through extracton system ................................................. 400
Fractonaton of PHW extracts n a pup m borefnery. Part I: a process concept ................ 402
Fractonaton of PHW extracts n a pup m borefnery. Part II: enhanced performance
of utraftraton ................................................................................................................... 404
Extracton of hemceuose and condensed tannn from spruce bark .................................... 406
Methods to remove fouants from wood extracts pror to utraftraton................................... 408
Purfcaton of hardwood-derved autohydroysates .............................................................. 410
Hot water extracton of hemceuose from softwood and sugarcane bagasse usng
mcrowave heatng technoogy ............................................................................................ 412
Modeng of hot water extracton of sawdust ....................................................................... 414
The knetcs of smutaneous aqueous extracton and hydroyss of spruce hemceuoses ........... 416
Acd functonazed carbon as heterogeneous cataysts for dehydraton of xyose to furfura ......... 418
Knetc study on the formaton of furfura from pentoses n compex sugar soutons.............. 420
D-Xyonate and xyto as borefnery products from hemceuose ........................................ 423
Seectve oxdaton of uronc acds nto adarc acds over god cataysts ............................... 425
In stu poymerzaton of poyanne n wood veneers ........................................................... 427
Pre- and post-processng of sod bofues and bo-ash nto new constructon materas ........ 429
Carbon footprnt of wood borefnery products - case Forchem ta o dervatve products ..... 431

Intatng a Pubc-Prvate Partnershp for borefneres

9
Tuesday, 23 October:
Biorefinery strategy and innovation


11
nitiating a Public-Private Partnership for biorefineries
Johan Elvnert
Forest-based Sector Technology Platform
Abstract
In Europe today borefnery research ntatves are pentfu but often fragmented and there are few
commtments to poo resources, knowedge and know-how. Furthermore, the research communty
as a whoe and ndustry ake have not, unt now, estabshed a cear way forward for achevng a
consodated route to optmsng borefnery technoogy and methodoogy.
In order to promote a more consstent pocy envronment and the deveopment of new busness
modes and ntegrated borefnery vaue-chans, t woud be recommendabe for the pubc and
prvate to form a partnershp that transcends tradtona vaue chans, pocy areas and research
domans and creates crtca mass for research, nnovaton and deveopment of new borefnng
concepts.
The EU funded Star-COLIBRI pro|ect (Strategc Targets for 2020 - Coaboraton Intatve on B-
orefneres), a 2-year Coordnaton Acton whch ended n 2011, set out to provde the necessary
steppng stones for a stronger and ess fragmented approach to borefnery deveopments n Eu-
rope. Towards the end of the pro|ect, the European Commsson was approached wth the sugges-
ton to nvte reevant ndustry representatves to a frst dscusson about the settng up of a future
partnershp. Around 40 eadng companes and the European Commsson s now preparng to-
wards a future pubc-prvate partnershp caed Bobased for Growth whch may be aunched n
2014. Bobased for Growth coud potentay aow for a doubng of the pace n whch new borefn-
ery concepts are ntroduced to the market. How the dea of ths potenta pubc-prvate partnershp
(PPP) came to fe and exampes of the compcated potca and practca procedure of estabshng
t s the topc of ths contrbuton.
What is a public-private partnership (PPP)?
The smpe way to expan how PPPs n the fed of EU-funded Research and Innovaton works s to
say that the European Commsson and a consortum of prvate stakehoders together manages a
"research programme" on a 50/50 prncpe of shared costs, governance and nfuence. Research
pro|ects funded by ths "programme" are seected through open and compettve ca procedures,
but the ndustry stakehoders have a very strong nfuence over the topcs of the ca. The m-
portance of research PPPs was recognsed n the Europe 2020 Strategy put forward by the Euro-
pean Commsson n March 2010. The strategy mentons that PPPs are mportant nstruments
through whch the EU can maxmse and acceerate the practca benefts of research for Europes
busnesses and SMEs.
Snce 2007, severa research PPPs have been estabshed wth the European Commsson as
(one of) the pubc partner(s). These PPPs are organsed n many dfferent ways and aso conduct
ther operatons dfferenty. However, there are two dstnct categores: Insttutona PPPs and con-
tractua PPPs. Insttutona PPPs, Caed | ont Undertakngs (| U) or | ont Technoogy Intatves
(| TI), requre a decson of the European Parament and the Counc and s, when operatona,
managed by a pubc European Agency.
The | TIs estabshed have tota budgets rangng between C 1 bon and C 3 bon for a 10 year
perod. In three | TIs (nnovative Medicines nitiative, Clean Sky, and Fuel Cells and Hydrogen),
pubc resources are excusvey composed of EU funds, provded through the budget of the | TI; n
the two other (ARTEMS and ENAC), they are combned wth funds of the partcpatng Member
States or countres assocated to FP7, provded through natona fundng agences.
Contractua PPPs are estabshed by a ega contract by on one hand the European Commsson
and on the other hand a prvate consortum. The day admnstraton remans wth the European


12
Commsson that aready manages the research and nnovaton budget, but the vson and mut-
annua roadmap prepared by the prvate stakehoders serve as the bass for a actvtes. Under the
European Economc Recovery Pan (2008), three contractua PPPs were created to represent a
powerfu means of boostng research efforts n the arge ndustra sectors of automotve ("Green
Cars"), constructon ("Energy-Effcent Budngs") and manufacturng ("Factores of the Future").
Why a European PPP for Biorefining?
First of all, size does matter! Whe the scope of the partnershp must be focused enough and
the partcpants few enough for the cooperaton to be practcay manageabe, a successfu partner-
shp must be wde enough for crtca mass. At the scae of European mut-bon Euro PPPs, bore-
fnng happens to be a very sutaby szed topc.
Second, the timi ng is right! A PPP on borefnng woud be tmey both n the perspectve of re-
newabe energy and mtgatng cmate change, as we as ndustra compettveness and |obs crea-
ton perspectve. Large companes are nvestng n research on new bomass pre-treatment meth-
ods, converson processes and new products for od and new markets.
Further on, the shared challenges and opportunities are grand! The benefts of a coser n-
tegraton of tradtona bobased ndustres go beyond substtutng foss feedstock wth a sustana-
be aternatve. It s ma|or opportunty for Europes ndustry and ctzens.
The actons of the prvate payers n the area of borefnng coud greaty nfuence the successfu
transton to a more sustanabe and compettve European economy, whch s the overarchng ob-
|ectve of the pocy makers, but especay the nvestment cost and technca rsk reated to brngng
a borefnng concept from the aboratory nto runnng producton capacty, s mmense.
Meanwhe the pubc decson-makers actons nfuence the busness of bobased ndustres and
ther capabty to pan and nvest n new borefnery capacty. For nstance, the prce of bomass has
become ncreasngy correated to energy prces, reguated agrcuture and food producton, rura
deveopment pocy, taxaton on green-house gas emssons and prortes of pubc nvestments n
nfrastructure and research nfuence strategc busness decsons amost as much as market pre-
dctons does.
The private stakeholders are ready! Many forest-based companes have started to deveop
new bobased products to markets whch often are equay attractve to energy companes, chem-
ca companes, agrotechnoogy companes, and thus ndrecty aso for farmer cooperatves and
forest owners. Those sectors have much n common n the borefnery area and are deveopng new
cooperatons, knowng they can add to each others respectve strengths.
Seeding an idea of a Biobased industries PPP
The EU-funded Star-COLIBRI pro|ect gathered fve ndustry-drven European Technoogy Patforms
representng the bofues sector, forest-based sector, agrtechnoogy sector, pant breedng sector
and sustanabe chemstry sector as we as researchers from fve dfferent research nsttutes.
The pro|ect ooked at modes for coaboraton between on-gong research pro|ects, by dentfy-
ng gaps and overaps n on-gong research efforts, to make better use of resources, whst creatng
crtca mass and synergy. It aso estabshed a centra nformaton repostory for borefnery-reated
research pro|ects whch resuted n the Star-COLIBRI Borefnery Porta (www.star-cobr.net). Sup-
ported by the research communty and stakehoders of the fve partcpatng technoogy patforms,
the pro|ect aso pubshed a | ont European Borefnery Vson for 2030 and a European Borefn-
ery | ont Strategc Research Roadmap. The roadmap whch covers the compete area of borefn-
ery-reated research descrbes prortsed research undertakngs from bomass to bo-based prod-
ucts. Advce s aso gven on some strategcay-mportant actons to be undertaken by pocy mak-
ers and ndustry. Fnay Star-COLIBRI produced two deverabes about how to organse pubc
research fundng and factatng the creaton of a European Pubc-Prvate Partnershp as a form of
ntensfed European coaboraton and t was aso the partners of the Star-COLIBRI pro|ect that

13
encouraged the European Commsson to nvte prvate stakehoders to dscuss a pubc-prvate
partnershp.
Biobased for Growth PPP the work start
Ths frst offca meetng, caed to by the European Commsson n February 2012, estabshed that
the ndustry was ready to nvest n a pubc-prvate partnershp f the format was satsfactory. For-
est-based companes such as Berud, Homen, Mond, Mets Group, Sapp, SCA, Stora Enso,
Smurft-Kappa, Sdra, and UPM |oned as foundng members of the prvate group preparng for a
the PPP wth other foundng members ncudng energy companes (e.g. DONG Energy and
Abengoa Boenerga) chemca companes (such as Carg, Carant, DSM, Kemra and Nortsucker),
botechnoogy/agro-chemca companes such as Novamont, Novozymes, and Roquette. Farmer
cooperatves and Forest owners are aso represented n the prvate group and t s mportant to
emphasze that the prvate partnershp s not a cosed cub. It s open to new members throughout
the duraton.
The companes nvoved n the preparaton of the PPP - has estmated that durng the perod
2014-2020 they woud be nterested n nvestng more than C2,8bn n coaboratve research, de-
veopment and demonstraton n bobased technooges, assumng that the approprate pocy
frameworks are n pace.
The PPP ntatve s aso supported by estabshed European Technoogy patforms: SusChem,
Pants for the Future, the Forest-based Sector Technoogy Patform, European Technoogy Pat-
form FoodforLfe, European Bofues Technoogy Patform, Manufuture; European sector organsa-
tons as COPA COGECA, CEPI, EuropaBo, European Seed Assocaton, ERRMA, European Bo-
pastcs, FoodDrnkEurope, and CEFIC.
Biobased for Growth PPP scope and aims
The focus of a future PPP s threefod:
Feedstock: creatng vaue chans and provdng secure and sustanabe suppy of bomass
Biorefineries: R&D and up-scang through arge scae demo/fagshp borefneres
Markets, Products and policies: ensurng market pu and optmsng pocy frameworks.
In partcuar the PPP woud am to address the chaenge of ntegraton between exstng bobased
vaue-chans
Fosterng a sustanabe bomass suppy: Improvng output from agrcuture, agro-food and
forestry n a sustanabe and foreseeabe manner for feedng the word and producng bo-
based products wth a vew of vaorsng oca resources; Budng ogstcs & nfrastructure
for more compettve transport of varous feedstock/bomass to the new borefneres
Optmzng effcent processng: borefneres as the core processng operatons nkng bo-
mass suppy to market demand, whe promotng the most effcent use of bomass
Deveopng markets, products and poces; For nstance, many we-known brand owners
have stressed ther ambtons to repace ther packagng materas wth bobased materas.
The PPP ams to deveop and dever those products and aongsde speed up the creaton of
new markets and new products.
Biobased for Growth political consensus and the challenges ahead
The European Commsson has proposed an C80bn budget for research and nnovaton from 2014-
2020 and ths proposa s currenty beng dscussed by the European Parament and EU Member
States. In these tmes of fnanca austerty, t s not surprsng that any knd of pubc nvestment s

14
under mmense scrutny and that the PPP stakehoders are faced wth the chaenge of showng to
European parament members, commssoners, and mnsters that nvestng 1 bon Euros n a
PPP for bobased ndustres s an nvestment superor to the many aternatves. The st beow us-
trates some of the numerous decsons that must to be taken questons to answer n order to bud
the partnershp and convnce decson makers:
Pubc fnanca commtment
Impact assessment: How many addtona |obs are created? Industry nvestments?
Avod overaps wth ntatves on boenergy and sustanabe process ndustres!
Expan why exstng EU Research Framework Programme s not appcabe!
Baance of research versus demonstraton?
Food producton versus non-food producton?
Materas versus energy producton?
Feedstock mtatons? Incude agae and other potenta bomass sources or not?
Are a reevant sectors ncuded n the process?
Number of member states represented by the members?
Roe for SMEs
Roe of prvate research nsttutes and unverstes?
The budget dscussed for the perod 2014-2020 s n the range of 2 bon Euro, but a fna decson
s pendng. One of the ssues for whch consensus has to be estabshed s the baance between
research and demonstraton actvtes, where the pubc representatves generay woud ke to see
more basc research and the ndustry see the need for nnovaton support and more fundng to
demonstraton and testng at a arger scae. Another pont of dscusson s the perceved confct
between food producton and non-food producton, especay now wth ths years dry weather and
ow crop yeds n the US. Whe the PPP strve to optmze and use and bomass effcency and not
to swtch producton capacty from food to non-food, Pubc concerns ke these st has to be ad-
dressed propery.
Next steps
The estabshment of a Pubc-Prvate Partnershp for Bobased ndustres woud have a very pos-
tve mpact on the future of the forest-based sector. However, a ong and dffcut potca process
has |ust started and meanwhe prvate partners have to get organsed and prepare a Strategc
Research and Innovaton agenda. In 2012 or eary 2013, a potca decson must have been taken
by the European Parament and Counc. In 2013, an agency has to be estabshed to admnstrate
the fundng of borefnng actvtes. If these processes go accordng to pan, the Pubc-Prvate
Partnershp Bobased for Growth, wth a tota estmated budget of 2 bon Euros, w commence
ts actvtes n 2014.
Reguatory and ega frameworks for wood borefneres n EU and Russa

15
Regulatory and legal frameworks for wood
biorefineries in EU and Russia
Kaisu Annala, Allan Flink, Mariia Kaikkonen, Petteri Nuolivirta,
Matias Pekkanen, Jarno Seppl

ndufor Oy, Tlnkatu 11 A, 00100 Helsinki, Finland
Abstract
The target of the paper s to carfy, what knds of chaenges have to be taken nto account, and n
whch stage of the nnovaton process those chaenges shoud be faced when deveopng wood
borefneres n the EU and Russa. The reguatons handed reate to wood and bomass sourcng,
products themseves and the envronment.
Dfferent EU countres have dfferent pocy nstruments for renewabe energy. Feed-n-tarffs,
premums, quota obgatons, nvestment grants, tax exemptons and fsca ncentves vary from
country to country. EU drectves are mpemented n dfferent ways n the member countres.
What comes to the wood raw matera tsef, dfferent countres have dverse reguatons for
wood harvestng. Each country has a forest pocy of ts own and the states own dfferent stakes of
the forests. The forest aws defne the forest management and varous permts are needed before
trees n the forest can be cut. In addton, the regeneraton reguatons aso vary. The topcs reated
to sustanabty of the operatons have become an mportant ssue and protected areas, andscape,
cutura aspects, recreatona areas, etc. need to be taken nto account.
What comes to Regstraton, Evauaton, Authorsaton and Restrcton of Chemca substances
(REACH), borefneres producng boenergy have a dfferent status compared to the borefneres
producng boproducts. Bopoymers s a cass of ts own. Chemcas aready sod n the market
have been regstered n REACH. To get the cence, negotatons wth the prevous regstrants are
requred n order to agree upon the nformaton and the costs occurred. Non-regstered chemcas
are another type of chaenge.
The envronmenta and soca ssues reated to borefneres w be dscussed. How deep of an
envronmenta and soca mpact anayss s requred, depends on the product. The queston s: how
to defne the scope. Not ony the authortes grantng the permts but aso the stakehoders must be
abe to rey on or at east not oppose to the resuts of the assessment. For rsk management pur-
poses, n addton to the envronmenta and soca mpact assessment, a soca cense to operate
must be earned. Therefore, the assessment requres cear quanttatvey comprehensbe sustana-
bty ndcators, whch can be used as a patform for dscusson and argumentaton. Moreover, the
assessment shoud cover the whoe fe-cyce of the borefnery products from the raw matera
procurement to the end use of the fna product.
Does the framework concentrated n the promoton of boenergy sector have an mpact on the
tradtona wood-based product ndustry and n the evovement of the boproduct ndustry? Is t eas-
er to deveop other types of renewabe energy than boenergy because of reguatons?
ntroduction
The target of the paper s to carfy, what knds of chaenges have to be taken nto account, and n
whch stage of the nnovaton process those chaenges shoud be faced when deveopng wood
borefneres n the EU and Russa. The reguatons handed reate to wood and bomass sourcng,
products themseves and the envronment.
The artce repes to the foowng questons: Does the framework concentrated n the promoton
of boenergy sector have an mpact on the tradtona wood-based products ndustry and n the
evovement of the boproduct ndustry? Is t easer to deveop other type of renewabe energy than
boenergy because of reguatons?


16
Biorefineries
In ths paper the term borefnery s used to descrbe the producton system for boenergy, bofue
and varous boproducts, whch are ether n the nnovaton ppene or aready n the market.
Policy instruments for renewable energy
In the EU the target for energy from renewabe energy sources (RES) s 20% by 2020. The hghest
targets percentagewse have been set for Sweden, Latva, Fnand, Austra, Portuga and Denmark,
a above or equa to 30%. The ma|orty of countres, ke Germany, France, Itay, Span and the UK,
start from a very modest eve but w have to mutpy the use of renewabe energy by 2020.
What comes to bofues n transportaton, European Commsson estabshed a goa of 5.75% by
2010. Ths target was reached ony n France (5.9%), Germany (6.2%) and Sweden (7.3%) of the
15 countres, whose reports have been pubshed. Nevertheess, a new target of 10% was set to
2020. The appcabe energy sources are eectrcty, hydrogen generated from RES and frst or
second generaton bofues.
The states have a freedom to choose, how to reach the targets of ths Renewabe Energy D-
rectve (RED), as shown n Fgure 1. Feed-n tarffs, premums, quota obgatons, nvestment
grants, tax exemptons and fsca ncentves are n use. There s varaton, how each state appes
these "carrots or stcks" from power generaton or heatng to transportaton fues.
These nstruments have not been too effectve at east by 2010. The EU Emssons Tradng Sys-
tem seems to be more effcent. For exampe, from the start of 2012, emssons from a domestc
and nternatona fghts arrvng at or departng from an EU arport w be covered by the EU Ems-
sons Tradng System. A arnes fyng through EU arspace are requred to pay 15% of ther pout-
ng carbon emssons. Around 4 000 arnes shoud pay for EU pouton permts. Consequenty,
severa ma|or arnes are movng towards bofue. As ASTM (used to be Amercan Socety for Test-
ng and Materas) approved the use of 50% bend of hydroprocessed esters and fatty acds
(HEFAs) fue to be mxed wth conventona kerosene n 2011, the prmary reason sowng down the
use of bofue s ts avaabty (and yes, the prce).
It can be expected that the growng use of bofue n avaton speeds up the pace n swtchng to
bofues aso on the ground and n sea transportaton, provded that sutabe bofue s avaabe.
The word s awatng for bobutano, whch s not ony more cose to dese n ts voumetrc energy
content but s sad to easy mx wth dese and to be ess corrosve than ethano.
In Russa the man concept s the Energy Strategy of Russa unt 2030. It was adopted n 2009
by the Russan government and concentrates many on the more effcent o, natura gas, coa
producton and energy securty. It contans though a few ssues focused on the second generaton
bofue. The Russan government resouton n | anuary 2009 set a quanttatve target of 4.5% for
RES n the energy producton. The percentage may frst sound ow unt understandng that hydro-
power s not counted as RES.
The downsde of the pocy nstruments s the voatty: the nstruments may change and do
change, maybe not overnght, but at east when swtchng from one government to another and
from a strategy round or budgetary season to the next one. Shoud the fnancng decsons for the
nvestments be done by forgettng any mpact of the poces prevang today as they may change
before the borefnery s up and runnng?

17

Fi gure 1. Dfferent pocy nstruments n the EU countres.
Regulations for Wood and Biomass Sourcing
Dfferent countres have dverse reguatons for wood harvestng. Each country has a forest pocy
of ts own and the states own dfferent stakes of the forests. Forest aws defne forest management
and varous permts may be needed before trees can be cut. The topcs reated to sustanabty of
the operatons have become an mportant ssue and protected areas, andscape, cutura aspects,
recreatona areas, etc. need to be taken nto account.
EU Forest Law Enforcement, Governance and Trade (FLEGT) w come nto force n March
2013. Seven years of dscussons reached a resut, whch mts the producton and consumpton of
ega tmber. As a consequence FLEGT censes w be ssued, ndependent montorng w be
apped and tmber w be controed at EU borders.
EU Tmber Reguaton (EUTR) w enter n force n a 27 EU Member States on 3 March 2013.
The reguaton w prohbt the pacng on the EU market not ony egay harvested tmber but aso
products derved thereof. The products ncude fue wood, sawn wood, pywood, packng matera,
pup and paper, wooden furnture, etc. Ony recyced products w escape the oop. Records of
suppers and customers have to be mantaned.
It s not possbe to forget Russas membershp n the Word Trade Organzaton (WTO), whch
came nto effect n 2012. It w have a postve mpact on wood and wood-based product trade n
the regon.
REACH and CLP
REACH reguaton came nto force n 2007. It requres the chemca manufacturers and mporters to
generate data for a chemca substances produced or mported nto the EU above one tonne per
year. The rsk management measures must be dentfed and communcated.
Penty of exceptons n the regstraton exst. The typca reason for exempton s that the sub-
stance aready beongs to another reguatng procedure (fertsers, detergents, exposves, pyro-
technc artces, drug precursors, pant protecton products, bocda products, hazardous substances
n eectrc/eectronc equpment, nanomateras, eco-abeed products, emssons to ar and water,
fuornated gases, ozone depetng substances, food/feed addtves or cosmetc products). The
exemptons above ony appy, when the chemca s used n that partcuar reguated appcaton as

18
the actve substance. Further exemptons are, f the substance beongs under waste drectve or s
reused as such or recovered, becomng end-of-waste. Aso poymers are exempt, but not monomers.
REACH permttng does not appy for substances "used as fue n mobe or fxed combuston
pants of mnera o products and use as fues n cosed systems", whch opens a queston, shoud
and does ths aow, fary enough, bofue to be exempted as we. There s an EBB (European
Bodese Board) Bodese REACH Consortum to ensure proper regstraton of bodese and reat-
ed substances. Scentfc work and demos are though aowed as ong as the matera voume s
beow one tonne per year.
REACH permttng s nether requred for ntermedate products, whch are consumed at the pro-
ducton ste. However, f the product s consumed by another company and there s addtonay an
ntermedate storage, permttng s requred even at the same ste.
The frst step s to fnd out, under whch reguaton the substance beongs to and f the substance
has aready been regstered. The producer or mporter shoud |on the consortum, who regstered
the substance. Constructve negotatons wth the man regstrant are needed, to secure that pro-
ducton and saes can be aunched as panned. If the substance s new n the EU and has not been
regstered before, the regstraton has to be done before startng the operatons.
CLP reguaton cannot be forgotten ether. It reguates cassfcaton, abeng and packagng of
substances and s agned wth GHS, the respectve Gobay Harmonzed System under the Unted
Natons. The target s to ensure a hgh eve protecton of both human heath and envronment n
both ndustry and transportaton, and to aow free movement of substances. The notfcaton has to be
devered one month before the substance enters the market by the producer and/or the mporter.
Russa s posed to adopt a reguaton consstent wth the EUs REACH. Russa has formed wth
Kazakhstan and Bearus a Customs Unon, where the chemca reguatons are handed. The Unon
became a snge economc space as of 1 | anuary 2012. The same reguatons w aso appy n the
Eurasan Economc Communty, whch n addton to the states of the Customs Unon, ncudes
Kyrgyzstan, Ta|kstan and Uzbekstan.
Sustainability for biorefineries
To ensure sustanabty of operatons, a wde set of requrements has to be fufed. Frst, the env-
ronmenta and soca mpacts and rsks have to be assessed. The abour and workng condtons
and the potenta mpacts for the heath, safety and securty of the workers and the communty have
to be studed. The and acquston process has to be handed wth care, not ony for the producton
ste of the borefnery but aso for the bomass producton regons. Speca attenton shoud be pad
to possbe nvountary resettement and to the (often confctng) nterests of oca resdents and
ndgenous peope. In case and s not owned, but eased or under some other type of contract
agreement, smar cauton sha be pad. Both the cutura hertage and conservaton of the bod-
versty have to be taken nto account. The mtgaton of the rsks and mpacts has to be presented.
Accordng to the prevang EU reguatons, a ths shoud be performed for two or three aternate
producton stes. After approva of ths ESIA, Envronmenta and Soca Impact Assessment, the
varous permts w be apped to one of the stes. A above has to be done before startng the con-
structon of the borefnery.
In Russa, smar concept s n effect, but n two forms. The frst one s SEE, State Envronmenta
Expertse, where a deveopers have to present the pro|ect pans to the Federa or Provnca SEED
departments. SEED may hre experts or teams to assst n evauaton of the envronmenta regua-
tons and the fna SEED resouton may be postve or negatve. The second concept s OVOS, the
assessment of the envronmenta mpacts, n whch the deveoper has to prepare an envronmenta
mpact statement and the authortes have to ntate the consutaton and pubc partcpaton pro-
cess. The envronmenta mpacts are then baanced aganst the soca and economc consdera-
tons. OVOS does not appy to a pro|ects as SEE, but to pro|ects sted n OVOS reguatons, a st
that s broader than the Espoo Conventon.
The reguatons vary somewhat from country to country aso nsde the EU. The fact s that no ma|or
company s n the poston to overook the sustanabty ssues today when pannng a ma|or nvestment

19
anywhere n the word. In ma|or nvestments requrng externa fnancng ths s sef-evdent as fnancers
woud not approve oans f the assessment woud end up n a negatve concuson.
Compance to aws, reguatons and censng requrements does not guarantee sustanabty. In
addton to meetng requrements prescrbed by the egsator, sustanabe companes go far be-
yond. They see themseves as a part of the surroundng envronment and accept certan roes and
responsbtes n t. They pan, start, execute and ext operatons n a way that does not cause
harm, but preferaby provde benefts to oca peope and the envronment - and at the same tme
vaue to the company. Ths paves the way for ganng acceptance and trust among stakehoders
and concurrenty reduces rsks and possbtes for confct.
Such a "soca cense to operate" dffers from other permts as t cannot be obtaned but has to
be earned. The consutaton processes of the ESIA and permttng processes s a good hep n
deveopng the dscusson and co-operaton between the bodes. When earned, the "soca cense"
s the best asset for mantanng reatons wth stakehoders, managng soca and envronmenta
rsks and chershng corporate reputaton.
Conclusions
Ths paper covers ony such reguatons whch most obvousy have to be comped wth n wood
borefneres. Before the green button can be pushed to start a borefnery, qute a ong st of var-
ous other permts must have been granted. We sha not forget the varous constructon and opera-
ton reated permts, whch dffer from country to country, from cty to countrysde, from a regon to
another.
It may sound that the pentfu reguatons woud prevent any new type of producton pant. At the
end, the target s the safety of operators, ctzens and pass byers. There are numerous exampes,
where everythng dd not go as we as t was orgnay panned.
There are no reguatory reasons, why a borefnery woud not succeed. The needed assess-
ments, paper work and procedures |ust have to be mpemented frst.
Forest borefneres - sustanabe busness opportuntes n Scandnava and North Amerca

20
Forest biorefineries sustainable business
opportuni ties in Scandinavia and North America
Annukka Nyh
1
, Hanna-Leena Pesonen
2

1
School of Forest Sciences, University of Eastern Finland
(School of Business and Economics, University of Jyvskyl), annukka.nayha@uef.fi
2
School of Business and Economics, University of Jyvskyl, hanna-leena.pesonen@jyu.fi
Abstract
The goa of ths study s to compose a hostc vew of the ssues affectng the deveopment and m-
pementaton of forest borefneres and present future vews for the forest custers n Scandnava and
North Amerca. The Deph study was conducted n three phases n 2008-2011: Frst, an nternet
survey wth reated quanttatve anayses was conducted. The foowng two phases were quatatve n
ther nature wth themed ntervews and ema nqures, and reated thematc anayss. The resuts
from a the Deph rounds ndcate that the key factors for forest borefnery deveopment and bofue
producton are qute smar n the studed countres. Hgh prce of o, natona securty of fue suppy
and ong-term poces are the most promnent macro-scae drvers. At the ndustres eve, the suc-
cessfu mpementaton of a borefnery busness requres effcent expotaton of exstng wood bo-
mass resources, avaabty of fnancng and coaboraton between dfferent vaue chan actors. At the
strategc eve an understandng of new markets and management of change as we as deveopment
of economc wood fractonaton technooges factate best the dffuson process. Overa, borefnery
busness s seen as a sustanabe when takng nto consderaton envronmenta, soca as we as
economc dmensons. Nevertheess, forest borefnery busness w further ntensfy the pressure of
forest-based ndustres towards forest-ecosystems whch n turn can ead to varous envronmenta
mpacts. Furthermore, both n the Scandnavan and North Amercan forest ndustres, the conserva-
tve organzatona cuture seem to create an mportant barrer to restructurng the busness.
ntroduction
Bomass-based energy (boenergy) and products (boproducts) pay an mportant roe n socetys
transton towards a more sustanabe, bo-based economy. Consstenty, a bo-based economy wth
reated new opportuntes offers ways for dversfyng busness n the forest custer. The need to
redefne busness modes s partcuary urgent n the mature pup and paper ndustry, wth ts fre-
quent m cosures (e.g. Chambost and Stuart, 2007; Toand, 2007). Wdey studed at the moment
are gnoceuosc, non-food bomass feedstocks and technooges for convertng these sources nto
economca, ow-carbon bofues (carbon s used as a shorthand for fe cyce goba warmng m-
pact, Farre et a. 2007) and boproducts (e.g. FAO, 2011; Hetemk, et a., 2011; | ohnson et a.,
2009; Perack et a., 2005). There has been penty of nterest n borefneres ntegrated nto the
pup and paper ndustry. In ths study, a forest borefnery s defned as a mut-product factory that
ntegrates bomass converson processes and equpment n order to produce a varety of boproducts
such as fues, fbers, and chemcas from wood-based bomass (e.g. NREL, 2012; Ragauskas, 2006).
However, n addton to consderabe opportuntes, there are aso many rsks reated to borefn-
ery mpementaton. Thus, as the emergng borefnng economes contnue to take shape, there s a
growng need for reastc estmates of the factors that affect the dffuson process of forest borefn-
eres both n the goba and the natona busness envronments. Overa, the chaenges reated to
borefneres must not be seen as purey technca probems nor as ssues unconnected to socety.
Nevertheess, studes reated to forest borefneres have argey been technoogcay focused unt
recent years (Sderhom and Lundmark, 2009).
The goa of ths Deph study s to compose a hostc vew of the ssues affectng the dffuson of
forest borefneres n Scandnava and North Amerca and present future vews for the forest cus-
ters n the studed areas.


21
Theoretical framework
nnovation and new technology diffusion
Accordng to Rogers (2003), diffusion s the process by whch nnovaton s communcated through
certan channes over tme among the members of a soca system. Technoogca dffuson can be
aso understood as referrng to the expanson of the utzaton of a new concept, be t a new prod-
uct, new processes or new management methods wthn and across economes (Stoneman, 1986).
Athough cassc modes of technoogca deveopment suggest a straghtforward, near path
from basc research and deveopment to technoogy commercazaton and adopton, n practce,
technoogy dffuson s more often a compex and teratve process. Technoogy can dffuse n mu-
tpe ways - dependng on the partcuar technoogy - across tme, over space, and between dffer-
ent ndustres and types. In addton, the effectve use of dffused technooges by companes fre-
quenty requres organzatona, workforce, and foow-on technca changes. (Baptsta, 1999; Free-
man, 1996; Peres et a., 2010)
Often, nnovaton research has focused on technca ssues and prmary concentrated ony on
those stakehoders drecty nvoved n the vaue-addng actvtes or market reatonshps, such as
the customers, compmentary nnovators and suppers. Further, technoogca nnovaton process-
es have been studed many tmes by exporng the mportance and reaton of research and deve-
opment (technoogy push) and actvtes that encourage commercazaton and mpementaton of
new nnovatons (market pu). (Dos, 1982; Freeman, 1996; Inoue and Myazak, 2008) Other envi-
ronmental, political, economic, social, networking and institutional factors are often gven ess em-
phass. Technoogy as such cannot guarantee success of an nnovaton f other aspects reated to
the nnovaton are not accepted by stakehoders. (e.g. Baptsta, 1999; Cora, 2001; Freeman, 1996;
Ma|ahan et a., 2000; Peres et a., 2010)
The dffuson of an nnovaton rarey takes pace n an unchangng envronment. Furthermore,
dffuson processes of new products and servces have become ncreasngy compex n recent
years. (Peres et a., 2010)
Analyzing the Business environment
| ohnson et a. (2008) have provded a framework for understandng the envronment of the organ-
zatons wth the am of hepng to dentfy key ssues and ways of copng wth change. Envronmen-
ta nfuences and trends can be thought of as layers around the organization. The outer ayer s
referred to as the macro-environment, whch s the most genera ayer, consstng of broad env-
ronmenta factors that mpact to some extent neary a organzatons. Wthn the macro-
envronment st industries or sectors, and the nner ayer stands for further strategic groups. These
are organzatons wth smar strategc characterstcs.
Data and methods
The study uses a Deph method, whch s a technque for obtanng forecasts from seected experts
(Landeta, 2006). The research was conducted n three phases n 2008-2011: Frst, an nternet
survey wth reated quanttatve anayses was conducted. A tota of 125 forest and boenergy sector
representatves responded to the survey, yedng a response rate of 24.5%. The foowng two
phases were quatatve n ther nature wth themed ntervews and ema nqures, and reated the-
matc anayss. The nne respondents, who partcpated n the frst phase, answered the questons
n the second research phase. In the thrd research round a tota of 23 representatves partcpated
n the themed, sem-structured expert ntervews n the U.S., Canada, Fnand and Sweden.

22
Results and discussion
Forest biorefi nery facili ties
Ths study created a pcture of a forest borefnery n the studed areas as a mut-product facty, n
whch hgh vaue-added boproducts together wth bofues are produced from forest-based feed-
stock |onty wth the other ocay avaabe bomasses. As a basc borefnery concept, respondents
ndcated factes wth 200 000 to 300 000 or even 500 000 tons per year of bofue producton
capacty n whch Fscher-Tropsch dese w be a prncpa product. Forest resdues (oggng tops,
pre-commerca thnnngs, stumps) and m resdues were consdered the most sgnfcant wood-
based bomass sources n future bofue producton. In Fnand many respondents aso beeved
that peat w pay a sgnfcant roe n forest borefnery factes. Moreover, experts hghghted the
evauaton of the potenta of varous feedstocks n addton to forest resdues. Urban organc waste
n partcuar was beeved to have future potenta. (see aso Nyh and Pesonen, 2012a; b) How-
ever, the sgnfcance of varous ow-voume, hgh-vaue bo-products n addton to hgh-voume
buk products were seen as cruca: synthetc poymers, vscose fber dervatves, fues, (butano,
ethano) chemcas, medcnes, cosmetcs, nanotechnoogy products, ntegent paper and packag-
ng, and composte materas. Estmates of the mportance of new products vared greaty, startng
from 10% of tota producton to the hghest estmates of 50%.
Key diffusion factors for the forest biorefineries
It has been shown by ths study that the forest borefneres can be mpemented n dfferent ways
wth case specfc varaton n raw materas, products, degree of ntegraton and consorta partners.
In addton, borefnery busness requres nvovement of dfferent ndustres and coaboraton be-
tween partners. Therefore, dffuson of forest borefneres s a mutfaceted process that s affected
by a varety of ssues. The compexty of the dffuson process has aso been addressed n many
other studes concernng the dffuson of new technooges (e.g. Baptsta, 1999).
The resuts from a the Deph rounds ndcate that the key factors for forest borefnery dffuson
(Fgure 1) are qute smar n the studed countres (see aso Nyh et a., 2011; Nyh and
Pesonen, 2012a). Based on three research rounds, the key eements that promote faster deveop-
ment of forest borefneres are presented n Fgure 1.

Figure 1. The key drvers for the forest borefnery dffuson.

23
4.3 Future views: Sustainability and Restructuring the Business
In the frst research round the respondents were asked to choose from four future vews - defned
as Business as Usual, Restructuring the Business, Sustainability, and Domestic Competencies
(vews are based party on work of Hyrynen et a., 2007) - the one that corresponds to ther m-
presson regardng the future of the forest custer (Nyh et a., 2011). Sustainability and Restruc-
turing the Business best descrbe the future deveopment of the forest custer, as 80% of the re-
spondents chose one of the two optons. In Scandnava, the Sustainability vew got more support
compared to North Amerca whereas n North Amerca the Restructuring the Business vew was
more common compared to Scandnava. Accordng to the Sustainability vew the forest custer s
successfu n a socety that respects ecoogca vaues and sustanabe forest utzaton. Sustana-
bty s the key ssue aso n fnanca decson-makng. Producton w be further deveoped towards
energy and raw matera effcency. Borefneres and reated new products sustanaby guarantee
the forest custers success. Accordng to the Restructuring the Business vew, the compettveness
of the natona, tradtona forest custer w dsappear, and reance on od producton structures
remans hghy rsky. Investments are amed at new markets and new busness concepts. Accord-
ng to ths vew, there s a strong nterest n an ncreasng amount of pro|ects geared towards bore-
fnery concepts and new products.
Interestngy, recent deveopments n the forest borefnery sector and the current trends wder n
socety ndcate that the future vews chosen as most key n 2008 have started to actuaze n
many contexts. A transton towards boeconomy - whch n a broad sense means the expotaton
and management of renewabe natura resources n a sustanabe way - s one of the most prom-
nent trends of the current socety (EC, 2011). Respectvey, many deas that are presented n the
Sustainability vew of ths research are consstent wth the boeconomy efforts. Accordng to the
Restructuring the Business vew, there s rsng nterest n and pro|ects workng wth forest borefn-
ery concepts and products. These statements have been reazed n many terms, as there are
many on-gong borefnery pro|ects both n Scandnava and North Amerca.
Overa, fndngs of ths Deph study ndcate that borefnery busness s seen as a sustanabe
when takng nto consderaton envronmenta, soca as we as economc dmensons. Accordngy,
envronmenta sustanabty s an mportant drver for the forest borefnery busness n genera. A
companys envronmentay sustanabe mage can aso be a compettve advantage. Even though
the borefnery busness was consdered to be sustanabe n genera terms, the responses aso
ndcated that harvestng feedstock s the part most chaengng to manage n the vaue chan, and
ts envronmenta mpacts are not suffcenty known. Moreover, accordng the respondents there
shoud exst appcabe sustanabty crtera for bomass raw matera and ts use (Nyh and Horn,
2012). Furthermore, t was beeved that raw matera demand of borefneres cannot be satsfed
soey wth wood-based bomass. A n a, n every research phase severa statements of the re-
spondents ndcated that forest borefnery busness w further ntensfy the pressure of forest-
based ndustres toward forest-ecosystems whch n turn can ead to varous envronmenta mpacts
and chaenges. Accordngy, the roe of NGOs, partcuary varous envronmenta groups, was
consdered mportant, especay n the U.S. In the U.S., envronmentasts seem to be more of a threat
whereas n Scandnava those groups are seen to go more hand-n-hand wth other stakehoders.
North Amercan and Scandnavan forest ndustres are facng the stuaton n whch restructurng
the busness s cruca, due to the mature - or even decnng - state of many parts of the busness.
The drvers for change are wdey recognzed, but pathways for the new busness argey st need
to be created (see aso Nyh and Pesonen, 2012b). In both the Scandnavan and North Amercan
forest ndustres, the conservatve organzatona cuture and ack of fnanca resources seem to
create mportant barrers to change. The scope of the change wth the needed transformaton actv-
tes and resources depends argey on contextua features such as the ocaton of the borefnery,
chosen technooges and raw matera avaabty. The roe of the forest ndustry n the forest bore-
fnery consortum s argey seen as a bomass provder. Operatng a commerca-scae forest bore-
fnery facty requres both new managera- and operatona-eve sks. Readness for change
need to be embedded n the organzatona cuture - and the key for attanng ths s open-mnded,
mut-dscpnary organzatona management. Innovatve personne are beeved to be found n

24
forest ndustry companes, yet current cuture does not encourage these peope to put forward ther
deas. The success n the borefnery busness cannot be acheved wthout coaboraton that com-
bnes the rght set of resources. Nevertheess, t w be chaengng to share profts among the part-
ners n the borefnery consortum.
Conclusions
There s a strong aspraton to move towards a bo-based economy n present socety, and boenergy
and boproducts pay an mportant roe n ths transton. Though the forest borefneres w certany
pay a roe n ths process n the comng years, at ths pont t s very dffcut to gve exact estmates
of how promnent ths roe w be and how dffuson of forest borefneres w expcty proceed.
Durng the research perod the perceptons have wdened from an exporaton of borefneres from
a purey technca perspectve to more hostc approaches. Moreover, ths study ndcates that for-
est borefneres have a mutfaceted dffuson process n whch a varety of ssues affect the dffu-
son. Thus ncentves that promote the borefnery busness must stem from severa sources.
Incentves for the borefnery busness dffer ony sghty n the studed areas, and there were no sg-
nfcant dfferences n the opnons between the sectors that were nvoved n the study. Therefore t can
be concuded that both studed areas seem to have potenta for success n the borefnery busness.
One of the most strkng aspects to emerge from ths study s the rather angud atttude of forest
ndustry companes towards new busness and nerta n the strategc management. Ths s nterest-
ng, as the nvoved ndustres themseves shoud work to actvey create strateges for managng
change and amng resources towards new busness. However, t was aso beeved that the forest
ndustry has been more future-orented than has been pubcy ndcated.
Overa, t seems that the hype that was reated to renewabes n genera and to the borefnery
busness has passed, and at a the eves of the busness envronment more reastc pans and
approaches are beng made, wth the actua steps n the form of commerca-scae borefneres.
References
Baptsta, R. 1999. The Dffuson of process nnovatons: A Seectve Revew. Internatona | ourna
of the Economcs of Busness 6(1), pp. 107-129.
Chambost, V., Stuart, P.R. 2007. Seectng the most approprate products for the forest borefnery.
Industra Botechnoogy 3(2), pp. 112-119.
Cora, | . 2009. Taxes, permts, and the dffuson of a new technoogy. Resources and Energy Eco-
nomcs 31(4), pp. 249-271.
European Commsson 2011. European Strategy and Acton pan towards a sustanabe bo-based
economy by 2020. Intatve, November 2011. Avaabe at http://ec.europa.eu/governance/
mpact/panned_a/docs/2010_rtd_055_sustanabe_bo_economy_en.pdf. Accessed 16.4.2012.
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Unversty of Caforna Press.
Freeman, C. 1996. The greenng of technoogy and modes of nnovaton. Technoogca Forecastng
and Soca Change 53(1), pp. 27-39.
Hetemk, L., Nnst, S., Sepp, R., Uusvuor, | . 2011. Murroksen |keen. Metsen kytn tue-
vasuus Suomessa |Utzaton of Fnnsh forest n future|. Metskustannus, Karsto Oy,
Hmeennna. (In Fnnsh.)
Hyrynen, S., Donner-Amne, | ., Nskanen, A. 2007. Gobasaaton suunta |a metsaan vahtoehdot
|Drecton of gobasaton and forest custer optons|. Unversty of | oensuu, Facuty of
Forest Scences. (In Fnnsh.)

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Inoue, Y., Myazak, K. 2008. Technoogca nnovaton and dffuson of wnd power n | apan. Tech-
noogca Forecastng and Soca Change 75(8), pp. 1303-1323.
| ohnson, K., Schoes, R., Whttngton, R. 2008. Exporng Corporate Strategy. 8th edton, Harow,
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| ohnson, B., | ohnson, T., Scott-Kerr, C., Reed, | . 2009. The Future s Brght, Pup and Paper In-
ternatona. October 2009, pp. 19-22.
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and Soca Change 73(5), pp. 467-482.
Maha|an, V., Muer, E., Bass, F.M. 1990. New Product Dffuson Modes n Marketng: A Revew
and Drectons for Research. | ourna of Marketng 54(1), pp. 1-26.
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htm?qp=ste%3Awww.nre.gov+ste%3Asam.nre.gov&qs=&qc=nre&ws=0&qm=0&st=1&
nh=10&k=1&rf=0&oq=&co=nre&qt=borefnery. Accessed 14.6.2012.
Nyh, A., Hmnen, S., Pesonen, H.-L. 2011. Forest borefneres - a serous goba busness oppor-
tunty. In: Aen, R. (Ed.). Chapter 4, Borefnng of Forest Resources. Bookwe Oy, Porvoo.
Nyh, A., Horn, S. 2012. Envronmenta sustanabty-aspects and crtera n forest borefneres. | ourna of
Sustanabty Accountng, Management and Pocy | ourna. (Accepted for pubcaton.)
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Technoogca Forecastng and Soca Change 79(6), pp. 1111-1120.
Nyh, A., Pesonen, H.-L. 2012b. The forest ndustrys strategc change towards the borefnng
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Peres, R., Muer, E., Maha|an, V. 2010. Innovaton dffuson and new product growth modes: A
crtca revew and research drectons. Internatona | ourna of Research n Marketng
27(2), pp. 91-106.
Perack, R.D., Wrght, L.L., Turhoow, A.F., Graham, R.L., Stokes, B.| ., Erbach, D.C. 2005. Bomass
as feedstock for a boenergy and boproducts ndustry: The technca feasbty of a bon-
ton annua suppy. U.S. Department of Energy, DOE/GO-102005-2135.
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bofues and pup producton. Industra Botechnoogy 2(1), pp. 55-65.
Rogers, E.M. 2003. Dffuson of Innovatons. Free Press, New York.
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nomche 40(4), pp. 585-606.
Sderhom, P., Lundmark, R. 2009. Forest-based borefneres: Impcatons for Market Behavor
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Toand, | . 2007. Hard tmes n Hesnk, Oso and Stockhom. Pup & Paper Internatona 49(12),
pp. 5.
Roadmap for advanced bo-based materas

26
Roadmap for advanced bio-based materials
Katja Salmenkivi, Petri Vasara
Pyry Management Consulting Oy

Advanced bo-based materas ncude a arge varety of products. Deveopment and commerca-
zaton has taken off thanks to resource constrants, ncreased demand for green products and ds-
coveres n enabng technooges. In genera, the advanced bo-based materas sector s n a
phase of expanson on many fronts smutaneousy and wthout coordnaton. The future ooks very
promsng wth aggressve demand growth n severa appcaton areas. New materas are contnu-
ousy beng deveoped, and breakthroughs may propagate qucky across end-uses. Some of the
most promsng end-use sectors are: Packagng, persona care (tssue and cosmetcs), consumer
eectroncs, constructon and furnture, automotve, and a group of uses ncudng pharmaceutcas
and ndustra textes. Pyry estmated current market szes for the advanced bo-based materas
to be 22 bon EUR n these respectve sectors. Market pro|ectons by end-use sector were deter-
mned to be as foows:
cosmetics and tissue/hygiene (value added consumer products) dominating at 14 bill.
EUR and 4 bill. EUR, respectively,
construction and automotive follow (2.6 bill EUR and 990 MEUR),
technical and medical textiles (470 MEUR) and
packaging, pharma and consumer (200 MEUR, 110 MEUR and 40 MEUR).

Market growth for these new materas rees heavy on the hgh number of r&d efforts that are
takng pace on severa fronts around the word. The ntatves to foow are actuay so numerous
that the probem of "nformaton overoad" s very much at the forefront - aong wth quaty ssues n
what s camed.
The Pyry BoCurve descrbes some of nterestng ntatves and ther deveopment phases from
dscovery to the tota market assmaton. The current status and the future possbtes of the se-

Roadmap for advanced bo-based materas

27
ected exampe materas are anayzed here by showng ther ocaton on the curve. It s crtca to
pass "the fence" and to be abe to |ump to the market.

It s mportant to reaze that successfu market penetraton s not enough when deang wth the bo-
based materas ndustry. The avaabty of bomass resources, technoogy deveopment and mar-
ket demand form a trad of key questons for growth of bo-based materas producton. In bomass,
there s great varaton n the vaue chan from fed to end user dependng on feedstock and geo-
graphca ocaton. Unt now bo-based materas have been produced from ma|or bomass com-
modtes such as starch, sugar, wood and vegetabe os. However, new raw matera sources have
to be ntroduced f bg scae operatons are pursued. It s st n many cases uneconomc and tech-
ncay not possbe to produce many hgh voume advanced bo-based materas from wood. How
about the future? Where can we fnd the most nterestng ntatves addng vaue n future? Where
woud the Nordc raw materas, wood have the most nterestng opportuntes?
The presentaton w specuate on where the most nterestng product opportuntes for Nordc
wood based bo refneres coud be found by presentng a roadmap for these.
Bo-based chemcas - success by maxmzng vaue and beng resource effcent

28
Bio-based chemicals success by maximizing value
and being resource efficient
Anna Holmberg
Arizona Chemical AB, P.O. Box 66, SE-820 22 Sandarne
Contents
Creatng vaue s a core task for any busness. The Arzona Chemca (Arzona) vaue creaton
mode buds on offerng the customer a green and nnovatve product wth a hgh functonaty. The
green product often substtutes one based on non-renewabe raw materas. However, beng green
s not enough. Instead the "greenness" must be combned wth a functonaty that brngs ad-
vantages to the customers producton process or mproves hs or her end product. It s ony when
the green nnovaton and the functonaty are combned that true vaue can be created.
Arzona appes ts vaue creaton mode n each of ts four focus markets. To the Adhesive mar-
ket, Arzona suppy bo-based resns for tack and adheson n hgh performance end appcatons.
We aso offer tackfers, whch extend the appcatons of water based adhesves nstead of sovent
based ones. To Tire producers, we provde tread enhancement addtves that work wth the tre to
mprove tracton and breakng dstance. The same addtves mprove the poymer-fer nteracton
and thus ower the rong resstance of the tre and save fue. In the Roads & Construction sector,
our nnovatons aow hgher use of recyced matera n new pavements rather than beng thrown
nto andfs, whch earer was often the case. Our resns aso ncrease the durabty and umnosty
of road markngs. To the Personal Care market, we provde bo-renewabe and safe products used
n varous appcatons, such as sun screens, p goss and mascara.
At Arzona we beeve n market drven product deveopment. We nteract wth the customer to
defne hs or her needs pror to startng the deveopment of a new product. We suppy a souton,
whch s tcked off by the customer pror to any busness transactons takng pace. Accordng to our
experence, appyng ths "outsde-n" perspectve s vta n budng sustanabe and proftabe busness.
In our day work, we foow the New Product Bueprntng (NBP) methodoogy deveoped by Ad-
vanced Industra Marketng Inc. Frsty; a thorough Market Research takes pace wth the target of
dentfyng the most attractve opportuntes. Secondy, we perform Dscovery Intervews wth exst-
ng and potenta customers to uncover unmet needs. Thrdy, we contnue wth Preference Inter-
vews to be abe to prortze among the dscovered unmet needs. Fourthy, we do a Sde-By-Sde
Testng to truy understand compettve offerngs that we face n the market pace. Ffthy, we defne
the product ob|ectves to be met and deveop ths further through Technca Branstormng. Fnay
we summarze by concudng whether or not we have a sod Busness Case.
We beeve that we know what we tak about when t comes to deveopng bo-refnery busness.
We run modern refneres wth over 80 years of experence. We have a proven track record of
commercazng new products and brngng vaue to the customer. And we are truy market drven
wth an "outsde-n" perspectve on busness.
When we rase our eyes from the pure busness perspectve and address the arger potca pc-
ture, we can see that our word s presenty facng severa tough chaenges. We are gong through
the worst fnanca crss n modern tmes, we are experencng a cmate change whch forces us to
rethnk many of our od beefs and we see an ever-ncreasng fght over resources. To address
these chaenges, we must deveop a resource effcent, ow carbon economy. Important focus
areas are fe cyce thnkng, effectve use of resources and sustanabe products. And we shoud
acheve ths whe mantanng the hgh quaty of fe that we are used to.
To acheve the resource effcent, ow carbon economy, Arzona advocates the mpementaton
of four fundamenta prncpes:
1. A natura raw matera sha aways be used to ts fu potenta through cascadng use
2. A eve payng fed sha exst between users of the same resource

Bo-based chemcas - success by maxmzng vaue and beng resource effcent

29
3. Sound busness s based on market economcs, not on ncentves
4. Focus sha be set on creatng hghest possbe vaue.
Cascadng use s a about makng the most out of a raw matera by securng ts fu potenta. Step
by step the ntrnsc vaue s extracted. Sde streams to the man producton fow are defned as co-
products. It s ony at the end of the cascade - when no further ntrnsc vaue remans - that the
resource shoud be defned as a resdue and be promoted for energy purposes.
A eve payng fed aows users to compete for the same raw matera on far and equa terms.
One appcaton shoud not be potcay favored for another - nstead ths shoud be eft to the
market to decde upon. Potca ncentves and subsdes create market dstorton by "pushng" raw
materas nto certan appcatons and by cuttng off the natura cascadng use prematurey. Ths
resuts n reduced resource effcency.
Basng new products on ncentves w never bud ong-term sustanabe busness. Incentves
are potcay decded and what mght seem ke a "safe haven" today can be gone tomorrow. In-
stead any new product must be strong enough to survve on ts own merts n the market economy.
By focusng on creatng hghest possbe vaue from a raw matera, a stakehoders n the vaue
chan are potenta wnners. It aso stmuates nnovaton and busness acumen and thereby bene-
fts the socety as a whoe.
The mportance of the four prncpes can be exempfed wth a rea fe exampe. Arzonas man
raw matera s Crude Ta O, or CTO, whch s a co-product of kraft pupng. CTO s a qud bo-
mass, whch s scarce, .e. ts suppy s mted. A we-estabshed appcaton s the one Arzona
represents, .e. bo-chemcas. A newer appcaton deveoped n the ast coupe of years s to use
CTO as a feedstock for a dese fue wth renewabe content.
When comparng the two appcatons, cear dfferences can be observed. Bo-chemcas make
use of every economcay vabe component n CTO and upgrade to specazed products. The bo-
chemcas contnue to create vaue over tme n ong fe cyce end appcatons. The bofues route
produces a fue, whch by defnton has a short fe cyce, and once burned, t cannot any onger
contrbute to vaue creaton. A further mportant dfference between the two routes s that bo-
chemcas are economcay compettve wthout any ncentves, whe for bofues, pocy nstru-
ments are very mportant - n some cases vta - to make ends meet.
Arzonas annua saes amount to approx. USD 1 bon, customers are served gobay and the
company empoys over 1 100 peope. Arzona has manufacturng stes n North Amerca and n
Europe. The executve offces are found n Amere, the Netherands and n | acksonve, Forda, US.
Roe of COST n European forest and forest products research

30
Role of COST in European forest and forest
products research
Sjur Baardsen
Chair, Cost Domain Committee for Forests, their Products and Services
sjur.baardsen@umb.no
Abstract
Ths artce descrbes COST - European Cooperaton n Scence and Technoogy - ts organsaton,
and man nstruments, and how to partcpate. It further outnes how COST works as a patform for
nnovaton by sharng nformaton and producng new knowedge. Some COST Acton exampes are
presented and the artce coses wth descrbng the expected future roe of COST n the European
Research Area (ERA).
COST coordnates natonay funded research actvtes through enhanced networkng. Ths s
frst of a carred out usng the so-caed COST Actons. Focus s on Europe, but the networkng
aso covers partcpaton from many non-European countres. COST does not fund research as
such; ts contrbuton to the ERA comes from the synerges that arse from the enhanced network-
ng of actve research groups.
Knowedge s a vauabe asset for creatng and sustanng advantages for ndvduas and organ-
satons. An obstace to knowedge sharng s the fact that knowedge s property. Ths s refected n
the fact that one s typcay rewarded for what one knows, not for what one shares. Therefore,
ncentve mechansms are needed n order to motvate ndvduas and organsatons to share ther
knowedge. COST nstruments are desgned to face ths chaenge, compensatng networkng costs
and encouragng nnovaton through synerges.
About COST and how to participate
About COST
Founded n 1971, COST s the frst and wdest European framework for the transnatona coordnaton
of natonay funded research actvtes. It s based on an nter-governmenta agreement between 35
European countres. COST s funded through the EU RTD Framework Programmes.
COST key features are:
budng capacty by connectng hgh-quaty scentfc communtes throughout Europe and
wordwde;
provdng networkng opportuntes for eary career nvestgators;
ncreasng the mpact of research on pocy makers, reguatory bodes and natona decson
makers as we as the prvate sector.
Through ts ncusveness, COST supports ntegraton of research communtes, everages natona
research nvestments and addresses ssues of goba reevance. Reachng out to over 30.000 re-
searchers across Europe, COST s a budng bock of the European Research Area, nstrumenta
for successfu nnovaton strateges and goba cooperaton.
The organsaton of COST refects ts nter-governmenta nature. Key decsons are taken at
COST Mnstera Conferences whch are usuay hed every fve years.
The Commttee of Senor Offcas (CSO) s the hghest decson-makng body and s charged
wth the oversght and strategc deveopment of COST. Each COST Member Country apponts up
to two representatves to the CSO, one of whom s the COST Natona Coordnator (CNC), the
natona contact pont.


31
The Doman Commttees (DCs) consst of scentsts coverng the 9 scentfc domans and nom-
nated by the COST Natona Coordnator. The DCs are
Bomedcne and Moecuar Boscences (BMBS);
Chemstry and Moecuar Scences and Technooges (CMST);
Earth System Scence and Envronmenta Management (ESSEM);
Food and Agrcuture (FA);
Forests, ther Products and Servces (FPS);
Indvduas, Socetes, Cutures and Heath (ISCH);
Informaton and Communcaton Technooges (ICT);
Materas, Physcs and Nanoscences (MPNS);
Transport and Urban Deveopment (TUD).
Each COST country may appont one representatve to each Doman Commttee. The DC reports
to the CSO and s responsbe for () Evauaton of proposas for new COST Actons; () Montorng
of COST Actons n progress and; () Assessment of competed COST Actons. The DCs aso
supervse the strategc deveopment of ther respectve domans.
In addton, Trans-Doman Proposas aow for broad, nterdscpnary proposas to strke across
the nne scentfc domans. A Trans-Doman Proposas Assessment Body (TDP-SAB) s respons-
be for the assessment of nterdscpnary proposas.
The COST Offce mpements the CSO decsons and supports the scentfc actvtes, e.g. the
COST Actons and DCs actvtes. The COST Offce n Brusses s provded by the European Sc-
ence Foundaton (ESF) based n Strasbourg, the mpementng agent for COST.
How to participate in COST
Foowng a bottom-up prncpe, appcants from any type of nsttuton can submt a COST Acton
proposa n any fed of nterest at any tme of the year (contnuous ca). Proposas are coected
twce a year and assessed n two stages.
The Premnary proposas (3-4 pages), submtted usng the on-ne form (see www.cost.eu/openca)
shoud provde a bref overvew of the proposa and ts ntended mpact. Egbe proposas are as-
sessed by the reevant Doman Commttee or Trans-Doman Proposa Standng Assessment Body
(TDP-SAB) n accordance wth the pubshed crtera (see gudenes on www.cost.eu/openca). App-
cants of the hghest ranked premnary proposas are nvted to submt a fu proposa. Fu proposas are
peer revewed accordng to the assessment crtera (see gudenes on www.cost.eu/openca). A fna
st s estabshed after the ora presentaton of the proposa (DC Hearngs). The decson of fundng
a proposa s taken by the CSO wthn eght months of the coecton date and the Acton shoud
expect to start wthn three months thereafter. COST supports the Actons by rembursng trave and
subsstence reated to Acton meetngs, short-term scentfc mssons, tranng schoos and pubca-
tons, and t aso grants some fnanca support to the oca organsers of Acton meetngs.
Athough the COST Actons form the man nstruments, COST aso funds two knds of strategc
actvtes. Frst, the Scence & Technoogy-drven Actvtes serve the dssemnaton of COST actv-
tes and outcomes, ntated by the DCs. Three categores of proposas can be presented under ths
umbrea: Transdscpnary Scence & Technoogy Strategc Events focusng on S&T deveopment
of transdscpnarty; Doman Specfc Scence & Technoogy Strategc Events focusng on S/T
novetes; and Acton Showcases focusng on dssemnaton of COST Acton outputs. Second, the
Pocy-drven Strategc Actvtes am to gve COST the necessary vsbty and to renforce ts cred-
bty n the mnd of pocy decson-makers. These actvtes are ntated by the CSO or the COST
offce drector. Fnay, COST has a sma budget reserve for ad hoc strategc ntatves.

32
COST as a platform for innovation
Knowledge sharing
COST s frst of a an organsaton that deas wth knowedge sharng through networkng. Before
focusng on what knowedge sharng eads to et us have a ook at what knowedge actuay s, why
t shoud be shared, and how the sharng may be hampered or boosted.
Knowedge s nformaton possessed n the mnd of ndvduas, t s personazed nformaton. It
s reated to facts, procedures, concepts, nterpretatons, deas, observatons and |udgements.
Knowedge s the resut of cogntve processng trggered by the nfow of new stmu. Informaton s
converted to knowedge once t s processed n the mnd of ndvduas and knowedge agan be-
comes new nformaton to others once t s presented n some nterpretabe form, for exampe as
text, graphcs, words, or as other symboc forms.
There are severa reasons why expct knowedge (knowedge that can be artcuated, codfed
and stored s sad to be expct, n contrast to tact knowedge ke e.g. the abty to rde a bke)
shoud be shared. Frst of a, the amount of nformaton and knowedge s growng rapdy, many
due to the exposon of ICT, ncreasng educaton eves and ncreasng R&D efforts. Athough ony
5% of those who have ever ved on mother earth are st ave, 90% of the scentsts are, and to
stay ave n the academc system they are supposed to pubsh new knowedge. And ICT obvousy
pays a cruca roe enabng us a to access and share ths sea of new and od knowedge.
Secondy, a necessary consequence of the ncreasng poo of knowedge s ncreased speca-
zaton. Let me exempfy wth amnated wood. Deveopng ths reatvey smpe product requres
competence n many sub-dscpnes of physcs, n chemstry (gue), n mechanca engneerng
(sawms), n ogstcs, ICT and forest management - to menton a few. No snge ndvdua can
keep abreast wth a new deveopments wthn ths broad range of requred competences. There-
fore, specasaton s requred.
A consequence of the exposon of knowedge and ts mpact on the evovng socety s that edu-
caton no onger shoud be regarded as a phase n fe, but rather as a fe-ong experence. Ths
mpes a renforced need for knowedge sharng far beyond what was requred a generaton ago,
and t eaves us the possbty of focusng more on permanent knowedge (ong astng knowedge
ke the theorems of Pythagoras and Archmedes as opposed to temporary knowedge e.g. on how
to run some specfc software) durng the basc study years. Ths, together wth the probems of
recrutng new students to studes n forestry - gobay, aso cas for speca attenton to the n-
creased need for knowedge sharng wthn the forest sector more specfcay.
Knowedge sharng may be hampered n severa ways. Knowedge s a vauabe ntangbe asset
for creatng and sustanng advantages for ndvduas as we as for organsatons, networks and
pro|ects. An obstace to knowedge sharng s the fact that knowedge s property and therefore
ownershp becomes very mportant. Iustratng s the fact that one s typcay rewarded for what
one knows, not for what one shares! Therefore, ncentve mechansms may be needed n order to
motvate ndvduas and organsatons to share ther knowedge. These ncentves may take many
forms. COST nstruments ke COST Actons, Exchange vsts and Strategc workshops are typca
exampes, desgned as they are for compensatng networkng costs and encouragng nnovaton.
Research has dentfed three mportant condtons for knowedge sharng between unverstes
and ndustry. Frst, the partners must trust each other, second geographc proxmty counts and,
thrd, poces for IPR, patents and cences must be n pace. Fang of any of these condtons w
hamper knowedge sharng.
The exposon of new knowedge makes t more mportant than ever to te reevant from rree-
vant nformaton n order not to drown n the sea of nformaton. Ths requres ways of fterng hgh
quaty nformaton and knowedge from garbage.
Knowedge sharng may be aso be boosted, frst of a by fghtng aganst those factors hamperng t.
Ths mpes puttng n pace ncentve mechansms that motvate knowedge sharng, ensurng trust
and rues for IPRs and patents, and assstng n quafyng nformaton and knowedge, n short
enabng easy transfer of knowedge. Ths mpes factatng estabshment of RTD networks, arrangng

33
hgh quaty conferences and workshops, dentfyng knowedge sources and appyng ICT n the
most hepfu way. Ths s exacty what COST does.
Knowledge sharing in COST
There are 36 member countres n COST, and another 38 countres, most of them non-European,
partcpate n COST Actons. COST creates networks aong and across dfferent European dmen-
sons. It has payed - and st pays - an extremey mportant roe n networkng and sharng suc-
cess between od and new and not (yet) EU member countres. It s we known that COST has
acted as a door opener to cooperaton wth researchers n many non-EU countres.
COST Actons may cover any part of scence. Therefore COST promotes knowedge producton
and knowedge sharng between research on the one hand and socety and ndustry on the other.
Socety gans when t comes to pocy-makng n governmenta and reguatory bodes, and the pr-
vate sector n any knd of ndustra producton, for exampe n the forest products ndustres.
Another dmenson whch s hghy emphassed n COST s the nteracton between senor and
|unor researchers. We beeve that there s much to be earned both ways and n nteracton, ead-
ng to synerges. No doubt ths s aso very future orented.
Cost ams at capacty budng, and t buds on the bottom-up approach nvtng researchers to
submt deas on any topc. Once a new COST Acton s estabshed any country s free to sgn the
MoU and appont ts members to the Acton.
COST aso puts gender baance nto practce, for exampe through the way proposas are as-
sessed, Actons are montored and meetngs are sought to be arranged n a famy frendy way.
No doubt the natonay funded research pro|ects are nnovatve, but through networkng these
pro|ects COST enabes boostng the nnovaton even further through synerges.
The knowedge sharng n COST enabes partcpants n research pro|ects to share knowedge
n order to create a common understandng of probems at hand, and to coordnate actvtes. Ths
appes to nformaton seekng, nterpretaton, anayses etc. ncudng tmng and sequencng of
research tasks and reportng.
A man reason for pubc fundng of research at natona eves s the fact that research pro|ects
often nvove a hgher rsk than what the prvate sector s wng to accept. In ths context t shoud
be noted that an mportant outcome of knowedge sharng s the substanta reducton of rsk.
Innovatons often seem to arse from synthess and re-combnaton of spread peces of
knowedge. These are peces aready exstng here and there, and whch may serve qute new
functons when put together n new and nnovatve ways.
Transfer of knowedge s a man key to humans success - from od to young, from sked to
ess sked, budng up common knowedge.
Therefore, what s typca for knowedge sharng s that synerges arse. It s ony the synerges from
cooperaton that makes research pro|ects and COST Actons egtmate for EU fundng.
Snce knowedge sharng eads to synergetc nnovaton t s now hgh tme that we get rewarded
not ony for what we know, but for what we actuay share!
Some COST Action examples
COST Acton FP0901: Anaytca Technques for Borefneres
Trees, annua and perenna pants, recyced fbres, and gnoceuosc sde streams from forest and
agrondustry are renewabe resources for the deveopment of natura materas, bochemcas, and
boenergy. The chemca compexty of pant materas, the feed matera of Borefneres, renders
the anayses of the feed consttuents, processes, and vaorsed products chaengng. The man
ob|ectve of the Acton s to deveop new and evauate exstng anaytca methods reated to forest-
based and agrondustra Borefneres. Thus, the Acton covers the anaytca methods for the Bo-
refnery feed matera and for processed bochemcas, bomateras, and process resdues. Espe-
cay anaytca pretreatments w be evauated. Crtca steps are the representatveness of the
sampng and sampes, the extracton, fractonaton, and sampe storage methods apped. New

34
methods w be apped and evauated for ther reevance. Other emphassed areas w be deve-
opment of anaytca on-ne appcatons, hyphenated technques, and appyng statstca mut-
component anayses to sort out the reevant data from the man data stream. The European forest-
based, boenergy-based and agrondustra ndustres w beneft from the Acton n recevng ree-
vant nformaton on ther deveopments of sustanabe and envronmentay bengn soutons for
nove utsaton of renewabe resources. The deveopment of anaytca toos w ead to cost effec-
tve and sustanabe processes and products.
COST Acton FP1003: Impact of renewabe materas n packagng for sustanabty - deveop-
ment of renewabe fbre and bo-based materas for new packagng appcatons.
Paper and board are made from renewabe resources and are ow carbon footprnt materas,
therefore gvng them an envronmenta advantage compared to other materas. However, n pack-
agng appcatons, paper and board are neary aways used n combnaton wth non renewabe
materas; e.g. barrer materas derved from o based pastcs or aumnum. To gve the forest
ndustry a compettve edge ths Acton w focus on packagng soutons based entrey on renewa-
be resources n order to remove the serous dsadvantages assocated wth future paper and board
packagng soutons that contnue to rey on non renewabe materas. The Acton w expore pos-
sbtes that the forest tsef can offer as a raw matera base for dfferent components wthn a
gven package, thus exporng the fu potenta of the fbres. The Acton s an opportunty and a
strategc ob|ectve for the forest sector vaue chan and w reduce envronmenta mpact thus mak-
ng t of potentay great mportance for contrbutng to European pocy. To fuy understand the
benefts t s mportant to assess the soutons from a sustanabty pont-of-vew takng account of
the tota packagng vaue chan. That s why the Acton aso addresses research n e.g. vaue chan
effcency, end-of-fe and suppy of raw matera.
COST Acton FP1105: Understandng wood ce wa structure, bopoymer nteracton and com-
poston: mpcatons for current products and new matera nnovaton
The prmary ob|ectve of the proposed Acton s to bud knowedge and understandng of fun-
damenta physca (sef assemby) processes and boogca systems (e.g. genetc contro) that drve
natura structures and bopoymer composton wthn the pant/wood ce wa and to use new
knowedge of sef assemby processes to support the deveopment of new bopoymer based mate-
ras. The Acton aso ams to quantfy the mpact of new knowedge on our understandng of the
mechanca propertes of the ce wa and how processes such as pupng, beachng recycng, ce
wa dsntegraton methods and ongong tree mprovement and botechnoogy programmes mpact
both postvey and negatvey on structure and composton of the ce wa. The ntent s to expore
how ths knowedge can be used to support ongong mprovement n these areas of actvty. An
overarchng goa s to deveop mutdscpnary competence and capabty to support these ob|ec-
tves and to work cosey wth commerca organsatons to promote effectve dssemnaton of
knowedge and the deveopment of a more economcay sustanabe Forest Based Sector.
The future role of COST in the European Research Area (ERA)
The COST strategy concentrates strengthenng ts current key features and on four strategc goas:
best performance n ts mpementaton; orentng COST Actons on output; mprovng cooperaton
wthn COST countres and beyond; and ensurng good governance.
The goa wth regard to best performance s to reman the most effcent and user-frendy re-
search networkng too for scentsts n the ERA. To acheve ths COST w agree easy and cear
common gudenes for appcants; adapt Acton ob|ectves and evauaton crtera to ts msson;
ensure adequate fnanca support of Actons; have user-frendy software toos gudng ts entre
process; ceary defne roes and responsbtes of COSTs decson-makng bodes; and annuay
evauate ts processes to scope further mprovements.
In order to deveop the output orentaton COST w have key performance ndcators nked to
ob|ectves;foow-up competed Actons, wth reguar mpact anayss; desgn an ambtous dssemna-
ton strategy; deveop concepts and crtera for strategc actvtes; and nteract strongy wth other
forums.

35
Better cooperaton wthn COST countres w be acheved by nkng research exceence n Eu-
rope; provdng networkng opportuntes for eary career researchers; enhancng tranng prospects
for nnovatve mnds; and by deverng support for further coordnaton of COST countres natona
research and nnovaton poces. In addton COST w be open to scentsts from a over the word;
deveop taored actvtes for neghbourng countres; mantan a daogue wth nternatona organ-
satons (such as the OECD, UN, WHO and UNESCO) on topcs of mutua nterest; and ensure ts
strategy compements the strategc European framework for nternatona scence and technoogy
cooperaton.
Good governance w be acheved through smpfyng COST rues and procedures to support
researchers needs; mpement ght-touch and more effcent mechansms for management and
montorng of COST Actons; carfy responsbtes to ensure a proper sense of ownershp of ts
actvtes and Actons; and enforce cear commtment to the COST Code of Conduct and the vaues
t expresses.
Fnay, n ne wth the COST Msson and the COST Strategy outned above, aso the COST
Poston Paper "The COST Framework - A Cornerstone of the ERA", the CSO has recenty pre-
pared an Acton Pan to "especay contrbute by networkng and supportng young promsng teams
n the fed of Research and Innovaton and contrbute to wdenng pan-European partcpaton,
whe renforcng cooperaton wth near neghbour countres based on mutua beneft.
References
The artce s based on the brochure About COST 2012-2013, offca COST documents and a
presentaton gven by the author n the European Parament 7 September 2011.
Understandng wood ce wa structure, bopoymer nteracton and composton: mpcatons for
current products and new matera nnovaton

36
Understanding wood cell wall structure, biopolymer
interaction and composition: implications for current
products and new material innovati on
Philip Turner
Director of the Forest Products Research nstitute, Edinburgh Napier University
Abstract
The paper outnes a new Cost Acton (FP1105) whch ams to bud our knowedge of fundamenta
physca processes that drve natura structures and chemca composton wthn the ce wa and
expore how we can use natura sef assemby processes to deveop new bopoymer based mater-
as. The Acton aso ams to expore how new knowedge of bopoymer structure and composton
of the ce wa can be used n the short medum term to support mprovement n exstng forest
products processes ncudng borefnery. A further am s the deveopment of a new patform for the
deveopment of new bopoymer based materas. It s aso antcpated that new knowedge w ead
to mprovement n tree breedng and botechnoogy programs that support the forest based sector.
ntroduction
For severa decades scentsts have ooked at the structure and bopoymer composton of the
wood ce wa and the roe t pays n the propertes of pant fbre-based materas such as sod
wood, paper and compostes. Despte ths work, there are st a number of gaps n our understand-
ng. As an exampe, a recent paper by Turner et a. 2011 hghghted a new approach to vewng the
crystane ceuose structure of pant ces, that has provded new nsghts nto the archtecture of
the wood ce wa. The work ndcates a compex, fracta ce wa structure n many tmber speces.
The pup and paper and broader forest products ndustry, s under ncreasng pressure to add
vaue, not ony to the prmary product of manufacture but aso to utze the resduas n hgher vaue
appcatons. Ths has ed to the evouton of a bo-refnery concept, whch requres an "n depth"
characterzaton of a compex package of bopoymers and to understand the processes requred to
extract dfferent components. Interest n the deveopment of wood as a bo refnery feedstock has
ed to advances n our understandng of ce wa utra-structure and bopoymer composton. How-
ever, as our knowedge mproves there s an ncreasng awareness that there s much st to earn.
Further compexty s added by a poor understandng of how prmary ndustra processes nfuence
and change ce wa utra-structure and overa composton, these processes may ater the assem-
by of the bopoymers n unntentona ways that ead to suboptma extracton and utzaton of the
resdua matera n whoe tree utzaton processes.
Wthn the fed of bochemstry and genetcs there s a growng understandng of some of the
factors under genetc contro but n other nstances, t s cear that there s st a poor understandng
of the ncredby compex phenotype (at the ce wa eve). Wthout ths understandng, t s mpos-
sbe to determne the reatve contrbuton of genes, envronment and the underyng physca pro-
cesses n determnng the structure, and composton of the ce wa. A hypothess has been pro-
posed (Turner et a., 2011) that the fracta structure of the tree and the ce tsef, aong wth the
ma|orty of boogca and norganc materas that are aowed to sef assembe (n what s tradton-
ay seen as a thermodynamcay drven process of dffuson mted aggregaton), s drven by the
underyng fracta structure of space-tme. Ths concept, has ganed consderabe momentum
through parae and ndependent research programs n theoretca physcs (Nottae and Auffrey
(2008). The prncpe has been demonstrated through the use of a modfed Schrdnger equaton
to mode boogca functons (morphogeness, dupcaton, mutscae herarchy of organzaton etc.)
and the ubqutous fracta structures found n boogca systems and the physca word. The hy-
pothess states that these structures are nfuenced by quantum mechancs and the fundamenta

Understanding wood cell wall structure, biopolymer interaction and composition: implications for
current products and new material innovation

37
geometric structures of space-time in a way that we are only just beginning to understand. The
physics underlying this work is already providing new, fundamental insights into the nature and
structure of matter.
The new COST Action is aimed at trying to improve our understanding of the multidisciplinary
challenges highlighted above.
COST Action structure

The COST Action is divided into three working groups illustrated below (Figure 1).

Figure 1. An outline of the three working groups and the key work activities to be included in the Action.
Working group 1: Understanding of the structure, biopolymer
composition and polymer interactions within the cell wall, what
determines these variables and their impact on cell wall properties
This work will start with the latest findings on the structure of the wood cell wall, which reveal a
common link with the structures of a broad range of biological and inorganic materials.
One of the objectives of the working group will be to test the hypothesis, that many biological
structures are driven by fundamental physical processes, rather than complex biological systems,
which can be modeled from first principles using quantum mechanics. A second hypothesis to be
tested is that the role of genes is to switch between different physical processes rather than

38
drvng the underyng structures we observe n boogca systems (A prncpe frst proposed by
Erwn Schrodnger n 1943). Workng group 1 w focus on coaboraton between physcs, bochemstry,
genetcs, anaytca chemstry and mcroscopy to deveop a better understandng of, genes, enzymes,
macromoecues and envronmenta factors controng ce wa formaton. It s antcpated that ths
n turn may assst n the deveopment of more focused breedng and genetc mprovement programs.
The key am w be to deveop a coectve understandng of the roe of fundamenta physca
processes n defnng ce wa structure, composton and bopoymer nteracton. Ths work w
ncude the deveopment of mproved modes of nano-scae and ce wa structures from frst prnc-
pes that coud ead to mproved predcton of the characterstcs wood, pup and paper, and other
wood based materas propertes. As an exampe, the cassca mode of a hghy orented S2 ayer
and ts mpact on ssues such as wood strength, stabty and creep needs a re-thnk. Structura
studes w focus on Fnte Eement Modeng (FEM) of the ce wa, ncudng the nteracton of the
ceuose skeeton and amorphous bopoymers to better understand the physca propertes of the
ce. FEM studes w be vadated through a program of testng of macro, mcro and nano-scae
structures for fbrs, ces, paper and sma cear wood sampes.
Working group 2: Fibre Processing
The second focus area nvoves usng the combned knowedge deveoped n workng group 1 to
support ongong mprovement n three key areas of nterest. These ncude:
Improvng exstng processes such as pupng, recycng and papermakng. There w be a
partcuar focus on how exstng processes mpact on bopoymer composton and how they
can be modfed to mprove quaty and performance of the end products. There w aso be
a focus on how processes such as pupng coud be mproved to factate the better utza-
ton of resdua products such as hemceuoses and gnn.
Deveopment of new or mproved chemca, enzymatc and mechanca processes to break
down the wood ce wa nto ndvdua bopoymers and monomers that can be used as bo-
refnery feedstock.
Investgaton and ongong deveopment of fractonaton technooges to ook at separatng
and refnng bopoymers nto chemca budng bocks that coud be used for a range of
downstream bo-refnery actvtes.
Working group 3: Self-assembly to develop new biopolymer based
materials
Ths workng group w ook at deveopng sef-assemby processes that coud ead to the deveop-
ment of a patform of new bopoymer based materas and products. Work w ncude:
Revewng and sharng state of the art sef-assemby processes. Ths knowedge w be
used as a startng pont for the deveopment of new sef-assemby processes.
Functonasaton of bopoymers whch can be used as budng bocks n the deveopment of
new materas.
Usng new knowedge of the underyng physcs drvng sef-assemby processes found n
boogca and norganc materas as a theoretca patform for the deveopment of new sef-
assemby processes. Materas scentsts are currenty focused on understandng and mm-
ckng boogca processes. Many boogca systems may we turn out to be purey physca
processes. Understandng how these systems work coud ead to nsghts nto the deveop-
ment of new sef-assemby processes at moecuar, nano-meter and macro scaes.
The work program proposed s mutdscpnary and requres the deveopment of a new mutdsc-
pnary network and patform of synergstc competences that can support nnovaton n both the

39
growng and processng ndustres. Ths w be factated through workshops, tranng schoos and
scentfc exchange as we as by supportng the deveopment of mutdscpnary research pro-
posas addressng the ob|ectves of the Acton.
COST Acton FP1105 was offcay started n May 2012 wth the frst workshop to be hed n
Stockhom on December 3
rd
and 4
th
2012.
The success of the Acton s predcated on partcpaton of a wde range of scentfc dscpnes.
The ob|ectve of ths paper s to nform a broader audence and to encourage wder partcpaton n
the Acton.
References
Nottae, L., Auffrey, C. 2008. Scae reatvty theory and ntegratve systems boogy: Macroscopc
quantum type mechancs. Progress n Bophyscs and Moecuar Boogy 97, pp. 115-157.
Turner, P., Kowakczyk, M., Reynods, A. 2011. New nsghts nto the mcro-fbr archtecture of the
wood ce wa. COST Acton E54 Book. Fne Structure of Papermakng Fbres. ISBN 978-
91-576-9007-4.
Genetcay engneered (GE) forest trees as borefnery raw materas - egsatve and scentfc
status

40
Genetically engineered (GE) forest trees as biorefinery
raw materials legislative and scientific status
Hely Hggman
1
, Marja Ruohonen-Lehto
2
1
University of Oulu, Department of Biology, P.O. Box 3000, F-90014 University of Oulu, Finland
2
Finnish Environment nstitute SYKE, Natural Environment Centre, Biodiversity,
P.O. Box 140, F-00251 Helsinki
Towards Future Forestry
One man drver of future forestry s the ncreasng word popuaton whch recenty (October 2011)
exceeded 7 bon and t s expected to exceed 9 bon by 2050. Increasng popuaton numbers
combned wth acceerated cmate change ncudng weather extremes, foods, droughts etc. (Ne-
emann et al. 2009) are predcted to ncrease the need for more food producton. The current est-
mates of Food and Agrcuture Organsaton (FAO, http://www.fao.org/wsfs/forum2050/wsfs-
forum/en/) ndcated that food producton must ncrease by 70% n the next 40 years and f more
and s not avaabe, 370 mon peope coud be facng famne by 2050. Ths w aso push new
demands for forestry and productvty n the future.
Accordng to the FAO report (2010) on Goba Forest Resource Assessment, goba forests cov-
er 4 bon hectares .e. 31 percent of the tota and area. The tota and area desgnated prmary
for wood producton has decreased by more than 50 mon hectares durng the ast 20 years and
the area desgnated for mutpe uses has ncreased by 10 mon hectares durng the same perod
ndcatng that aso the future forest area w have to serve mutpe purposes, ncudng conserva-
ton, recreaton and wood producton. Thus, there s a defnte need for effcent tmber producton
usng margna and whch s not sutabe for economcay vabe agrcutura uses. In ther opnon
paper n 2002 Fennng and Gershenzon aready emphaszed the roe of pantaton forestry on a
ong-term bass to mt the harvest pressures on natura forests and, furthermore, they suggest
botechnoogy toos to be apped to tree mprovement processes n order to save tme.
Bioeconomy / Biorefineries The Players of Future Forestry
Accordng to the EU Whte Paper (2011) "The European Boeconomy 2030", boeconomy, ncudng
borefneres as key components, refers to sustanabe producton and converson of bomass nto a
range of food, heath and fbre as we as ndustra products and energy. Today, word economes
are faced by the urgent need to fnd aternatves to the decreasng foss fue resources (especay
o and gas). Ths means that more support w be drected at the use of renewabe energy. The
ncreasng support together wth ncreasng prce of o or CO
2
w defntey ead to hgher demand
for wood energy, wood fbers and other bo-products such as bo-chemcas, bo-pastcs, bo-fues,
food addtves etc. derved from sustanabe forestry (FPAC, The Forest Products Assocaton of
Canada, 2011). Thus, boeconomy concept w provde mutpe new producton possbtes whch
w affect the whoe forestry sector.
Genetically Engineered Crop Species
Genetcay transformed crops, aso caed botech crops, have a 16 years track record of commer-
ca depoyment wth a cumuatve area of over 1 bon hectares panted by 2010 and a tota area of
160 mon hectares panted n 2011 (| ames 2011). Ths makes GE crops the agrcutura technoo-
gy wth the hghest ever adopton rate and farmers from 29 countres, the goba economsts and
researchers are reportng mutpe economc and envronmenta benefts. At the same tme, numer-
ous scentfc studes have not found any ncdence of harm. Aso the premnary nformaton on the
year 2012 (ISAAA press reease n August 17, 2012) ndcates that US farmers contnue to demon-
strate overwhemng trust and confdence n botech crops and the goba adopton of botech crops

status

41
s expected to contnue to grow partcuary n deveopng countres. Furthermore, the EU pubca-
ton "A decade of EU-funded GMO research under the Framework programmes 2001-2010" de-
scrbes 50 research pro|ects ncudng 400 research groups, funded by 200 mon Euros. In these
pro|ects the focus was on scence, safety aspects, envronmenta mpacts and rsk assessments of
genetcay modfed organsms (GMOs) and the man concuson was that botechnoogy, and n
partcuar GMOs, are not per se more rsky than e.g. conventona pant breedng technooges.
Genetically Engineered Forest Trees the History of 25 Years
The frst report on GE forest tree speces Populus alba grandidentata was pubshed n 1987 by
Fatt et al. The transformaton was done usng Agrobacterium tumefaciens and neomycn phos-
photransferase (npt) as a marker gene and the bactera 5-enopyruvy-shkmate-3-phosphate
(EPSP) synthase gene (aroA) conferrng herbcde toerance. Snce then the transformaton protocos
have been deveoped and/or mproved for severa conferous and decduous tree speces. Moreover,
severa new genetc transformaton appcatons (e.g. artfca mRNA, vrus nduced gene sencng,
targeted mutageness) are or w be ncuded n the methodoogca toobox of forest trees.
Compared to crop pants forest trees may st be consdered undomestcated. They are charac-
terzed by cross ponaton, ong generaton ntervas, ong vegetatve perods and many of the
economcay mportant speces are wnd-ponated. Generay, the conventona tree breedng
strateges are based on seecton of "pus trees" and estabshment of seed orchards etc. However,
the genetc mprovement s mted compared to genetc engneerng whch s fast and can be de-
sgned specfcay to end-use purposes. GE trees are aso we suted to the aready adopted pan-
taton forestry practces and management procedures. To nvestgate GE trees under natura env-
ronments, the trees need and are evauated n the scence-based fed tras. Gobay, more than 10
tree speces have been tested n over 700 fed tras. In these tras no negatve GE tree specfc
ecoogca or heath effects have been found (Water et al. 2010). Moreover, n Chna commerca
transgenc popar pantatons aong wth conventonay bred varetes have been estabshed. The
tota area of the pantatons s 300 to 500 hectares ncudng more than 1.4 mon Bt-trees confer-
rng nsect resstance. The odest trees are aready 15 years od. Up to date no harm for the env-
ronment has been found. Ths s mportant nformaton because outbreaks of forest nsect pests
damage around 35 mon hectares of forest annuay, prmary n the temperate and borea zones
(FAO report on Goba Forest Resource Assessment, 2010).
In the case of GE trees, as n the case of a new technooges, the potenta rsks and benefts
must be dentfed and quantfed. Transgene technoogy coud contrbute to preservaton of the
natura forest and to reducton of deforestaton of arge areas. However, due to the ong fe cyces
of trees and ther partcuar sgnfcance n many terrestra ecosystems, concerns of potenta m-
pacts of transgenc trees have been rased. The pubc concern s especay focused on potenta
uncontroed spread of transgenes va vertca or horzonta gene transfer as we as on peotropc
and unntended effects on non-target organsms.
Cost Action FP0905
Research on bosafety of GE trees has been ntated n severa European and non-European coun-
tres and numerous fed tras have been used for the scence based evauaton. Resuts of these
studes are, however, scattered or dffcut to access and there s a need to put together the aready
exstng nformaton. Ths was aso the reason to propose the Cost Acton FP0905 Bosafety of
transgenc trees: mprovng the scentfc bass for safe tree deveopment and mpementaton of EU
pocy drectves. The char of the acton s Dr. Crstna Vettor (Itay), the vce char s Dr. Matthas
Fadung (Germany) and the COST Scence Offcer s Meae Langben. The man ob|ectve of the
Cost Acton s to evauate and substantate the scentfc knowedge reevant for bosafety protocos
of GE trees by puttng together the aready exstng nformaton generated n varous European and
Non-EU Countres. Ths work provdes bass for the future EU pocy and reguaton for the env-
ronmenta mpact assessment and safe deveopment and practca use of GE trees. The actvtes
status

42
of the acton s arranged n four workng groups n whch WG1 covers boogca characterzaton of
GE trees, WG2 deas wth envronmenta mpact assessment and montorng of GE trees n the
whoe producton chan from pantaton to fna products, WG3 focuses on soco-economc mpca-
tons and recommendatons for the use of GE trees and WG4 s responsbe on management of
ntranet - nternet webstes and dssemnaton (http://www.cost-acton-fp0905.eu/).
Legislation
EU legislation
In EU a research and commerca appcatons usng GE methods have to be approved n ad-
vance. In case of research and fed tras ths s done by natona authortes of a gven Member
State (MS). Commerca cutvaton (pacng on the market) s authorzed by a quafed ma|orty
decson n the EU reguatory commttee composed of MS representatves. The Drectve
2001/18/EC of the European Parament and of the Counc on the deberate reease nto the env-
ronment of genetcay modfed organsms reguates fed tras and pacng on the market (mport,
processng and cutvaton) of GMOs. The Drectve gves gudance on rsk assessment, rsk man-
agement and montorng of GMOs. Drectve 2009/41/EC of the European Parament and of the
Counc on the contaned use of genetcay modfed mcro-organsms reguates aboratory re-
search. In Fnand, the natona Gene Technoogy Act (377/1995) mpements these two drectves.
Moreover, the natona Gene Technoogy Act aso reguates aboratory and greenhouse research
carred out wth pants and anmas.
The man task when preparng a GE appcaton, be t for research or commerca purposes, s
envronmenta rsk assessment. The prncpes of rsk assessment are the same as for e.g. chem-
cas rsk assessment.
Identfcaton of characterstcs whch may cause adverse effects
Evauaton of the potenta consequences of each adverse effect, f t occurs
Evauaton of the kehood of the occurrence of each dentfed potenta adverse effect
Estmaton of the rsk posed by each dentfed characterstcs of the GMO(s)
Appcaton of management strateges for rsks from the GMO(s) (n case of fed tras and
commerca cutvaton)
Determnaton of the overa rsk of GMO(s).
The appcant provdes a necessary nformaton of the GE appcaton, the used organsms and the
reease ste ecosystem, ncudng cmate, fora and fauna. The appcant carres out the rsk as-
sessment and the authortes evauate and approve the assessment. The EU reguaton dentfes
some potenta adverse effects of GMOs. Envronmenta adverse effects coud ncude effects on
the dynamcs of popuatons of speces n the recevng envronment and the genetc dversty of
each of these popuatons. Aso effects on bogeochemstry (bogeochemca cyces), partcuary
carbon and ntrogen recycng through changes n so decomposton of organc matera woud be
consdered as adverse effects.
The EU egsaton does not ncude specfc gudance on how to carry out rsk assessment of GE
trees.
nternational agreements and guidance
The Cartagena Protoco on Bosafety (hereafter Protoco) s an nternatona agreement on bosafe-
ty as a suppement to the Conventon on Boogca Dversty. The Protoco seeks to protect boog-
ca dversty from the potenta rsks posed by vng modfed organsms (LMOs) resutng from
modern botechnoogy. In accordance wth the precautonary approach, the ob|ectve of the Proto-
status

43
co s to contrbute to ensurng an adequate eve of protecton n the fed of the safe transfer, han-
dng and use of LMOs that may have adverse effects on the conservaton and sustanabe use of
boogca dversty, takng aso nto account rsks to human heath, and specfcay focusng on
transboundary movements. The Protoco entered nto force n 2003. Each Party mpements the
Protoco n ther natona egsaton.
Durng four ast years there has been ntensve work on the deveopment of rsk assessment
gudance under the Protoco. Ths gudance ncudes a rsk assessment roadmap, specfc gudance
on dfferent types of LMOs and gudance on montorng. Ths gudance and ts status w be ds-
cussed n Hyderabad, Inda n October 2012 where the 6
th
Conference of the Partes to the Conven-
ton on Boogca Dversty servng as the meetng of the Partes to the Protoco meets. Ths gud-
ance ncudes specfc gudance on rsk assessment of GE trees.
OECDs Workng Group on Harmonzaton of Reguatory Oversght n Botechnoogy (hereafter
Workng Group) works to ensure that the nformaton used n envronmenta rsk/ safety assessment
of GE organsms, as we as the methods used to coect such nformaton, s as smar as possbe
among countres. Its am s to mprove mutua understandng, ncrease the effcency of envron-
ment rsk/safety assessment and avod dupcaton of effort. It aso reduces barrers to trade. The
most mportant current pro|ects ncude e.g. envronmenta consderatons to be taken aboard an
envronmenta rsk assessment process. The Workng Group has prepared severa boogy pubca-
tons on dfferent tree speces.
References
Cartagena Protoco on Bosafety to the conventon on boogca dversty (2003).
Consensus Documents for the Work on Harmonsaton of Reguatory Oversght n Botechnoogy:
Boogy of trees: Norway spruce (Pcea abes); Whte spruce (Pcea gauca); Popars
(Popuus spp.); Stka spruce (Pcea stchenss); Eastern whte pne (Pnus strobus); Euro-
pean whte brch (Betua pendua); | ack pne (Pnus banksana); North Amercan arches
(Larx ya, L. occdentas, L. arcana); Western whte pne (Pnus montcoa); Dougas-Fr
(Pseudotsuga menzes); Lodge poe pne (Pnus contorta); Back spruce (Pcea marana).
http://www.oecd.org/env/chemcasafetyandbosafety/bosafety-bo
track/consensusdocumentsfortheworkonharmonsatonofreguatoryoversghtnbotechnoogy.htm.
Drectve 2001/18/EC of the European Parament and of the Counc on the deberate reease nto
the envronment of genetcay modfed organsms and repeang Counc Drectve
90/220/EEC.
Drectve 2009/41/EC of the European Parament and of the Counc on the contaned use of genet-
cay modfed mcro-organsms.
EU Whte Paper, 2011. The European Boeconomy 2030.
FAO, 2010. Goba forest resources assessment 2010. FAO Forestry Paper 163, Rome
http://www.fao.org/docrep/013/1757e/1757e.pdf.
Fennng, T.M., Gershenzon, | . 2002. Where w the wood come from? Pantaton forests and the
roe of botechnoogy. Trends Botechno 20, pp. 291-296.
Fatt, | .| ., Semer, | ., McCown, B., Hassg, B., Coma, L. 1987. Agrobacterum medated trans-
formaton and regeneraton of Popuus. Mo Gen Genet 206, pp. 192-199.
FPAC, 2011. The new face of Canadan forest ndustry. The emergng bo-revouton. The Bo-
pathways pro|ect. http://www.fpac.ca/pubcatons/BIOPATHWAYS%20II%20web.pdf.
status

44
| ames, C. 2011. Goba status of commercased botech/GM crops: 2011. ISAAA Bref No. 43,
ISAAA, Ithaca, New York.
Neemann, C., MacDevette, M., Manders, T., Eckhout, B., Svhus, B., Prns, A.G., Katenborn, B.P. (Eds.).
2009. The envronmenta food crss - The envronments roe n avertng future food crses. A
UNEP rapd response assessment. Unted Natons Envronment Programme, GRID-Arenda.
http://www.grda.no.
Water, C., Boer|an, W., Fadung, M. 2010. The 20-year envronmenta safety record of GM trees.
Nat Botechno 28, pp. 656-658.
Used wood sortng, utzaton and recycng n dfferent vaue chans

45
Used wood sorting, uti lization and recycling in
different value chains
Juha Hakala
1
, Gerard Deroubaix
2

1
VTT Technical Research Centre of Finland
2
nstitute Technologique FCBA
Abstract
Wood waste generated from end of fe products forms a sgnfcant source of wood matera. Est-
matons of 29.6 Mm3 of recovered wood to be utzed n 27 countres n Europe and the addtona
potenta of at east 52.5 Mm3 exst (COST E31 & UNECE document). Remarkabe share of the
dentfed resource s ether not recyced at a, or s used n a ow vaue appcatons.
DEMOWOOD pro|ect Optimisation of material recycling and energy recovery from waste and
DEMOlition WOOD n dfferent vaue chans s ntroduced. It s part of WoodWsdom-Net Research
Programme Sustainable, competitive processing and end-use concepts for forest-based industries.
In DEMOWOOD, recovered wood ncudes a knds of wooden matera avaabe at the end of ts
use as a wooden product. Genera am of the pro|ect s to nvestgate vaorzaton concepts for
ncreasng the added vaue of waste wood n vaue chans for pup producton (TMP) for paper
products, for partce board producton, for CHP pants and for qud bofues producton. Pro|ect
resuts w hep n savng the forest resource and ncreasng the use of a renewabe re-source, n
reducng the GHG emssons n the materas and n energy sectors and n reducng the envron-
menta mpact of waste wood management. Pro|ect coordnator s Insttut Technoogque FCBA.
Work package specfc ob|ectves are presented.
ntroduction
Wood s a matera whch s n very wde use n Europe. It s used n arge quanttes n many dffer-
ent sectors and s a part of our everyday ves. Wood waste generated from end of fe of wooden
products forms a sgnfcant source of wood (aso caed as post-consumer recovered wood).
COST Acton E31, "Management of Recovered Wood", presented ts fndngs on the amounts of
recovered wood avaabe over twenty European countres. A summary of these fndngs s present-
ed n Tabe 1.
Table 1. Resuts of a survey conducted by COST Acton E31 (Mer et a., 2007).
Quant ity (ton/year)
Reuse 535 142
Recycng 10 872 383
Energy 9 996 395
Compostng 916 822
Others, unknown 4 147 127
Landf 3 125 083
Total 29 592 953

Based on COST E31 fndngs, estmatons are quoted n the UNECE document (Hetsch, 2009):
28.6 mon m
3
of recovered wood are estmated to be utzed n 27 countres n Europe and the
addtona potenta s estmated to be at east 52.5 mon m
3
. Recovered wood s the argest poten-


46
ta source for addtona wood suppy for socety growng needs f natve forest s not accounted
(whch s the man wood suppy). Remarkabe share of the dentfed resource s ether not recyced
at a, or s used n a ow vaue appcatons.
One of the great advantages of wood s that t can be recyced severa tmes before, eventuay,
beng dsposed of by ncneraton wth energy recovery. The prce of recovered wood has been
ncreasng every year throughout Europe.
The partceboard ndustry s a tradtona user of ndustra wood resdues and recovered wood.
Ths sector s experencng ncreasng competton for ts raw matera suppy, many from the fast
growng green energy generatng sector. The harsh raw matera competton forces the European
wood-based pane ndustry to search for new matera sources and the waste wood becomes, more
than before, an ndustra matera source. In the sx man European countres over 30% of the raw
matera s comng from recovered wood n the partceboard producton.
The pup ndustry s not usng recovered wood up to now, because n many cases the purty re-
qurements for the pupng process and for the paper quaty and for characterstcs have stopped ts
use as a raw matera. Recovered wood may be contamnated and contan non bomass materas.
The bomass energy fed s the fastest growng sector among the wood users. The European
and member states poces are strongy supportng the deveopment of renewabe energes and
namey of bomass energy. The European Commttee for Standardzaton has pubshed 27 tech-
nca specfcatons regardng sod bofues between 2003 and 2006, and they have been upgraded
recenty to EN-standards; the most mportant ones are regardng cassfcaton and specfcaton of
sod bofues (wood chps and hog fue) (EN 14961). However, demoton wood, whch s n the
scope of DEMOWOOD pro|ect, s not ncuded n EN 14961. The EU-pro|ect BoNormII (2009) has
addressed the ssue of waste wood cassfcaton n the context of EN 14961 - part 1. The resuts of
BoNormII w be n beneft n DEMOWOOD pro|ect, where the ssue s addressed more on a con-
ceptua eve.
There are mon tons of waste wood whch are dsposed by andfng or ncneraton, or com-
busted wthout effcent energy recovery. These generate envronmenta mpacts and can even
reduce the postve envronmenta profe of wood product. Increasng the eve of matera recycng
and energy recovery from recovered wood s today, to a very arge extent, a reguatory ob|ectve
and a European wde pubc pocy.
DEMOWOOD project
DEMOWOOD pro|ect Optimisation of material recycling and energy recovery from waste and
DEMOlition WOOD in different value chains receved ts fundng through 2
nd
| ont Ca for Research
and Deveopment Proposas wthn the WoodWsdom-Net Research Programme Sustainable, com-
petitive processing and end-use concepts for forest-based industries
Pro|ect started n | anuary 2011 and w end n December 2013. Tota budget of the pro|ect s
1 750 k-C of whch pubc fundng 900 k-C.
In DEMOWOOD, the man sources of recovered wood are packagng materas, demoton
wood, tmber from budng stes, and fractons of used wood from resdenta, ndustra and com-
merca actvtes.
Genera am s to nvestgate vaorzaton concepts for ncreasng the added vaue of waste wood
n vaue chans for:
pup producton (TMP) for paper products
partce board producton
CHP pants and qud bofues producton.
Pro|ect resuts w hep n savng the forest resource and ncreasng the use of a renewabe re-
source, n reducng the GHG emssons n the materas and n energy sectors and n reducng the
envronmenta mpact of waste wood management.

47
Drvng force for the pro|ect s that 25% of the dentfed resource s ether not recyced at a, or
has a ow-vaue use. Addtona potenta s estmated to be at east 52.5 Mm3 of recovered wood
(Hetsch, 2009).
Pro|ect coordnator s FCBA (French Insttute of Technoogy for forest based and furnture sectors).
DEMOWOOD s structured accordng to Fgure 1:

Figure 1. DEMOWOOD pro|ect structure.
Work packages in DEMOWOOD
Waste wood management inventory
Work package 1 Waste wood management inventory ob|ectve s to obtan an overvew about the
waste wood sources n Fnand, France, Germany, Swtzerand and Austra.
Waste sources consdered are the constructon / demoton sector, and end-of-fe furnture. Both
the orgna sources of waste wood, and the present management practces by the waste manage-
ment sector, are anayzed.
A typoogy of waste wood s defned, to characterze the dfferent types of sources n terms of
matera and chemca contamnaton, amounts avaabe and coected; ocasaton of these
sources, prce eves and ogstcs of coecton are aso estmated. The types and casses of waste
wood as sorted presenty by the waste management actors w be characterzed n the same way.
The natona cassfcaton systems (ega, normatve and ndustra practces) w be recorded
and anaysed and suggestons for harmonsaton and ratonasaton of cassfcaton systems at
European Scae s made.
Fast detection and sorting technol ogi es
Work package 2 Fast detection and sorting technologies focuses on evauaton of detecton and
sortng technooges n the range of waste wood recycng.
Speca focus s on the needs of paper ndustry, pane producton and energy recovery. Together
wth other work packages aso the requrements arsng from recycng and energy recovery (ncud-

48
ng bo-fues) are evauated, as we as the current adequacy of exstng technooges. Based on
ths, better or new soutons are searched for performng the sortng and detecton processes.
Enhanced separaton of meta partces s aso evauated as the detecton of emssons of for-
madehyde, VOC, PCB and ndane. The pro|ect partners w ook for fuy new ways of detecton
and sortng technooges and make recommendatons for new deveopments.
Mechanical pulp production
The recovery and the sortng of wood wastes devers raw materas to be used as furnsh for the
producton of thermomechanca (TMP) fbres.
The ob|ectve of the workpackage 3 Mechanical pulp production s to demonstrate the nterest of
ntroducng such raw materas n a conventona TMP process and to determne the mpact on the
pupng process, on the pup quaty, on the pup beachabty and on the generated effuents.
Maxmum content of wood wastes nto conventona wood used n TMP process that does not af-
fect the process s determned.
Panel board production
Partceboard producton of Germany and France together reached n 2008 amost one thrd of the
whoe European producton.
German partceboard producers and recycng companes, as operators of waste treatment n-
staatons, have to appy the German "Ordnance on the Management of Waste Wood". Accordng
to ths drectve for the producton of partceboards, ony certan categores of waste wood are per-
mtted (A I and II). These categores contan wood n ts natura state (ony mechancay treated and
most nsgnfcanty contamnated wth foregn bodes), or bonded, panted, coated, acquered or
otherwse treated wood wth no haogenated organc compounds n the coatngs and no wood pre-
servatves (A II). In practce, the coatngs of category A II to A IV (A III: contamnated wth haogen-
ated organc compounds; A IV: treated wth wood preservatves) are dffcut to dstngush n the
pant, so that for safety reasons the producer re|ects the matera from a three categores.
Am of work package 4 Panel board production s to argey ncrease the amount of recovered
wood from categores A II to A IV, fufng the condtons set n the reguatons for producng part-
ceboards. The nnovatve dea s to consder a recovered wood (A II to A IV) beng the same, and
process t through a ceanng system whch breaks the wood down to partces of medum sze and
sort cean wood chps out, as we as to produce other more contamnated fractons for other uses.
On a wood treatments, whch are apped on the top surfaces of the wood, an enveope of treated
wood s formed. Once chpped nto smaer partces, the chps w ether be free of treatment or be
contamnated.
Tradtonay used separaton technques and newy deveoped technooges (WP 2) are tested
to obtan the hghest amount of cean wood from the recycng process.
Bioenergy and biofuels
The behavour of used wood as a fue s n prncpe smar to that of cean wood. Used wood s
often dry, thus the net caorfc vaue can be hgher than for common fresh wood fues (e.g. bark).
Used wood (.e. waste wood) has hgher amount of contamnants, whch may acceerate deposts n
the boer as we as corroson, as we as change the composton of ash. Thus the deveopment of
sortng practces and advanced processes to upgrade used wood s crtca.
The quaty of shredded used wood has mproved sgnfcanty compared to prevous producton
process (ony shreddng and magnet) and s approachng the quaty of cean wood fues. In Fnand
shredded used wood can be cassfed as cean bofue (out of the waste fue cass) based on the
mt vaues presented n the report of the Fnnsh Technca Research Centre (VTT-R-04989-08).
Ob|ectves of the work package 5 Bioenergy and biofuels are:

49
Determnaton of the combuston characterstcs of waste wood n pot scae experments
and assessng combuston aternatves
Determnaton of the sutabty of waste wood to botechnca ethano producton n aboratory
scae experments and producton of data for the mode of ethano producton and feasbty
evauaton
Recommendatons for mprovement of quaty of waste wood for fue handng and effcent
combuston.
Technical , economic and environmental assessments
The ob|ectves of work package Technical, economic and environmental assessments are:
To generate and seect end of fe waste wood utzaton pathways accordng to the pro|ect scope
To ook at sustanabty for the seected pathways, especay takng nto account matera
recycng, energy recovery and economcs
Further, the effects of ogstca aspects are consdered. Envronmenta benefts for seected
pathways are evauated based on Lfe Cyce Assessment (LCA) prncpes.
Dfferent pathways for sustanabe utzaton of end of fe waste wood are created accordng to
pro|ect scope. They are based on common practces today and on effcent technques handed n
other work packages. The target s to mprove matera recycng and energy recovery. Especay
pathways to paper products and to wood panes, and ssues of energy recovery are under consd-
eraton accordng to pro|ect scope. The most promsng pathways are seected for further evauaton.
For the seected concepts process/m eve matera and energy baances are created as nput-
output modes. Matera recovery and utty consumptons are consdered. Drect costs and ncome
estmates on the bass of the created modes are cacuated.
Dfferent waste wood utzaton pathways wth the concept specfc reference eve, and wth the
possbe concept aternatves, are compared by usng specfc m eve key fgures. Proftabty
comparson s based on drect costs (nvestment costs can be consdered, f nformaton s gven by
pro|ect partners) and senstvty for the man cost components w be studed.
The envronmenta assessment s carred out based on LCA prncpes. Parameterzed database
based on the data coected s created. Senstvty anayses are performed on the foowng aspects:
The nfuence of parameters nked wth ogstcs (truck oad, truck consumpton, transport dstances
between the dfferent sortng, treatment and recycng stes), the reevance of oca utzaton of
waste wood and the mportance of takng nto account temporary carbon storage n the cacuaton
of greenhouse gas effect dependng on the number of years the carbon s stored.
Acknowledgements
Partners n the pro|ect are from Germany, France and from Fnand. Insttutes and ndustres are
sted beow. They a are actve members of DEMOWOOD pro|ect, and partcpatng n the work.
The matera presented here s based on pro|ect pan and on contrbuton of a the partners sted
beow, nvovng a arge number of experts:
Insttutes: Germany: Papertechnsche Stftung (PTS) and Fraunhofer-Insttut fr Hozforschung -
Whem-Kaudtz-Insttut (WKI); France: Insttut Technoogque FCBA and Centre Technque
du Paper (CTP); Finland: VTT
Industry: Germany: Entsorgungstechnk Bavara GmbH, Schumann-Anaytcs Pfederer
Hozwerkstoffe GmbH, TITECH GmbH and RTT Stenert GmbH; France: SITA Recycage,
Veoa and Norske Skog Gobey; Finland: Lassa & Tkano|a Oy| (L&T) and Fnnsh Wood
Research (FWR).

50
References
1. BoNormII. 2009. Pre-normatve research on sod bofues for mproved European standards.
Pro|ect number 038644. 1.1.2007-31.12.2009. EUs 6th framework programme.
2. Hetsch, S. 2009. Potenta Sustanabe Wood Suppy n Europe. Geneva Tmber and Forest
Dscusson Paper 52. UNECE.
3. Mer, A., Humar, M., Okstad, T., Pcardo, V., Rbero, A., Steerer, F. 2007. Amounts of Recov-
ered Wood n COST E31 Countres and Europe. COST E31 Fna Conference, Kagenfurt,
May 2nd to 4
th
, 2007.
The Forest Refne pro|ect - deveopment of effcent forest bomass suppy chans for borefneres

51
The Forest Refine project development of efficient
forest biomass supply chains for biorefineries
1

Magnus Matisons
1
, Jonas M. Joelsson
2
, Tero Tuuttila
3
,
Dimitris Athanassiadis
4
, Tommi Risnen
5

1
Biofuel region
2
Processum Biorefinery nitiative AB
3
Kokkola University Consortium Chydenius
4
Swedish University of Agricultural Sciences
5
Finnish Forest Research nstitute Metla
Abstract
The need for energy s contnuousy ncreasng gobay, due to e.g. ncreases n ndustrazaton
and popuaton. Unfortunatey, petroeum s n danger of becomng short n suppy wthn comng
decades. In ths paper exstng and panned borefnery ntatves n Sweden and Fnand are dent-
fed and descrbed. Standng voumes, annua growth and harvested voumes of forests n Sweden
and Fnand are descrbed together wth an overvew of forest bomass suppy chans. Raw matera
quaty demands of borefneres may dffer from those of tradtona forest ndustres and energy
pants and effcent suppy chans for the provson of borefneres wth forestry bomass have to be
desgned and deveoped. The Forest Refne pro|ect s a Swedsh/Fnnsh cross-border co-operaton
workng to mprove the whoe forest suppy chan. The partcpants have comprehensve knowedge
about borefnng, forest energy suppy chans and tradtona forest suppy chans.

Keywords: Forest bomass, wood bomass, boenergy, borefnery, fractonng, characterzaton,
forest suppy chans
ntroduction
The goba need for energy s contnuousy ncreasng as a resut of, for exampe, ncreases n n-
dustrazaton and popuaton. Gobay, petroeum s the snge argest energy suppy source, ac-
countng for 33% of the tota prmary energy suppy n 2009 |1|. The transportaton sector con-
sumed 62% of the o products |1|. There s an awareness that petroeum s n danger of becomng
short n suppy wthn comng decades. It s estmated that 54 of the 65 ma|or o producng coun-
tres have aready peaked n producton and that others are cose to ther peak |2|. Sweden and
Fnand have aready repaced most of the o used for heatng wth bomass but more than 90% of
the transports st rey on foss o mport. As t stands now, t s more dffcut to fnd renewabe
soutons for the transport sector than for heat and eectrcty producton.
In Sweden and Fnand, forest bomass resources have provded the bass for sgnfcant ndus-
tra actvtes for more than a century. Sawn tmber products and pup and paper products have
domnated the use over a ong tme but the use of forest bomass for energy purposes has grown
rapdy over the past decades. In the near future, the use of forest bomass n borefneres s ex-
pected to ncrease. The nfrastructure and suppy chans of forest bomass that are present today
have been deveoped many to suppy the producton of sawn tmber, pup, paper, heat and power
and may therefore not be optma for future borefneres. Borefneres w most key be mted n
sze, because the reatve buky forest bomass must be transported economcay from a mted
suppy area. The cost for harvest, transport, storng and handng of the bomass s of prme m-
portance when cacuatng the overa cost for borefnng. Borefneres are ong term nvestments
wth severa decades of expected operaton tme that w be affected by future changes n, for exam-

1
The authors acknowedge fundng from the County Admnstratve Board of Vsternorrand, Regon Vsterbotten, the
Regona Counc of Ostrobothna and the Botna Atantca program of the European Unon Regona Deveopment Fund.


52
pe, raw matera costs, transport costs and end-product markets. Therefore, t s mportant to deveop
effcent forest bomass suppy systems that are as robust as possbe wth respect to these uncertan-
tes, and whch can suppy borefneres wth a suffcent amount of raw matera at compettve cost.
The Forest Refne pro|ect s a Swedsh/Fnnsh cross-border co-operaton where the partcpants
have comprehensve knowedge about borefnng as we as wood suppy chans. It s run by Bo-
Fue Regon between | anuary 2012 and Apr 2014. Swedsh partcpants are BoFue Regon,
Swedsh Unversty of Agrcutura Scences (SLU) and Processum Borefnery Intatve. Fnnsh
partcpants are Fnnsh Forest Research Insttute (METLA), Centra Unversty of Apped Scences,
Ostrobothnan Rura Insttute and Kokkoa Unversty Consortum Chydenus.
Clusters, networks and research
Borefnery-reated research s conducted at amost a Swedsh and Fnnsh unverstes and at
research nsttutes such as nnventi a (Sweden) and VTT (Fnand). There are many borefnery-
reated custers and centres for coordnaton of research, deveopment and nnovaton.
Swedsh exampes are: the Biorefi nery of the Future, comprsng ndustry, academy and socety
coordnated by Processum biorefinery initi ative, ocated n rnskdsvk; NumberOne forest
ndustry network centered n Sundsva; ETC (Energy Technology Centre) n Pte, focusng on
thermochemca processes; Swedi sh Gasificati on Centre, wth academc and ndustra stakehoders
wthn bomass gasfcaton technoogy; Swedish Knowledge Centre for Renewable Transportation
Fuels (f3) centre for the deveopment of foss-free fues for transportaton; Wallenberg Wood Science
Center for research on new matera products from forest s a |ont ntatve of the Royal nsti tute of
Technology (KTH) and Chalmers University of Technology.
Fnnsh exampes are: the Finnish Bioeconomy Cluster FBC Oy (prevousy Forestcuster Ltd)
organsng companes, research nsttutes and unverstes to mpement a Strategc Research
Agenda; CEEN Ltd (Custer for Energy and Envronment) coordnatng ndustry drven energy and
envronmenta research. FIBIC Oy and CLEEN Ltd are part of the Strategic Centres for Science,
Technol ogy and nnovation (SHOK); Benet Bioenergy Network wth 6 expert organzatons,
admnstrated by the Benet Ltd; the Forest ndustry Future cooperaton between Fnnsh centres
of expertse seekng new soutons for the ndustry, especay sma and medum-szed frms; the
Energy Technol ogy custer focusng on manufacturers of energy technoogy equpment.
Forest supply chains
The tota standng stemwood voume of Swedsh and Fnnsh forests s around 3 200 and 2 284
mon m
3
(Mm
3
), respectvey. The annua growth s about 120 Mm
3
n Sweden and 104 Mm
3
n
Fnand. In average, the voume of a feed stems (ncudng unharvested stems) was 90 Mm
3
n
Sweden and 63 Mm
3
n Fnand. Hence, the voume of standng stemwood ncreased by around
30 Mm
3
and 41 Mm
3
, as an annua average, n Sweden and Fnand, respectvey. Amost a of the
harvested roundwood s used domestcay - ony 1 Mm
3
s exported.
In 2010, 16 and 19 Mm
3
of wood, consstng many of bark and forest chps, was consumed n
heat and power pants n Fnand and Sweden, respectvey. Addtonay, 6.7 Mm
3
of wood was
consumed by househods, many as frewood, both n Sweden and n Fnand. |3, 4, 5|
Harvesters are empoyed to fe, demb and cross-cut the trees nto pupwood and sawogs whe
forwarders transport the ogs to the roadsde. The ogs are then transported to the pup ms and
saw ms by trucks. The harvest of energy bomass (oggng resdues, stumps and sma dameter
trees) s ntegrated wth the harvest of sawogs and pupwood, whch makes the producton of ener-
gy bomass more cost-effcent. Typcay, the coecton and terran transport of oggng resdues to
the roadsde s done n spruce domnated stands by modfed forwarders. The oggng resdues are
ether chpped at the roadsde and transported by trucks to the end-users (heatng or combned
heat and power pants) or transported as oose matera to a termna or an end-user and chpped
there. Stumps are, typcay, extracted by tracked excavators wth purpose-but heads and trans-
ported to the roadsde by modfed forwarders, where they are stored for a coupe of seasons and

53
then transported by truck to the end user. Sma dameter trees from eary thnnngs are cut by sma
harvesters and transported to the roadsde by forwarders. The trees are ether chpped at the road-
sde or transported to an end user and chpped there.
In the Fnnsh Natona Forest Programme, a goa has been set to ncrease the use of forest
chps. The am for annua use s 8-12 Mm
3
by the year 2015. In 2010, the Governments mnstera
workng group for cmate and energy pocy stated that the consumpton of forest chps n heat and
power pants s amed to be ncreased to 12-13 Mm
3
by the year 2020 |3|. Athough n Sweden no
such target has been set, t s estmated that the annua consumpton of forest chps n heatng and
power pants w be around 10 Mm
3
by 2020 (n 2010 t was 6 Mm
3
).
Biorefinery initiatives in Finland and Sweden
Ths secton reports on a survey of exstng and panned borefnery pro|ects n Sweden and Fnand.
The nformaton has party been gathered from web pages and secondary sources, whch may not
aways be up to date, and w be verfed n forthcomng work of the Forest Refne pro|ect. A seecton
of pro|ects s gven n Tabe 1. A comprehensve st w be pubshed n a work report |6|.
The pro|ects appy dfferent technooges to separate wood components. Ceuose hydroyss
and ethano technoogy has been demonstrated and s consdered ready for arger-scae appca-
tons, but no such pro|ects have been announced. Exstng demo pants are seekng new forms for
contnued operaton, or endng operatons.
Seven out of totay eght Fnnsh and Swedsh boenergy pro|ects that apped for NER300 n-
vestment grants (a fnancng nstrument funded by emsson aowances set asde n the "New En-
trants Reserve") were gasfcaton pro|ects and one pro|ect concerned pyroyss of bomass. After
the recent reease of a prortsaton st for the NER300 grants, ony one out of three Fnnsh pro-
|ects appears to proceed wth ther pans. Further, Fnnsh UPM s pursung a pro|ect n France.
A number of pyroyss pro|ects are underway, where the pyroyss o w prmary repace fue o
but coud n the future be upgraded to motor fue. There are aso pro|ects for demonstraton of bo-
mass torrefacton - a pre-treatment of bomass to smpfy ong dstance transports and processng.
Torrefed bomass coud repace foss coa n exstng power pants.
The pup ndustry s actve wthn the deveopment of new borefnery processes, for exampe to
deveop of pup fbers nto new types of materas and products (e.g. textes, composte materas,
nanoceuose etc.); upgrade resdue streams to marketabe products (back quor gasfcaton;
gnn extracton, fermentaton of hemceuose; gasfcaton or hydroyss of fbre sudge); mpement
processes for co-producton of process steam and marketabe products (gasfcaton, pyroyss);
extract usefu substances from ncomng raw matera (hemceuose pre-extracton). Ta o from
pup ms s ncreasngy beng used as feedstock for motor fues and varous chemcas.
Extracton of sma-voume, hgh-vaue substances from wood s more of a nche area where
some research and deveopment s ongong, concernng, for exampe, antoxdant substances and
repeents for anmas feedng on young trees. There s a growng nterest from the chemcas ndus-
try to deveop arge-voume based chemcas from forest bomass.
Table 1. A seecton of Swedsh and Fnnsh borefnery actvtes.
Project etc.
(1) (2)
Description
Hydrolysis &Ethanol
EPAB D S Pilot plant for cellulosic ethanol production in rnskldsvik (~200 m
3
/yr). Owned by Ume University,
Lule University, SEKAB.
NBE Sweden D S Development plant for cellulosic ethanol production in Sveg (3 000 t/yr). Owned by NBE Co. Ltd., HMAB,
Hrjedalen municipality.
ST1 P F St1 biofuels are currently producing ethanol from sugar- and starch-containing waste in several plants and
are researching technology for ethanol production from cellulose.
Chempolis D F Chempolis Ltd is an R&D company developing biorefinery technologies, specialised in non-food, non-
wood raw materials. Has a biorefinery park in Oulu.

54
Gasification
BLG DME DP1 S S Black liquor gasification demonstration plant. Pressurised (30 bar), oxygen-blown entrained flow gasifier
(3 MWth) with a DME demo plant. Technology developed by Chemrec AB.
IVAB S S Pressurised entrained flow wood powder gasification pilot plant (1 MW, 15 bar) in Pite.
MIUN S S Circulating fluidized bed, indirect gasification (150 kW) with fuel synthesis, Hrnsand.
WoodRoll S S Indirect gasification technology demo (150 kW) in Kping. Developed by Cortus.
Chalmers D S A 24 MWth indirectly heated gasifier integrated on the return leg of a 12 MWth CFB boiler
Vrnamo IGCC D S IGCC demo plant (18 MWth). Planned rebuild for syngas production was cancelled. Mothballed.
NSE Biofuels D F Neste Oil and Stora Enso built a wood gasification demo (12 MWth) in Varkaus. Syngas combusted in
lime kiln. The aim was a commercial BTL plant, but it has not been prioritised for NER300 support.
Vaskiluodon Voima P F 140 MW gasification plant for CHP under construction in Vaasa
Vallvik biofuel P S Planned black liquor gasification plant with methanol production at the Rottneros mill in Vallvik. Applied for
NER300 support but has not been prioritised.
Rottneros biore-
finery
P S Planned gasification plant for methanol production at the Rottneros mill in Rottneros. Applied for NER300
support but has not been prioritised.
WoodRoll Kping P S Cortus is planning 5 MW gasifier with upscaling to 25 MW in a second step.
Hagfors P S Planned fluidized bed gasifier for methanol production (1 000 000 t/yr) by Vrmlandsmetanol. Uhde
selected as technology supplier.
Norrtorp P S Prestudy for 250 MW methanol and SNG plant by Vrmlandsmetanol, EON, SAKAB and others.
GoBiGas P S 20 MW plant for SNG under construction by Gteborg Energi. An 80100 MW unit is planned for a second
phase. Has been prioritised for NER300 support.
E.ON Bio2G P S SNG plant planned by EON, up to 200 MW. On the reserve list for NER300 support.
UPM Rauma P F Planned gasification/FT plant in either Rauma (Finland) or Strasbourg (France). Strasbourg plant priori-
tised for NER300 support and Rauma plant on the reserve list.
Ajos BTL P F Planned gasification/FT-plant. Mets group recently withdrew from the project. Vapo Oy are pursuing the
project and are seeking new partners. Prioritised for NER300 support.
Pyrolysis &Torrefaction
Metso D F 2 MW pyrolysis R&D plant in Tampere.
Pyrogrot P S Planned pyrolysis oil plant at the Billerud pulp mill in Skrblacka. Prioritised for NER300 support.
Fortum P F Plant for pyrolysis oil production (50 000 t/yr) in Joensuu.
Green Fuel Nordic P F Three facilities for pyrolysis oil production to be built. Expected output 270 000 t/yr.
BioEndev D S Torrefaction demonstration plant planned in Ume.
Torkapparater D S Torrefaction demonstration project located on Gotland.
Preseco D F Bio-char demonstration plant in Lempl.
Pulp-mill based
Domsj P S Production of specialty cellulose, ethanol and lignin at industrial biorefinery site in rnskldsvik.
Sdra Cell P S Development of new materials such as specialty cellulose and composite materials. Lignin extraction from
black liquor.
SunPine/Preem P S Production of diesel (Evolution Diesel) from tall oil.
Arizona Chemicals P S Production of a range of chemicals from tall oil.
UPM BioVerno P F Planned tall oil based diesel (BioVerno) production facility in Lappeenranta.
(1)
Demonstraton/deveopment (D) or producton (P) pant.
(2)
Geographc ocaton: Fnand (F) or Sweden (S).
Discussion
The raw matera quaty demands of future borefneres may dffer from those of tradtona forest
ndustres and energy pants. Ths w have an nfuence on the raw matera suppy chans. Im-
portant parts of the suppy chan ncude harvest, terran transport and storage at andng, termna
handng and fractonng, characterzaton of dfferent fractons, devery and, fnay, processng at
the borefnery. Forest bomass (the tree) can be dvded nto ts tree parts (e.g. stemwood, bark and
needes) and man chemca components (ceuose, hemceuoses, gnn and extractves). The
reatve amounts of tree parts and chemca components vary wthn tree speces and among dffer-
ent tree speces dependng on factors such as age and growng condtons. Extractves normay
represent ony a few percent of a tree, but may be a source of hghy vauabe chemca substances.
It s thus of mportance to utze a the avaabe raw matera effcenty. It has been suggested that

55
bomass shoud be utzed n a smar manner as crude o; wth arge amounts of the bomass used
as fues, whe smaer but economcay sgnfcant amounts are further refned to products of hgher
vaue. Optmum use requres that the advantages and dsadvantages of each type of forest bo-
mass (e.g. stem wood, bark, foage, stumps and roots of the dfferent speces) can be dentfed for
each appcaton. For exampe, n contrast to current heatng pants, whch often prefer a ow share
of fresh needes, a future borefnery may prefer a hgh share of fresh needes to maxmze the
producton of vauabe chemcas.
The optma technoogy and wood converson process used as we as pant sze w vary de-
pendng on the avaabe oca feedstock and the suppy system used. If raw matera s upgraded
(by e.g. tree component fractonng) at a termna, the raw matera suppy area can be ncreased
thus aowng arger refnng processes to take pace. To avod ncreased competton and bomass
shortage, new bomass termnas, n whch the bomass s fractonated nto varous assortments and
supped to dfferent borefneres, mght be requred to utze every component of the bomass n
the best possbe manner.
The forest bomass resources are extensve n Sweden and Fnand, but the suppy chan has to
be optmzed for hgh cost-effcency of the borefnery processes. However, today t s not known
what tree- and wood components w meet the demands of the whoe borefnery ndustry. Nether
s t known how the ogstca systems from the stump to the pant w affect the quaty of the de-
sred feedstock. It s the ndustry and the end product whch w set the requrements on the phys-
ca and chemca composton of the forest bomass. The concept of borefnng covers a wde range
of possbe ndustra actvtes, whch s aso refected n the varety of deveopment paths foowed
n current pro|ects. Industra compexes that utze a components of a tree are pausbe, as we
as specazed ndustres that process ony specfc tree parts. It s aso concevabe wth an ndustry
structure where the ma|orty of the ndustres process by-products from a few types of ndustres
that process prmary forest raw matera. Exstng pup ms or future arge-scae bofue pants are
exampes of canddates for such prmary forest raw matera processng ndustres. Each aternatve
borefnery structure puts dfferent demands on the raw matera suppy chan. The contnued study
of dfferent suppy chan and borefnery optons coud hep forest owners and borefnery stake-
hoders n makng the rght prortes for the future.
The pro|ects purpose s to anayze and mprove the raw matera suppy to borefneres. The
dea wth the pro|ect outne s to work wth the whoe suppy chan from the forest to a borefnery.
Ths aso ncudes cacuaton of potenta amounts avaabe for severa decades n northern Swe-
den and Fnand of dfferent bomass components. Ths s vta nformaton for the desgn and oca-
zaton of a borefnery.
References
1. IEA. 2011. Key Word Energy Statstcs 2011. Pars, France: Internatona Energy Agency.
2. Aekett, K. 2005. The O Suppy Tsunam Aert, Assocaton for the Study of Peak O and Gas
(onne). Avaabe: http://www.peako.net/Aekett/O_Market_Tsunam_Aert.pdf.
3. Fnnsh Forest Research Insttute, 2012. Fnnsh Statstca Yearbook of Forestry 2011. Ytao, E.,
(ed.). ISBN 978-951-40-2330-9.
4. Fnnsh Forest Research Insttute, 2010. Wood Fue Used for Energy Generaton 2010. Ytao, E.,
(ed.). Forest Statstca Buetn, 2011, 7. ISSN 1797-3074 (In Fnnsh.)
5. Swedsh Forest Agency 2011. Swedsh Statstca Yearbook of Forestry 2011. ISBN 978-91-
88462-95-4.
6. | oesson, | .M., Tuutta, T. The hstory and current deveopment of forest borefneres n Fnand
and Sweden. Work Report of the Forest Refne pro|ect. (Forthcomng.)
ForestSpeCs fndngs on byproducts of forest ndustry: coud bark be more vauabe than tmber?

56
ForestSpeCs findings on byproducts of forest industry:
could bark be more valuable than timber?
H.M.T. Hokkanen
1
, T. Ahlns
2
, S. Alakurtti
3
, N. Demidova
4
, J. Fuchs
5
, D. zotov
6
, H. Kleeberg
7
,
S. Koskimies
3
, M. Langat
8
, J. Lynch
8
, . Menzler-Hokkanen
1
, D. Mulholland
8
, H.-J. Schrer
5
,
A. Shikov
9
, L. Tamm
5
, P. Tammela
1
, J. Yli-Kauhaluoma
1

1
University of Helsinki, Finland;
2
Granula Ltd, Finland;
3
VTT Technical Research Centre of Finland;
4
Northern Research nstitute of Forestry, Russia;
5
Research nstitute for Organic Agriculture,
Switzerland;
6
Far East Forestry Research nstitute, Russia;
7
Trifolio-M GmbH, Germany;
8
University of Surrey, UK; North-West State Medical University named after .. Mechnikov, Russia
Abstract
The EU-pro|ect FORESTSPECS provdes research based boogca and technca understandng
and soutons needed for upgradng wood reated resdues and humc substances to vaue-added
chemcas and materas. Ony through such knowedge-based approach t s possbe to deveop
nnovatve appcatons to the potentay huge varety of boactve substances avaabe n these by-
products, currenty consdered as waste. These substances represent a rch source of aromatc and
other compex structures, whose upgradng to vaue-added specaty chemcas and materas pro-
vdes an opportunty to the forest sector to create new types of vaue chans. Appcaton opportun-
tes ncude medca, pharmaceutca, agrcutura, and envronmenta remedaton uses.
We focus our study on wood resdues, such as the bark of Betula, Pinus, Picea, Larix, Abies and
Populus, as we as on peat, as raw matera. The work conssts of nnovatve natura products
chemstry, extracton and process technoogy; as we as basc research on the mode of acton and
the structure-functon reatonshps n order to ncrease the knowedge-base, essenta for the
emergng bo-economy. Products arsng from the use of these rapdy renewabe natura raw mate-
ras coud repace petrochemca-based products not ony n hgh vaue-added segments (e.g. med-
cne, cosmetcs, pant protecton), but aso n technca products such as adhesves, coatngs, sur-
factants and cheatng agents. Furthermore, ths pro|ect creates optons for addng vaue to the tota
resource of processed wood and peat resdues, e.g. n remedaton and so condtonng, so that no
wastes reman, and the overa operatons are envronmentay sustanabe and economcay attractve.
The outcomes of ths pro|ect are expected to be of sgnfcant mportance to the forest, farmng,
medca and pharmaceutca sectors, wth ma|or postve spn-off mpacts to human heath and the
envronment.
The ForestSpeCs project
The FP7 research pro|ect "Wood Bark and Peat Based Boactve Compounds, Specaty Chem-
cas, and Remedaton Materas: from Innovatons to Appcatons" (ForestSpeCs) had as a startng
pont the vson to repace certan arge-voume, o-based chemca materas wth bo-renewabe
and nnovatve products based on wood-reated resdues and humc substances. In partcuar, the
pro|ect has amed to fnd ways to produce hgh vaue added, boactve compounds such as phar-
maceutcas and boogca pant protecton products, to deveop new envronmentay bengn ndus-
tra chemcas and poymers, and to create economcay attractve optons for the tota use of pro-
cessed wood and peat resdues ether as a whoe, or after extracton of the man boactve fractons,
for exampe n so remedaton. After amost three years of research by seven academc and two
SME partners from Fnand, Russa, Germany, Swtzerand, and the UK, emergng economc oppor-
tuntes for addng vaue to forest "waste" appear wder than ever.


57

Figure 1. The strategy and vaue chan for upgradng of wood resdues and substances of humc
orgn to vaue-added chemcas and materas n FORESTSPECS. The chart descrbes the two
man types of basc raw materas as the startng ponts (bark on the eft and peat on the rght hand
sdes of the chart), the vaue-added secondary raw materas (towards the mdde), and ther possbe
appcaton areas (mdde of the chart) as boactve substances (upper part, ght bue), specaty
chemcas (mdde part, turquose), as core substances n remedaton materas (ower part, dark bue),
or as sources of energy (bottom; not a topc for FORESTSPECS).
Upgrading forest residues: a wealth of opportunities
The Hesnk-based ForestSpeCs-pro|ect has been searchng for nnovatve ways to utze hgh-
voume sde products of the forest ndustry, wth focus on bark from the most mportant tree speces
and on humc substances avaabe n peat. Bark as a raw matera represents exceent opportun-
tes for commerca deveopment based on the huge varety of boactve compounds contaned n
bark. Furthermore, bark s an abundant source of rapdy renewabe organc bomass, and therefore
of great nterest as a source for energy and other arge-scae appcatons such as andscapng
materas and growth substrate.
A race for the resource
Annuay about 20 mon m
3
of bark s produced n the EU. It has ong been consdered as waste,
and ts current man appcaton optons ncude use n andfs, burnng for energy, organc much
for andscapng, compostng to produce so, and many mnor uses. Bark s becomng hghy attrac-
tve n the search for renewabe energy based on bomass, and s a key resource n the cacuatons
concernng future sources of energy. However, other uses may be more attractve because of hgh-
er economc vaue. Besdes energy, the other arge-scae appcaton area for bark s ts potenta to
repace peat as a growth substrate for hortcuture, and as so amendment to remedate poor and
contamnated sos.
PHARMACEUTICALS
COSMETICS
PEST CONTROL
FUNGICIDES
SURFACTANTS
COATINGS
LUBRICANTS
ADHESIVES
CHELATING AGENTS
CEMENT ADDITIVES
REMEDIATION
ENERGY
WOOD RESIDUES
(Bark)
EXTRACTIVES
SUBERIN
PHENOLICS
SUBERIN ACIDS
PEAT
HUMIC/FULVIC
ACIDS
RESIDUE

58
Growth substrate
Bark aready s composted to some extent to produce growth substrate for home gardenng and the
hortcuture ndustry. Amost a growth substrate currenty, however, s based on the sowy renew-
abe peat abundant n some countres, but scarce n most. Severa countres are now competey
bannng the use of peat for ths purpose, and an ntensve search for other sources s ongong.
Improved compostng processes, researched n ForestSpeCs, coud make bark the most mportant
opton as peat repacement. Interestngy, the hortcuture ndustry n Europe uses annuay cose to
20 mon m
3
of peat - amost the same voume as the tota producton of bark - and home garden-
ng equas or even exceeds that n terms of voume. Thus for a compete repacement of peat, the
domestc producton of bark n Europe s not enough, and f everythng s used for the producton of
growth substrate, nothng remans for the energy sector.
Remediation of poor and toxic soils
In many parts of the word, the boogca productvty of the so s severey mted by the ack of or-
ganc matter. Bark can form a base for mprovng such sos and may become an mportant too n
combatng desertfcaton. Bark from certan tree speces s hghy resstant to decay, whch mght be
usefu under some tropca condtons where rapd oss of organc matter from the so s a probem.
Furthermore, bark s an exceent growth substrate for specfc mcro-organsms, whch can add m-
portant ecoogca functons to the composted bark. Desgner-composts can be produced for specfc
purposes, such as boremedaton of sos contamnated wth heavy metas or organc toxc poutants.
Experments n the ForestSpeCs pro|ect show for exampe a hgh potenta to remedate toxc andfs
from the mnng ndustry, hepng to re-vegetate such stes and to convert them nto productve forest.
Compounds for cosmetics and specialty chemicals
Bark and peat are rch sources for specaty chemcas and compex organc moecues, whch can
easy be extracted and used as such, or as a startng pont for chemca processes. Promsng
appcatons studed n ForestSpeCs ncude the use of betun (the whte compound n brch bark)
and ts dervatves n cosmetcs, appcatons of subern dervatves as surface actve compounds,
bodegradabe ubrcants, and bnders for coatngs and composte materas. Peat dervatves coud
become mportant n many ndustra processes such as wood gung e.g. n partce board and
pywood appcatons, as fotaton agents n the mnng ndustry, as cheatng agents n water purf-
caton and as addtves (super pastczers) n cement and concrete. Whe numerous hghy proms-
ng appcaton areas have been dscovered, progress s sowed down by the ack of ndustra
avaabty of the compounds of nterest. For exampe, hgh-grade betun woud have good mar-
kets, but so far ony sma amounts are avaabe.

Figure 2. Structures of upane skeeton (1), betun (2) and betunc acd (3).
H
H
H
H
COOH
H
HO
H
H
H CH
2
OH
H
HO
H
H
H
3
28
1
2 3

59
Bioactive compounds for medical and other uses
Some of the most exctng dscoveres n ForestSpeCs are the many hghy boactve compounds
found n severa bark speces. Severa of these have aready we-known medca appcatons, or
appcatons n the food and feed ndustry as functona components of detary sgnfcance. For
exampe severa specfc, hghy vauabe medca compounds are found n ampe quanttes n bark,
and coud form a bass for a fourshng commerca expotaton. One of them s the man compo-
nent s a pant extract currenty entrey supped to the word market by Chna. The current produc-
ton process s compex, wth ow yeds of varabe quaty, and often connected wth pestcde res-
due probems. Ths can now easy be obtaned at hgh quanttes from bark of European orgn from
trees that fuf organc producton crtera. One of the most mportant dscoveres n ForestSpeCs
may be n the area of pant protecton. Compounds from certan bark speces have exhbted exce-
ent propertes n the contro of mportant pant pests and dseases n arge-scae cutvatons. These
boactve compounds appear to equa or even outperform the current synthetc pestcdes, some of
whch w be banned from use durng the next few years.
Adding value to waste
A comparson of the optons to add vaue to forest ndustry waste reveas that whe the energy
vaue of bark s approxmatey 20 C per ton (wth o prce at 60 USD per barre), the current saes
prces of one ton of bark for andscapng s about 100-150 C, and for composted bark about 150-
200 C per ton. The commerca vaue of the compounds obtanabe from one ton of bark for cosmetc,
medca and pant protecton uses are astronomca compared wth any of the other uses. Addton-
ay, after extracton of specfc compounds, the remanng bomass can st be used for energy, or
for compostng, or some other purpose.
Table 1. Economcs of bark resdues.
Use of bark Value C/t
Energy 20
Much 100
Ordnary compost 150
Puverzed heath ps 200 000
Vaue of extracted, purfed compounds Depends on suppy/demand

Supportng processes n borefneres by correct water treatment

60
Supporting processes in biorefineries by correct
water treatment
lkka Virkajrvi, Michael Recktenwald, Timo Hrm, Veli-Matti Vuorenpalo
Kemira Oyj
ntroduction
The term borefnery has many defntons, whch are used n dfferent occasons and contexts.
Based on the defnton by the Internatona Energy Agency (IEA), a borefnery s the sustanabe
processng of bomass nto a spectrum of marketabe products and energy. However, when ookng
at the matera streams wthn a borefnery, a borefnery seems to be a water pumpng and treat-
ment nstaaton. Water quantty and quaty management (WOOM) ncudes the contro of ncomng
raw water quaty, optmzaton and reuse of process water, and mnmzaton of wastewater. In a
borefnery the technques and rues of ndustra water and wastewater treatment generay appy.
The man chaenges and aso benefts n a borefnery WOOM can be found n the nterna process
water treatment and utzaton of waste streams. The amount of water consumpton n typca bore-
fnery schemes are 3 to 9 tmes that of the man product. In addton to that, water recyce streams
can be arger than the consumpton, easy by a factor of 3. Proper WOOM can brng sgnfcant
savngs n operaton and producton costs. As an exampe from food and beverage sde n 2011,
the Coca Coa Company emnated $500 mon n operatng expenses by appyng water effcent
soutons |1|.
Raw water treatment technologies
The used raw water treatment methods depend on the borefnery process. Dfferent treatment
methods can be used for dfferent operatons: heatng, coong, processng, ceanng, and rnsng
processes to mnmze operatng costs and rsks. Insuffcent contro of raw water quaty can cause
serous probems n the borefnery processes e.g. scang and corroson n ppes, vesses, and
steam boers. Raw water treatment contans severa steps whch are brefy descrbed beow.
Suspended solids
Turbdty reates to the amount of suspended sods n water. Specay desgned coaguants and
foccuants can remove suspended sods very effectvey. However, sowy settng focs can cause
dffcutes n the coaguaton processes. These focs can be frage and negatvey affected by hy-
drauc forces n setters and fters. To strengthen these focs and factate the settng, coaguaton
ads can be used. Organc poymers are the most wdey used foccuants n raw water treatment.
These synthetc poymers are organc eectrcay charged hgh-moecuar-weght compounds. They
mprove the coaguaton and foccuaton process even at ow water temperatures from natura
sources.
Disinfection
The roe of dsnfecton s the contro of harmfu mcroorgansms and the protecton of water dstrbu-
ton systems from mcroba growth. Every borefnery needs specfc strategy for dsnfecton.
Before dsnfecton, the water needs to have ow coour and turbdty and ow number of partces
whch a can consume dsnfectant. Therefore raw water may need pre-treatment. Dependng on
the quaty of the water, remova toxns, heavy metas, pestcdes and ntrate ons may aso be
needed. Dsnfecton can be carred out by heat, chemcay, or physcay wth UV radaton or
membranes. Heat s used ony for sma water quanttes due to the hgh energy need. Chemca
dsnfecton uses chorne or oxdzng agents such as chorne doxde, choramnes, hypochortes,


61
performc acd, and ozone. UV radaton s an effectve method to reduce mcroorgansms by nfu-
encng the genetc matera and prevent re-growth. Low turbdty s essenta to ensure effcency of
UV treatment. The method s ganng popuarty and t s often used n combnaton wth other dsn-
fecton methods. Protozoa ncudng Cryptosporidea oocytes, whch are resstant to most chemca
dsnfecton methods, can be removed by fne ftraton.
Desalination
Desanaton s most commony used to produce potabe water from seawater or bracksh water, but
ndustra water ncudng utrapure water can aso be generated by desanaton. There are two
prmary desanaton methods: therma and membrane desanaton. In therma desanaton, raw
water s vaporzed and then condensed as pure water. Membrane desanaton uses a sem-
permeabe membrane to separate the dssoved sats from water. Membrane desanaton s ess
energy ntensve and has taken over the therma one n most parts of the word.
Dependng on the water quaty and the desanaton technoogy used, the specfc steps n de-
sanaton vary. The pre-treatment step s crtca for keepng the membrane surface cean from
organc and norganc foung eadng to a drop n fux, sat re|ecton effcency, and utmatey short
ftraton cyces. In the pre-treatment, suspended sods are removed and sat precptaton and
mcroba growth are prevented. One conventona pre-treatment method s chemca coaguaton,
foccuaton and sedmentaton.
Scae contro by specfc poymerc antscaants ncreases membrane and equpment fetme.
These antscaants are desgned for mneras encountered wth bracksh, sea or hgh dssoved
sod content water. Products need to be compatbe wth most membranes and the chemcas used
n water pre-treatment.
Corrosion inhibition
Raw water can be corrosve eadng to ncreased rsk of damage to the process equpment. A vare-
ty of substances, ncudng copper and ron, can be dssoved from ppng and equpment and thus
contamnate the water. Severa factors affect corroson: pH, akanty and cacum concentraton.
These a can be controed by chemca ad|ustments.
Color
Coor s caused by dssoved organc matter e.g. humc and fuvc acds, or mnera mpurtes such
as ron and manganese. Reducton of coor s a contro parameter for preventon damage to the
process. Chemca coaguaton s an effectve method to acheve coor reducton.
Metals
Heavy metas are n many cases adsorbed to suspended sods. Remova of suspended sods thus
reduces heavy meta content. Heavy metas can aso be dssoved n the raw water. The ad|ustment
of the pH to a eve where heavy meta hydroxdes are formed enhances remova by precptaton.
Waste handling
Large nvestments are needed n the treatment of effuents from the water-ntense borefnery n-
dustres. The targets of these nvestments are the compance wth ega dscharge mts, the mn-
mzaton of the envronmenta mpact of the ndustra actvty, and the producton of pure water
mosty for reuse, but aso for reease to the natura recpent. Many modern borefnery producton
stes fuf the target of zero reease, meanng fu recycng of purfed wastewater back to the process.
Carbon (C), ntrogen (N) and phosphorus (P) are the man chemca components of wastewater
n the sod and qud phase. The enrchment of those nutrent compounds n the water cyce eads
to uncontroed boogca growth, producton dsturbance, and process nstabty. Carbon occurs as

62
sods n the form of sudge, or as dssoved poymerc or short-chan compounds. Ntrogen and
phosphorus occur n form of norganc ons ke ammonum and phosphate, but aso as organc
compounds ke protens and DNA debrs. In addton, wastewater contans mnor amounts of su-
phur, akane earth metas, aka metas, and other waste from the processes. The amount of ox-
dzabe organc matter s anaysed as Chemca Oxygen Demand (COD). The reducton of COD
characterzes the performance of the wastewater treatment process. Insde the EU, strct rues
appy for the dscharge of COD, ntrogen, and phosphorus to the natura recpent.
The wastewater treatment process s a sequence of dfferent process steps where the snge
compounds are degraded and emnated. The quaty of the effuent determnes the actua treat-
ment setup.
Low solids effluent
Effuents wth ow sod content are treated by an anaerobc step, a subsequent aerobc treatment,
and some after-treatment steps e.g. by carfer, reverse osmoss or evaporaton. Due to the ack of
essenta nutrents n the nfuent, a seecton of macro and mcro nutrents s added before enterng
the wastewater crcut n order to get a better degradaton of the carbonaceous matter. Macronutr-
ents ke phosphate and ntrogen are added to the net of the anaerobc treatment n form of phos-
phorc acd and ammonum. The target s to acheve the baance of the nutrents C:N:P. Mcronutr-
ents are added n form of speca meta mxtures. There s often a ack of mportant metas ke co-
bat, ncke, seenum or tungsten, for an effectve mcroba metabosm. Wth the optmum nutrent
suppy, the anaerobc mcrobes are abe to metabose soube carbonaceous matter to methane.
An ncreased bogas yed n the anaerobc step mnmzes the COD oad to the subsequent aerobc
treatment.
Hgh performance IC-reactors (nterna crcuaton) transfer amost a easy avaabe COD to
methane wthn a few hours (3 to 5 h) of hydrauc resdence tme (HRT). Peets consstng of an-
aerobc mcrobes form a bed that s passed by the qud wth the degradabe COD. Long-chan
compounds are converted to easy degradabe short-chan compounds. In a fna step, they are
transformed to methane by methanogens. A subsequent aerobc treatment degrades the remanng
COD, N and P producng boogca sudge. The sudge s separated n carfers, by ftraton, or
decanter centrfuges. It can be reused n the process after e.g. hydroyss, but s aso dsposed by
ncneraton and andfng.
As the anaerobc treatment produces energy n form of methane, and the aerobc treatment con-
sumes energy n form of ar bowng power, operators of such factes are keen to optmze the
anaerobc step.
High solids effluent
Effuents wth hgh sod contents are treated by a process that conssts of a prmary treatment n
form of a setter, of a secondary treatment (boogca treatment), often foowed by a tertary treat-
ment (after-poshng). Each of the three treatment steps produces a prmary, secondary or tertary
sudge. The three sudge types are mxed and forwarded to a fna anaerobc dgeston for waste
voume mnmzaton and methane producton.
In the prmary treatment, the sods are emnated and concentrated to a prmary sudge. In the
secondary treatment, the cear phase undergoes a boogca treatment consstng of nterchangng
aerated and non-aerated steps where N and P are emnated under consumpton of COD. The
resutng boogca sudge s thckened n a carfer. In many cases ths treatment s suffcent to
fuf purty standards. A tertary step s necessary for the achevement of a very ow dscharge mt.
Here a chemca sudge s produced.
As the mxed sudge from ths treatment contans arge amounts of sod matter, the transfor-
maton to boogcay degradabe matter, the so caed hydroyss, takes severa days dependng on
the chosen setup. Due to dgeston grades of 60 % and reasonabe methane yeds, ths method s
chosen for effectve energy generaton and waste voume mnmsaton for dsposa.

63
Membranes in wastewater treatment
Membrane Boreactors (MBR) offer some advantages compared to the conventona wastewater
treatment. The MBR setups are compact and have a hgh retenton performance for harmfu com-
pounds. MBRs produce a hgh quaty effuent. The purfed wastewater can easy be reused n
ndustra processes and agrcuture. MBRs produce ony sma sudge voumes compared to con-
ventona treatment pants. However, the energy consumpton per voume treated water represents
more than 60 % of the tota operatng costs.
Sludge dewatering
The man target of sudge dewaterng s the mnmsaton of voumes for transport and dsposa,
snce e.g. fees for ncneraton and andfng contrbute to amost 50% of the waste handng costs.
In recent tmes, the vew on waste has changed dramatcay, as t s consdered to be a vauabe
source of energy, and raw materas can be recyced back to the process. The poces of the pro-
ducton stes, strct envronmenta reguatons and reease mts put hgh demands on ths fna
treatment step. As a consequence, efforts are made to produce as pure waste streams as possbe.
The addton of process ads s the key to compy wth the hgh demands for an effectve sod-
qud separaton. Typca process ads for dewaterng are foccuants (organc poymers) and co-
aguants (meta sats). They mnmse the repeng forces between the sod partcuate matter so
that the waste streams from centrfugaton or ftraton resut n pure sod and cear qud fractons.
The benefits of process water treatment and WQQM in biorefinery
case examples
General biorefinery process water scenario
The technooges vary dependng on the borefnery raw materas, products and unt operatons.
Borefneres can be cassfed n many ways: by product, by process, or by raw matera. A bore-
fneres hande arge amounts of water. Even Fscher-Tropsch gasfcaton uses sgnfcant amounts
of water n syngas scrubbng.

Figure 1. A gnoceuosc borefnery. Smutaneous saccharfcaton and fermentaton (SSF). Com-
bned heat and power boer (CHP). Redrawn |2|.

64
A gnoceuosc borefnery s schematcay presented n Fgure 1. Ths borefnery uses wood
chps whch are steam expoded n mdy acdc condtons as raw matera. In ths step the dry
matter content s 30%. Then the bomass s duted to 20% concentraton by recyced water. In ths
scheme ceuose hydroyss to sugars and fermentaton take pace smutaneousy. When fermentaton
s compete the ethano s dsted. The waste stream of stage dstaton contans gnn n the sod
fracton, whch s separated and eventuay peetzed. The water fracton s evaporated and the
condensed vapor s used as duton water and party goes to wastewater treatment. The concen-
trated fracton s fed to the boer. The state of art dry bomass concentraton n pretreatment s
30%, and n hydroyss sghty ess, and at the end of fermentaton water content s cose to 80%
(Tabe 1). The fux of recyced water s more than seven tmes that of the product ethano
(18 500 kg/h). Ony wth adequate WOOM the operaton costs w be economcay feasbe.
Table 1. Water concentraton and water fow rates n a bochemca borefnery |3|.
Step Water concentrati on
[ %]
Wat er fl ow rat e
[kg/h]
Corn stover 20 20 800
Pretreatment 71 224 000
End of fermentaton 84 378 000

Wastewater 93 000
Water recyce 132 000
Water consumpton 80 000
Bioethanol production
Boethano s the most common product of pubshed borefnery schemes. There are many dfferent
technooges proposed, but aso smartes. Here we ook at a boogca, enzyme hydroyss bore-
fnery as an exampe n WOOM reated ssues.
The most common pretreatment step n a bochemca borefnery s dute acd asssted steam
exposon. Ths makes gnoceuosc bomass more susceptbe for enzymatc hydroyss. After the
pretreatment, pH s ad|usted to a sutabe eve for the subsequent steps. Ths s done by base
addton rasng the onc strength of the water and possby requrng sat remova n the water recyce.
Water s used pror to the enzymatc hydroyss n order to ad|ust the dry matter concentraton. Ths
water must be free of enzyme and yeast nhbtors and have a correct onc eve. The nhbtors
found n recyced water ncude furan dervatves (furfura and 5-hydroxymethyfurfura), phenoc
compounds, weak organc acds (evunc, formc, and acetc acd), and heavy meta ons (ncke,
aumnum, chromum). The remova technques of these nhbtors ncude on exchange resns,
actve charcoa, accase enzymatc detoxfcaton, aka treatments, and overmng wth cacum
hydroxde. The appcaton of these usuay causes sugar osses and addtona ftraton steps. Thus
carefu process desgn s needed for effcent operaton.
In dstaton deposts, especay gnn compounds can be formed on the heat surfaces. Here an
antscaant mght proong the dstaton tme and reduce wastewaters from washng step.
In boethano producton, the stage contans arge amounts of organc sods, organc acds and
sats, thus creatng a arge chemca oxygen demand (COD) and makng the recycng a chaengng
operaton. Gran ethano process s abe to process stage nto a feed product. In gnoceuosc
ethano borefneres, the voumes of ths stage are arger than n gran processes, as bomass
concentraton s ower n the process. Thus handng of stage w form a sgnfcant part of the
costs, even though the gnn content of the stage can be used as an energy source. The sod

65
fracton separaton of stage must be effcent to factate economc evaporator operaton. If that s
carred out by centrfugaton, evdence exsts that foccuants can mprove the effcency.
The water vapors to be reeased to atmosphere (e.g., from dryng) must be treated to reduce
voate organc compounds (VOCs) and odor to the requred eve.
A recent NREL report |3| gave the foowng water baance for an ethano pant of 18 000 kg eth-
ano per hour producton whe the pant had a water consumpton of 5.35 tres per tre ethano.
However, the recyced amount of process water n the process was 376 000 kg/h .e. 2.5 tmes that
of raw water, and 20 tmes the produced ethano amount. In ths exampe, the recyced water
stream from boer and coong tower bow down, pretreatment fash and stage evaporaton wa-
ters. These streams are coected, anaerobcay and aerobcay treated, carfed, ftered by re-
verse osmoss, and party evaporated before recycng back to process. The cost for the water
treatment (equpment, nstaed cost) s 21% of tota nstaed cost for the pant. The varabe opera-
ton cost comng from raw water treatment represent 0.5%, wastewater treatment chemcas 4.3%,
boer chemcas 2.3%, and coong tower chemcas 0.1% of tota varabe operatona costs.
Utilization of algae in biorefinery
Cost-effectve methods of harvestng and dewaterng the aga bomass are needed for agae bore-
fnery to become economcay feasbe. Chemca foccuaton and foc separaton by sedmentaton
or fotaton can be effcent methods for separaton of agae. Further, dewaterng of the separated,
ow-dry-content bomass, can be acheved by tradtona ftraton or by centrfugaton. Ths dewater-
ng can be mproved by chemcas. Utzng norganc coaguants and poymer foccuants n the
range of 100 ppm and 1 ppm eves respectvey, separaton effcences over 98% have been
acheved. The treatment condtons (chemcas, dosages, tmng) s affected e.g. by agae type,
concentraton, pH, and charge. The end-use and downstream processng of the agae bomass may
aso restrct the types of chemcas to be used. In subsequent dewaterng of the bomass by ftra-
ton method, chemcas have enhanced dewaterng as we as preventng bockage of the fter me-
dum. Dry mass contents up to 15-20% have been acheved. Kemra has deveoped a method to
montor and optmze the harvestng effcency. The same fow cytometry based method can aso be
apped for agae cutvaton montorng.
Production of micro crystal line cel lulose at pulp mill
Mcro crystane ceuose (MCC) s a versate product, whch can be used n many ndustra app-
catons, e.g. n food, pharmaceutca, cosmetcs, paper and board and many other appcatons. The
chaenges of MCC producton have been rather sma producton capacty, the ack of effcent
recovery of used acd, as we as utzaton of effuents. The Cean Technooges Research Group
at Aato Unversty has together wth Kemra been nvestgatng the possbty to ntegrate MCC
producton to an exstng kraft pup m |4|. The new borefnery process can utze amost 100% of
the wood bomass convertng t nto MCC wth a hgh yed, whereas hydroyss products can be
used as a raw matera for boethano. In addton, utzaton of on-ste pup m chemcas as we as
exstng chemca recovery can be acheved.

66

Figure 2. Integraton prncpe of nove MCC process to a kraft pup m.
In the tradtona producton of MCC hgh oads of hydroyss products (COD) are dscarded n to the
wastewater treatment pants. Ths affects the producton costs negatvey n the form of raw matera
oss and wastewater treatment. However, n ths specfc MCC producton concept aso wastewater
and wastewater management was taken n to account. Hydroyss stream, contanng vauabe
sugars after neutrazng, can be utzed as a raw matera for sustanabe way to produce green
chemcas such as ethano and xyan or methane. Dssoved sugars from MCC process can aso be
treated n the exstng effuent treatment system f not utzed n e.g. boethano producton.
Production of organic acids from dilute side streams
Organc acds, such as formc, acetc, proponc, and actc acds, are conventonay produced by
ndustra processes usng non-renewabe natura raw materas predomnanty n the form of mnera
o. However, sde streams of boethano producton coud be consdered as an aternatve raw matera
for producton of sma organc acds. References of boprocesses have been pubshed from the
20s to recent years |5, 6|. However, most of the descrbed processes have been found economcay
non-feasbe due to ether an extensve raw matera purfcaton need (n case of crude gycero), or
due to too ow fna productvty and dute product concentratons n the fermentaton broth.

67

Figure 3. Fermentaton process wth cosed oop process.
The process s very water ntensve and n the prevous approaches vauabe raw matera was
party dscarded nto arge wastewater stream. Treatment of ths stream woud have been very
costy. New process desgn descrbed n the Fgure 3. enabes not ony sgnfcant wastewater re-
ducton but aso hgh gycero converson to vauabe products, mnma chemca consumpton for
pH ad|ustment n both fermenter and extractor, mproved acd yed n extractor, smaer extractor
sze and ower nvestment cost. Furthermore, ow extractant resdue of tota recyce mnmzes tox-
cty effects n fermentaton. The oop cosure was enabed by extracton and membrane process.
Due to process modfcatons and cosed water oops the wastewater dscharge was reduced overa
by 85%. However, the rea drvng force was the 30 % reducton n the producton cost of bobased acd
due to new process desgn enabed by water treatment based on extracton and membrane separaton.
Conclusions
Water s the snge argest component n borefnery mass baance. Athough the cost of raw mate-
ra and the yed are the argest factors n borefnery economy, the correct WOOM can brng sav-
ngs n capta and operatona cost.
Correct and adequate raw water treatment ensures smooth, troube free operaton and ncreases
equpment fetme. Baancng economcay water recyces n borefnery optmses costs, reduces
wastewater voumes, and saves energy.
Effcent wastewater treatment can produce energy whe fufng envronmenta reguatons, and
mnmzes waste treatment costs.
References
1. Frost & Suvan. 2012. CEO 360 Degree Perspectves of the Water and Wastewater Treatment
Market n the Goba Food and Beverage Industry, M7DE-15, August 2012.
2. Barta, Z., Reczey, K., Zacch, G. 2010. Techno-economc evauaton of stage treatment wth
anaerobc dgeston n a softwood-to-ethano process. Botechnoogy for Bofues 3(21),
http://www.botechnoogyforbofues.com/content/3/1/21.
3. Humbrd, D., Davs, R., Tao, L., Knchn, C., Hsu, D., Aden, A., Schoen, P., Lukas, | ., Othof, B.,
Worey, M., Sexton, D., Dudgeon, D. 2011. Process Desgn and Economcs for Bochem-
ca Converson of Lgnoceuosc Bomass to Ethano, Dute-Acd Pretreatment and En-
zymatc Hydroyss of Corn Stover. NREL/TP-5100-47764, May 2011.
4. Dah, O., Vanhatao, K., Parvanen, K. 2011. A Nove Method to Produce Mcroceuose,
WO2011154600.
5. Sherman, | .S. Proponc acd fermentaton by the use of mxed strans of proponc bactera,
US1865146.

69

Wednesday, 24 October:
ndustri al developments

Actua and future trends n dssovng pup manufacture

71
Actual and future trends i n dissolvi ng
pulp manufacture
Herbert Sixta
1
, Mikhail akovlev
1
, Lidia Testova
1
,

Annariikka Roselli
1
, Michael Hummel
1
,
Marc Borrega
1
, Adriaan van Heiningen
2

1
Forest Products Technology, Aalto University, F-00076 AALTO, Finland
2
Department of Chemical and Biological Engineering, University of Maine, USA
Abstract
Heren, we report about exstng and nove dssovng pup processes provdng the bass for an
advanced borefnery. The SO
2
-ethano-water (SEW) process has the potenta to repace the acd
suphte process for the producton of rayon-grade pups, owng to a hgher fexbty n the seecton
of the raw matera source, substantay ower cookng tmes, and the near absence of sugar deg-
radaton products. Speca attenton s pad to deveopments that target toward the seectve and
quanttatve fractonaton of paper-grade pups nto hemceuoses and ceuose of hghest purty.
Ths target has been accompshed by the IONCELL process where the entre hemceuose
fracton s seectvey dssoved n an onc qud n whch the H-bond bascty and acdty are ade-
quatey ad|usted by the addton of a co-sovent. At the same tme, pure hemceuose can be re-
covered by further addton of the co-sovent, whch then acts as a non-sovent. The resdua pure
ceuose fracton may then enter a Lyoce process for the producton of regenerated ceuose
products.
ntroduction
The upturn of dssovng wood pups (DWP) n the market durng the ast 10 years may be attrbuted
to a consstent growth of regenerated ceuose fber producton, partcuary n Chna, where 61% of
the current goba rayon producton capactes are ocated |1|. The annua DPW producton n 2011
was 4.2 mon t, of whch 2.9 mon t accounted for commodty appcatons, e.g. rayon, whe the
resdua 1.3 mon t were converted to specates, e.g. to ceuose acetate |1|.
Market studes ceary ndcate that ths trend of ncreasng demand of regenerated ceuose f-
bers and thus dssovng pups w preva durng the next decades.
The goba producton of texte fbers s predcted to ncrease from 72.5 mon t n 2010 to 133.5
mon n 2030 by both an ncrease n per capta consumpton (10.5 to 15.5 kg per capta and year,
respectvey) and popuaton (6.9 to 8.3 bon) |2|. The nherent physoogca propertes of ceuose
fbers ensure an adequate mosture management that cannot be acheved by synthetc fbers.
Snce these propertes are requested n many fber products, a mnmum constant share of ceuo-
sc fbers, ncudng both natura and man-made fbers, of 33 to 37% on the goba fber consump-
ton has been pro|ected |2|. Wth ths assumpton, the annua per capta consumpton of ceuosc
fbers w ncrease from ts present 3.7 to 5.4 kg n 2030. At the same tme, the cotton producton
w stagnate at a eve of about 26 mon t per year (3.1 kg per capta n 2030) due to the estmated
shrnkage of the cotton growng area and the concomtant ncrease of the annua specfc yed from
presenty 800 to 925 kg per hectare n 2030. The ony way to compensate for the resutng ceuose
fber gap of 1.7 kg per capta s to nvest n addtona capactes of man-made ceuosc fber pro-
ducton (vscose, Lyoce, ceuose acetate, cupro, etc.), whch, n absoute terms, transates nto an
addtona annua goba producton of 14.8 mon t (from the present 4.2 to 19.0 mon t n 2030) |3|.
The growng demand for hghy purfed ceuose pups s, however, not ony mted to texte appca-
tons, but t aso concerns the manufacture of ceuose acetate for hgh vaue-added fms, pastcs,
and coatngs as we as ceuose mxed ethers for acquers and prntng, ceuose ethers, and ceu-
ose powder, whch have found mportant appcatons n the food and pharmaceutca ndustres.
Moreover, dssovng pups seem to be the preferred substrate for the manufacture of nanofbrated
ceuose (NFC), a future precursor of advanced materas.


72
Parae to the necessary nvestments n new vscose and Lyoce fber capactes, addtona ca-
pactes n the producton of dssovng pups, the raw matera for the manufacture of man-made
ceuose fbers, have to be nstaed. Dssovng pup refers to pup of hgh ceuose content, com-
prsng a mnmum amount of norganc and non-ceuosc organc mpurtes |4|.
Currenty, dssovng wood pups are produced by the acd sufte and the vapor-phase prehydroyss
kraft (PHK) processes, whch were both deveoped n the 1950s. Whe the former remaned techn-
cay argey unchanged, a modern dspacement cookng procedure was adopted to the steam pre-
hydroyss kraft process |4|.
The growng demand for hgh purty dssovng pups, however, requres the deveopment of nove
process concepts whch that both the reazaton of advanced borefnery concepts and the manufac-
ture of pure ceuose pups, reveang a quaty profe comparabe to that of cotton nters. Changng
from steam to water prehydroyss (autohydroyss) aows the seectve separaton of ma|or parts of
hemceuoses n the form of ogo- and monosacchardes and acetc and formc acds. Unfortunate-
y, stcky precptates are formed from dssoved acd soube gnn, whch currenty hampers the
commerca appcaton of autohydroyss as a pre-treatment of akane degnfcaton processes |5|.
Andrtz recenty deveoped cookng system upgrades for retroft to DPW operaton n contnuous
dgesters, ncudng a prehydroyss reactor vesse for water prehydroyss. In the meantme, ths
technoogy has been devered or s about to be devered to severa customers n Asa |6|. For the
batch cookng technoogy, the processabty of water prehydroyss s ensured by an n-stu adsorp-
ton of the reeased reactve gnn fractons on actvated carbon, as recenty suggested |7, 8|.
Autohydroyss of hardwood acceerates the degnfcaton rate durng subsequent kraft or soda-
anthraqunone (SAO) pupng, presumaby due to better accessbty and the ceavage of LLC
bonds as demonstrated by knetc studes |9, 10|. Thus, mder cookng condtons, expressed n
ower H-factor and/or chemca charges, are suffcent to acheve the requested degree of degnf-
caton. However, akane degnfcaton methods foowng autohydroyss pre-treatment of wood,
even under md condtons, are assocated wth hgh ceuose osses due to b-emnaton (peeng)
reactons. Ceuose yed remans amost unaffected by autohydroyss up to reatvey hgh ntens-
tes, whe the degree of poymerzaton (DP) s decreased by the hydroytc ceavage of gycosdc
bonds, thus creatng new reducng end groups (REGs). Snce the extent of akane peeng reac-
tons s proportona to the concentraton of REGs, subsequent akane treatment, such as kraft
pupng, eads to substanta yed osses |11, 12|. The combnaton of prehydroyss wth acd su-
phte cookng s, however, no aternatve because of nsuffcent degnfcaton owng to the deact-
vaton of gnn structures towards sufonaton |13|. Thus, nove process concepts need to be deve-
oped that aow the seectve and quanttatve remova of hemceuoses and gnn, to reaze ad-
vanced borefnery concepts and to satsfy the growng demand for hgh purty dssovng pups.
Ths study provdes an overvew on nove process concepts for the manufacture of dssovng
pups comprsng both further deveopments of exstng technooges as we as radca nnovatons.
Experimental
Raw materi al
Brch, spruce, and pne wood chps were devered from a pup m n Fnand and Eucalyptus
globulus from pantatons n Uruguay. The chps were screened (SCAN-CM 40:01) upon devery
and subsequenty stored n a freezer. The composton of the wood chps s summarzed n Tabe 1
(% on odw).

73
Table 1. Composton of wood chps.
Species Cel l (A)X GGM KL ASL
Brch 43,1 27.2 2.5 21.7 4.4
E. globulus |14| 48.7 21.1 1.9 22.7 4.7
Spruce |15| 44.1 8.0 17.7 *27.7
Pne 41.1 8.5 17.2 25.9 0.7
Cacuaton accordng to | anson |16|. KL =Kason gnn; ASL =acd soube gnn. (*) tota gnn

A commerca ECF-beached brch kraft pup comprsng contents of 25.4% xyan, 1.0% gucomannan,
and 73.6% ceuose (accordng to | anson |16|) was used for the converson to a dssovng pup by
CCE and IONCELL treatments.
Autohydrolysi s
Hot water extractons were conducted n a 10 L batch reactor equpped wth a heat exchanger and
temperature contro. A predetermned amount of deonzed water was added to reach a qud-to-
wood (L:W) rato of 3:1 g/g. A hgh-pressure pump was used to contnuousy recrcuate the water
through the chp bed. The ntensty of standard autohydroyss was descrbed by the P-factor usng
an actvaton energy of 125.6 k| /mo as determned for the remova of fast reactng xyan |4, 17|,
whe for the ntensty of reinforced autohydroyss, an actvaton energy of 180 k| /mo was apped
to compute a modfed P-factor, og P-X
S
, correspondng to the remova of the recactrant xyan
fracton n brch wood |18|.
Pulping experi ments
Soda anthraqunone (SAO) of brch chps and SO
2
-Ethano-Water (SEW) treatments of spruce
chps were conducted n an o-bath reactor, contanng 8 rotatng autocaves of 225 m each. In
SAO cookng, an aqueous souton contanng caustc soda (22% NaOH on odw) and AO (0.1 or
1.0% odw) was added, reachng a L:W rato of 3:1 g/g. Sodum borohydrde (SBH) was added as a
reductve stabzaton agent to the SAO pupng quor. The temperature n the reactor was rased to
150C and kept constant for 60 mn, reachng an H-factor of about 200 hours. SAO pupng of Eu-
calyptus globulus chps was conducted n a 10-L dgester wth forced quor crcuaton, usng the
contnuous batch cookng (CBC) mode |19|. The same equpment was used for acd sufte pupng
of spruce chps wth the standard procedure beng descrbed n |20|. The detaed composton of
the acd sufte cookng quor and reacton temperatures s provded n the Resuts part. The cook-
ng quor for SEW fractonaton of spruce chps was prepared by n|ectng gaseous SO
2
nto a cod
ethano/water mxture (55% v/v) unt a concentraton of 1.88 moe/L was reached. More detaed
nformaton can be found n |15|.
Seected SEW and PHSAO pups were ECF beached to fu brghtness. The apped beachng
sequences are sted n Tabes 2 and 3.
Pre- and post-alkaline extraction
Akane pre- and post-extracton (CCE) of Eucalyptus globulus chps and kraft pup are descrbed n
|14| and those of brch chps n |21|.

74
ONCELL process
The brch kraft pup was treated wth a mxture of |emm|OAc and a moecuar co-sovent n a vert-
ca kneader at 60C for 3 hours. The dssoved xyan was precptated by further addton of the co-
sovent. The sovent mxture was removed by thorough washng n hot water pror to anayss.
Analyti cal methods
Chemca composton of wood and pup sampes was determned after a two-stage tota hydroyss,
accordng to the anaytca method NREL/TP-510-42618. The ASL was measured n a Shmadzu UV-
2550 spectrophotometer at a waveength of 205 nm and usng an absorpton coeffcent of 110 L/(gcm)
|22|. The monosacchardes were determned HPAEC-PAD n a Donex ICS-3000 system. The kap-
pa number and ntrnsc vscosty of the pups were determned accordng to the SCAN-C 1:100 and
SCAN-CM 15:99 methods, respectvey. Moar mass dstrbuton of pups was determned by ge
permeaton chromatography (GPC) n DMAc-LC souton accordng to Scheosky |23|.
Results
Acidic fractionation processes
Acd sufte (AS) pupng offers a good bass for the reazaton of the borefnery concept, aowng
the recovery of the three gnoceuosc poymers as pure ceuose pup (DWP), monomerc sugars,
and gnosufonate n economcay attractve quanttes. In severa ndustra AS dssovng pup
pants, products from hemceuoses (furfura, ethano, yeast, acetc acd) and gnn (gnosu-
fonates, vann) are produced, enhancng the proftabty of the ms. AS pupng, however, shows
mmanent drawbacks characterzed by ts ow fexbty n the seecton of raw matera sources,
ong overa cookng tme due to very sow mpregnaton, neffcent recovery of cookng chemcas,
and the converson of substanta amounts of monomerc sugars to adonc acds. SO
2
-ethano-
water pupng (SEW) has the potenta to be a vabe aternatve to meta-based acd sufte cookng |15|.
The presence of ethano n the cookng quor moderates ts acdty and aows fast transport of the
pupng agents to the reacton stes nsde the wood. In ths way, the overa cookng tme can be
substantay reduced. Further, ethano s known to be a better sovent for gnn and gnosufonate
than water. The absence of a base n the process modfes the recovery cyce to smpe dstaton
of ethano and unreacted SO
2
. Ethano does not partcpate n the reactons and can thus be recov-
ered amost quanttatvey. Snce the pK
a
of SO
2
.H
2
O ncreases from 1.8 n pure water to about 2.7
n 55% v/v ethano-water (30C), the |HSO
3
-
| and |H
+
| concentratons are sgnfcanty ower n the
SEW quor than n an AS quor. As a consequence, the degree of sufonaton of the dssoved
gnn s substantay ower (S/C
9
-0.24 for spruce at 1.88 moe/L SO
2
|15|) as compared to the
gnosufonates orgnatng from acd suphte pupng (S/C
9
-0.50 for spruce at 1 moe/L SO
2
|24|).
The ow |HSO
3
-
| aso prevents the formaton of adonc acds from dssoved monosugars, whch
aows hgher and easer sugar recovery. Degnfcaton to very ow kappa numbers as known from
AS dssovng pup cookng s, however, not possbe n SEW cookng, due to ower |HSO
3
-
| and |H
+
|
(Fgure 1a). At a gven pup vscosty (or yed) the kappa number of spruce SEW pups cannot be
reduced beow 10, whe spruce AS pups show kappa numbers beow 5.

75

(a)

(b)
Figure 1a. Yed vs. kappa number of AS and SEW cooks of spruce. 1b. Yed vs. hemceuose
content of unbeached SEW and AS pups.
Fgure 1b reveas a comparabe reatonshp between the yed (vscosty) and the hemceuose
content n the pups from both acdc processes, whch, however, shows a dependency on the L:W
rato.
ECF-beached SEW and AS dssovng pups exhbt comparabe propertes. They both meet the
specfcaton requested for rayon pups (Tabe 2). Surprsngy, acceptabe rayon pup propertes
were acheved wthout hot caustc extracton (HCE), as exempfed for the SEW-2 pup. Ths was
confrmed by a good to very good quaty of the vscose prepared by the SEW-2 pup usng
Trebers method |25| (Fgure 2).
Table 2. Specfcaton of ECF-beached SEW- and MgS rayon pups from spruce (average of two
beachng seres). SEW-1: 1.88 moe/L SO
2
, L/W =6/1, 60 mn at 150C, 55% v/v EtOH, 60 mn; SEW-2:
ke SEW-1, but L/S =3/1, 50 mn. MgS: 1.07 moe/L tota SO
2
, 0.24 moe/L MgO, L/W =3.2/1,
110 mn at 145C.
Process Sequence Total yiel d Bri ghtness Viscosity R18 Xylan Mannan
% odw % SO mL/g % % %
SEW-1 EO-D-O-P 39.8 90.2 478 94.4 1,7 1,5
SEW-2 O-D-EP-O-P 41.7 89.3 478 93.2 1.7 2.2
MgS E-O-D-P 40.9 89.9 552 94.8 1.7 1.9
0 10 20 30 40
35
40
45
50
SEW: 1.88 moe/L SO
2
; 135C; L:S=3:1
SEW: 1.88 moe/L SO
2
; 135C; L:S=6:1
MgS: 0.73 moe/L SO
2
; 0.25 moe/L MgO; 145C; L:S=3.2:1
Y
d
,

%

o
d
w
Kappa number
2 4 6 8 10
35
40
45
50
2 4 6 8 10
0
300
600
900
1200
P
u
p

v
s
c
o
s
t
y
,

m
L
/
g
Hemceuoses (M+X), % od
SEW: 1.88 moe/L SO
2
; 135C; L:S=3:1
SEW: 1.88 moe/L SO
2
; 135C; L:S=6:1
MgS: 0.73 moe/L SO
2
;
0.25 moe/L MgO, 145C; L:S=3.2:1
Y
d
,

%

o
d
w
Hemceuoses (M+X), % od

76

Figure 2. Fterabty vs. partce voume of vscose sampes prepared from dfferent dssovng pups.
Alkaline fractionation processes
The manufacture of hgh-purty dssovng pups (R18>96%) wth a narrow moar mass dstrbuton
(MMD) s convenenty accompshed by the two-stage PHK or PHSAO processes. Currenty, the
sugars and acetc acd from the hydroysate are not recovered pror to the akane degnfcaton
step because prehydroyss s amost excusvey conducted n vapor-phase. Now, wth the deve-
opment of techncay feasbe water prehydroyss processes for the contnuous and batch produc-
ton, the hydroysate can be used as a source for food addtves and patform chemcas |6, 7|. The
concomtant producton of patform chemcas and rayon pup from brch wood was studed n ab
tras. Whe the amounts of xyose, xyo-ogosacchardes, and acetc acd n the hydroysate were
confrmed expermentay, the fna yeds of the purfed patform chemcas, furfura and acetc acd,
were assumed, based on terature data and ndustra experence. In an addtona experment, the
potenta of ncreasng the pup yed through the addton of sodum borohydrde (SBH) to the cook-
ng quor was nvestgated. The resuts are shown n Tabe 3:
Table 3. Summary of process condtons, product specfcaton and yeds of akane fractonaton of
brch wood.
Processes
Unbleached ECF bleached pulp Extract By-products
Kappa Yield Yield R18 Xn [h] B Xyl AcOH F AcOH
%odw %odw % % mL/g %ISO %odw %odw %odw %odw
PHSAO 8.3 36.8 34.1 95.8 4.7 507 90.4 *8.4 1.2 4.9 1.0
PHSAO-B 8.2 38.8 36.2 95.5 6.0 572 91.4 *8.4 1.2 4.9 1.0
K-CCE 18.0 51.5 39.6 6.5 **8.3 n.d.
PH: L/W =4/1; 65% of hydroysate recovered; P-factor =1 000; SAO(B): L/W =3.5/1; 22%EA; 0.1%AO; (0.5% SBH); H-factor =300-350;
Beachng: O-A-D-EP-P; (*) 50% monomer, 50% ogomer; (**) as poymer: Mw =11.7 kDa. 80 mo% xyose converson to
furfura (F) |26|; 85% AcOH recovery based on ndustra experence.

0 10 20 30 40 50 60
0
100
200
300
400
500
600
excellent
very
good
good
satis-
factory
V
s
c
o
s
e

f
t
e
r
a
b
t
y
Partce voume, ppm
SEW-1
SEW-2
MgS
PH-SAO
SAO-CCE
E-SAO-CCE
K-X-CCE-EG
Cotton Lnters
poor

77
The addton of SBH resuted n 1.5% hgher ceuose and 0.6% hgher xyan yed. Thus the add-
ton of REG stabzers s no vabe opton, snce t deterorates ceuose purty, whch cannot be
compensated uness prehydroyss ntensty s ncreased, whch n turn reduces both yed and vs-
costy. The recovery of more than 8% xyose on odw from the reeased hydroysate and ts potenta
converson to 4.9% furfura on odw sgnfcanty contrbutes to the economy of the fractonaton
process. Hence the saes of the DPW producton ncrease by amost 60 C/t of wood, assumng the
current furfura market prce of 1 200 C/t (-15-20% of the DPW saes).
The brch PHSAO dssovng pup shows rather ow ceuose purty (Tabe 3), whch s suffcent
for rayon appcaton as confrmed by reasonaby good vscose quaty (Fgure 2), however, not
suffcent at a for ceuose acetate producton, where a resdua xyan content of 1.5% consttutes
the mnmum requrement. In a seres of experments, where the ntensty of prehydroyss was
graduay ncreased to very hgh eves, the reatonshp between pup yed after subsequent SAO
cookng and the resutng xyan content and the vscosty of the unbeached pups was montored.
Fgure 3a reveas the substanta yed oss from 34% to 23% on odw when the xyan content s
reduced from 4.5% to 1.5% by ntensfed prehydroyss.

(a)

(b)
Figure 3a. Yed and vscosty reated to the xyan content n a PHSAO pup as a functon of
prehydroyss ntensty expressed as og(P-X
S
) as shown n Fgure 3b |11|.
The ow pup yed combned wth the ow pup vscosty of 300 mL/g excudes ths producton
concept for the manufacture of acetate grade pups. Hardwoods wth substantay ower xyan
content than brch, such as Eucalyptus urograndis or saligna, mght be a sutabe raw matera
source for the producton of ow-quaty acetate grade pup by means of PHSAO cookng ony,
avodng addtona refnng steps.
In recent years, severa studes focused on the converson of paper-grade to dssovng pups by
smpy extractng the hemceuoses (many xyan aso n the case of SW pup) n aqueous 1.5-3.0 M
NaOH souton at 20-30C (CCE) |19, 27|. In ths way, ceuose yed s not affected, whch consttutes
a cear commerca beneft over the PHK procedure (Tabe 3). Further, the CCE-treated kraft pup
(K-CCE) reveas a hgher aka resstance, expressed as R18, and a more narrow moar mass
dstrbuton (MMD) than the PHK-pups |19|. However, an aka-nsoube xyan fracton (4%) of
hgh moar mass remans n the pup even at hgh NaOH concentraton |28|. Further drawbacks of a
CCE treatment consttute the parta converson to ceuose II occurng at NaOH concentraton >2 M
as we as the aggregaton of the mcrofbrs, whch, upon dryng, resuts n a compacton of the
supramoecuar structure. These ateratons of the ceuose structure, possby together wth the
entrapped hgh moar mass xyan, party expan the poor quaty of the vscose made from CCE-
treated pups (Fgure 2). Dfferent to PHK and AS dssovng pups, the outer ce wa ayers, P and
S1, of CCE-treated paper-grade pups are preserved to a greater extent |19, 29|. Thus, the sweng
capacty of the S2 s restrcted by the rgdty of the outer ce wa ayers. The reduced sweng

0 1 2 3 4 8
0
10
20
30
40
50
Acetate (1.5% X)
Y =23 (24)
SAO / 0.1 % AO
SAO / 1.0% AO
SAO / 1.0% SBH S
c
r
e
e
n
e
d

Y
d
,

%

o
d
w
Xyan, % odp
Rayon (4.5% X)
Y =34 (36)
Birch
0
200
400
600
900
1200
1500
300 mL/g
V
s
c
o
s
t
y
,

m
L
/
g
780 mL/g

0,0 3 4 5 6
0
500
1000
1500
0.1 % AO
1.0 % BH
1.0% AO

P
u
p

v
s
c
o
s
t
y
,

m
L
/
g
og (P-X
S
)

78
capabty n turn causes a ower accessbty and, therefore, ower fter vaues wth hgh partce
numbers, as ustrated n Fgure 2. The hgh sweng resstance due to a thck prmary wa |30| s
presumaby aso the reason for the poor vscose quaty prepared from cotton nters (Fgure 2). It
was shown that an endogucanase post-treatment coud mprove the accessbty of a CCE-treated
kraft pup, whch transates to a sght mprovement of the vscose pup reactvty (Tabe 3). At the
same tme, t aows the precse ad|ustment of the degree of poymerzaton of the pup |27|.
The unduted ftrate of the CCE stage s a rewardng source of poymerc xyan because the
amount of concomtant mpurtes, such as gnn, extractves or hydroxyacds, or akane sugar
degradaton products, s ow. In a frst step, the xyan s concentrated by utraftraton foowed by
daftraton to maxmze the xyan-to-NaOH rato. The xyan s precpated by the addton of an
acoho or a non-sovent or smpy by acdfcaton. The xyan yed depends many on the raw
matera source and the condtons n the CCE step. From a brch kraft pup, 8.3% of xyan on odw
and from a Eucalyptus globulus kraft pup, 6.6% |31| of xyan on odw were soated as dry powder
when usng 2.5 M NaOH souton at 20C |32| and 2.25 M NaOH souton at 30C for one hour,
respectvey (Tabe 3). Snce poymerc xyan from aka extracton of hardwood has no defnte
market yet, no vaue can be attrbuted to ths product. For exampe, aka-extracted xyan can be
modfed to a fm for packagng appcaton after dervatzaton to a water soube poymer as
recenty demonstrated by the converson to carboxymethy xyan (CMX) of dfferent DS vaues |32|.
oncel l process
Athough about 50% of the hemceuoses and about 10% of ceuose are ost durng kraft cookng |33|,
t s by far the most seectve process for the separaton of gnn from gnoceuosc bomass. Thus,
the resutng paper-grade pup s the most attractve raw matera for the manufacture of pure and
hgh moar mass ceuose and hemceuoses, provded that a process can be deveoped that a-
ows the seectve separaton of these poymers. As prevousy shown, the exstng protocos for the
remova of hemceuoses, such as autohydroyss or akane extracton, are a accompaned by
unwanted sde and degradaton reactons or parta converson of ceuose I to ceuose II. Ths can
argey be avoded by sovent extracton usng an aqueous N(tren) souton |34, 35|. However, ths
protoco s handcapped by the necessty of an effectve remova of the resdua ncke and by the
fact that gucomannan from softwood pup remans amost nsoube under these extracton condtons.
In 2002, Rogers et a. frst demonstrated that some onc quds (ILs) coud soubze ceuose |36|.
Currenty, |emm|OAc s regarded as one of the best, f not the best ceuose sovent. In an attempt
to predct the ceuose dssouton propertes of ILs, the emprca concept of net-bascty, b-a, was
suggested, whch accounts for the acdty mparted by the caton |37|. It was shown that a ILs
reported to dssove ceuose are ocated n an emprca soubty wndow defned by 0.35 <b-a <0.9
wth b >0.8, expressng a necessary baance between acdty and bascty.
In the consderatons to fnd a sovent system that coud seectvey dssove hemceuoses from
a hemceuose-rch pup, e.g. paper-grade kraft pup, t was hypotheszed that the requrements for
a sovent regardng H-bond bascty are ower as compared to those for ceuose-dssovng ILs.
The ower moar mass, the amorphous structure, and the reduced abty to form nter- and ntramo-
ecuar H-bonds due to the absence of the exocycc hydroxymethy group shoud factate dssou-
ton. Indeed, the addton of a defned amount of a moecuar co-sovent to |emm|OAc to ower H-
bond bascty, b, and the net bascty, b-a, was successfu n the quanttatve and seectve dssou-
ton of hemceuoses from a hem-rch paper-grade pup (Fgure 4a), whe both poymers remaned
competey unchanged n moar mass and yed (Fgure 4b).

79

(a)

(b)
Figure 4a. Net bascty, b-a, potted aganst b, showng the soubty wndows for ceuose and
hemceuose, respectvey. 4b. Moar mass dstrbuton of brch kraft pup and the pure components,
ceuose and xyan, separated thereof by seectve dssouton of the atter n |emm|OAc+Co-sovent.
In ths way, a new process, IONCELL, was deveoped, whch aows the converson of a cheap
paper-grade pup to a dssovng pup of hghest purty. At the same tme, pure xyan can be recov-
ered by further addton of the co-sovent, whch then acts as a non-sovent. The resdua pure ceu-
ose fracton may then enter a Lyoce process for the producton of regenerated ceuose products.
Conclusions
There s no doubt that the exstng dssovng pup processes, AS and PHK, consttute a commer-
cay attractve borefnery patform. Whe borefnery concepts have aready been reazed n ndus-
tra scae on the bass of the AS process, ths was not the case for the PHK process so far. Now,
wth the deveopment of techncay feasbe water prehydroyss processes, the way s open to
utze the wood hydroysate as a source for hgh vaue-added chemcas. The nove SEW fractona-
ton process has the potenta to repace the AS process owng to a hgher fexbty n the seecton
of the raw matera source, substantay ower cookng tmes, and the near absence of sugar deg-
radaton products. However, no dfferences are seen n the propertes of the dssovng pups resut-
ng from both acdc processes.
The genera drawback of the ndustra processes s that they experence severe ceuose osses
once the demand on purty ncreases beyond the typca rayon grade quaty. A exstng protocos for
the remova of hemceuoses are assocated wth oss reactons or, n the case of the converson of a
paper-grade pup by cod caustc extracton, wth a parta converson of ceuose I to ceuose II as
we as resdua hemceuoses contents too hgh for the manufacture of hgh-purty ceuose products.
Based on systematc nvestgatons of the soubty propertes of ILs towards poysacchardes, the
IONCELL process was recenty deveoped, whch permts the producton of hgh-purty dssovng
pups from a hemceuose-rch paper-grade pup. Owng to the hgh seectvty and effcency, the
IONCELL process coud be the breakthrough for a new generaton of dssovng pup processes,
provded that the seected ILs can be recyced n an economcay feasbe way.
References
1. Brce, R. 2012. Hgh purty ceuose through 2020. In: The Ceuose Gap 2012: Monte Caro.
0,0 0,6 0,8 1,0 1,2 1,4
-0,2
0,1
0,4
0,7
1,0
partial
Hemicellulose
Window
LC/DMAc
|emm|-based
|bmm|-based
|TMGH-based
NMMO*H
2
O
|emm|OAc+CoSovent
NMMO*XH
2
O
b

-

a
b
Cellulose Window
full
3 4 5 6 7 8
0,0
0,2
0,4
0,6
10.5% consstency
BIRCH PAPER PULP, 25 % XYLAN
15 wt% co-sovent
d
w
/
d
o
g
(
M
M
)
og MM
pure
ceuose
fracton
Xyan <2%
pure
hem
fract
nta pup

80
2. Haemmere, F.M. 2011. The ceuose gap. Lenz. Ber. 89, pp. 12-21.
3. Shen, L., Pate, M.K. 2010. Lfe cyce assessment of man-made ceuose fbers. Lenz. Ber. 88,
pp. 1-59.
4. Sxta, H. 2006. Pup Propertes and Appcatons, In: Handbook of Pup, H. Sxta (Ed.) Wey-
VCH. Pp. 1009-1067.
5. Leschnsky, M., Sxta, H., Patt, R. 2009. Detaed mass baances of the autohydroyss of
Eucayptus gobuus 1t 170C. Boresources 4(2), pp. 687-703.
6. Wey, E. 2011. The Practcates of convertng to DP technoogy. Andrtz Pup&Paper.
7. Guetsch, | ., Sxta, H. 2012. Regeneraton of spent actvated charcoas used for gnn remova
from prehydroyss-kraft prehydroysates. Ind. Eng. Chem. Res. 51(25), pp. 8624-8630.
8. Guetsch, | ., Leschnsky, M., Sxta, H. 2011. Process for mproved processabty of hydrothermo-
yzates of gnoceuosc matera by hydroyss and adsorpton.
9. Schd, G., Mueer, W., Sxta, H. 1996. Prehydroyss kraft and ASAM paper grade pupng of
eucaypt wood. A knetc study. Das Paper 50(1), pp. 10-22.
10. Rauhaa, T. et a. 2011. Effect of autohydroyss on the gnn structure and the knetcs of
degnfcaton of brch wood. Nord. Pup Pap. Res. | . 26(4), pp. 386-391.
11. Borrega, M., et a. 2012. Potenta of hot water extracton of brch wood to produce hgh-purty
dssovng pup after akane pupng. Boresour. Techno. 2012. (Submtted.)
12. Testova, L. et a. 2012. Ceuose degradaton n akane meda upon acdc pretreatment and
stabzaton Carbohydr. Poym. (Submtted.)
13. Faschng, M. 2005. Prehydroyss sufte revsted. Macromo. Symp. 223, pp. 225-238.
14. Sxta, H. et a. 2011. Progress and chaenges n the soaton of xyan from Eucayptus Wood.
In: 5th Internatona Cooquum on Eucayptus Pup. Porto Seguro, May 8-11.
15. Iakovev, M., Henngen, A.v. 2012. Effcent fractonaton of spruce by SO
2
-ethano-water treatment:
cosed mass baances for carbohydrates and sufur. ChemSusChem 5, pp. 1625-1637.
16. | anson, | . 1974. Anaytk der Poysaccharde n Hoz und Zestoff. Faserforschung und Texttechnk
25, pp. 375-382.
17. Sxta, H. 2006. Mutstage Kraft Pupng. In: Handbook of Pup, Wey-VCH, Edtor, Wey-VCH.
Pp. 325-365.
18. Borrega, M., Nemnen, K., Sxta, H. 2011. Degradaton knetcs of the man carbohydrates n
brch wood durng hot water extracton n a batch reactor at eevated temperatures.
Boresour. Techno. 6, pp. 1890-1903.
19. Schd, G., Sxta, H. 2011. Sufur-free dssovng pups and ther appcaton for vscose and
yoce. Ceuose 18, pp. 1113-1128.
20. Sxta, H. et a. 2004. Infuence of beech wood quaty on bsufte dssovng pup manufacture.
Part 1: Infuence of og storage on pupng and beachng. Hozforschung 58, pp. 14-21.

81
21. Sxta, H. et a. 2011. Progress and chaenges n the separaton and purfcaton of xyan from
hardwood. In: 3 rd Nordc Wood and Borefnery Conference (NWBC) 2011. Stockhom, March.
Pp. 22-24.
22. Swan, B. 1965. Isoaton of acd-soube gnn from the Kason gnn determnaton. Svenska
Papperstdnng 68, pp. 791-795.
23. Scheosky, N., Roeder, T., Badnger, T. 1999. Momassenverteung ceuosscher Produkte
mttes Groessenausschusschromatographe n DMAc/LC. Das Paper 53(12), pp. 728-738.
24. Wobodt, P. 2011. Lgnosufonate characterzaton. Wood KPus.
25. Treber, E. 1962. A sma scae aboratory vscose pant for testng rayon grade pups. Das
Paper 16, pp. 85-94.
26. Xng, R., O, W., Huber, G.W. 2011. Producton of furfura and carboxyc acds from waste
aqueous hemceuose soutons from the pup and paper and ceuosc ethano
ndustres. Energy&Envronm. Scence 4(6), pp. 2193-2205.
27. Gehmayr, V., Schd, G., Sxta, H. 2011. A precse study on the feasbty of enzyme treatments
of a kraft pup for vscose appcaton. Ceuose 18, pp. 479-491.
28. Wobodt, P. et a. 2010. Accessbty, reactvty and supramoecuar structure of E. gobuus
pups wth reduced xyan content. Wood Sc. Techno. 44(4), pp. 533-546.
29. Sxta, H. 2000. Comparatve evauaton of TCF beached hardwood dssovng pups. Lenz. Ber.
79, pp. 119-128.
30. Temmng, H., Grunert, H. 1973. Temmng Lnters. Peter Temmng AG, Gueckstadt.
31. Sxta, H., Schd, G. 2009. New generaton kraft process. n 2nd Nordc Wood Borefnery
Conference. Hesnk.
32. Aekhna, M. et a. 2012. Preparaton and characterzaton of bodegradabe carboxymethy
xyan based fm. Carbohydr. Poym. (Submtted.)
33. S|strm, E. 1993. Wood Chemstry. Fundamentas and Appcatons. Academc Press.
34. | anzon, R. et a. 2008. Upgradng of paper-grade pups to dssovng pups by ntren extracton:
yeds, moecuar and supramoecuar structures of ntren extracted pups. Ceuose 15(5),
pp. 739-750.
35. Pus, | ., | anzon, R., Saake, B. 2006. Comparatve remova of hemceuoses from paper pups
usng ntren, cuen, NaOH and KOH. Lenz Ber 86, pp. 63-70.
36. Swatowsk, R.P. et a. 2002 Dssouton of ceuose wth onc quds. | . Am. Chem. Soc.
124(18), pp. 4974-4975.
37. Hauru, L.K.| . et a. 2012. Roe of sovent parameters n the regeneraton of ceuose from onc
qud soutons. Bomacromoecues, on-ne.
Andrtzs new technoogy apped to dssovng pup grades - a dfferent approach

82
Andritz's new technol ogy appli ed to di ssolvi ng
pulp grades a different approach
Hannu Rmark, Aaron Leavitt
Andritz Oy
Abstract
Suphte cookng has domnated the producton of dssovng pup n the past. Because of envron-
menta reasons, suphte cookng has decreased and nstead has become pre-hydroyss kraft cookng.
Earer s was done ony wth batch cookng technoogy, but due to ncreasng demand of dssovng
pup, a process based pre-hydroyss kraft cookng done wth contnuous cookng technoogy has
been deveoped. Ths new souton has been through extensve aboratory tras and subsequenty
nstaed and operated wthn an exstng pup m orgnay desgned for beached kraft market pup.
The new process and equpment desgn have addressed the negatve experences encountered on
prevous attempts to appy contnuous cookng technoogy for dssovng pup manufacturng. Both
new and exstng pup ms can beneft from the new process souton, whch s aso aowng cam-
pagn producton of dssovng pup or paper grade pup wth the same fber ne. The quaty of the
hydroysate taken out from the system s extremey good, whch makes t possbe to use t for fur-
ther refnng.
ntroduction
Dssovng pup (DP) demand from ceuose experenced extreme voatty n 2010 to 2011. Ths
was due n arge part to the ncreased consumpton of texte fber n Asa as we as a seres of
dffcut cotton harvests and ncreasng envronmenta pressure on the producton of texte fbers
from cotton and synthetc o based dervatves. Prces for DP doubed from typca eves and man-
taned these hgh eves for severa quarters. These hgh prces nstgated a goba nterest n the
abty to convert exstng market pup capacty nto DP grades.
In recent hstory, dssovng pup from ceuose had been domnated by batch cookng technoogy.
A percepton had been formed from the 1980s and 90s that contnuous cookng presented too
many dffcutes n stabe operaton to produce a hgh purty product ke DP. Some of the best docu-
mented evdence for contnuous cookng technoogy n DP manufacture can be found n the 1981
paper dscussng a converson pro|ect at Ahstrom Varkaus usng a two vesse cookng system |1|.
Ths process was based on the acd hydroyss of brch, whch s among the hghest hemceuose
contanng wood speces and therefore very chaengng for DP manufacture. There were aso add-
tona nstaatons usng snge vesse cookng systems ocated n Russa and Braz.
Andrtz ntated a vgorous DP process deveopment program based on contnuous cookng n 2008
when the frst ndcatons of market voatty appeared. Severa new technoogy soutons had been fuy
deveoped over the prevous decades that added to the attractveness of such a deveopment program,
ncudng Damondback chp steamng |2|, TurboFeed chp pumpng |2|, Lo-Sods Cookng |3| and new
contro technooges.
Laboratory nvestgatons ceary showed the atest contnuous cookng technoogy coud be
easy adapted to produce DP wth a reduced wood consumpton and an mproved overa energy
effcency. Whe ths nta aboratory work was performed on North Amercan softwoods, smar
studes have snce been performed dupcatng the resuts on varous furnshes ncudng other
softwood, hardwood and Eucayptus speces from around the gobe.
Laboratory results
Due to the synergy wth hemceuose based byproducts, straght away Andrtz focused on water
prehydroyss nstead of the prevous acd prehydroyss process. A water or auto-hydroyss process


83
was frst deveoped n the 1960s n Germany |4|. The process rees on the naturay formng acetc
acd reacton products generated to mantan an acdc pH typcay beow 4. By controng the re-
tenton tme and temperature of the reacton, a desred hemceuose remova rate can be
acheved. In addton, acd soube gnn and organc acds are extracted from the chps durng the
auto-hydroyss phase of the DP process.
Foowng auto-hydroyss, the chps are washed wth hot water to recover the hemceuose ex-
tracted and acetc acds generated. Ths dedcated washng step s a nove feature of the new sys-
tem and t enhances the remova of hemceuoses from chps. It s desgned to mprove recovery of
the vauabe byproducts whe mtng the carryover of undesrabe byproducts nto the dgester
vesse. If aowed to carryover, these byproducts w consume arge amounts of aka n a neutra-
zaton step pror to the akane cookng phase.
The hemceuose extracted chps are cooked n the dgester to reduce kappa eve to the de-
sred target. Wth the effcency of the auto-hydroyss process, the kappa eve out of the dgester
can be rased severa kappa unts above the typca target for batch cookng. The hgher kappa
target can mprove yed by severa percentage ponts.
Both aboratory and m resuts have shown the pup s extremey easy to oxygen degnfy,
reachng a kappa eve of 3-5 unts ndependent of wood speces. Beachng can be done n a va-
rety of sequences.
ECF or Lght ECF (ECF wth very sma amount of CO
2
and wth O
3
stage) sequences are typ-
cay used for beachng.
Process design
The ma|or drawback of the prevous contnuous cookng systems appeared as repettve and un-
controabe scang wthn the process. Ths scang manfested tsef prmary around the ocaton
of drastc pH change. In the two vesse system, Fgure 1, wth the tradtona chp feedng technoo-
gy of the perod the metaurges were nsuffcent for the process condtons and therefore extra
equpment was ntroduced to protect the hgh pressure feeder from extremey ow pH envronments.
The Dragos separator soated the 4-5 pH envronment around the hgh pressure feeder from the
1-2 pH envronment n the mpregnaton vesse. Whe ths addressed the probems wth materas
of constructon, t ncreased the eve of compexty n an aready chaengng cookng system to
keep n precse contro.
Addtonay, the two vesse reference deveoped a scae contro program that requred the sys-
tem be converted to kraft pup every 2-3 weeks n order to remove scae budup partcuary n the
bottom of the mpregnaton vesse and around the screens. Ths scae coud be removed by the
swtch from acdc to akane condtons.
Snge vesse systems were aso beng used to produce dssovng pup. In addton to the mta-
tons n chp feedng technoogy, a ma|or pH change was occurrng wthn the cookng vesse that
was dffcut to contro. As the chp voume and dgester fow varatons occurred, the pH nterface
ocaton aso moved up and down n the cookng vesse. Ths promoted scang and t was common
for these snge vesse systems to take more frequent conversons to paper grade for severa days
at a tme for ceanng.
Whe both system types produced dssovng pup for many years n campagn form wth kraft
pup, eventuay the drawbacks n the system desgn resuted n the converson back to fu tme
kraft pup producton. Some of these conversons to produce ony kraft pup aso concded wth
dffcut market stuaton of dssovng pup grades n the md 1980s.
Gven the experences that DP coud be manufactured usng contnuous technoogy and the
promsng resuts wth the new auto-hydroyss process n the aboratory, Andrtz deveoped and
sod ts frst DP system converson n | anuary of 2011, Fgure 2. The converson was made to a
2009 Andrtz snge vesse nstaaton successfuy makng market pup from Eucayptus. Wth the
addton of the pre-hydroyss vesse (PHV) and auxary equpment, the system was successfuy
converted to DP producton by November of 2011.

84
The ncuson of the Damondback (DB) chp steamng system, where extremey effectve chp
steamng removes substantay a the ar, s a key to the new process. Ar-free chps aow for ex-
tremey rapd qud penetraton and reduced tmes for heat transfer. The voume of chps s eveny
metered nto the system wth the DB system aowng for precse contro of L/W ratos and heatng
n the top of the PHV, over 60C n ony severa mnutes n the vapor-phase top.
After a defned retenton tme dependent on wood speces, the water wth acetc acd s extracted
from the vesse through nterna screens smar to dgester vesse screens. Due to a sghty exo-
thermc reacton, the extracton temperature s typcay 5C hgher than the top quor phase temper-
ature of the PHV. Hot water added to the bottom of the vesse s aso extracted from the screens to
create a counter-current washng zone smar to a H-Heat washng zone wthn the dgester. Ths
wash zone further removes those reacton products st wthn the chps at the tme of extracton by
dspacement and dffuson.
In the transfer between reactors, whte quor can be added to aready begn the neutrazaton
process. At the top of the dgester, the man addton of whte quor s added to neutraze any acd-
c quor that carry nto the dgester. Ths addton aso ensures that the concentraton of dssoved
organcs does not exceed the threshod for precptaton and can nstead be removed n the frst
dgester extracton. As the chps are fuy mpregnated wth water, dffuson of the aka nto the
chps s extremey fast. Very ow re|ect eves have been observed n the aboratory and n the m
operaton usng the new auto-hydroyss process.
Usng Lo-Sods Cookng prncpes, ftrate s added to further wash dssoved organcs through
dspacement and dffuson from the chps whe addng addtona fresh whte quor for the fna
degnfcaton phase n the dgester. Degnfcaton contnues to a wood specfc mt to preserve
vscosty and overa yed. For Eucayptus, 9-12 kappa s the target out of the cookng system.
Fnay, the extracted hydroysate from the PHV and the extracton quors from the dgester can
be processed separatey or together to recover heat energy, keepng the operatona cost of the
system n contro whe avodng excessve hot water generaton. By seectng a kette type reboer
as the heat recovery unt, any steam generated and used n the bn s free from the rsk of aka
contamnaton.
In washng, screenng and beachng, no ma|or changes were done. DP pup s easy the oxygen
degnfy, re|ect amount after cookng s extremey ow, CO
2
consumpton has decreased about
50% and COD oad n effuent 33% compared to kraft pup.
Results
After nta startup and before compete optmzaton occurred, m DP sampes were evauated
aganst the aboratory smuatons and other ms DP wth smar Eucayptus chps. Tabe 1 shows
ths comparson on fna beached pup. Optmzaton has further mproved pentosan content
(<2.5%) and apha ceuose content (95-97%).
Andrtz was reeased from ste coverage wthn 2 months of startup. Among the most postve re-
suts, the m has been abe to produce dssovng pup for over 3 months before ther frst sched-
ued mantenance downtme. DP quaty has been good wth severa vscose fber producers provd-
ng postve feedback. Competng DP fber suppers have aso ndcated the quaty to be accepta-
be for potenta future converson dscussons. Severa addtona converson pro|ects have aready
been sod and are n executon phase.
Whe addtona optmzaton work on the system remans as wth any new technoogca deve-
opment, the future of contnuous cookng technoogy used for dssovng pup manufacturng s
agan coorfu and brght.

85

Fi gure 1. Tradtona two vesse cookng system wth acd pre-hydroyss.

Figure 2. Andrtzs new dssovng pup cookng system wth pre-hydroyss vesse.

86
Table 1. Comparson of aboratory, m and pubshed targets for Eucayptus based dssovng pup.
Andritz DP Results Lab / Mill South American DP Producer Eucalyptus Specs
Species Eucalyptus Eucalyptus Standard Special High Grade
Vscosty 400-550 520 350-599 250-599 500-599
Brghtness 91+ 90.2 88-90 89-92 >90.5
S18 1.4-2.8 3.3-3.8 3.0-4.0 2.3-3.0 <2.3
S10 2.1-3.8 4.7-6.4 -7 4.0-7.0 4.0-5.5
Ash 0.11-0.14 0.13 0.03-0.12 0.03-0.10 0.03-0.08
Extractves <0.20 <0.10 <0.20 <0.15 <0.10
Apha 94.5-97.4 94.7 94.5-96.0 95.0-96.0 95.5-96.5
R18 97.2-98.6 96.2 96.5-97.0 96.5-98.0 >97.2
R10 96.2-97.9 93.6 -93 93-95 -95
Pentosans 3.0-4.0 3.0 3.0-4.0 2.5-3.5 1.5-2.5
References
1. Arhppanen, B., Nevaanen, P., Marttaa, T., Bom, U., Hnnnen, E., Nkua, M. 1981. Deveop-
ment of the Ava Prehydroyss Process (parts 1 and 2).
2. Wey, W.E., Stromberg, B. 2003. The Deveopment of an Innovatve Chp Feedng System for
Contnuous Dgesters.
3. Marcocca, B., Laakso, R., McCan, G. 1996. Lo-Sods pupng: prncpes and appcaton.
4. Rydhom, S. 1965. Pupng Processes.
5. Sxta, H. 2006. Handbook of Pup.
Forest borefnery custer - a possbe path to bobased products

87
Forest biorefinery cluster a possible path to
biobased products
Mariya Marinova
1
, Sari Hmlinen
2
, Hanna-Leena Pesonen
2

1
Chemical Engineering Department, cole Polytechnique de Montral, Canada
2
School of Business and Economics, University of Jyvskyl, Finland
Abstract
The forest borefnery provdes an opportunty to ncrease the proftabty of the pup and paper ms
n North Amerca and Scandnava by producng vaue-added bobased products. Dfferent techno-
ogca routes to generate fues and chemcas are avaabe, however cear choces on what to
produce must be taken. The ob|ectve of ths study s to assess the technca feasbty, advantages
and chaenges of a hypothetca forest borefnery custer but around a pup and paper m. The
custer conssts of a dssovng pup m wth borefnery for furfura producton on ts ste and a
chemca pant for tetrahydrofuran and a poytetramethyene ether gyco producton. The custer s
techncay feasbe. The partcpants n the custer ntatve produce bobased products, share re-
sources, access new markets and generate profts. Partners ocaton, capta sourcng, seng
products to new markets and nteractons wth new customers are among the chaenges to be
addressed.
ntroduction
Today, many companes, especay n the chemca and pharmaceutca sector, seek bobased raw
materas and products; t s expected that the demand for bochemcas ncreases n the ong term.
It s estmated that the market for bobased pastcs, n partcuar, w reach 3.45 Mt by 2020 |1|.
However, the market potenta of bobased products s cosey reated to foss fue prces |2|, whch
n the future w probaby rse substantay and new busness opportuntes for bobased products
w be opened. Consderng borefnery produced chemcas, poymers seem to have the greatest
market potenta n the future |3|.
In an ntegrated forest borefnery (IFBR) bobased products can be generated, together wth
pup and paper (P&P), by usng avaabe and underutzed wood components as a feedstock. Var-
ous technoogca routes to produce fues and chemcas are avaabe, however cear choces on
what to produce w have to be made. These choces have to be based on companys own compe-
tences |4|; t s apparent that the seecton of the technoogca path w be unque for each m,
dependng on ts busness pan, process constrants and nfrastructure n pace. However, the
choce of product s not ony a technca decson but t s reated to the current and expected eco-
nomc envronment. The IFBR may generate a fna market-ready product or an ntermedate prod-
uct for further transformaton. It s key that the addtona transformaton w be made by other
ndustra sectors, for exampe the chemca ndustry, as t has the requred knowedge and equp-
ment n pace. Ths coud be an attractve opton for companes currenty manufacturng products
derved from foss fues. A drect nterface between the IFBR and the chemca ndustry may be
deveoped |5|; ths nterface can be estabshed wthn the boundares of a borefnery custer, where
a P&P m, a borefnery pant and a chemca makng pant coaborate by sharng resources n a
sustanabe way.
An ndustra custer s a group of companes that cooperate wth each other and wth the oca
communty to effcenty share resources eadng to mproved envronmenta quaty, economc
gans, and equtabe enhancement of human resources for both the busness and oca communty |6|.
The advantages to be ganed from the custer coud resut from the use and share of a common
prmary feedstock, mutuay benefca supper and consumer reatonshp, heat and power genera-
ton as we as market accessbty for fna products. Despte the strength of the forest ndustry
arsng from the avaabty of bomass, exstng nfrastructure and suppy chans, the ack of capta


88
s among the man constrants to the deveopment of borefnery custer |3|. Factors such as geo-
graphca constrants, P&P process, the energy and matera requrements shoud be taken nto
account whe deveopng a custer. The proxmty of the products end user or the target market to
the borefnery custer s aso mportant f further transformaton of the product s requred and woud
not be carred out wthn the IFBR |7|.
The ob|ectve of ths study s to evauate the feasbty of a forest borefnery custer consstng of
a dssovng pup m wth a pant for hemceuoses converson nto furfura and a nearby chemca
manufacturer producng tetrahydrofuran (THF) and convertng t nto poytetramethyene ether gy-
co (PTMEG). Future opportuntes for bobased chemcas generated n the custer are frst evau-
ated. Then, the structure of the forest borefnery custer, together wth the correspondng techno-
ogca pathways, s descrbed and potenta benefts for the partcpants n the custer are assessed.
Fnay, chaenges n partnershp deveopment are dscussed.
Future perspective for biobased chemicals
Due to ow producton costs, Chna s the argest producer of furfura and THF today |8-10|. The
word market for furfura s estmated at about 200 000-210 000 t/y, and there w be a steady
growth n furfura demand n the future |10|. Today, the THF market s about 200 000 t/y |11|, but t
s expected that t w exceed 800 000 tons by 2017 |9|. A ma|or part of the growth w occur n
Chna and PTMEG s the fastest growng market for THF |9, 11|. Ths ndcates that bobased
PTMEG, THF and aso furfura have market potenta n the future. Bobased chemcas are rea
opportuntes for a forest borefnery custer.
Today, the share of bobased THF and PTMEG s qute sma compared to the tota producton of
these chemcas. For that reason, arge chemca companes, whch have a scae advantage, may
not be nterested n such a sma nche. Ths coud be a good opportunty for medum szed enter-
prses for whch a smaer market s attractve. Ths coud be the case of the chemca manufactur-
ng pant nvoved n the forest borefnery custer. By creatng a custer, the chemca ndustry part-
ner and the pup m get access to competences requred for producton, marketng and saes of
chemcas.
Case study definition
A dssovng pup m s the core of the proposed hypothetca custer. Dssovng pup s a ow yed
chemca pup wth hgh ceuose content sutabe for makng rayon, ceuose acetate and ceo-
phane. The process for producng dssovng pup s a varaton of the Kraft process wth a pre-
hydroyss stage pror to pupng. Durng pre-hydroyss hemceuoses are soubsed by acton of
steam, water or chemcas to produce monosacchardes (arabnose, xyose, mannose, gaactose,
gucose), ogosacchardes (gaactogucomannan, gucuronoxyan), and other mnor chemca com-
ponents (weak acds, furans, phenoc compounds). The hemceuosc sugars can be converted
nto a range of vaue-added products. A borefnery for furfura producton s consdered n the pre-
sent study, as furfura s a hgh-vaue product and a budng bock n the chemca ndustry. The
pre-hydroysate stream s usuay duted, therefore t s recommended to concentrate t usng mem-
branes n order to save energy and decrease operatng costs. The concentrated pre-hydroysate s
then transferred n a reactor, where C
5
-sugars are converted nto furfura by dehydraton n the
presence of an acd catayst. Furfura s separated and purfed usng azeotropc dstaton.
The furfura generated n the borefnery s shpped to the nearby chemca makng pant where t
s used as a feedstock for THF producton. THF s a precursor of PTMEG, a raw matera for the
producton of poyurethanes, eastc fbers (Spandex or Lycra), eastomers, and copoyesters. The
current ndustra process for THF producton nvoves cataytc dehydraton and cyczaton of 1,4-
butanedo to THF, the ntermedate 1,4-butanedo beng obtaned from foss resources |12|. The
producton of THF usng a bobased process was empoyed between 1949 and 1961 by a ma|or
chemca company but was abandoned because of the competton wth the THF from petroeum

89
feedstocks |13|. However, chemcas producton from bobased resources has reganed nterest n
the recent years.
The THF producton from furfura nvoves two steps - the decarbonyaton of furfura to furan
and ts subsequent hydrogenaton to THF. The decarbonyaton s done n the presence of paad-
um as a catayst. Furfura s usuay refuxed under pressure at 200C, whe furan and CO are
contnuousy removed from the reacton mxture by dstaton |8|. The resutng furan s hydrogen-
ated to THF n the presence of Raney-ncke cataysts.
In the chemca makng pant, THF s further converted to PTMEG. It s frst poymerzed over a
heterogeneous catayst n presence of acetc anhydrde to form poytetramethyene ether dacetate
(PTMEA). The non converted THF, recovered from the reactor effuent by strppng, s purfed and
recyced to the reactor. Then, PTMEA s converted to PTMEG by reactng wth an excess of meth-
ano n presence of a basc catayst. Methyacetate (MEAC) s formed as a by product. The subse-
quent process steps are neutrazaton of crude product, ftraton, and recovery of purfed methano
and dsposa of methano-MEAC azeotrope. Fnay, ogomers from crude PTMEG are removed by
vaporzaton at hgh vacuum and addtves are ntroduced to the fnshed poymer |14|.
Technical feasibility of the cluster
The dssovng pup m s supped wth 2 000 odt/d of hardwood chps, fresh water and chemcas.
Fresh water s treated, heated and used n dfferent process areas. Steam s produced by burnng
the degnfcaton quor n the recovery boer and power s generated n a cogeneraton pant. The
m produces 720 odt/d dssovng pup and generates around 4 000 t/d dute pre-hydroysate, from
whch 20 000 tones of furfura are produced annuay.
The IFBR exports to the chemca pant furfura, heat and power. The water effuents produced n
the chemca makng pant are treated n the effuent treatment system of the pup m. Furfura
converson nto THF proceeds at 80% yed, whch represents an annua producton of 16 000
tones. In the chemca makng pant, about 80% of the THF s converted nto PTMEG at the rate of
13 000 t/y. From the technca perspectve the coaboraton between a P&P m wth a borefnery
pant on ts ste and a nearby chemca makng pant s feasbe. The partcpants nvoved n the
custer ntatve produce bobased products, share resources and generate profts.

Figure 1. Overvew of the borefnery custer.

90
Benefits of the partnership
Proftabty of bobased chemcas depends on prces of raw materas and energy. Furfura pro-
duced n the dssovng pup m based borefnery s a vauabe feedstock for the chemca makng
pant, snce t costs ess that the feedstock shpped from Chna. Buyng furfura from the nearby
company avods expensve transportaton costs. The geographc proxmty of the companes s an
mportant factor for the proftabty of the custer |7|. In addton, the P&P m ses to the chemca
company heat and power at an advantageous prce. Sharng nfrastructure, such as heat and power
pant and effuent treatment system reduces the operaton costs of the chemca manufacturng
pant. Usng fewer resources aso reduces the envronmenta mpacts of the custer.
Severa studes have shown that partnershps have many benefts n busness n genera |15-21|
and ths appes aso to the forest borefnery custer. The partnershp between the P&P m and the
chemca manufacturng pant adds a compettve advantage for both companes and n that way
ncreases ther market share and revenues. By means of coaboraton the companes nvoved n
the custer get an access to key resources such as raw materas, nformaton and capta. Partner-
shp between these companes aso enabes the chemca producer to manufacture bobased products
and gets for the P&P company an access to the chemca market. In addton, coaboraton pro-
vdes new contacts outsde of the custer, whch can brng new knowedge, compementary sks
and competences to both companes. It s aso possbe to share rsks of new busness area by
coaboraton.
Challenges of partnership development
The producton of bobased chemcas needs capta resources. The process for furfura producton
usng pre-hydroysate from dssovng pup m requres nvestments for reactor, concentraton and
separaton equpment. Heatng, coong and power resources used n the furfura borefnery and n
the chemca makng pant are supped by the utty system of the pup m. However, nvestments
for ppng requred to transport uttes and resources, as we as for grd shoud be made.
Producng bobased chemcas s a new busness area to the P&P ndustry. Bochemcas are df-
ferent from pup or paper to hande and se. There s aso much egsaton n the area, snce var-
ous statutes and norms reguate chemcas producton, warehousng and transport. The P&P com-
pany uses many chemcas aso n ts present busness, but st egsaton of chemcas coud be a
new word to t and t has much to earn. In addton, producton of bochemcas needs aso new
technca, chemca and busness know-how. So, the P&P m and the chemca company have to
assess ther exstng competences and the need for earnng new capabtes whch are requred
on the new markets |22|. In addton, they have to fnd an access to the chemca market and over-
come barrers to entry, snce exstng chemca producers w probaby try to prevent new compettors.
In other words, the P&P m and the chemca manufacturer have to thnk about how they coud
compete wth Chnese companes who domnate the present furfura, THF and PTMEG markets.
A prce of the product s often cruca factor n purchase decsons. For that reason, the bobased
chemcas produced wthn the custer shoud not be substantay more expensve than foss based
ones. In genera, t s assumed that a new product has to be cheaper than the product t s ntended
to repace n order to succeed |23|. But the prce of a product tes to a customer aso about ts qua-
ty |23|. In that sense, a hgher prce coud aso be a beneft and a way to dstngush from the com-
pettors. The prce of a product s not the ony factor whch affects the success of a product on the
market. Accordng to a study of Hart and Tsokas |23|, product advantages are the most sgnfcant
factors to success n the market pace. For bochemcas, sustanabty s a ma|or component of
ther added vaue.
However, formng partnershps can be compex and expensve snce trust budng requres tme
and efforts |18, 22, 24|. So, t s mportant to the P&P company to consder coaboraton and net-
workng ssues when makng decsons on borefnery processes and products. In addton, for suc-
cessfu coaboraton, coordnated decson makng and communcaton are essenta |15, 25|.

91
Conclusions
The creaton of a borefnery custer as possbe path to bobased products s evauated. The cus-
ter, consstng of a P&P m wth a furfura pant on ts ste and a chemca makng pant producng
THF and PTMEG, s techncay feasbe. Bobased PTMEG, THF and aso furfura have market
potenta n the future. The partcpants n ths ntatve gan the possbty to produce bobased
products, share resources, access new markets and generate profts. However, severa chaenges
have to be addressed to deveop successfu coaboraton between a P&P m and a chemca
company.
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Producton of surface actve agents from hemceuoses extracted from wood chps

93
Production of surface active agents from
hemicelluloses extracted from wood chips
Bevan Jarman, Marion Sanglard, Christine Chirat, Dominique Lachenal
Grenoble NP PAGORA
461 rue de la papeterie BP 65 38402 Saint Martin d'Hres Cedex France
Christine.Chirat@pagora.grenoble-inp.fr
Abstract
Ths research pro|ect ams at convertng a Kraft pup m nto a borefnery, by extractng hemceu-
oses from wood chps and vaorse them nto aky poygycosdes whch are surface actve agents,
n parae to the producton of ceuose fbres.
After the extracton of the hemceuoses n the pre-hydroysate the mxture of sugars (the buk of
whch are xyose) can be reacted wth n-butano and H
2
SO
4
to produce aky poygycosdes. How-
ever t was dscovered that mpurtes n the pre-hydroysate prevented the drect converson to
surface actve agents. We then set out to nvestgate whch mpurtes were nterferng wth the
reacton and methods of processng the pre-hydroysate so that the reacton coud occur.
ntroduction
The concept of turnng a Kraft pup m nto a borefnery s a smpe one. In a tradtona m the
ceuose s effcenty extracted and converted nto vaue-added products. The remanng back
quor s then burnt to produce energy. However the hemceuoses wthn the back quor have a
much ower energy content than the gnn so ths represents a poor use for them. Snce t s very
dffcut to remove the hemceuoses from the back quor another method s requred. Autohydro-
yss of the wood before Kraft pupng s one souton.
There are many reports n the terature about the extracton of xyans from wood, by ether auto-
hydroyss or acd hydroyss, wth up to 90% of the hemceuoses abe to be extracted |1-7|. Whe
the pre-hydroysates contan sugars (of whch xyose s the ma|or component), they aso have a
arge varety of mpurtes, ncudng dssoved gnn, organc acds (acetc acd and formc acd),
sugar dehydraton products (furfura and hydroxymethyfurfura) and sats |3-5|.
Surface actve agents are wdey used n modern socety. In an effort for more sustanabe prod-
ucts, surface actve agents from renewabe sources have been deveoped |8|. One wdey used
cass of surface actve agents are aky poygycosdes, where the sugar acts as the hydrophc
head, whe a fatty acoho s the hydrophobc ta. Gucose s a very common feedstock for ths, and
the products are often used n products ke cosmetcs snce they cause ess rrtaton of the skn. If
the sugars n the pre-hydroysate coud be drecty converted nto surface actve agents wthout a
arge number of purfcaton steps needed, ths woud represent a very usefu vaue-added product
abe to be derved from the extracted hemceuoses.
The process for producng aky poygycosdes s smpe, as shown wth xyose and n-butano n
Fgure 1. The sugar s refuxed n the fatty acoho aong wth an acd; the water whch s produced
can be removed va a Dean-Stark type apparatus whch drves the equbrum to the rght. As the
reacton s proceedng t s aso possbe that nstead of the hydroxy group of the acoho condens-
ng wth the sugar, a hydroxy group from another sugar n the mxture w condense nstead. Ths
eads to the formaton of aky poygycosdes wth mutpe sugars n the head group. Ths s termed
the degree of poymersaton (DP), wth an aky poygycosde wth one sugar caed DP 1 and two
sugars DP 2 and so on. When anaysng the resutng product, one of the mportant propertes s the
average DP of the aky poygycosde formed.


94
O
HO
HO
OH
OH
O
HO
HO
OH
O
HO
H
2
SO
4
H
2
O

Figure 1. The producton of aky poyxyosde showng the DP 1 product.
Experimental
Production of surface active agents
The reacton was done n a 250 mL |acketed gass reactor equpped wth a condenser wth a Dean-
Stark apparatus and a mechanca strrer. A 2.8 excess of n-butano and 2% of 96% H
2
SO
4
were
added (both compared to xyose) and heated to 120C under atmospherc pressure. A syrup con-
tanng xyose (50 g) at a concentraton of 65% was added drop wse under strrng. In the case of
addng mpurtes to the syrup, the amount water added was ad|usted so that the concentraton of
the syrup remaned at 65% xyose. Water was removed from the reactor by dstaton usng the
water/butano azeotrope. After the reacton mxture had reached a water content of approxmatey
8%, the reactor was aowed to coo to room temperature and the product removed. The resutng
product was a homogenous syrup.
Analysis of surface active agents by GC-FD
Sampes were frst syated usng hexamethydsazane (HMDS), trmethychorosane (TMCS) and
pyrdne wth trdecano or nonano added as an nterna standard. The anayss was carred out on
a meta SIMDIST HT-CB coumn (10 m 0.53 mm, fm thckness 0.5 m) wth heum carrer gas.
One L of sampe s n|ected, the n|ector s at 300C whe the detector s at 350C. The tempera-
ture program starts at 60C for 3 mnutes and ramps to 350C at 8C per mnute and hods for 12
mnutes.
The pre-hydroysates were frst concentrated to syrups of 65% xyose content. When the reacton
was carred out on ths pre-hydroysate the reacton faed to work wth ony very mnor traces of
aky poygycosde observed. In order to determne what mpurty f any n the pre-hydroysate was
causng the probem, a seres of experments were carred out on xyose syrups wth added mpur-
tes. Frsty a pure xyose syrup was reacted as a contro. The next step was to take a xyose syrup
and add dfferent mpurtes at the same concentraton as was found n the pre-hydroysates. These
mode syrups were reacted under the same condtons and the product was anaysed by GC-FID to
determne the amount of remanng xyose as we as how much aky poyxyosde had been pro-
duced. The mpurtes tested ncuded acetc acd, formc acd, furfura, hydroxymethyfurfura, gno-
sufonate, sodum chorde, magnesum chorde, cacum chorde and D-gucuronc acd. The re-
suts are summarsed n Tabe 1. Fgure 2 shows the spectrum for the 65% xyose syrup. There are
two peaks found for both xyose and the DP 1 aky poyxyosde snce mutarotaton causes both the
a and b anomer to form. Ths produces a very arge number of dfferent somers for the hgher DP
vaues meanng that ndvdua somers cannot be soated and ony the overa peak area for each
hgher DP vaue can be determned.
The anayss showed no ma|or dfferences between the pure xyose syrup and the syrups wth
the mpurtes n ether the amount of resdua xyose or the produced aky poyxyosde. The ony
observabe dfference was that some mpurtes produced darker products than others. Ths coour

95
dfference was not consdered a ma|or ssue snce under ndustra condtons the resutng surface
actve agents are beached to remove coour.
Table 1. Resuts of the dfferent tras n the producton of aky poyxyosdes, showng the amount
of resdua xyose eft, the percentage of each DP fracton and the average DP.
Reaction conditi ons
% xyl ose
unreact ed
Percent age of APX as: Average
DP
DP 1 DP 2 DP 3 DP 4
65 % Xyose 10 74 17 7 2 1.4
65 % Xyose +Furfura 14 74 17 6 3 1.4
65 % Xyose +HMF 12 74 17 7 2 1.4
65 % Xyose +Acetc acd 11 72 18 7 3 1.4
65 % Xyose +Formc acd 9 68 19 9 4 1.5
65 % Xyose +D-Gucuronc acd 11 74 18 8 0 1.3
65 % Xyose +gnosufonates (5 g) 15 75 17 6 2 1.3
65 % Xyose +gnosufonates (11.5 g) 14 80 15 5 0 1.3
65 % Xyose +Pheno 11 78 15 7 0 1.3
65 % Xyose +Na
+
as NaC 14 74 16 7 3 1.4
65 % Xyose +Mg
2+
as MgC
2
12 81 15 5 0 1.2
65 % Xyose +Ca
2+
as CaC
2
11 83 13 5 0 1.2

Snce there was some dffcuty n fndng a good mode compound for the gnn n the pre-
hydroysates t was thought that the gnn mght be causng the dffcutes wth the reacton. To test
ths, the pre-hydroysate was treated wth actvated charcoa by strrng overnght and fterng the
resutng suspenson. When the resutng pre-hydroysate was reacted the anayss showed that
aky poyxyosde had been formed as we aky poygycosdes derved from the other sugars pre-
sent (gucose, mannose, arabnose and gaactose), athough n much ower quanttes. Ths can be
seen n Fgure 2 whch shows the spectrum, wth many more peaks found between 12-20 mnutes.
Ths much arger amount of dfferent products n the resutng mxture ed to ssues wth quantfca-
ton because of overappng peaks. It s mpossbe wth ths method to separate the DP 2 and hgh-
er fractons nto the dfferent aky poygycosdes group. Ths meant that an average DP vaue coud
not be cacuated. The peak area of the DP 1 aky poyxyosde was compared to that of the contro
groups and showed that a smar proporton of DP 1 aky poyxyosde had been formed. The
amount of resdua xyose was 16%. Ths was at the hgher end of the range seen n the pure xy-
ose experments but st a smar resut.


96

Figure 2. Porton of some GC-FID spectra, the upper spectrum shows the 65% xyose syrup, whe
the ower spectrum s for the pre-hydroysate that has been treated wth actvated charcoa.
Concl usi on
It was found that the raw pre-hydroysate coud not be drecty reacted to produce the desred sur-
face actve agents. However t was shown that ftraton of the pre-hydroysate wth actvated char-
coa to remove gnn produced a product that coud be used drecty to form aky poygycosdes.
The other products found n the hydroysate dd not seem to have any sgnfcant effect on the pro-
ducton of APX. Further work needs to be carred out to better anayse the resutng compex mx-
tures of aky poygycosdes formed when usng pre-hydroysates.
Xyose
APX - DP 3
APX - DP 2
APX - DP 1
10 12 14 16 18 20 22 24 26 28 30 32 34
Tme (mn)

97
Acknowledgements
Ths pro|ect s funded by the French Natona Research Agency (ANR) and s done n coaboraton
wth Fbre Exceence and SEPPIC.
References
1. Garrote, G., Para|, | .C. 2002. Non-sotherma autohydroyss of Eucayptus wood. Wood Sc-
ence and Technoogy 36(2), pp. 111-123.
2. Chrat, C., Lachena, D., Sangard, M. 2012. Extracton of xyans from hardwood chps pror to
Kraft cookng. Process Bochemstry 47(3), pp. 381-385.
3. Leschnsky, M., Sxta, H., Patt, R. 2009. Detaed mass baance of the autohydroyss of Eucayptus
Gobuus at 170C. Boresources 4(2), pp. 687-703.
4. Garrote, G., Domnguez, H., Para|, | .C. 1999. Md autohydroyss: an envronmentay frendy
technoogy for xyoogosaccharde producton from wood. | ourna of Chemca Technoogy
& Botechnoogy 74(11), pp. 1101-1109.
5. Tunc, S.M., Van Henngen, A.R.P. 2008. Hydrotherma dssouton of mxed southern hard-
woods. Hozforschung 62(5), pp. 539-545.
6. Wafa A-Da|an, W., Tschrner, U., | ensen, T. 2009. Pre-extracton of hemceuoses and subse-
quent kraft pupng. Part II: acd- and autohydroyss. Tapp | ourna 8(9), pp. 30-37.
7. Bose, S., Barber, V., Aves, E., Keme, D., Stpanovc, A., Francs, R. 2009. An mproved method
for the hydroyss of hardwood carbohydrates to monomers. Carbohydrates Poymers
78(3), pp. 396-401. Do: 10.1016/|.carbopo.2009.04.015.
8. Kervedo, S., Brancq, B. 2008. Tensoactfs bass sur des sucres. LActuat Chmque, Oct-Nov
2008. p. 35.
The Forest Borefnery: Canadan drvers and ongong actvtes

98
The Forest Biorefinery: Canadian drivers and
ongoing activities
Thomas Browne
FPnnovations, 570 boul. Saint-Jean, Pointe-Claire, QC Canada H9R 3J9
Abstract
The Canadan forest sector s n need of transformaton as the demand for severa of ts tradtona
products s n decne. A unquey Canadan approach has been deveoped over the ast severa
years, drven by unque crcumstances. Ths approach has been defned by:
A coaboratve mode, but on a coordnated approach by ndustry, academa, research cen-
tres and governments;
The concept of maxmzng the use of exstng assets and nfrastructure, n order to mnmze
the cost of nta transformatve steps;
Large ntatves focused on a sma number of we-defned ob|ectves, based on the concept
of nnovaton (.e. R&D pus depoyment); ths mpes concurrent R&D, engneerng and
market deveopment, and cose coaboraton wth downstream users and customers;
A natona approach, supported by ndustry and the federa government, wth regona-eve
mpementaton carred out n coaboraton wth the provnces.
A range of programs have supported ths approach and have ed to eary successes.
The Canadian context
Much has been wrtten recenty about the bo-refnery n genera and the forest bo-refnery n par-
tcuar. Ths concept must be consdered n terms of regona dfferences: bomass s buky and wet,
and s therefore expensve to shp; ts use must be oca. Ths paper expores the Canadan context
and the unque set of responses necessary to deveop and mpement the forest bo-refnery there.
Energy pri ces
Foowng a decade of hgh prces, North Amercan natura gas prces are now at hstorc ows.
Drven by the deveopment of cheap technooges for expotng abundant shae gas beds, natura
gas prces at the wehead have been we beow $2.50/G| for the ast severa years |1|. (A prces
assume party between US and Canadan currences.) Natura gas quds, such as ethane, pentane
and butane, are more vauabe than the natura gas tsef, and provde ncentves that encourage
exporaton and drng even n the presence of hstorcay ow gas prces. In response, arge scae
gas-to-ethyene pants are beng but n the US South; LNG termnas to export gas to Asa are n
pannng for the Canadan West Coast; and operators of ma|or truckng feets are convertng ther
ntercty feets to operate on compressed or quefed natura gas. These drvers w conspre to
drve up gas prces n the medum term; pubc concern around the envronmenta mpact of hydrau-
c fracturng processes may aso have an mpact. However, t s st key that gas prces w stay
beow hstorca averages for some tme to come.
Tradtonay, West Texas Intermedate (WTI) o has traded at a dscount of $10 to $15/bb beow
Brent crude; the dscount s now at hstorcay hgh eves, wth WTI n the $85-$95/bb range (about
$15/G| ), and Brent n the range $110-$120/bb (about $19/G| ). At the same tme, spot market
prces for Aberta heavy crude (Western Canadan Seect, WCS) have been at east $15/bb beow
WTI |2|; at these prces, severa o sands pro|ects have been put on hod. Low WCS prces are
drven by a ack of refnery capacty desgned to take heaver crude, compounded by shortages n


99
ppene capacty nkng Aberta and US Guf Coast refneres. As wth gas from shae, the voumes
of o avaabe are arge, and whe the envronmenta concerns cannot be negected, the kehood
s that WCS prces w reman ower than WTI prces for the foreseeabe future.
Eectrca power prces are aso ow across Canada. Rates are a provnca responsbty, but
arge ndustra users can generay negotate purchase contracts n the $0.05/kWh to $0.07/kWh
range ($14/G| to $19/G| ), whe producers of bomass power can expect to se ther power nto the
grd for prces n the $0.10/kWh range ($28/G| ).
Gasone prces at the pump are currenty around $1.30 per tre ($37/G| ) n Canada, and around
$1.00 per tre ($28.50/G| ) n the US. These numbers are hstorcay hgh, but st do not compare
wth prces of C1.30 per tre or more (amost $60/G| ) n typca European contexts.
Fnay, whe some oca efforts have been made n North Amerca, there s an absence of any
coordnated effort to mpose a cost on carbon emssons (whether by carbon tax, renewabe fue
standard or other pocy measure). Renewabe fue standards have ed to a gut of conventona
ethano as fue demand has dropped. Furthermore, many nvestors are reuctant to nvest where
the busness case rests too heavy on government acton.
The ow cost of energy and of carbon emssons n North Amerca conspre to produce an env-
ronment where stand-aone bo-fue processes are unkey to be commercay vabe n the short
term. A few exceptons, such as exports of wood peets from Canadas West Coast to EU ports,
are drven n part by arge dfferences n carbon poces, and woud not be economcay sensbe
gven consstent carbon prces n the EU and NAFTA. Energy costs n Canada w have to be sg-
nfcanty hgher than they are today before bo-fues, especay wood-based bo-fues produced
usng sow-growng northern speces, are economcay vabe on ther own - hgh vaue co-products
are an absoutey crtca component of the forest bo-refnery n Canada, at east for the medum term.
On the other hand, there are opportuntes to be found even n the context of ow energy prces.
For nstance, the shft to natura gas-based ethyene pants, and away from the tradtona naphtha-
based pants, means that there s a oomng shortage of by-products from the naphtha-based pro-
cess, for exampe butyene and other petrochemcas used n the manufacture of synthetc rubbers
and eastomers. There are other such opportuntes, where shftng processes n the petrochemcas
ndustry eave wndows of opportunty for bo-based chemcas. The recent focus on succnc acd
and actc acd from bo-based sources |3| s a further ndcaton that bo-chemcas provde oppor-
tuntes that are not avaabe to un-ntegrated bo-energy pants.
Wood supply, product portfolio and infrastructure ecology
Canadas forests cover mutpe ecoogca zones across 85 degrees of ongtude |4|, and are char-
acterzed by a wde range of wood speces and arge regona dfferences between forest type and
age. The borea forests represent the argest snge eco-system, but even n the borea forest, df-
ferences n propertes, both between and wthn speces, are arge. Gven the costs of shppng
bomass, one souton w not ft the entre country.
As wth energy resources, managng forestry resources s a provnca responsbty. There ex-
sts a wde range of forestry ownershp and tenure programs across the country. Nova Scota s
unque n that approxmatey haf the forests are n prvate hands; esewhere the forests are argey
on Crown ands where forest management agreements must be negotated wth the ndvdua pro-
vnca government. So costs and reguatons around forest use aso vary across the country.
There s a broad range of nfrastructure assets. In the East, many pup and paper ms are but
on stes that were ntay deveoped over 100 years ago. Intay, many of these ms were not
connected to a road network or power grd, but reed on rver power to run the m, suppy raw
materas, and shp goods to market. Whe a have been upgraded over the decades, the average
age of assets s hgher, and the average producton rate per ne ower, than n newer western ms.
There s aso a regona dfference n pupng processes. Mechanca pup ms predomnate n
Eastern areas where the avaabty of cheap hydro-eectrc power makes them more cost effectve
than a kraft m when wood prces are hgh. Western ms, but more recenty, tend to be arger,
snge-ne kraft ms wthout the egacy of oder assets.

100
In many cases, there s a symbotc reatonshp wth sawms, especay n the case of ms usng
softwood speces. Few pup ms can afford whoe ogs; sawms can make more money from a
gven og by convertng t nto dmensona umber. Resdues are converted to chps and sod to pup
ms or used for fabrcated panes of varous sorts. Bark and sawdust are burned for heat and power.
The mpcaton here s that a sump n the sawm ndustry w ead to chp shortages (and hgher
prces) for pup m operators; n the reverse case, sawm operators cant se ther chps.
Shppng opportuntes are aso hghy varabe. Coasta ms n Brtsh Coumba have deep sea
ports and easy access to Asan markets, whe eastern coasta ms are coser to Rotterdam than
Chcago. Ms n the centre of the contnent rey argey on ra or truck to suppy centra US cus-
tomers. The end-user for any nove vaue-added products w need to be dentfed n ths context.
Hstorcay, the Canadan ndustry has reed heavy on US saes. Wth the smutaneous co-
apse of the US housng market and US newsprnt demand, the chp suppy remans reatvey ba-
anced over most of the country, athough there are ocatons where the decne n newsprnt s hurtng
sawms as we. If the sawmng ndustry recovers, there w be a huge need for new outets for
chps, especay softwood chps. Exports of peets to the EU w ony be proftabe as ong as car-
bon prcng poces permt, and as ong as sawms can afford to se chps for energy rather than
for pup. New, hgh-vaue products to consume these chps need to be dentfed qucky.
So the ecoogy n whch the Canadan forest ndustry operates s compex and regona. There s
a crtca need to dentfy regona soutons that ft the varous constrants across the country.
The Canadian approach to industry renewal
Response to the range of drivers
We have seen how the Canadan context requres a unque approach. The souton has been char-
actersed by:
Coaboraton between ndustry, academa, research centres and governments;
A focus on a sma number of we-defned ob|ectves, drven by sod economc, engneerng
and market anayss eary n the process;
A pan-Canadan technoogy deveopment approach, supported by ndustry and the federa
government, wth regona mpementaton n coaboraton wth the provnces;
Maxmzng the use of exstng assets and nfrastructure, n order to mnmze the cost of nta
steps towards a transformed ndustry.
The ast pont, n partcuar, refects the concept of the refnery, where a feedstock s transformed
nto successvey ower-vaue products. A resdue remans, from whch no hgher vaue can be ex-
tracted and whch s therefore best converted to an energy product, Fgure 1. Sawdust to peets,
bark to combned heat and power (CHP) pants, and gasfcaton of muncpa sod wastes eadng
to synthetc fues are three such outcomes. Ths mode, of converson of resdues to energy prod-
ucts, necessary mpes the exstence of a heathy prmary ndustry to generate these resdues.

101

Figure 1. A conceptua mode of a refnery desgned to extract maxmum vaue from the resource.
A range of programs have heped to bud ths mode. The Pup and Paper Green Transformaton
Program (PPGTP, |5|) provded ncentves for Canadan pup and paper ms to enhance energy
effcency and envronmenta performance. Pro|ects undertaken ncuded boer and turbne up-
grades, and nstaaton of emsson-contro equpment. One ma|or mpact was to mprove the abty
of Canadan ndustry to effectvey ntegrate nove processes nto exstng stes and nfrastructure.
The Transformatve Technooges Program (TTP, |6|) contnues to map out nove pathways to
new products from wood. Ths coaboraton between Natura Resources Canada (NRCan) and
FPInnovatons has supported fundamenta research work n a wde range of non-tradtona areas.
The Transformatve Technooges Pot Demonstraton Program (TTPDP, |7|) has heped move
severa of these new technooges to the demonstraton scae, where they can be evauated on a
arger scae than the aboratory-scae work possbe under the TTP. The Investments n Forest
Industry Transformaton (IFIT, |8|) funded a seres of near-commerca scae pants. Whe amed at
arger scae nstaatons than the TTPDP program, these are st demonstraton pants and are not
expected to be commercay vabe on ther own due to poor economes of scae, even though they
are meant to prove concepts by makng and seng product.
NSERC, Canadas Natona Scence and Engneerng Research Counc, drects funds to unver-
sty researchers. Its Forest Sector Research and Deveopment Intatve |9| provded $34M over 5
years to create a seres of 8 word-cass R&D networks, nvovng over 100 senor academc staff
across the country n research of reevance to the deveopment of nove products from wood. In
many cases, these researchers and ther teams are new to forestry, brngng new vewponts and
knowedge of ndustres not usuay assocated wth forestry. The networks are nked by FIBRE, an
overarchng organsaton desgned to bud synerges n partnershp wth FPInnovatons, NRCan,
NSERC and the Forest Products Assocaton of Canada (FPAC).
The Bo-Pathways pro|ect |10| set up an economc framework for evauatng nove processes
and products eary n the deveopment stage. Managed by NRCan, FPAC and FPInnovatons, the
toos use a common approach; resuts aow research managers to qucky dentfy wnnng path-
ways and focus resources on sovng crtca probems that mght mt or mpar mpementaton |11|.
The R&D and mpementaton processes descrbed above have generated a arge number of po-
tenta pathways to new products. Some pro|ects are further aong than others; one common thread
s that mpementaton requres support from provnca governments. A range of provnca govern-
ment ntatves, such as the Centre for Research and Innovaton n the Bo-Economy (CRIBE) n
Ontaro |12|, have asssted mpementaton of technooges that are most reevant gven crcum-
stances specfc to the regon. As an exampe, CRIBE s a partner, wth Resoute Forest Products,

102
NRCan, FPInnovatons and NORAM Engneerng and Constructors n the Bo-Economy Technca
Centre, a facty desgned to evauate promsng technooges on a sem-ndustra scae. Located
wthn the Resoute Forest Products m n Thunder Bay, ON, the Centre has evauated a methano
purfcaton process for strppng TRS compounds from strpper condensate off-gasses, and s pres-
enty evauatng nove pathways to extract and modfy gnn from back quor at a 100 kg/d scae.
An example
The varous programs descrbed above have begun to show resuts, n terms of new fe for forestry
towns and ndustres where tradtona products are no onger proftabe. The st of pro|ects sup-
ported by these programs s ong and w not be repeated here; most are descrbed n the refer-
ences. Most foow the made-n-Canada approach descrbed above: a coaboratve approach
across ndustry, academa, governments and research nsttutes; bot-on addtons to exstng nfra-
structure; a focus on vaue-added products frst wth resdues converted to energy products; natona-
eve coordnaton, but wth a focus on regona mpementaton.
CeuForce s one notabe exampe of how the system has worked. An nta patent obtaned by
researchers at McG Unversty showed how to extract a purey crystane ceuose chan from
kraft pup fbres by seectvey dssovng the amorphous regons n ceuose. Ths nano-scae product,
dubbed nano-crystane ceuose (NCC), proved to have a wde range of exctng characterstcs,
ncudng hgh tense strength and a tendency to sef-agn nto structures wth unque optca prop-
ertes. However, t remaned a aboratory curosty for a number of years as the processes to make
the product had not been scaed up beyond the mgram scae.
Coaboraton between FPInnovatons and NRCan soon ed to a pot pant capabe of producng
kogram-scae quanttes, whch aowed potenta end-users to obtan and test sampes n the
search for nove products. As end-uses became cear, desgns for a tonne-scae facty were pre-
pared wth NORAM. Fnay, CeuForce, an ndependent |ont venture between Domtar and FPIn-
novatons, was formed |13| to bud such a pant and market the product. Fundng came from Dom-
tar, the TTPDP and Oubecs Mnstre des ressources naturees et de a faune; FPInnovatons
contrbuted ts nteectua property portfoo n the fed. The pant has now been but next to the
Domtar m n Wndsor, OC and operatons are underway. As a component of a bo-refnery, t re-
es on the host m for steam, power and effuent treatment servces; sugar-rch resdues from the
process are currenty converted to a bogas n an anaerobc dgestor; the bogas s burned n the
host ms CHP pant. Future, hgher vaue uses of the resdue stream are under deveopment.
Conclusions
Unque contexts w requre a unque approach to mpementaton of the forest bo-refnery. In Can-
ada, ths mpes:
Regona soutons;
Soutons that are hghy ntegrated nto the exstng ndustra andscape (both forestry and
non-tradtona partners);
Soutons whch have a arge focus on vaue-added products;
Bo-energy products (heat, power, sod or qud fues) w come from the resdues generated
by these heathy prmary ndustres, and are necessary but not suffcent for success;
In the short term, bot-on addtons w domnate n order to save capta and reduce rsk dur-
ng nta mpementaton phases;
Coordnated efforts across academa, research organsatons, ndustry, and federa and pro-
vnca governments on both pocy and |ont actvtes wth government-run aboratores.
The unque approach descrbed here has proven to generate usefu soutons, at a reasonabe cost.

103
References
1. http://www.ea.gov/dnav/ng/hst/n9190us3m.htm, vsted 31 | uy 2012.
2. http://www.thegobeandma.com/report-on-busness/ndustry-news/energy-and-resources/crude-
gut-prce-punge-put-o-sands-pro|ects-at-rsk/artce4230759/, vsted 30 | uy 2012.
3. http://www.bo-amber.com/boamber/en/products/succnc_acd, vsted 31 | uy 2012.
4. http://atas.nrcan.gc.ca/ste/engsh/maps/envronment/forest/forestcanada/forestedecozones,
vsted 30 | uy 2012.
5. PPGTP: http://cfs.nrcan.gc.ca/pages/231, vsted 30 | uy 2012.
6. TTP: http://cfs.nrcan.gc.ca/pages/166, vsted 30 | uy 2012.
7. TTPSD: http://cfs.nrcan.gc.ca/pages/182/2, vsted 30 | uy 2012.
8. IFIT: http://cfs.nrcan.gc.ca/pages/232?ang=en_CA, vsted 30 | uy 2012.
9. NSERCs Forest Sector Research and Deveopment Intatve: http://forest-foret.nserc-crsng.gc.
ca/ndex_eng.asp, vsted 30 | uy 2012.
10. BoPathways process overvews may be found here: http://cfs.nrcan.gc.ca/pages/171?ang
=en_CA and here: http://www.fpac.ca/ndex.php/en/bo-pathways, vsted 30 \| uy 2012.
11. Browne, T.C., Sngbe, D. et a. 2010. Bo-energy and Bo-chemcas Synthess Report. Pre-
pared for the Forest Products Assocaton of Canada and FPInnovatons, November 2010.
http://www.fpac.ca/pubcatons/bopathways/Bo%20Energy%20Fna_En.pdf.
12. CRIBE: http://www.crbe.ca/, vsted 31 | uy 2012.
13. CeuForce: http://www.ceuforce.com/en/ndex.php, vsted 31 | uy 2012.

Economc and ecoogca assessment of borefneres - fndngs of the German borefnery roadmap
process

104
Economic and ecological assessment of biorefineries
findings of the German biorefinery roadmap process
Uwe R. Fritsche
1
, Magnus Frhling
2
, Jochen Gerlach
3
, Arne Grngrft
4
, Armin Gnther
5
,
Jens Gnther
6
, Birgit Kamm
7
, ngo Klenk
8
, Sophia Laure
2
, Jrn-Christian Meyer
2
, Jrg Schweinle
9
,
Heinz Stichnothe
9
, Kathrin Strohm
9
, Frederik Trippe
2
, Dietmar Peters
10
, Kurt Wagemann
11
1
nternational nstitute for Sustainability Analysis and Strategy (NAS)
2
Karlsruhe nstitute of Technology (KT)
3
Sd-Chemie AG
4
German Biomass Research Center (DBFZ)
5
Air Liquide Global E&C Solutions, Lurgi GmbH
6
German Federal Environmental Agency
7
Research nstitute Bioactive Polymer Systems F biopos e.V
8
Sdzucker AG
9
Johann Heinrich von Thnen nstitute (vT),
Federal Research nstitute for Rural Areas, Forestry and Fisheries
10
Agency for Renewable Resources (FNR)
11
DECHEMA e.V.
Abstract
Borefneres are assumed to become mportant matera and energy users of bomass. Greenhouse
gas mtgaton, resource effcent and sustanabe bomass utzaton as we as postve economc
effects aong the vaue chans are drvers for borefnery concepts but these potenta benefts have
to be acheved and proven. In dong so, economc and ecoogca assessments pay an mportant
roe. Borefneres are a heterogeneous research and deveopment fed. Intated by the German
Federa Mnstres for Agrcuture, Food and Consumer Protecton as we as Educaton and Re-
search (BMELV) and organzed by the German Agency for Renewabe Resources (FNR) members
from potcs, ndustry and research eaborated the German borefnery roadmap. Ths roadmap
ams at systematcay determnng the state of deveopment of borefneres n Germany and at
anayzng strengths and weaknesses, as we as opportuntes and threats (SWOT) of promsng
future borefnery concepts n order to dentfy a strategy of research and pocy measures for dec-
son makers. Wthn ths roadmap process a subgroup deat wth the ssues of economc and eco-
ogca anayses and assessments. Ths paper summarzes the key fndngs of ths subgroup. Gen-
era aspects for anayss and assessment of borefneres are sketched. Chaenges wth regard to
data and methodooges are dentfed and concusons are drawn.
ntroduction
The Bobased Economy frst emerged as a pocy concept nkng renewabe resources and
(bo-)processes through ndustra scae bo- and chemca technooges to produce sustanabe
products, |obs and ncome. A successfu transton to a Bobased Economy w depend on a num-
ber of technoogca, economc, envronmenta and soca factors. However, n the course of ths
process, t s mportant to understand the fu envronmenta and economc mpcatons of the
changes that ths transton w enta. Borefneres promse n the best case to contrbute to green-
house gas mtgaton, acheve a hgh eve of resource effcency and a neary resdue-free and
sustanabe utzaton of renewabe raw materas. Addtonay, postve economc effects aong the
vaue chan such as a strengthenng of agrcuture and forestry, deveopment of regona econo-
mes, busness opportuntes for process technooges and cost reductons are expected.
Intated by the German Federa Mnstry of Food, Agrcuture and Consumer Protecton and the
German Federa Mnstry of Educaton and Research and supported by further mnstres a workng

process

105
group consstng of members from potcs, ndustry and research eaborated the German borefn-
ery roadmap |1|. Ths group ed by DECHEMA e.V. and organzed by the German Agency for Re-
newabe Resources (FNR) systematcay determned the state of deveopment of borefneres n
Germany and anayzed strengths and weaknesses, as we as opportuntes and threats (SWOT) of
promsng future borefnery concepts n order to dentfy a strategy of research and pocy measures
for decson makers.
Sustanabty assessment can be used to steer the borefnery deveopment at an eary stage
and to provde urgenty needed nformaton for ndustry and potcs to dentfy the most promsng
sustanabe concepts and to support nvestment decsons. To fnd broad soceta acceptance the
expected advantages have to be proven and expaned. Wthn ths context economc and ecoog-
ca anayss and assessment of borefneres pay an mportant roe. Further, a sound data bass for
communcaton and dscusson of borefnery concepts wth the pubc can be but. For ths purpose
a subgroup was formed wthn the German borefnery roadmap process that deat wth the above
mentoned topcs. The works wthn the economc and ecoogca assessment subgroup of the
German roadmap borefnery process provde a frst evauaton and sem-quanttatve dscusson of
essenta assessment aspects.
The presentaton covers key fndngs of ths subgroup. The focus es on ssues of partcuar re-
evance for the economc and ecoogca assessment aong the whoe vaue chan. Consdered are
sugar and starch borefneres, pant o and agae pd borefneres, gnoceuoses and green
borefneres as we as synthess gas borefneres. For a defnton of these types the reader s
referred to |1|. Based on these anayses chaenges for the economc and ecoogca assessment
are dentfed. These cover both, the need for provson of data as we as the need for methodoog-
ca mprovement n deang wth mutpe output systems, and dynamc markets.
General aspects
The assessment of borefnery concepts has to cover a stages of the vaue chan. Ths comprses
growng and harvestng of the feedstock, the converson processes as we as the use and the end-
of-fe phase as we as storage and transport aong the vaue chan. A comparson of dfferent bo-
refnery concepts s dffcut due to the arge number of possbe varatons n terms of feedstock,
ogstca confguratons, apped technooges, products and markets, capactes, deveopment
stages and the dependences on regona condtons. Nevertheess, such assessments can be
carred out wth methods from matera and energy fow baancng, matera and energy fow anay-
ss, economc and fe cyce assessment (LCA). It s necessary to address the partcuartes of
borefneres eadng to gaps wth regard to data and methods.
Raw material provision
The sustanabe provson of the necessary amounts of feedstock n proper quaty at reasonabe
cost s a cruca factor for most borefneres as t s for other bomass conversons. The possbtes
for ths depend nter aa on feedstock competton wth exstng but aso further (future) bomass
utzatons. The dscusson about borefneres and securng ther raw matera bass eads therefore
to dscussons on the effcent aocaton of avaabe and n agrcuture and forestry under consd-
eraton of the precedence of food and fodder producton.
The pcture for the dfferent feedstocks of the nvestgated borefnery types, .e. sugar and starch
pants, o seeds, green bomass, straw and wood from forests and short rotaton pantatons s
dfferent. Detas concernng the feedstock anayses can be found n |1|. In comparson to foss raw
materas the accrua of renewabe raw materas s many determned not by technca but by natu-
ra factors such as cmate, weather, seasons, so, and spata dstrbuton of the growng areas.
These have to be consdered n growng, harvestng, transport and storage. Partcuary reevant
factors are often the ength of the harvestng season, the dspersed nature of the bomass suppy,
hgh water contents and ow buk denstes. These are probematc because of mted storabty of
many agrcutura feedstocks and unfavorabe ong dstance transports n terms of costs and emssons.
process

106
To enhance storabty and transportabty condtonng steps such as peetzng, torrefacton, pyroyss,
hydrotherma conversons aso n combnaton wth ogstca network desgn measures such as a
spata or tempora decoupng of parts of the vaue chan are dscussed.
Provson of raw materas for borefneres has to acheve at east () a postve greenhouse gas
emsson baance over the whoe fe cyce from feedstock growng to resdue utzaton, () an
avodance of so degradaton, () toerabe matera nputs and outputs and (v) cosed matera
cyces for the resdues (cf. |2|).
Biorefineries
In tota 13 dfferent possbe confguratons of the nvestgated genera borefnery types are ds-
cussed on the bass of exstng terature and studes from a technoogca subgroup of the German
borefnery roadmap group from an economc and ecoogca pont of vew. For a detaed defnton
of the nvestgated confguratons the reader s referred to |1|. The sem-quanttatve, .e. a mosty
quatatve anayss, comprsng frst quanttatve consderatons for gnoceuoses and synthess
gas borefneres, covers aspects of deveopment stage, sutabe ocatons, capacty n terms of raw
matera demand, possbe product types and amounts, orders of magntude of nvestments and
further ma|or economc and ecoogca success factors. The nvestgated concepts dffer to a arge
extent n these crtera. Comparaby sma borefneres such as green borefneres are assumed to
be but n cose vcnty to the raw matera source. They are estmated to convert approx. 90 000
metrc tons of grass (20% dry matter) and are estmated to requre tota capta nvestments n the
order of magntude of approx. 15 mon Euro. Large borefnery systems such as synthess gas
borefneres are dscussed up to feedstock capactes of 500 000 to 2 000 000 metrc tons and are
assumed to requre tota capta nvestments n the order of magntude of 250 to 1 000 mon Euro.
The deveopment stages vary between ab scae, e.g. for agae pd borefneres to demonstraton
pants for e.g. gnoceuoses borefneres, synthess gas borefneres or bottom-up further deve-
opments of exstng bomass converson pants e.g. n the case of starch and sugar borefneres.
Dependng on the borefnery concept, aspects of the ntegraton nto exstng (chemca) produc-
ton stes (economes of scope), energy costs, utty costs, especay for enzymes and cataysts
can pay a cruca roe, both regardng economc as we as ecoogca assessments. For the atter
two t s hard to determne ther nfuence n advance. Addtonay, the envsaged process effcen-
ces n terms of product yeds but aso e.g. enzyme and sovent recovery have to be acheved
when the concepts are upscaed to an ndustra pant. In genera, the frst of ts knd ndustra pant
shows dsadvantages wth regard to the tota capta nvestment but aso operatona costs n com-
parson to succeedng nstaatons. Severa nstaatons are needed n order to reaze earnng and
experence curve effects to reduce specfc nvestments and costs and enhance effcences. Hgh
vaue matera utzaton of a product streams are essenta n many cases to acheve proftabty
of the often more compex borefnery converson processes. To am at buk chemcas such as
acohos provdes the advantage of exstng markets at the costs of exstng and often more mature
vaue chans. Fne chemcas producton offers the possbty of yedng hgher prces through
product dfferentaton. Nevertheess, assocated markets are generay smaer. Ths w demand
for the deveopment of sutabe new product famy trees and portfoos.
Challenges for the economic and ecological assessment
The presented sem-quanttatve anayss provdes frst orentaton for further deveopment and
optmzaton strateges. For a quanttatve assessment of the nvestgated borefnery concepts and
ther varants severa chaenges exst. Frst of a, the arge dfferences between the genera con-
cepts hnder a vad and |ust comparson between them. A drect comparson of dfferent concepts
s because of ncompatbty of the nvestgated systems often not goa orentated. Nevertheess, a
detaed nvestgaton of the snge concepts and ther varants over the whoe fe cyce under con-
sderaton of ocaton dependent factors possbe.
process

107
Wth regard to the data bass for such detaed assessments gaps occur. Regonay and sea-
sonay dsaggregated matera fow anayses for raw materas, especay organc resdues, are
mssng so far. Further, for some of the named borefnery concepts ony frst rough estmates for
matera and energy baances exst. Here a further eaboraton of pant concepts and specfcatons,
of processes and an expermenta vadaton of matera and energy fows n pot and demonstraton
pants are necessary to come to meanngfu dsaggregated data on condtonng and converson
processes.
Besdes ths mssng data methodoogca chaenges exst, demandng for further comprehen-
sve studes. Here especay common baancng standards for ecoogca ndcators are needed.
Further the accountng for humus formaton, ntrous oxde and ammona emssons from resdues,
mpacts on (oca) water quaty and avaabty, drect and ndrect and use change and and use
effcency, bodversty and ecosystem servces, tempora assessment, and regona specfc mpact
assessments are necessary when assessng the envronmenta mpacts of feedstock provson
thoroughy. The combnaton of fe cyce assessment wth fe cyce costng (LCC) and soca fe
cyce assessments (SLCA) can ead towards a more comprehensve assessment regardng a
pars of sustanabty. The number of dfferent ob|ectve crtera, nfuencng factors, concepts and
varants s arge. Despte the compexty of the factors to consder the regarded systems have to be
kept as smpe as possbe to aow meanngfu concusons. Expectatons and needs of the dfferent
stakehoders shoud be taken nto account. Ths requres sutabe approaches for mut-crtera dec-
son makng. In genera, sutabe approaches to account for data uncertantes and approxmatons
are needed.
For concusons about the advantages of borefneres n comparson to exstng utzatons of b-
omass but aso foss resp. mnera-based vaue chans the defnton of sutabe reference systems
and accordng data determnatons, especay for matera products are necessary. An estmaton of
the contrbuton of borefneres to cmate change mtgaton, raw matera securty and economc
deveopment wthn the context of mted raw matera and and avaabty and resutng compet-
ton requres a consderaton of the dynamc deveopment of these reference systems wthn the
tme frame for the borefnery deveopment, .e. 2020-2030, as we as regona, natona and nter-
natona aspects.
Conclusions
A detaed anayss of borefnery concepts under consderaton of ocaton-reated factors can ena-
be a quanttatve assessment of these, even n eary deveopment stages. Thus, key fgures for
sustanabty of these concepts and drectons for the further deveopment can be dentfed. The
comparson wth reference systems, other bomass utzatons and foss-based vaue chans aows
for drawng concusons about the advantages and prospects of borefnery concepts. In a sem-
quanttatve study 13 promsng dfferent borefnery concepts are anayzed under economc and
ecoogca aspects. Thus a frst sem-quanttatve characterzaton and dscusson of these concepts
s undertaken. A detaed anayss woud requre coverng the whoe vaue chan. Therefore detaed
data s needed wth regard to raw matera provson, condtonng and converson processes, ogs-
tcs and reference systems. The sze of the knowedge gaps vares to a arge extent between the
concepts. Methodoogca chaenges exst wth regard to aspects of fe cyce assessment, mut-
crtera anayses and the treatment of uncertan data.
An approach to resove the named ssues s the exempary detaed assessment of seected bo-
refnery concepts n further studes wth harmonzed methods and data. Ths can enabe a further
evauaton of the advantages of the envsaged concepts n comparson to exstng bomass utza-
tons and vaue chans based on foss respectve mnera raw materas. Addtona reference data
for further studes woud be provded. To carry out such an assessment for a nvestgated borefn-
ery concepts s aborous but necessary to draw the ntended concusons. A two-step approach
coud reduce the efforts and drect the research. In a frst step, a hot spot anayss, aggregated
ndcators are seected to dentfy economc key fgures and map envronmenta mpacts, e.g. carbon,
water or ntrogen footprnts. In a second step, detaed case studes are carred out for seected
process

108
borefnery concepts wth regard to the key fgures dentfed n the hot spot anayss. Thus, exem-
pary the questons on the reevance and nfuence of dfferent factors such as enzyme and cata-
yst usage, water usage and and use change can be deat wth and souton approaches can be
deveoped and dscussed. Ths woud aso contrbute to harmonzaton of methodooges. The eab-
orated data coud serve as a bass for regona, natona and nternatona system studes concern-
ng economc and ecoogca contrbutons of borefneres but aso other bomass utzatons. Such
studes coud be based on resuts from other research pro|ects, e.g. |3|, |4|, |5|, |6|, |7|. A vad data
bass for foss and mnera reference systems s to be deveoped. Besdes one snge assessment,
a montorng of the soco-economc and ecoogca effects on the dfferent stages n the deveop-
ment process can dentfy probems and ntate correctons. Due to the mmanent uncertantes
assessments of borefnery concepts w aways ead to bandwdths. Nevertheess, they can ac-
company the dscusson and deveopment of borefnery concepts and other bomass utzatons
and contrbute to achevng the goas connected wth these.
References
1. Roadmap Boraffneren. 2012. German Federa Government (ed.). Bern. URL: http://www.
bmev.de/SharedDocs/Downoads/Broschueren/RoadmapBoraffneren.pdf.
2. Bodenschutz bem Anbau nachwachsender Rohstoffe, Recommendatons of the commsson so
protecton at the German Federa Envronmenta Agency. 2008. Dessau URL: http://www.
umwetdaten.de/pubkatonen/fpdf-/3472.pdf.
3. BoCoupe - Koppung der stoffch/energetschen Nutzung von Bomasse. 2011. Wupperta
Insttut, Fraunhofer Umscht, ko-Insttut, Wupperta, Oberhausen, Darmstadt. URL:
http://www.energetsche-bomassenutzung.de/feadmn/user_upoad/Downoads/Endberc
hte/Endbercht_BoCoupe.pdf.
4. Boraffnere2021: Energe aus Bomasse - Neue Wege zur ntegrerten Boraffnere", URL:
http://boraffnere2021.de/.
5. Potpro|ekt "Lgnoceuose-Boraffnere". 2010. DECHEMA e.V. (ed.). Frankfurt. URL:
http://www.fnr-server.de/ftp/pdf/berchte/22014306.pdf.
6. Star-COLIBRI: Strategc Targets for 2020 Coaboraton Intatve on Borefneres. URL:
http://www.star-cobr.eu.
7. Kaundborg Ceuosc Ethano Pro|ect (KACELLE). URL: http://www.nbcon.com/Pro|ects/KAC
ELLE/Pages/KACELLE_Pro|ect.aspx.
New pot-pant facty of the "German Lgnoceuose Feedstock Borefnery Pro|ect" n Leuna -
experences wth frst tme operatons

109
New pil ot-plant facility of the " German Lignocellulose
Feedstock Biorefinery Project in Leuna experiences
with first time operations
Moritz Leschinsky
1
, Gerd Unkelbach
1
, Jochen Michels
2
, Thomas Hirth
3

1
Fraunhofer CBP, P.O. Box 1111, 06234 Leuna, Germany
2
DECHEMA e.V. Theodor-Heuss-Allee 25, 60486 Frankfurt am Main, Germany
3
Fraunhofer GB, Nobelstr. 12, 70569 Stuttgart, Germany
Abstract
The Fraunhofer-Center for Chemca-Botechnoogca Processes opened on 2
nd
of October 2012.
Ths new research center ocated at the chemca ste of Leuna focusses on the scae-up of bore-
fnery technooges and the deveopment of patform chemcas from bomass. Severa new pro-
cesses are transferred nto the pot scae and dfferent pot pants are gong to start operaton n
2012. One of these pot pants s part of the "German Lgnoceuose Borefnery Feedstock Pro-
|ect". The ob|ectve of ths pro|ect s to estabsh an economca and sustanaby ntegrated process
for the compete usage of a the components of gnoceuose on a arge ndustra scae and to
produce bo-based budng bocks and poymers for the ndustra botechnoogy and the chemca
ndustry. The pot pant s desgned to fractonate one ton of beech wood per week usng an Orga-
nosov process wth the am to provde a ma|or fractons (gnn and sugars) n suffcent amounts
for the deveopment of new vaue chans.|1|. The desgn of the pot pant s moduar to aow opt-
msaton of pupng and downstream processng. The gnoceuose s fractonated usng ethano-
water pupng. The ceuose s enzymatcay hydroysed to gucose whch s used for varous fer-
mentatons n the pro|ect. The gnn fracton s used by the pro|ect partners for the deveopment of
duro-and thermopastc appcatons.
ntroduction
The Fraunhofer-Center for Chemca-Botechnoogca Processes ocated at the chemca ste of
Leuna resuts from the cooperaton of two mother-nsttutes: the Fraunhofer Insttute for Chemca
Technoogy ICT n Pfnzta and the Fraunhofer Insttute for Interfaca Engneerng and Botechnoogy
n Stuttgart. It s the man task and busness fed of the new center to acceerate the ndustra m-
pementaton of processes for the producton of bobased chemca products. Therefore, the CBP
offers a broad range of pot-scae factes whch are suted for the scae-up of chemca and bo-
technoogca processes.
The tota nvestment sum of 46 mon C for the whoe CBP s fnanced together by the federa
state of Saxony-Anhat, the Federa Mnstry of Educaton and Research (BMBF), the Federa Mnstry
of Food, Agrcuture and Consumer Protecton (BMELV), the Federa Mnstry for the Envronment,
Nature Conservaton and Nucear Safety (BMU) as we as by the Fraunhofer Socety and the
chemca ste Leuna. The offca nauguraton on 2
nd
of October has termnated the constructon
perod of ess than two years.
Development and construction of the Lignocellulose Biorefinery pilot
plant
One mportant consttuent of the CBP s the pot facty for the fractonaton of wood, whch s con-
structed and w be operated n the natona |ont research pro|ect "Lgnoceuose Feedstock Bore-
fnery". The am of the pro|ect s the deveopment of patform chemcas servng as key-components
for bobased products. The pro|ect consortum consstng of 13 partners from academa and ndustry


110
s coordnated by DECHEMA. In 2007 the BMELV started fundng the deveopment of a gnoceu-
ose-borefnery based on beech and aspen wood. Durng the frst pro|ect phase, the systematc
comparson of dfferent processes resuted n the seecton of ethano-water-pupng as the most
benefca fractonaton technoogy for the compete utzaton and maxmum vaorsaton of German
hardwood speces. The degnfyng effect of ethano-water mxtures had been dscovered n Ger-
many n the 1930es by KLEINERT and TAYENTHAL |1|. The process was optmzed up to a batch
dgester voume of 10 L and a varety of potenta appcatons for the sugar and gnn fractons
were dentfed and tested. In parae, an economc (and soco-economc) evauaton confrmed the
feasbty to run a producton pant wth an annua wood consumpton of 400 000 t n Germany |2|.
For ndustra mpementaton of the process, the constructon and operaton of a pot pant s an n-
tegra part of the second pro|ect term from 2010 to 2013 wth the ams, on the one hand, to optmze
the pupng and fractonaton process and, on the other hand, to gan suffcent amounts of gnoceu-
ose fractons (sugars and organosov-gnn) for the deveopment of bobased vaue chans.
The pot pant s desgned to produce 80 kg of pure organosov gnn, 120 kg of gucose and
35 kg of xyose from 315 kg dry wood per week. If requred, the wood processng capacty may be
ncreased to one ton dry wood per week. A smpfed process scheme s depcted n Fgure 1.
The ethano-water pupng s carred out dscontnuousy n a dgester that can be operated wth a
maxmum pressure of 40 bar at 200 C. Two addtona pressure vesses and one atmospherc tank
aow the preparaton, preheatng and storage of the cookng and washng quors. The precptaton
of the gnn from the pupng quor after separaton of the fbre fracton s carred out ether by
means of dstaton of the sovent or by addng water. Thereafter the gnn s ftered, washed and
dred. The hemceuoses present n souton after ftratng of the gnn are purfed and concentrated.
The ceuose fracton s dsntegrated and washed. After dewaterng, the enzymatc hydroyss of
ceuose s carred out n a strred tank reactor. The gucose souton obtaned can fnay be con-
centrated for preservaton by means of evaporaton. The pupng sovents are recovered by means
of rectfcaton. The optmum operaton condtons for pupng, gnn precptaton and enzymatc
hydroyss were determned by the pro|ect partners n parae to the constructon of the pot pant.
Competon of the pot pant was acheved n September 2012, foowed by the cod commssonng
phase. Frst tme operaton wth wood s panned n November.
Wth the start of operaton the pro|ect partners w be supped wth the fractonated wood con-
sttuents to be abe to scae up ther product deveopments. The sugars (C5 and C6 sugars) are
ether chemcay converted to poyacohos servng as a bass for e.g. poyurethanes, or they are
tested for a range of dfferent fermentatons:
- Acetone, butano, ethano
- Succnc acd
- Lactc acd
- Acetc acd.
The gnn s used for the deveopment and testng of pheno-resns, poyurethane foams and ther-
mopastc compounds. Lgnn resdues are degraded nto vauabe phenoc mono- and ogomers
by pyroyss or hydrotherma crackng processes.

111

Figure 1. Smpfed process scheme of the "Lgnoceuose Borefnery" pot pant n Leuna.
In the pot pant, the scae-up of a the dfferent process steps on scaabe unt operatons s per-
formed. Ths s the bass for the further scae-up of the process nto the demonstraton scae.
The man focus of the process optmzaton at the pot scae s on the mprovement of the energy
baances and the cosure of water oops.
Based on the resuts of the optmzed process, the economc vabty of the process s evauated
as we as the sustanabty of the products.
Acknowledgement
The |ont pro|ect "Lgnoceuose Feedstock Borefnery - Phase 2" s funded by the Federa Mnstry
of Food, Agrcuture and Consumer Protecton (BMELV), and supported by the fundng agency
Fachagentur Nachwachsende Rohstoffe e.V. (FNR) under grant numbers 22029508, 22019009,
22019109, 22019209, 22019309, 22019409, 22019509, 22019609, 22019709, 22019809, 22019909,
22020009, 22020109, 22020209, 22022109.
References
1. Kenert, Th., v. Tayentha, K. 1931. ber neuere Versuche zur Trennung von Ceuose und Inkrusten
verschedener Hzer. Angew. Chem. 44, pp. 788-791. Do: 10.1002/ange.19310443903.
2. Mches, | ., Wagemann, K. 2011. The German gnoceuose feedstock borefnery pro|ect. 3
rd

Nordc Wood Borefnery Conference, Stockhom, Sweden. P. 70.
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The LgnoRef pro|ect: A natona research ntatve to enhance borefnery process deveopments n
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112
The LignoRef project: A national research initiative to
enhance biorefinery process developments in Norway
Karin yaas
1
, Kai Toven
1
, ngvild A. Johnsen
1
, Swarnima Agnihotri
2
, Strker Moe
2
, Al MacKenzie
3
,
Vincent Eijsink
3
, Nils Dyrset
4
, Roman Netzer
4
, Bjarte Holmelid
5
, Tanja Barth
5
, ngvar Eide
6

1
Paper and Fibre Research nstitute (PF), Hgskoleringen 6B, NO-7491 Trondheim, Norway
2
Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway
3
Norwegian University of Life Sciences (UMB), NO-1432 s, Norway
4
SNTEF Materials and Chemistry, NO-7465 Trondheim, Norway
5
University of Bergen (UoB), NO-5007 Bergen, Norway
6
STATOL Research Centre, NO-7005 Trondheim, Norway
Abstract
The LgnoRef pro|ect ("Lgnoceuoscs as a bass for second generaton bofues and the future
borefnery") gathers centra Norwegan payers (R&D and ndustry) aong the vaue chan from
gnoceuosc bomass to bofues/bochemca products (Fgure 1). The overa ob|ectve of ths
R&D pro|ect s to estabsh fundamenta knowedge about centra processes nvoved n the conver-
son of gnoceuosc bomass to second generaton bofues and vaue-added products. Centra
processes studed n ths work ncude bomass pretreatment and separaton, enzymatc hydroyss,
fermentaton and thermochemca converson of bomass and process by-products. A further ob|ec-
tve of the pro|ect has been to |on centra natona payers n the borefnery area n order to pro-
mote natona progress n ths fed.

Figure 1. Lay-out of the LgnoRef pro|ect. (PFI =Paper and Fbre Research Insttute, NTNU =Nor-
wegan Unversty of Scence and Technoogy, UMB =Norwegan Unversty of Lfe Scences).
ntroduction
LgnoRef (2009-2012) s a competence budng pro|ect funded by the Research Counc of Norway
and ndustry. The pro|ect consortum conssts of R&D and ndustry partners, wth the Paper and
Fbre Research Insttute (PFI) as pro|ect owner. The R&D partners span the vaue chan from fun-

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113
damenta knowedge of the fbre raw matera va the enzymatc breakdown of sugar poymers to
the converson of bomass monosugars and gnn to fues and chemcas.
Bomass pretreatment (sufte based, organosov, steam exposon) and separaton (gnn, hem-
ceuose) studes are performed by PFI n cooperaton wth the Norwegan Unversty of Scence
and Technoogy (NTNU). Steam exposon pretreatment s performed by the Norwegan Unversty
of Lfe Scences (UMB). Focus of the pretreatment studes s on desgnng pretreatment and sepa-
raton schemes that w sut the raw matera propertes of dfferent bomass nputs, amng at hgh
sugar yeds, hgh separaton effcency and mnma formaton of degradaton products.
Enzymatc carbohydrate hydroyss s studed by UMB. The focus s on deveopment of nove
enzymes and heper proten systems that make the hydroyss of ceuose and hemceuoses more
effectve. The work ams at understandng and expotng the enzymes nvoved as we as on de-
sgnng enzyme cocktas that ensure effectve hydroyss.
Mcroba converson of the gnoceuosc sugars, focusng on the deveopment of nove mcro-
organsms that ensure effectve converson of both C6 and C5 sugars to bofues/bochemcas s
performed by SINTEF Materas and Chemstry. Focus s on the deveopment of nove genetc toos
sutabe for engneerng robust ndustra yeast strans for effcent converson of a gnoceuose
derved carbohydrates to fues and chemcas.
Thermochemca converson of gnn to a qud bo-o comprsed of vauabe components (e.g.
fue components, "green" chemcas) by sovoyss s studed by the Unversty of Bergen. The work
s performed n cose cooperaton wth Stato Research Centre whch has a hgh competence on
charactersaton of os.
Energy densfcaton of bomass by torrefacton s studed by PFI.
The research s performed n cose coaboraton wth ndustry partners, rangng from forest owners
(Askog) va bomass converters (Camb, Borregaard, Weyand, Xynergo/Norske Skog) to fue/energy
producers (Stato, Hafsund).
Experimental
Materials, methods
Lgnoceuosc raw materas were coected, dred and charactersed pror to use, ncudng Norway
spruce, wheat straw, bagasse and bark (spruce).
Intay, consderabe efforts were undertaken to estabsh reabe anaytca methods for chem-
ca charactersaton of raw matera nputs, as we as process ntermedates. Ths was especay
mportant as we ncuded raw materas that were new to us (e.g. bagasse). To be abe to compare
resuts obtaned by the dfferent partners, Round Robn tests were undertaken. Chemca anayses
were based many on standardzed methods, e.g. dry matter (ISO 638), gnn and structura carbo-
hydrates (NREL/TP-510-42618), carbohydrate composton (HPAEC; Donex ICS-5000), saccharf-
caton potenta (NREL/TP-510-42629).
Imagng methods amed at vsuazng morphoogca fbre changes (e.g. fbre surface and cross
sectons) resutng from dfferent treatments were deveoped, usng scannng eectron mcroscopy
(SEM) and Fed emsson SEM n combnaton wth advanced mage anayses (Image | ava).
Pretreatment processes
Pretreatment tras were undertaken usng sufte, organc sovents (ethano/water) or steam. The
work has focused on obtanng hgh sugar yeds, good separaton effcency and ow nhbtor for-
maton. Hemceuose pre-extractons were performed usng conventona hot water or mcrowave
setups. Pretreatment for thermochemca converson of the bomass was based on torrefacton.
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Enzymatic hydrolysis
Enzymatc hydroyss of carbohydrate poymers has been focused n part on fundamenta studes of
the hydroyss process, n partcuar studes of the favourabe effects of the recenty dscovered ytc
poysaccharde monooxygenases that promote breakdown of crystane ceuose. Furthermore, the
work has ncuded apped testng of enzymes/enzyme mxtures (amng at reastc condtons, e.g.
hgh DM concentratons) as we as a targeted search for nove gnoceuose degradng enzymes.
Mi crobial conversion of C5 and C6 sugars
Metaboc engneerng approaches are based on ndustra S. cerevisiae wd type ATCC96581 as
host stran. Key enzymes for converson of C5 sugars (xyose reductase and xyto dehydrogenase)
from Pichia stipitis and xyuose knase from S. cerevisiae have been ntegrated nto the genome of
S. cerevisiae ATCC96581, to make ths stran capabe of effcent pentose and hexose utzaton.
Lignin conversion and bio-oil characteri sati on
Thermochemca gnn converson to bo-o s performed usng a sovoytc approach (base case
380C, 24 h, formc acd/ethano sovent). A "test-battery" of methods sutabe for both petro- and
bo-os s estabshed. Ths nvoves "fngerprntng" technques ke mass spectrometry (ESI-MS),
gas chromatography (GC-MS) and FTIR. The data are nterpreted usng chemometrcs n order to
evauate smartes between sampes and to characterze homoogous seres.
Pretreatment processes
Sufte pretreatment: A sufte pretreatment method termed "ow temperature suphonaton" has
been deveoped, gvng a hghy suphonated gnn, effectve gnn dssouton and hgh enzymatc
saccharfcaton of the carbohydrates. The method whch has been demonstrated for softwood
provdes good contro of hemceuose degradaton (ow nhbtor formaton). The pretreated chps
need no further refnng pror to enzymatc hydroyss. Water soube gnosufonates wth hgh de-
gree of sufonaton can be obtaned as a by-product. The method s descrbed n the poster; "Low
temperature sufonaton of gnoceuose for effectve bomass deconstructon and converson".
Organosov pretreatment: Up to 70% of spruce gnn coud be removed (ethano/water sovent),
resutng n a yed after enzymatc hydroyss of 80%. More effectve gnn dssouton was found for
bagasse than for spruce at ower temperatures n the process setup used.
Steam pretreatment: Steam pretreatment of wheat straw has demonstrated hgh gucose yeds.
However, furfura formaton remans a probem, causng adverse effects on the fermentng organ-
sm. Resuts are pubshed n .a. Horn et a., 2011 and n Chacha et a., 2011.
Hemceuose extracton: Hemceuose pre-extracton pror to pretreatment amed at ow depo-
ymersaton. Conventona hot water extracton and mcrowave-asssted extracton gave smar
resuts. Both extracton tme and temperature were mportant. A hgher degree of poymerzaton
(DP) was obtaned for hemceuoses extracted from bagasse than from spruce. Further, ess pro-
nounced depoymerzaton was found wth tme for bagasse than for spruce. Ths s further de-
scrbed n the poster; "Hot water extracton of hemceuoses from softwood and sugarcane ba-
gasse usng mcrowave heatng technoogy".
Torrefacton pretreatments have demonstrated that med, torrefed spruce (approx. 0.25 mm
partces), may be suted for use n entraned fow gasfers (thermochemca converson).
As expected, the pretreatment studes have shown that dfferent raw materas behave very df-
ferenty n the varous pretreatment processes.
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Enzymatic hydrolysis
Studes are focused on addressng how the recenty dscovered ytc poysaccharde monooxygen-
ases from bactera and fung, currenty referred to as CBM33s and GH61s (see Vaa|e-Kostad et
a., 2010) can be utzed to better degrade bomass nto bofue precursors. The studes have
shown that the accessory enzymes act synergstcay wth ceuases to mprove the ceuose hy-
droyss of pre-treated bomass (resuts n Forsberg et a., 2011; Westereng et a., 2011). Other
casses of specfc enzymes, such as mannanases, are aso beng tested for the same purpose.
Addtonay, a search for nove bomass degradng enzymes s undertaken n coaboraton wth
other pro|ects at UMB. Resuts are pubshed n Pope et a., 2012 and MacKenze et a., 2012. A
custer of genes whch appears mportant for bomass degradaton n the gut of Svabard rendeer
has been dentfed and the characterstcs and potenta use of these enzymes n bomass conver-
son are beng expored. Nove custers of bactera genes (Poysaccharde Utzaton Loc, PUL)
whch appear to be mportant n degradng detary bomass, have been dentfed and characterzed.
The resuts suggest that these enzymes and protens are adapted to the degradaton of -gycans,
xyogucans, as we as gucomannans and gaactomannans, ndcatng the potenta of these en-
zymes for hydroyss of e.g. spruce hemceuoses.
The fundamenta enzyme dscovery and characterzaton work s combned wth process-
deveopment studes amed at deveopng effectve enzymatc converson protocos for LgnoRef
substrates, n partcuar pretreated spruce and bagasse.
Mi crobial conversion of C5 and C6 sugars
S. cerevisiae s the most promsng canddate for producton of ethano from gnoceuose (exceent
gucose fermentaton capabty, hgh ethano toerance, resstant to nhbtors). However, as natve
S. cerevisiae strans cannot utze xyose nether for growth nor for ethano producton, metaboc
engneerng s used to deveop S. cerevisiae mutant strans abe to utze xyose. Genes for xyose
utzaton from the yeast Pichia stipitis have been ntroduced nto the chromosome of an ndustra
S. cerevisiae stran by usng a combnaton of genetc engneerng and random mutageness n an
teratve way. Resutng mutant strans are shown to convert xyose effcenty to ce bomass (growth).
In addton, nove genetc toos for conng and recombnant proten expresson n S. cerevisiae
strans are constructed, factatng the deveopment of hgh potenta yeast strans for cost-effcent
converson of gnoceuose to bo-ethano and vaue-added fne chemcas.
The xyose utzng ndustra S. cerevisiae mutant constructed can serve as host stran for fur-
ther genetc engneerng. A new S. cerevisiae vector system has been constructed for conng and
nducbe gene expresson. New vectors wth dfferent promoter systems for recombnant gene
expresson n ndustra S. cerevisiae strans are under constructon.
Lignin conversion and bio-oil characteri sati on
Thermochemca converson of gnn to bo-o usng a sovoytc approach s studed. The prevousy
deveoped gnn-to-qud (LtL) process s further deveoped wth respect to raw matera and reac-
ton condtons (resuts n Kenert et a., 2011). Anayss of post sovoyss fragmentaton patterns
has shown that dfferent gnns behave rather smar durng sovoyss and that the LtL process s
robust. However, dfferences n the detaed composton of products are observed. Furthermore,
back quor wth hgh sufur contents s not sutabe due to the formaton of H
2
S.
Mechanstc studes amng to descrbe the chemca reactons nvoved n the LtL process have
gven new knowedge of the processes nvoved and form a bass for the further optmzatons.
Usng mode compounds 5 centra reacton pathways nvoved have been dentfed as descrbed n
Homed et a., 2012. Dfferent sovent systems have been studed (e.g. formc acd, paraformade-
hyde, water), showng that water s an aternatve "green" sovent system for ths converson.
Catayst screenngs to mprove reacton effcences are on-gong, amng to deveop systems
where the depoymersaton of gnn, remova of oxygen and ncorporaton of hydrogen n the products
s effectve at ow temperatures (beow 360C), see Luguor et a., 2011.
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Methods suted for anayss of both petro- and bo-os were estabshed, ncudng standardzed
methods for anaysng fues, as we as new methods for anaysng components not normay found
n petro-based products. The methods are used to determne needs for upgradng of bo-os to
transport fue quaty. Ths ncudes the use of mass spectrometry based "fngerprntng" technques
and chemometrcs (as descrbed n Carson et a., 2012 and Geerstedt et a., 2008).
Conclusions
The LgnoRef pro|ect gathers centra Norwegan payers nvoved at dfferent stages aong the vaue
chan from gnoceuosc bomass to bofues/chemcas. Fundamenta knowedge about centra
processes nvoved n the deveopment of cost-effectve converson of gnoceuoses has been
estabshed. These processes ncude pretreatment and separaton, enzymatc hydroyss, fermen-
taton and thermochemca converson of both bomass and process by-products. The pro|ect has
been and s st promotng natona coaboraton and progress n the borefnery area.
Acknowledgement
We gratefuy acknowedge The Research Counc of Norway (grant no. 190965/S60), Stato ASA,
Borregaard AS, Askog BA, Camb AS, Xynergo AS/Norske Skog, Hafsund ASA and Weyand AS
for fnanca support.
References
1. Geerstedt, G., L, | ., Ede, I., Kenert, M., Barth, T. 2008. Chemca structures present n bofue
obtaned from gnn. Energy & Fues 22(6), pp. 4240-4244.
2. Carson, | .E., Gasson, | .R., Barth, T., Ede, I. 2012. Extractng homoogous seres from mass
spectrometry data by pro|ecton on predefned vectors. Chemometrcs and Integent La-
boratory Systems 114, pp. 36-43.
3. Chacha, N., Toven, K., Mtu, G., Katma, | ., Mrema, G. 2011. Steam pretreatment of pne (Pnus
patua) wood resdue for the producton of reducng sugars. Ceuose Chem. Techno. 45
(7-8), pp. 495-501.
4. Forsberg, Z., Vaa|e-Kostad, G., Westereng, B., Bunaes, A.C., Stenstrom, Y., MacKenze, A.,
Sore, M., Horn, S.| ., E|snk, V.G.H. 2011. Ceavage of ceuose by a CBM33 proten.
Proten Scence 20(9), p. 1479-1483.
5. Homed, B., Kenert, M., Barth, T. 2012. Reactvty and reacton pathways n thermochemca
treatment of seected gnn-ke mode compounds under hydrogen rch condtons. | our-
na of Anaytca and Apped Pyroyss In Press, Avaabe onne 31 March 2012.
6. Horn, S.| ., Nguyen, O.D., Westereng, B., Nsen, P.| ., E|snk, V.G.H. 2011. Screenng of steam
exposon condtons for gucose producton from non-mpregnated wheat straw. Bomass
and Boenergy 35(12), pp. 4879-4886.
7. Kenert, M., Gasson, | .R., Ede, I., Hmen, A.-M., Barth, T. 2011. Deveopng sovoytc conver-
son of gnn to qud (LtL) fue components: Optmsaton of quaty and process factors.
Ceuose Chemstry and Technoogy 45(1-2), pp. 3-12.
8. Luguor, L., Barth, T. 2011. Paadum-Nafon SAC 13 cataysed depoymersaton of gnn to phenos
n formc acd and water. | ourna of Anaytca and Apped Pyroyss 92(2), pp. 477-484.
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9. MacKenze, A.K., Pope, P.B., Pedersen, H.L., Gupta, R., Morrson, M., Wats, W.G., E|snk, V.G.
2012. Two SusD-Lke Protens Encoded wthn a Poysaccharde Utzaton Locus of an
Uncutured Rumnant Bacterodetes Phyotype Bnd Strongy to Ceuose. App Envron
Mcrobo 78(16), pp. 5935-5937.
10. Pope, P.B., Mackenze, A.K., Gregor, I., Smth, W., Sundset, M.A., McHardy, A.C., Morrson, M.,
E|snk, V.G. 2012. Metagenomcs of the Svabard rendeer rumen mcrobome reveas
abundance of poysaccharde utzaton oc. PLoS One 7(6):e38571. Epub | un 6.
11. Vaa|e-Kostad, G., Westereng, B., Horn, S.| ., Lu, Z., Zha, H., Sre, M., E|snk, V.G. 2010. An
oxdatve enzyme boostng the enzymatc converson of recactrant poysacchardes. Sc-
ence 330(6001), pp. 219-222.
12. Westereng, B., Ishda, T., Vaa|e-Kostad, G., Wu, M., E|snk, V.G., Igarash, K., Same|ma, M.,
Sthberg, | ., Horn, S.| ., Sandgren, M. 2011. The putatve endogucanase PcGH61D from
Phanerochaete chrysosporum s a meta-dependent oxdatve enzyme that ceaves ceu-
ose. PLoS One 6(11), e27807. Epub Nov 23.
Fnnsh BoRefne - new bomass products programme - RD&D on bofues and borefneres n
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118
Finnish BioRefine new biomass products programme
RD&D on biofuels and biorefineries in Finland
Programme Manager Erja mmlahti
1
, Programme Coordinator Tuula Mkinen
2

1
Tekes, Finnish Funding Agency for Technology and nnovation
P.O. Box 69, F-00101 Helsinki, Finland
2
P.O. Box 1000, F-02044 VTT, Finland
Abstract
The BoRefne - New Bomass Products Programme of Tekes, Fnnsh Fundng Agency for Tech-
noogy and Innovaton, for 2007-2012 has amed to generate new and unque expertse n pro-
cessng of bomass and to appy t to the creaton of processes, products and servces reated to
borefneres. A further ob|ectve has been to promote the deveopment and use of second-
generaton producton technooges n bofues for transport.
A broad Fnnsh effort to deveop new borefnng competences and technooges has been co-
ordnated under the umbrea of the BoRefne programme. The BoRefne programme together wth
the FuBo programmes of Fnnsh Boeconomy Custer FIBIC Ltd (former Forestcuster Ltd) and the
speca pot and demo fundng of the Mnstry of Empoyment and the Economy has formed an
extensve network of natona and nternatona coaboraton. Ths entty has harnessed an exten-
sve network of natona research nsttutes, unverstes and enterprses. The tota voume of the
pro|ects funded by Tekes n the BoRefne programme has aready reached C285 mon.
The pro|ects of the programme cover a spectrum of products - bofues, chemcas, materas -
utsng bomass n a varety of forms. One of the man focus areas has been forest-based borefn-
eres. In addton to forest-based raw materas aso opportuntes of agro bomass, waste fractons
and new bomass sources, ke agae and mcrobes, have been worked wth.
The research, deveopment and demonstraton of producton technooges of bofues has had a
arge roe, e.g. technooges for producng bofues for transport va the synthess-gas route and the
fermentaton route and new qud bofue concepts based on ntegratng a fudzed-bed boer and
fast pyroyss have been deveoped and demonstrated. Aso the use of bofues has been demon-
strated, e.g. n the fed tests wth a bus feet n the Hesnk Metropotan area. Aso opportuntes of
agae producton and utzaton n bofue and boenergy producton have been studed. Green-
house gas and other envronmenta mpacts of producton and use of bofues have been assessed.
Severa nove routes to produce materas and chemcas from bomass have been deveoped.
Pro|ects of the programme have focused e.g. on new fractonaton methods of bomass, cost-
effectve methods to produce sugars from bomass, producton of bopoymer foams, and methods
to modfy gnn nto materas appcabe for compostes, coatng adhesves and barrers. The pro-
gramme has aso been a patform for sma and medum-szed companes to carry out deveopment
pro|ects together wth research nsttutes and unverstes.
The programme has factated nnovatons on the boeconomy, and hence t has ntensvey
paved the way for boeconomy n Fnand.

More nformaton about the programme can be found at www.tekes.f/programmes/borefne

The Doms| borefnery - how to make more from the tree

119
The Domsj biorefinery how to make
more from the tree
Lars Winter
Domsj Fabriker AB, Sweden (a part of the Aditya Birla group)

Pup and papermakng has, snce the substtuton of ump to ceuosc fbres, been focused on
usng the fbres from trees for manufacturng of paper, tssue or packagng grades. The dfferent
pupng methods that have been deveoped are a based on the quaty requrements for the dffer-
ent end products whch have ed to severa dfferent processes n whch varyng shares of the con-
sttuents of the tree are converted nto pups of dfferent propertes.
The dfferent pupng processes a have n common an ambton n achevng the best possbe
pup quaty at the owest possbe raw matera consumpton. Ths has ed to that the consttuents of
the tree to the argest achevabe extent shoud be mantaned n the fna product. In other words,
the fna product shoud consst of the hghest possbe amount of ceuose, hemceuoses, gnn
and extractves whch s achevabe wthout compromsng the quaty of the pup and the product
that s produced thereof.
Snce the man focus of the pupng processes was to mantan as much as possbe of the con-
sttuents of the wood n the fna product, a of the matera that has been removed from the tree
was ntay consdered as waste matera. Ths waste matera was dsposed of to the nearest re-
cpent or deposted on andfs at owest possbe cost. Wth growng envronmenta concerns and
ncreasng energy prces the waste streams were recyced nto the process and aso used to create
vaue by recoverng the energy content of the organc part and heat vaue of the waste stream as
we as for recovery of chemcas for the pupng process. Ths s aso the current status of the ma|or
part of the pup and paper ndustry - a man product s beng produced from the tree resource and
excessve matera from the process s beng recyced n order to recover chemcas and energy n
the producton process.
In Doms| we have taken another approach n our deveopment from a pup producer for the pa-
per, tssue and board ndustres to becomng the gobay frst Borefnery based on natura materas
from the tree. From the 1930s the Doms| Suphte pup m has been producng specaty ceuose
as a raw matera for Vscose Stape Fbre (VSF), to varyng extents and wth varyng success. Even
though the man focus was the producton of chemca pup Doms| aready the 1940s deveoped
severa other suppementary products from the waste streams of the suphte pup producton. Ths
was the crade of the organc chemca ndustry n Sweden that subsequenty was further deveoped
n Stenungsund to a currenty prosperous compex. From ths perod the ethano producton re-
mans on the ndustra ste n Doms| as a separate company, SEKAB, whch s supped wth bo-
ethano from Doms| together wth operatons owned by Akzo Nobe that manufactures chemcay
modfed ceuose products.
After a troubesome perod from 1980 durng whch the m was sub|ect for decsons to be shut
down severa tmes t experenced a revva wth new ownershp durng 2000 and wth a renewed
focus on specaty ceuose as we as ncreased focus on creatng addtona vaue added products
from the secondary process streams from the ceuose producton. Ths has ed to refnement of
the concept of producng organc chemcas from the waste streams whch was ntay estabshed
n the 1940s, nto the current Borefnery. Snce 2000 the Doms| Borefnery has changed the
manufacturng focus from beng many a producer of chemca pup for mut-purpose usage nto
becomng a ma|or supper of a wde varety of sustanabe product such as specaty ceuose for
dfferent appcatons, bo-ethano, bo-gnn, bogas, bo-CO
2
and bo-energy based on sustanabe
producton processes wth ow envronmenta mpact.
The converson from beng a chemca pup supper nto a supper wth an wde assortment of
sustanabe products has been possbe snce the ong tradton and experence of producng sever-
a dfferent products from the wood resource, descrbed earer, has to a arge extent been pre-
served wthn or cose to the ndustra ste. Ths strong competence and knowedge n the currenty

The Doms| borefnery - how to make more from the tree

120
dfferent organsatons DomInnova, MoRe Research as we as the Processum custer has rendered
vauabe networks and everage to the research performed nternay as we as been a channe for
ntroducng research competence and nnovaton from the Unverstes n the nearby regons. Ths s
aso an mportant foundaton for the future deveopment of the Doms| Borefnery.
The future deveopment of the Borefnery ncudes both mprovng the current product assort-
ment and ntroducton of new sustanabe bo-products. The wood consttutes a sustanabe re-
source of raw matera of growng future mportance for manufacturng of vauabe aternatves cur-
renty based on mted and unsustanabe resources. Borefneres based on trees as raw matera
w n the future become ncreasngy mportant substtutes for the producton of aternatve textes,
fues and other organc compounds. In such way the further deveopment of our and other Borefn-
eres w become the foundatons for the prosperty and preservaton of the natura envronment of
comng generatons.
Snce Apr 2011 Doms| s aso a part of the goba Indan group Adtya Bra, whch among oth-
ers s a gobay eadng producer of VSF. Ths has ed to renewed drectons n mantanng as we
as deveopng the poston of Doms| as the eadng Borefnery based on sustanabe wood re-
sources.
Hence, currenty as we as n the future the Doms| Borefnery makes more of the tree and we
make t better than others.

UPM - producng fues of the future from wood-based raw materas

121
UPM producing fuels of the future from wood-based
raw materials
Sari Mannonen
UPM-Kymmene Corporation, UPM Biofuels, Etelesplanadi 2, P.O. Box 380, F-00101 Helsinki, Finland
Abstract
UPM ams to become a ma|or payer n Europe n the producton of renewabe, advanced bofues.
The company has made the frst bofue nvestment decson on a borefnery to Lappeenranta, South-
Eastern Fnand. Other UPM bofue pro|ects are currenty many n the deveopment and potng
stage. Sustanabty of operatons has been one of the man crtera for the deveopment of the UPM
bofues busness and the producton of bofues w not be based on materas sutabe for food.
UPMs frst bofue pro|ect, borefnery to Lappeenranta, s based on hydrogenaton process. The
nvestment decson has been made n the begnnng of February 2012 and budng of the borefnery
has started n | une 2012. The borefnerys man product w be renewabe, advanced bodese.
The raw matera w be crude ta o, a wood based resdue of pup makng process.
UPMs advanced bodese, UPM BoVerno, s an nnovaton whch w decrease greenhouse
gas emssons of transport up to 80% n comparson to foss fues. The products characterstcs
correspond to those of the tradtona o-based fues and hghy compement todays vehces and
fue dstrbuton systems.
UPM pans to bud a bomass-to-qud (BTL) borefnery ether to Rauma, Fnand or to Stras-
bourg, France. It w be usng energy wood as the raw matera and the man product woud be
renewabe, advanced bodese.
UPM borefneres w be ocated n connecton of companys current pup and paper ms. Ths
way UPM w gan synerges n, for exampe, nfrastructure, energy and ogstcs. In addton, UPM
takes part n bofue reated |ont deveopment pro|ect n bo o, whch s aso referred to as pyroyss o.
UPM s aso studyng the possbty of usng the pyroyss o for the producton of transportaton fues.
Hydrogenation biorefinery
UPM has made an nvestment decson on a hydrogenaton borefnery producng bofues from crude
ta o n Lappeenranta. The ndustra scae nvestment s the frst of ts knd gobay. The borefnery
w produce annuay approxmatey 100 000 tonnes of advanced second generaton bodese for
transport, equatng to 120 mon tres of bodese. Constructon of the borefnery has begun n the
summer of 2012 at UPMs Kaukas m ste and be competed n 2014. UPMs tota nvestment w
amount to approxmatey EUR 150 mon and s competed wthout pubc nvestment grants.


122

Figure 1. The facty of the UPM borefnery s ocated n Lappeenranta, Fnand, and w produce
bodese from crude ta o at UPMs Kaukas m ste.
Lappeenranta s the frst step on UPMs way n becomng a sgnfcant producer of advanced se-
cond generaton bofues. Ths s aso a foca part n the reasaton of UPMs Bofore strategy, com-
bnng bo and forest ndustres.
Raw materi al
The man raw matera of UPMs frst hydrotreatment borefnery s crude ta o, whch s a resdue
of chemca pup producton, many generated n the producton of suphate ceuose from soft-
wood. A sgnfcant part of the raw matera comes from UPMs own pup ms n Fnand.
UPMs wood sourcng s based on the prncpes of sustanabe forest management, chan of
custody and forest certfcaton. By further processng crude ta o UPM s abe to utse the wood t
uses for ts pup producton n a more effcent way wthout ncreasng wood harvestng or and-use.
UPM does not use raw materas sutabe for food.
Biodiesel process
UPM has been deveopng an nnovatve producton process n Lappeenranta Borefnery Center,
Fnand. The whoe process from crude ta o to the fna product, pure second generaton bo-
dese, s performed and controed at the same borefnery ste. The man steps of the process are
pretreatment of crude ta o, hydrotreatment, recyce gas purfcaton, and fractonaton.

Figure 2. The bodese process n Lappeenranta borefnery.

123
Product
UPMs advanced bodese, UPM BoVerno, s an nnovaton whch w decrease greenhouse gas
emssons of transport up to 80% n comparson to foss fues. The products characterstcs corre-
spond to those of the tradtona o-based fues and hghy compement todays vehces and fue
dstrbuton systems.
UPM BoVerno has been tested for ts propertes, functonaty, and effect on dese engnes n var-
ous aboratores such as VTT n Fnand and n FEV (Forschungsgeseschaft fr Energetechnk und
Verbrennungsmotoren GmbH) n Germany. In addton, numerous vehce tests wth both bended and
pure bodese proved that UPM BoVerno functoned as drop n fue (drect repacement for foss
dese) n a tested engnes and vehces, and reduced greenhouse gas emssons sgnfcanty.

Figure 3. UPM BoVerno s an nnovaton that serves as a non-food orgn drop-n fue for dese
wth 80% reducton n greenhouse gas emssons.
Biomass-to-liquid (BTL) biorefinery
UPM s nvestgatng the producton of varous advanced bofues. One of the ongong pro|ects s bo-
mass-to-qud (BTL) borefnery producng advanced bodese, UPM BoVerno, from energy wood.
Raw materi al
In BTL borefnery, UPM s pannng to produce hgh-quaty, advanced bodese from forest energy
wood. The raw materas to be used n the producton of UPMs bodese woud many consst of
sustanaby sourced energy wood: oggng resdues, woodchps, stumps and bark. UPM w not use
raw materas sutabe for food.
Gasifi cation technology
UPM has been deveopng gasfcaton technoogy for bodese producton wth Andrtz/Carbona. The
nta testng programme was competed at Gas Technoogy Insttute n the Unted States as panned.

124
Location
Locatng the BTL borefnery ad|acent to an exstng UPM pup and paper m w enhance the abty
to utze wood-based raw materas effcenty and mnmze the requred capta nvestments. Energy
ntegraton w offer further benefts. The possbe ocatons for a borefnery producng advanced
bodese are Rauma paper m n the cty of Rauma, Fnand and Strace paper m ste ocated n
Strasbourg, France. The envronmenta mpact assessment has been competed n Rauma and
started n Strasbourg.
EU' s NER300 grants
UPM has apped for EUs NER300 grants for BTL borefnery from Fnand (Rauma) and from France
(Strasbourg). Both appcatons were passed on to next step to European Investment Bank and UPM
has been shortsted n ther evauaton. UPM has announced that the BTL borefnery nvestment
decson w be made ony after the EUs grants are decded. EUs NER300 grant decsons are
expected on the second haf of 2012. In addton to an nvestment grant, the nvestment decson
w be sgnfcanty mpacted by the ong-term outook for wood prce and avaabty n the market.
The European Unons NER300 programme (New Entrants Reserve) s funded from the sae of
emsson aowances n Europe, .e. the fundng comes from the European companes who need to
buy emsson aowances for ther busnesses. The purpose of the programme s to fnance and
advance nnovatve new technoogy. The programme s aso one of the potca decsons targeted
for reducng Europes carbon footprnt. The amount of fundng avaabe s expected to be around
EUR 1.3 - EUR 1.5 bon.
EU 2020 targets create a demand for sustainable biofuels
The demand for bofues s expected to grow by approxmatey 7% a year n the EU. The target of
the EU s to ncrease the share of bofues n transport fues to 10% by the year 2020. In Fnand,
the correspondng target s even more chaengng wth an ncrease of 20%.
The EUs renewabe energy drectve (RED) favours advanced bofues, whch are produced
from gnoceuose, waste and resdue-based raw materas. Accordng to the drectve, these bofues
are doube counted UPMs bofues exceed the current and contnuousy tghtenng sustanabty
requrements set by both the EU and Fnand. when cacuatng the renewabe target. Thus 5% of
UPMs advanced bofues woud be regarded as 10% when countng the share of bofues n
transport.
UPM utses ts own deveopment work and sustanabe wood-based raw materas. As a resut
UPM produces a cost-compettve hgh quaty transport fue that truy decreases emssons and s
fuy compatbe wth todays vehces and fue dstrbuton systems. UPM borefnery n Lappeenranta
s the frst sgnfcant nvestment n a new and nnovatve producton facty n Fnand durng the
ongong transformaton of forest ndustry.
UPMs bofues exceed the current and contnuousy tghtenng sustanabty requrements set by
both the EU and Fnand. The annua producton of the Lappeenranta borefnery w contrbute
approxmatey one fourth of Fnands bofue target n transportaton fues f sod entrey on the
domestc market.
Scang up Borregaards BALI borefnery concept

125
Scaling up Borregaard's BAL biorefinery concept
Anders Sjde, Martin Lersch
Borregaard ndustries Ltd., P.O. Box 162, NO-1701 Sarpsborg, Norway
anders.sjode@borregaard.com
Abstract
Over the ast few decades Borregaard has evoved nto one of the words most advanced borefn-
eres n operaton. In recent years Borregaard has drected substanta resources nto deveopng
the BALI borefnery concept. The concept ncudes a sufte pretreatment process and yeds a
water soube gnn whch can easy be separated from the ceuose pup. The ceuose pup s
then enzymatcay hydroyzed n a nove process runnng at hgh tota sods concentratons. The
ow vscosty acheved aows a hgh throughput and the use of conventona equpment. Ths n
combnaton wth dentfed appcatons for a streams makes for an attractve process economy.
Borregaard has nvested 130 mon NOK to scae up the BALI concept to 1.2 t/day. The process
runs contnuousy and s fuy automated. Inta experences from scae up of the feedstock handng,
pretreatment and enzymatc hydroyss w be presented.

New Swedsh programme Ethano Processes - status and chaenges

126
New Swedish programme Ethanol Processes
status and challenges
Lars Vallander
Swedish Energy Agency P.O. Box 310, SE-631 04 Eskilstuna, Sweden
ntroduction
The Swedsh forest s a natura resource of great mportance and has been so for severa centures.
As much as 55 % of Sweden s covered wth forests. They have gven us raw matera to bud
houses, shps, provde fue to heat our homes, to make pup and paper products, to produce tar and
coke, the atter needed n ron and stee makng. The forests have aso provded us a andscape for
recreaton, wdfe and food. Wth ncreasng knowedge we have earnt to use the forest resource
for more and dfferent purposes.
We ve n a tme, when the chaenges and threats our panet faces today are manfod and often
reated. Resource depeton s comng nto focus more and more, be t o, natura gas, cean water,
mneras, fsh, bodversty and atogether a functonng ecosystem. The cmate probem s goba
and compex and to put t smpy, there s an urgent need to act now, f we serousy mean to as-
sume responsbty for provdng reasonabe vng condtons for vng creatures, who are |ust about
to enter ths word.
In ths context, renewabe raw materas are agreed by many to be one cornerstone for the
goba deveopment we see ahead of us. But ths has to be combned wth an effcent use of them
and a other resources. The word effcent shoud be understood as effcent n a goba context.
Wth these ntroductory words, I w now narrow down the perspectve to the theme of ths confer-
ence - bo refneres - and to the sub|ect of my presentaton, the new Swedsh Ethano programme.
Biorefineries and renewable raw materials
Even though the term bo refnery has appeared n the terature for a few decades, t s many
durng the ast ten years that bo refnng has attracted a great dea of attenton. There are severa
reasons for that:
- Pup and paper ndustry n Scandnava and North Amerca has met ncreased competton,
due to cheaper, fast-growng wood n southern countres.
- There s ess demand for certan paper products.
- Companes see a need to consder ther product portfoo and to deveop strateges and
pans for a more proftabe producton mx, whch can ncude new busness areas.
- Due to the cmate probem, governments and companes ook at ways of substtutng foss
raw materas to renewabe.
- Foss raw materas are fnte and are becomng depeted, whch s aso a reason to ntro-
duce renewabes as a substtute n manufacturng processes, n combnaton wth efforts to
mprove effcency n processng and to recover and reuse a knds of materas.
- Bo refneres offer one way to address these chaenges where a combnaton of dfferent
products can be made at one pace.
There are numerous defntons of a bo refnery. Common to some of them s that they pont out
three categores of products, .e. materas, energy carrers and chemcas.
Energy carrers ke eectrcty, dstrct heat, peets and process steam are we estabshed and
motor fues s a fary new member n ths group.


127
A perceved advantage of a bo refnery s that producton of varous products at one ste coud
resut n a more resource-effcent producton n terms of raw matera, energy and nfrastructure.
Previous Swedish ethanol programmes
Lookng back, Swedsh ethano research based on gnoceuosc raw materas started on a sma
scae n 1980. In the years 1993-2011 three ethano programme perods were executed n Sweden.
An mportant prerequste for the achevements obtaned has been the contnuous governmenta
support to ths research.
What were the ma|or chaenges and resuts durng ths perod?
- Understandng the bascs of hydroyss regardng hemceuose and ceuose. Intay the
focus was on hardwoods snce these materas are more easy attacked by the enzyme sys-
tems of wood-degradng org mcroorgansms.
- In the ast two decades, Swedsh ethano research has focused on softwood, whch s con-
sdered to be a more chaengng and recactrant raw matera.
- Ordnary sma-scae aboratory studes need to be verfed on a arger scae and the ndvd-
ua steps n the ethano process ne need to be studed together n varous process confgu-
ratons.
- Upscang a batch-wse aboratory process a coupe of hundred tmes to a contnuous pro-
cess ne n the pot pant has been a bg undertakng. To deveop the technoogy n pot
scae proved to be more dffcut and tme consumng than was antcpated n the begnnng.
- In the end, pot pant tras have to produce suffcenty good resuts, showng a perfor-
mance, whch s needed n a commerca process.
The outcome of these programmes ncudes varous types of resut:
- Technca progress regardng process chemstry, process technoogy and deveopment of
mcroorgansms
- Techno-economca: deveopment of process modes
- Creatng academc competence n severa research groups,
- Secure Inteectua property, such as patents
- Educatng peope to be empoyed by the ndustry
- Budng a versate research nfrastructure, where the arge aboratory-scae Process deve-
opment unt, PDU, n Lund and the Pot pant n rnskdsvk shoud be mentoned.
On the whoe, the goas set up n the three ethano research programmes have been accompshed.
The ethano pot pant has become a we -functonng unt, where contnuous operaton for severa
weeks of the whoe process ne have been demonstrated.
Laboratory resuts have been verfed n the PDU and n the pot pant.
Usng softwood, where the ma|or part of the carbohydrates conssts of 6-carbon sugars, hexoses,
tras n the ethano pot have verfed a yed of ethano, based on ncomng hexoses, at a eve of
70 % of the theoretca. Ethano yeds of as much as 80 % have been demonstrated n the PDU.
Fermentatons n cubc meter scae reguary gve an ethano concentraton of 4 weght-% (and
hgher) whch s needed to mt the steam demand n dstaton to an acceptabe eve.
In ater years, tras wth other raw materas have successfuy been run n the PDU and n the
pot, many agrcutura-based gnoceuosc materas.
Techno-economca modeng based on resuts acheved n the PDU and pot pant have pro-
duced nput data for up-scang to commerca pant sze.

128
The new Swedish Ethanol programme " Ethanol processes
In | une 2011 the Swedsh Energy Agency started a new four-year-ong ethano programme, whch
w go on to | une 2015. The annua governmenta fundng has ncreased over the years. It s cur-
renty around 30 mon SEK per year, wth a tota budget of 130 mon Swedsh kronor (SEK) for
the whoe programme perod, roughy equvaent to 16 mon Euro.
What are the present chaenges?
- The resuts obtaned n prevous programmes have many been concerned wth the ethano
process ne. But ethano s sedom the ony product from a pant. The new ethano pro-
gramme has been gven the name "Ethano processes" n order to address questons reated
to a wder concept where ethano from gnoceuose s |ust one output from a pant - for n-
stance a bo refnery.
- Ths wder scope opens the programme for concept wth other products as we. One aspect
of ths s System studes. How can a resource-effcent mutproducton pant (bo refnery)be
organzed?
- The programme s of course aso open for mprovng the ethano process ne. How can bet-
ter process effcency be acheved when sub|ect to hgher dry matter concentraton, ess
dosage of enzyme and yeast, whe st fufng process goas ke yed, productvty and
concentraton.
- Couped to the prevous pont, techno-economc modeng can aso have an mportant roe to
pay n defnng the ay-out of mutproduct pants.
- The economy of a process s of nterest to researchers, deveopers, fnancers and market.
However, cacuatons are hghy uncertan as ong as a process has not been mpemented
and run successfuy for a coupe of years n commerca scae. W an ethano process be
abe to compete wth other uses of the raw matera?
A constant chaenge has been how to make companes and fnancers nterested to engage n
deveopment and to nvest n ths fed. Ths s st a ma|or probem n Sweden and esewhere, even
though technoogy soutons have proven to be successfu n pot and demonstraton pants and are
consdered rpe for mpementaton.
Borefnery ntatves mpemented by Nppon Paper - torrefacton of wood bomass for co-frng n a
puverzed coa boer

129
Figure 1. Laboratory kn for torrefacton test.
Kn (5 L)

Eectrc heatng

Biorefinery initiatives implemented by Nippon Paper
torrefaction of wood biomass for co-firi ng in
a pul verized coal boil er
Hiroshi Ono, Hiroshi Shinkura, Tomonori Kawamata, Hiroyasu Ebinuma
Nippon Paper ndustries Co., Ltd.
Abstract
Nppon Paper Industres (NPI) has modfed ts carbonzaton pant for paper sudge nto a pot
torrefacton pant for wood bomass. The carbonzaton pant was operated at 700-800C and the
torrefacton pant was operated at 200-300C. NPI has operated the pot torrefacton pant durng
the perod from October 2011 to | anuary 2012 and conducted co-frng tests of torrefed wood bo-
mass n the puverzed coa boer at Yatsushro paper m ths March. In ths paper, physca prop-
ertes (especay for grndabty) of the torrefed wood bomass prepared n the pot torrefacton
pant are dscussed as we as the resuts of co-frng test of the torrefed wood bomass n the
Yatsushro paper m.
ntroduction
Torrefacton s a pre-treatment technoogy consstng of md pyroyss between 200-300C to make
bomass more sutabe for co-frng n a puverzed coa boer. In order to reduce carbon doxde
emsson n a coa boer, bomass s beng co-fred n many paces around the word. But the co-
frng rato s mted at a maxmum of 3%. Torrefacton can mprove grndabty and hydrophobcty
of wood bomass and ncrease the co-frng rato. However, no commerca torrefacton pant exsts
so far. In ths study, to proof the torrefacton concept, co-frng tests of torrefed bomass n a puver-
zed coa boer were carred out. Especay the grndabty of torrefed bomass has been nvest-
gated. Ths research was funded by New Energy Deveopment Organzaton n | apan.
Experimental
Laboratory torrefaction
A aboratory kn equpped wth a thermo-
coupe measurng the torrefacton tempera-
ture was used. The kn sze was about 5 L
and 20 g of sampe was torrefed. | apanese
cedar bark ground usng a hammer m nto
szes smaer than 50 mm was used for the
torrefacton experments. The sampe was
dred from 50% to 0% mosture content and
then torrefed n the aboratory kn. Torre-
facton temperature was set to be n the
range from 225 to 300C and the resdence
tme was 30 mnutes. Ntrogen was purged
nto the kn durng torrefacton to ensure the
absence of oxygen. Mass and energy yed
were measured. Hardgrove Grndabty Index
(HGI) was evauated.

puverzed coa boer

130

Torrefacton gas exts and combustng wth fue o burner
Pi lot torrefaction pl ant
A commerca carbonzaton pant for paper sudge was modfed nto a pot torrefacton pant for
wood bomass. The maxmum nput rate of the pot torrefacton pant was 1 000 kg/h. The process
dagram of the pot torrefacton pant s shown n Fgure 2. | apanese cedar bark peets produced n
the Forest Energy Kadokawa co. were used for torrefacton. | apanese cedar bark peets were
dred usng a drum dryer and the mosture content of peets became ess than 10%. Dred peets
were torrefed through an Anter kn (Hroshma gas techno servce co.) whch has severa exts of
torrefacton gas whch can combust wth the fue o burner. Temperature nsde the Anter kn was
decreased from 700-800C for carbonzaton to 200-300C for torrefacton. The resdence tme of
drum dryer was 15 mnutes and that of the kn for torrefacton was 30 mnutes. Torrefed | apanese
cedar bark peets were cooed through the coong kn for 10 mnutes and temperature of the pe-
ets was ess than 50C to prevent sef-gnton. Mass and energy yed were cacuated by nput and
output mass and caore vaues. Propertes of torrefed peets such as tendency of cause dust ex-
poson were evauated.

Figure 2. Process dagram of pot torrefacton pant.

Figure 3. Schematcs of anter kn wth severa exts of torrefacton gas.
Pilot roller mill grindability of torrefied wood biomass
Grndabty mprovement after torrefacton of wood bomass s the most mportant property.
Hardgrove Grndabty Index (HGI), whch s a we-known anayss technque to determne the
grndabty of coa, produces very conservatve resuts for torrefed wood bomass compared to
coa. The hgher HGI vaue the better the grndabty. Bergan et al. (2005) deveoped new way to
determne the grndabty of torrefed wood bomass usng a heavy duty cuttng m and measurng
puverzed coa boer

131
the eectrc power consumpton from coarse partces to 0.2 mm partce sze. However, puverzed
coa boer power pants nstaed roer m for grndng coa s not a cuttng m and a cuttng m
may get favourabe grndabty resuts for resstant fbrous wood bomass. In ths study, a pot roer
m (Kotobuk RM10) was prepared to measure the eectrc power consumpton from coarse part-
ces to 0.076 mm partce sze (200 mesh screen) of torrefed wood bomass and coa.

Figure 4. Pot roer m for grndabty evauaton of torrefed bomass.
Co-firing test in a pulverized coal boiler
Yatsushro paper m has a puverzed coa boer to produce eectrcty and steam for paper pro-
ducton, and ses surpus eectrcty to outsde. Three roer ms (IHI co.), whch have an average
grndng rate of 11.1 t/h of coa for each, were n seres wth a puverzed coa boer (Fgure 5). In
the coa stock yard, torrefed | apanese cedar bark peets were mxed wth Austraan Wambo coa
whch had a HGI of 51, and were carred to Yatsushro paper m. The mxng percentage of torre-
fed | apanese cedar bark peets to the coa were 5%, 10%, 15% and 20% for the co-frng test.
Torrefed peets and coa mxture was fed nto one of three roer ms. The roer m grndabty
such as eectrc power consumpton was observed n the co-frng test.

Figure 5. Process dagram of puverzed coa boer n Yatsushro paper m.
a) Overvew of pot roer m b) Insde of roer m
puverzed coa boer

132
Results
Laboratory torrefaction
The effect of torrefacton temperature on mass and energy yed of | apanese cedar bark are shown
on the eft hand sde of Fgure 6. Mass and energy yed of | apanese cedar bark decreased as the
temperature ncreased. Energy yed was about 10 ponts hgher than mass yed n the temperature
range from 225C to 300C. HGI of torrefed | apanese cedar bark s shown n rght hand sde of
Fgure 6. HGI of | apanese cedar bark before torrefacton was 17. After torrefacton for 30 mnutes,
HGI of | apanese cedar bark became about 50 n the temperature range from 225C to 300C. In
the puverzed coa boer of NPI, the coa whch HGI s from 40 to 60 and ths s acceptabe for
grndabty. In terms of grndabty, torrefacton temperature at 225C woud be suffcent.

Figure 6. Mass and energy yed of | apanese cedar bark wth torrefacton temperature.
Pi lot torrefaction pl ant
In the pot torrefacton pant, 900 kg/t of | apanese cedar bark peets were fed nto the torrefacton
process whch operated for 6 hours per day. Fnay, 60 tons of torrefed | apanese cedar bark peets
were produced n an operaton astng 3 week. Torrefacton temperature was 260C as measured
by the thermocoupe ftted nsde of anter kn.
puverzed coa boer

133
Table 1. Propertes of torrefed | apanese cedar bark peets compared to a coa.

Mass and energy yed were about 90% and 96%, respectvey. HGI of | apanese cedar bark peets
was 25. After torrefacton, HGI of torrefed | apanese cedar bark peets had ncreased to 35. Prop-
ertes of torrefed | apanese cedar bark peets are shown n Tabe 1. Except for buk densty, the
propertes of torrefed peets were amost the same as a coa. HGI of torrefed peets were sghty
ower than that of coa.
Pilot roller mill grindability of torrefied biomass
Austraan Wambo coa (HGI =51) was fed nto the pot roer m at the rate of 5 kg/mn. After 10
mnutes, the pot roer m reached a steady state and ground Wambo coa bown at the same rate
as the feedng rate .e. 5 kg/mn. After 40 mnutes, the feed of coa nto roer m was stopped and
then the remanng coa was ground and bown out. In ths experment, the feedng rate of sampes
was fxed at 5 kg/mn and eectrc power consumpton at steady state was evauated.
Indonesan Senakn coa (HGI =40) consumed about 40% hgher eectrc power on average than
that of Wambo coa because of ts ower HGI whch means harder grndabty. When Wambo coa
contanng untorrefed 10% | apanese cedar bark peets was ground n a pot roer m, the eectrc
power consumpton of ths matera on average became about 30% hgher than that of 100% Wam-
bo coa. On the other hand, when Wambo coa contanng 10% torrefed | apanese cedar bark pe-
ets was ground n the pot roer m, the eectrc power consumpton of ths matera became a-
most the same as that of 100% Wambo coa. The grndabty of | apanese cedar bark peets was
mproved dramatcay by torrefacton. However, when the percentage of torrefed | apanese cedar
bark peets was ncreased to 20% n a mxture wth Wambo coa, the eectrc power consumpton n
average became about 20% hgher than that of 100% Wambo coa (Fgure 7).
| apanese cedar
bark peets
Torrefed
| apanese cedar
bark peets
Coa
Buk densty
g/cm
3
0.60 0.55 0.80
HGI 25 35 40 - 60
Ignton temperarure
1)
465 456 480 - 530

Lower exposve mt
2)
g/m
3
120 80 60
Sef-exothermcty
3)
130 124 147

1) ASTM E 659
2) | IS Z 8818, SAP12-10
3) The temperature of 1 L sampe, whch was eft at ambent temperature of 120
for 24 hours
puverzed coa boer

134

Figure 7. Power consumpton of pot roer m grndng torrefed bomass and coa.
Co-firing test in a pulverized coal boiler
The mng amperage of co-frng tests s shown n Fgure 8. When the Wambo coa (HGI =51)
contanng 10% of torrefed | apanese cedar bark peets (HGI =35) was ground troube-free n one
m, mng amperage was about 8% hgher than that of 100% Wambo coa wthout any for 6 hours.
On the other hand, when the Wambo coa contanng 20% of | apanese cedar bark peets was
ground n one roer m, mng amperage became about 30% hgher than that of 100% Wambo
coa. These resuts ndcated that grndabty of torrefed bomass has to be cose to the coa for
ncreasng co-frng rato of torrefed bomass.

Figure 8. Power consumpton of roer m at co-frng test n Yatsushro paper m.
a) Co-frng test of 10 % torrefed peets

b) Co-frng test of 20 % torrefed peets

puverzed coa boer

135
Conclusions
NPI has modfed a carbonzaton pant for paper sudge nto a pot torrefacton pant for wood bo-
mass and produced 60 tons of torrefed | apanese cedar bark peets. In the Yatsushro paper m,
Wambo coa contanng 20% of | apanese cedar bark peets was ground n one roer m and co-
fred n a puverzed coa boer. In ths test, eectrc power consumpton n one roer m ncreased
about 30%. Therefore, mprovement of grndabty by torrefacton n hgher temperature woud be
requred for ncreasng percentage of co-grndng rato of torrefed | apanese cedar bark peets.
References
1. Bergman, P.C.A, Boersma, A.R., Zwart, R.W.R, Ke, | .H.A. 2005. Torrefacton for bomass co-
frng n exstng coa-fred power statons, ECN-C-05-013.
2. Bergman, P.C.A, Ke, | .H.A. 2005. Torrefacton for bomass upgradng, ECN-RX-05-180.
3. Koukous, E.G., Mavrokoukouaks, | ., Abatzogou, N. 1982. Energy densfcaton of bomass.
Proc. 1
st
Natona Conf. On Soft Energy Forms, Thessaonk.
4. Ameda, G., Brto, | .O., Perre, P. 2000. Aternatons n energy propertes of eucayptus wood
and bark sub|ected to torrefacton: The potenta of mass oss as a synthetc ndcator. Bo-
resource Technoogy 101(24), pp. 9778-9784.
Pressurzed entraned fow gasfcaton of bomass powder - nta resuts from pot pant
experments

136
Pressurized entrained flow gasification of biomass
powder initial results from pilot plant experiments
Fredrik Weiland
1, 2
, Henrik Wiinikka
1, 2
, Henry Hedman
1
, Magnus Marklund
1
, Rikard Gebart
2

1
Energy Technology Centre, Pite, Sweden
2
Division of Energy Science, Lule University of Technology, Lule, Sweden
Corresponding author email: fredrik.weiland@etcpitea.se
Abstract
Drect gasfcaton of wood resdues based on a pressurzed and oxygen bown entraned fow con-
cept foowed by cataytc converson of the resutng syngas s an attractve aternatve for produc-
ton of renewabe transportaton fue. In order to acceerate the technoogy deveopment, a pot
pant (0.5 MWth at 6 bar) for oxygen bown Pressurzed Entraned-fow Bomass Gasfcaton
(PEBG) has so far been operated for -150 h at ETC n Pte, Sweden. The technoogy concept s
based on a hgh temperature entraned fow gasfcaton process, whch shoud gasfy bomass
powders to a syngas wth ow tar, soot and other genera hydrocarbon contents. So far, reatvey
fne powders produced from stem wood and bark has been gasfed wth good resuts consderng
the resutng carbon converson and gas composton. The reactor process temperatures have been
vared n the nterva 1 100-1 300C at oxygen excess ratos up to 0.45, whch resuted n reatvey
ow H
2
/CO moar ratos (around -0.5) n the fna syngas composton (wth no steam added). Fur-
thermore, the effect of usng ntrogen or carbon doxde as process nert gas was nvestgated.
Durng the PEBG experments, the pant was operated at 2 bar and a therma fue oad of 0.2 MWth.
ntroduction
It s estmated that the tota word energy demand w ncrease by 40% over the next 20 years and
one of the fastest growng sector s the transportaton sector |1|. Oxygen bown hgh temperature
entraned fow gasfcaton s one aternatve route for syngas generaton and transportaton fue
synthess from bomass. Producton of synthetc fue or chemcas from coa gasfcaton s a proven
technoogy. However, commerca bomass gasfcaton pants for transportaton fue producton are
st under deveopment |2-3|. Pot and demonstraton scae Methano- and BoDME producton
have been demonstrated from back quor gasfcaton |4-5|.
To ncrease the knowedge regardng fue synthess from hgh-temperature gasfcaton of woody
bomass, severa ssues have to be nvestgated pror to process commercazaton.
In the present study, an oxygen bown pot scae Pressurzed Entraned-fow Bomass Gasfca-
ton pant (PEBG) was desgned, constructed and operated. The man chaenges for a ong term
success wth ths type of process nvove effcent fue preparaton, robust fue feedng, controed
ash/sag handng, durabty of contanment materas, safe pant operaton and to obtan an optma
syngas composton wth hgh cod gas effcency. The ob|ectve was to provde vauabe nformaton
to the understandng of auto-therma entraned fow bomass gasfcaton. The genera am wth ths
pro|ect was to characterze the process and evauate whether bomass resdues can be utzed as
raw matera n the gasfer. Ths paper provdes resuts from gasfcaton experments wth spruce
bark, bark mxture and stem wood bomass. The focus was to evauate the syngas quaty wth
respect to down-stream synthess of motor fues.

experments

137
Experimental
Pilot plant
The PEBG pant was desgned for hgh process temperature (1 200-1 500C), oxygen bown, sag-
gng gasfcaton of bomass wth a therma throughput of maxmum 1 MW
th
and pressures up to 11
bar. A schematc process fow dagram s shown n Fgure 1.
Fue powder was prepared by mng n a hammer m and the partce sze dstrbuton was con-
troed by the hammer m seve sze before the fue powder was transported to the ock hoppers.
Fue feedng was accompshed by a twn based mechanca ock hopper system where the twn
hoppers (1 m
3
) were sequentay fed and aternatey operated n order to keep the pressurzed
process n contnuous operaton. An Auger screw feeder controed the fue feedng rate. A mxture
of oxygen and nert gas was added through the oxdant regster of the burner. Both gas streams
were controed by mass fow controers. The gasfer conssted of a ceramc ned reactor (nner
dameter 0.52 m and the ength of vertca reactor wa 1.67 m) foowed by a bubbng quench for
syngas coong and smet/partce separaton.
Pror to process start-up, the reactor ceramcs was heated by an eectrca heater mounted at the
reactor centre ne. The heater was removed before the gasfcaton process was started. Thermo-
coupes measured the process temperature at dfferent ocatons nsde the reactor.
A water cooed ntrogen purged camera probe, mounted on top of the reactor and sghty tted
towards the reactor axs, vsuazed the fame and the nteror of the reactor. Ths was a quatatvey
vauabe too for operaton, especay at process start up. The generated syngas was cooed down
beow 100C by water sprays at two dfferent eves n the quench tube. Partces (.e. ash and char)
are coected ether at the quench bottom or n the sedmentaton vesse downstream the quench
water outet.
System pressure was controed by a reguatng vave on the syngas outet after the quench. The
man syngas stream was ncnerated n the fare on top of the budng. A LPG (Lght Petroeum Gas)
pot fame was used as a contnuous gnton source.

Figure 1. Schematc process fow dagram of the PEBG pant.
TC
TC
TC
TC
TC
Cam
TC TC
Lock
hopper 1
Lock
hopper 2
Fuel feeder
Reactor
Quench
Pressure
regulator
Flare
Pilot flare
Quench spray registers
experments

138
Operational conditions
The fues used n ths study were spruce bark, bark mxture from the Smurft Kappa Kraftner paper
m and pne stem wood. The fues utmate anayses are shown n Tabe 1.
Table 1. Utmate anayss of the dfferent fues.
Ult imate analysis (wt % dry) Ash C H O N S
Spruce bark 4.2 52.2 5.6 37.5 0.41 0.037
Bark mx 2.2 52.6 6.4 38.3 0.38 0.026
Stem wood 0.4 50.9 6.3 42.4 0.10 <0.01

Tabe 2 summarzes the gasfcaton condtons n ths study. As can be found n Tabe 2, spruce
bark powder was produced wth 1.0 mm screen sze nstaed n the hammer m, whereas the other
fue powders were produced wth 0.75 mm hammer m screen sze. Ths was done n order to
acheve smar partce sze dstrbutons for the dfferent fues.
The oxygen excess rato (ambda, ) was defned as the rato between the actuay supped oxygen
and the stochometrc oxygen demand (for compete combuston).
Syngas characteri sati on
Syngas sampng was performed by ettng a sma sp stream of the produced syngas fow from the
syngas ppe, through partcuate remova equpment foowed by a water condenser. The dred
syngas was then anayzed consecutvey by a FTIR nstrument and a GC.
The concentraton and sze dstrbuton of partcuates n the syngas was measured by a Dekat
Low Pressure Impactor (DLPI).
Table 2. Expermenta settngs.
Parameter Unit Spruce Bark Bark mi x Stem wood Stem wood + CO
2

Fue sze
a)
mm 1.0 0.75 0.75 0.75
Fue feedng rate kg/h 40 40 40 40
Tota Ntrogen net kg/h 13 16 14 0
Oxygen net kg/h 24 27 25 27
Oxygen excess rato () - 0.44 0.45 0.44 0.48
System pressure bar 2 2 2 2
Ouench water eve
b)
% 30 30 30 30
a)
Fue sze fgure corresponds to the seve sze used n the hammer m.
b)
Bubbng quench f the water eve >20%.
Exampe of reactor process temperature profe over tme from a typca experment s presented n
Fgure 2. The graph show the average md reactor process temperature (eft ordnate) and CO, N
2

and H
2
dry product gas composton n mo-% (rght ordnate). The reactor was eectrcay heated to
experments

139
approxmatey 1 020C, after whch the heater was removed and the gasfer ntrogen purged. After
a frst process start-up and approxmatey 30 mnutes of operaton, the process had to be shut-
down and re-purged wth ntrogen. After the second start-up the pant was contnuousy operated
for 6 h 50 mn. Durng the frst 90 mnutes after the second start-up, the operated was 0.50 n
order to qucky reach a desred hgh process temperature (>1 200C). A mnor process tempera-
ture dp n an otherwse contnuous temperature ncrease occurred when the operated was re-
duced to 0.44. Between process tme 310 mn and 470 mn the temperature ncrease was approx-
matey 20C/h. The gas composton was stabzed at the new process condtons approxmatey 30
mnutes after the -reducton. Hence, the gas composton seems unaffected of temperature wthn
the range 1 190-1 250C. The ragged part of the curves, .e. from process tme 470 mn and for-
ward n Fgure 2, arose from rreguar ntrogen addton to the fue feedng system. Immedatey after
the expermenta run a arge voume of ntrogen gas was fushed through the reactor for purgng the
reactor system resutng n a sharp temperature drop and ntrogen peak n Fgure 2.
The resutng reactor temperatures and dry gas compostons are presented n Tabe 3 for the
dfferent campagns. For comparson, approxmate gas composton from back quor gasfcaton
(BLG) descrbed by |6| s aso presented n the tabe.

Figure 2. Process temperature profe (eft ordnate) together wth the resutng CO, N
2
and H
2
con-
centraton profes (rght ordnate) from a typca experment.
experments

140
Table 3. Resutng reactor temperatures and gas compostons (dry gas) for the dfferent campagns.
Back quor gasfcaton (BLG) gas composton added as a comparson.
Unit Spruce bark Bark mi x Stem wood Stem wood + CO
2
BLG
Reactor temperature C 1 100-1 145 1 190-1 230 1 190-1 250 1 200-1 220 -1 050
Dry gas composition
H
2
mo% 22.7 23.6 22.7 21.5 -27
N
2
mo% 17.7 17.1 18.1 0.3 -21
CO mo% 40.1 42.8 39.8 47.5 -21
CO
2
mo% 15.8 13.7 16.7 29.7 -28
CH
4
mo% 1.9 1.6 1.9 1.6 -1
C
2
H
4
mo% 0.1 <0.1 0.1 0.1 n.a.
C
2
H
2
mo% 0.1 0.1 0.2 0.2 n.a.
H
2
S mo% - - - - -1
Syngas LHV M| /kg
dry
7.82 8.25 7.70 7.48 5.7
H
2
/CO mo% 0.57 0.55 0.57 0.45 1.3

Gasfcaton of wet bomass fues, e.g. back quor, generates a syngas wth hgher H
2
/CO rato
compared to dry bomass gasfcaton. Smutaneousy the process temperature becomes ower.
Introducng steam drecty to the PEBG gasfer woud most probaby have the same effect on the
syngas quaty and process temperature.
The CO
2
campagn resuted n ncreased CO and decreased H
2
content of the syngas, ndcatng
that the ncreased amount of CO
2
promotes the formaton of CO and H
2
O by the reversed water-
gas shft reacton.
Conclusions
Oxygen bown entraned fow gasfcaton of bark, bark mxture and stem wood powder was
verfed.
Carbon doxde (CO
2
) was successfuy used as nert gas to the process nstead of ntrogen (N
2
).
The CO concentraton n the syngas was reatvey hgh whch resuted n a H
2
/CO rato
around 0.5. Ths mpes that shftng the syngas towards hgher H
2
/CO rato s necessary f
the syngas s ntended for cataytc synthess of motor fues such as DME or Fscher-
Tropsch dese.
Acknowledgement
The fnanca support from the Swedsh Energy Agency, IVAB, Sveaskog, and Smurft Kappa Kraft-
ner s thankfuy acknowedged. Parta fundng aso came from the Bo4Energy coaboraton and
experments

141
the Swedsh Bomass Gasfcaton Centre. Thanks aso for the exceent coaboraton wth IVAB
and Lue Unversty of Technoogy.
References
1. Word Energy Counc. Poces for the future - 2011 Assessment of country energy and cmate
poces |PDF|. http://www.wordenergy.org/documents/wec_2011_assessment_of_energy_
and_cmate_poces.pdf. (Accessed May 24, 2012.)
2. Swanson, R.M., Paton, A., Satro, | .A., Brown, R.C. 2010. Techno-economc anayss of bo-
mass-to-quds producton based on gasfcaton. Fue 89(Supp. 1), pp. S11-S19.
3. Zhang, W. 2010. Automotve fues from bomass va gasfcaton. Fue Process Techno 91(8),
pp. 866-876.
4. Hggstrm, C., hrman, O., Rownagh, A., Hedund, | ., Gebart, R. 2012. Cataytc methano
synthess va back quor gasfcaton. Fue Process Techno 94(1), pp. 10-15.
5. Granberg, F., Nevng, H., Landv, I. 2010. Producton of dmethy ether (DME) from back quor
for use n heavy duty trucks.
6. hrman, O., Hggstrm, C., Wnkka, H., Hedund, | ., Gebart, R. 2012. Anayss of trace com-
ponents n synthess gas generated by back quor gasfcaton. Fue 102(7), pp. 173-179.
Green Fue Nordc - The Smart Way: Utsng RTP technoogy to produce sustanabe 2nd
generaton bo-o from oca feedstocks

142
Green Fuel Nordi c The Smart Way: Util isi ng RTP
technol ogy to produce sustainable 2
nd
generation
bio-oil from local feedstocks
Timo Saarelainen, Jerkko Starck
Green Fuel Nordic Oy
Abstract
Transtonng to a ow-carbon economy s one of the ma|or goba megatrends of our tme. Ths
deveopment trend unocks new busness opportuntes for open-mnded, responsbe companes
that have operatons based on e.g. technoogy deveopments everagng nnovatve, renewabe raw
materas or on the commerca mpementaton of these technooges.
Green Fue Nordc Oy s a Fnnsh borefnng company. Companys busness dea s to utze
the aready commercay proven RTP technoogy for producton of second-generaton bo-o
from oca, renewabe forest-based bomass.
The Rapd Therma Process (RTPTM) unt s at the core of the rapd pyroyss-based borefnery.
Bomass s fed nto the reactor and then gasfed by a crcuatng fudzed bed of hot matera
(sand). The gas that s generated s ed to a cycone, where the bed matera and char are mechan-
cay separated from the gas stream. The gas moves from the cycone nto a condenser, where t s
cooed and condensed nto bo-o. The off-take s a qud, ow-carbon and sufur-free bo-o that
can drecty repace ght and heavy fue o n renewabe energy appcatons.
Operating environment for renewable liquid biofuels
Dependence on exhaustbe, non-renewabe foss natura resources and the cmate change
caused by ther use are sgnfcant forces drvng potca, soca and busness deveopment. Trans-
tonng to a ow-carbon economy s one of the ma|or goba megatrends of our tme. Reducng ener-
gy consumpton and repacng the use of foss natura resources wth renewabe raw materas are
mportant means for reazng ths deveopment process.
The am to reduce energy consumpton s very chaengng. The energy need n deveopng
economes w grow as ndustrazaton ncreases and the consumpton by popuatons wth rsng
affuence grows. As popuaton growth contnues, a shortage of food w emerge and food prces
w rse. The food shortage can be partay attrbutabe to envronmenta dsasters and the ndustra
utzaton of the food chans raw materas for non-food producton.
Dependency on foss o s reated to ts utzaton not ony as an energy source and fue for
transportaton, but aso as a raw matera for chemca ndustry products ke pastcs.
The scarcty of foss o that can be utzed cost-effectvey ncreases ts prce. At the same tme,
the compettveness of new bo-os s mprovng, and progress s beng made n the deveopment
efforts to utze them n appcatons beyond energy producton, e.g. n the chemca ndustry. The
CO
2
-neutraty of second-generaton bo-based fues, emnatng the need for CO
2
emssons aow-
ances, aso boosts compettveness.
Ths deveopment trend unocks new busness opportuntes for open-mnded, responsbe com-
panes that have operatons based on e.g. technoogy deveopments everagng nnovatve, renew-
abe raw materas or on the commerca mpementaton of these technooges.
The EUs ntenton of mtgatng cmate change has ed to severa drectves and ncentves gud-
ng the actvtes of member countres. These ncude the so-caed 20-20-20 target and the reated
Renewabe Energy Sources (RES) target of 38% for Fnand. They unock attractve busness op-
portuntes for renewabe bo-o n Fnand and esewhere n Europe.
The growng forest assets aso favor Fnand as a ocaton for borefneres. The growth of we
managed forests sgnfcanty exceeds the ndustra use of sustanaby utzabe wood. The con-


143
ventona forest ndustrys structura dstress aso reeases more wood for new types of appcatons,
e.g. for use as feedstock for borefneres.
Green Fuel Nordic Oy
Green Fue Nordc Oy s a Fnnsh borefnng company. Its busness concept s based on utzng
commercay proven, nnovatve RTP technoogy to produce second-generaton bo-o.
Utzng exstng technoogy acceerates the start-up of refnery operatons and the commsson-
ng of commerca bo-o producton and t enabes dstrbuted energy producton. In the near future,
the company pans on budng severa borefneres cose to Fnnsh feedstock. In dong so, t s
contrbutng to the achevement of the targets set for Fnands renewabe energy producton and
supportng energy sef-suffcency.
The chosen technoogy can be used to produce qud, ow-carbon and sufur-free bo-o from o-
ca, renewabe forest-based bomass. Bo-o can be utzed drecty n ndustra and muncpa
eectrcty and heat producton, repacng ght and heavy fue o.
The Smart Way
The need to bud an ncreasngy ower-carbon socety that s ess dependent on foss energy
sources w grow the demand for renewabe bofues, among other thngs. Ths strong deveopment
path s aso one of the drvers of Green Fue Nordcs bo-o refnng busness. Another sgnfcant
drver s the decson to utze exstng, commercay proven technoogy.
Ths RTPTM technoogy can be used to produce second-generaton qud, sufur-free bo-o
from oca, renewabe forest-based bomass. Fnands sustanaby managed and wdey certfed
forests grow over 100 mon cubc meters per year. Industra wood use amounts to about 50 m-
on cubc meters per year. However, sustanabe use woud aow the utzaton of 70-75 mon
cubc meters of wood on a yeary eve.
So there s no shortage of forest bomass sutabe for bo-o producton, especay snce the
conventona forest ndustry s not ncreasng ts use of wood n Fnand. RTP technoogy aso
makes t possbe to use sawm and pup ndustry by-products as feedstock.
Green Fue Nordcs borefnery nvestments support dstrbuted energy producton, whch s stra-
tegcay mportant for Fnand, and strengthen energy sef-suffcency. Moreover, the companys
operatons support the achevement of Fnands RES target. At the same tme, t offers empoy-
ment opportuntes for oca communtes affected by forest ndustry restructurng as we as a new,
oca refnng path for forest bomass.
The storage and transportaton propertes of RTP Green Fue bo-o support fexbe energy
dstrbuton.
Bo-o can be utzed drecty n ndustra and muncpa eectrcty and heat producton, repac-
ng ght and heavy fue o. Emergng aongsde of these appcatons s the use of bo-o to power
marne dese engnes.
In the near future, t w be possbe to upgrade bo-o aso nto products comparabe to norma
transportaton fues. Interestng appcatons n the onger term are found n the chemca ndustry.

144

Figure 1. Some man steps of the Smart Way of Green Fue Nordc Oy.
Renewable, local feedstock
Fnands sustanaby managed and wdey certfed forests grow more than 100 mon cubc meters
per year. Industry uses about 50 mon cubc meters of wood annuay. Sustanabe use woud
enabe a sgnfcanty hgher voume of wood to be used, .e. ndustra utzaton of 70-75 mon
cubc meters annuay.

Figure 2. Forest baance n Fnand 1960-2011. Sources: Meta, Fnnsh Forest Industres.

145
The raw matera Green Fue Nordc uses for bo-o s renewabe bomass drecty from forests or n the
form of wood-based by-products of sawms and the pup ndustry. Bo-o refned usng RTP technoo-
gy s a second-generaton qud bofue that doesnt use any raw materas from the food chan.
Bo-o producton s a new and sustanabe refnng path to put the yed of Fnnsh forests to
good use. Ths s partcuary sgnfcant n the communtes ht by structura changes n the conven-
tona forest ndustry and where the forest has aways been a sgnfcant source of |obs and ncome.
RTP
TM
Production Technology
Green Fue Nordc Oys bo-o producton process conssts of severa parts that together form a
functonng borefnery. In the borefnery, renewabe wood-based raw matera s converted nto
second-generaton bo-o.

Figure 3. Green Fue Nordcs RTP
TM
producton process.
The Rapd Therma Process unt s at the core of the rapd pyroyss-based borefnery and s where
the preprocessed bomass s converted nto bo-o. Bo-mass that has been preprocessed to the
correct partce sze and mosture content s fed nto the reactor and then gasfed by a crcuatng
fudzed bed of hot matera (sand). The gasfcaton takes pace n vrtuay oxygen-free condtons
and thus no combuston occurs.
The gas that s generated s ed to a cycone, where the bed matera and char are mechancay
separated from the gas stream. The gas moves from the cycone nto a condenser, where t s cooed
and condensed nto bo-o. Fnay, the bo-o produced s ftered before extng the RTP unt.
The char (bocoa) that s produced as a by-product returns from the cycone to the boer to heat
the reactors bed matera; ths s where t s burned and generates the therma energy requred by
the process. The product gas generated as a by-product n the condensng process s used n the
dryng of the bomass.

146
Before reachng the RTP unt, the bomass s processed nto the correct partce sze and mos-
ture content. Feedstock processng requres numerous screens and grndng equpment. Dryng
takes pace n a dryng drum that uses the therma energy of the RTP unts hot fue gases. After
dryng, the most fue gas s ed to the fue-gas scrubber, where the ma|orty of the envronmentay
harmfu substances are separated from the fue gas.
The ftered bo-o produced n the RTP unt s fed nto day tanks and the quaty s anayzed be-
fore beng pped to storage tanks.
RTP
TM
Green Fuel Applications
The man appcatons for qud bofue are ndustra boers, dstrct heatng and me kns that can
utze bo-o wth ony mnor modfcatons to the exstng systems. Other feasbe appcatons are
marne appcatons, partcuary sow- and medum-speed dese engnes. Future appcatons can
be found n upgradng bo-o nto transportaton fue and extracton of chemcas for the use n
chemca ndustry, pharmaceutcas, cosmetcs, and many more.
References
1. Brdgwater, A., Meer, D., Raden, D. 1999. An overvew of fast pyroyss of bomass. Organc
Geochemstry 30, pp. 1479-1493.
2. Brdgwater, A. 2004. Bomass Fast Pyroyss. Revew paper. BIBLID 0354-9836, 8, pp. 21-49.
3. Oasmaa, A., Kuoppaa, E. 2003. Fast Pyroyss of Forestry Resdue. 3. Storage Stabty of Lqud
Fue. Energy & Fues 17, pp. 1075-1084.
Towards ndustra producton of mcroba o for hgh quaty traffc fues

147
Towards industrial production of mi crobial oil for
high quality traffic fuels
Perttu Koskinen
1
, Miia Mujunen
1
, Simo Laakso
2
, Ossi Pastinen
2
, Petri Lehmus
1

1
Neste Oil Oyj
2
Aalto University, School of Chemical Technology
Abstract
Neste O s word-wde the argest producer of paraffnc hydrotreated vegetabe os (HVO) wth
annuay 2 mon tonnes NExBTL renewabe fue producton capacty. A cear prorty of the com-
panys strategy s to expand the raw matera base of ts NExBTL refnng process wth sustanabe
and commercay feasbe feedstock from resdues and sde streams. Waste and resdue-based
mcroba o has been n recent years the ob|ect of ntensve research efforts n a cose co-operaton
between Neste O and Aato Unversty, where feasbty of mcroba o as a feed for the NExBTL
process has been demonstrated n aboratory and bench scae. Mcroba o technoogy aows
effcent converson of waste and resdue materas, such as gnoceuosc materas, nto o. As a
step towards ndustra producton of mcroba o the company decded n ate 2011 to nvest nto a
mcroba o pot facty, whch serves to generate necessary data for desgn of a commerca scae
reference pant. Ths proceedng summarzes some key features of the mcroba o concept and
gves an update from the path towards ts ndustrazaton.
Broadening the feedstock base
Materas cassfed as waste, resdues, or by-products accounted for 41% of the renewabe raw
materas used by Neste O n 2011 for producton of renewabe HVO-type NExBTL dese. Increas-
ng the use of waste, resdues and by-products for renewabe fue producton beyond 50% s a
strategc ob|ectve set by the company and strvng for t requres strong R&D efforts.
Severa prerequstes have to be fufed when seectng potenta new raw materas for renewa-
be dese producton. Avaabty of the raw matera s an mportant requrement for arge-scae
ndustra producton. Sustanabty crtera are of ma|or mportance and ncude carbon and water
footprnt, and use effcency and nutrent use. Technca and commerca feasbty of the raw mate-
ra are aso key requrements for ndustra use.
Microbial oil research
Lab and bench-scal e demonstrati on
Interest towards deveopng mcroba o producton from gnoceuosc raw materas rose remark-
aby when n a co-operaton wth the bochemstry group of Aato Unversty t was demonstrated
that mcrobes convert gnoceuosc sugar nto an o whch can be used to produce NExBTL de-
se. Furthermore, the converson process was found to be very effectve as sugars from both ceu-
ose and hemceuose were equay effectvey converted nto mcroba o, whch ncreases the
overa utzaton of a gnoceuose raw matera.
Mcroba o technoogy utzes speca mcroorgansms that are abe to produce and accumuate
hgh amounts of o when cutvated on waste and resdue materas. Mcroba o producton s
performed n fermentor-type boreactors and the process concepts are beng deveoped for m-
proved mcrobe and o productvty. Fgure 1 shows o-rch funga ces, whch n a coupe of days
producton cyce can produce o n quanttes up to 80% from ther ce dry weght.
Mcroba o conssts of trgycerdes resembng thus vegetabe os. Comparson of the fatty acd
dstrbuton of mcroba o wth rapeseed o and especay wth pam o (Fgure 2) shows that from


148
refnng pont of vew mcroba o s a drop-n souton for the NExBTL process. Fatty acds n m-
croba o are hghy saturated (ow odne number) makng t hghy sutabe for producton of paraf-
fnc fues such as NExBTL renewabe fues (Tabe 1).

Figure 1. O-rch funga ces; the whte spots nsde ce hyphae are o (>50% o from ce dry weght).
Magnfcaton 400x.

Figure 2. Fatty acd chan dstrbuton makes mcroba o an exceent feed for the NExBTL process.
0
10
20
30
40
50
60
70
C14:0 C16:0 C18:0 C18:1 C18:2 C18:3 Others
Fatty acids
%

o
f

t
o
t
a
l

f
a
t
t
y

a
c
i
d
s
Rapeseed o
Pam o
Funga speces A
Funga speces B

149
Table 1. Chemca composton of vegetabe os and mcroba os.
Rapeseed oi l Pal m oil Fungal species A Fungal species B
Ogomers 0 0 1 1
Trgycerdes 96 89 95 88
Dgycerdes 3 6 3 7
Monogycerdes 0 0 0 0
Carboxyc acds 1 4 2 4

Iodne number 115 53 54 66

Raw materi als and oil production potential
O-producng mcroorgansms are very versate n raw matera utzaton. Potenta raw materas
as feed for mcrobes ncude gnoceuosc materas such as agrcutura resdues straw, bagasse
and stak, pup and paper ndustry resdues and hemceuose sde streams. In addton, gycero
resdues from tradtona FAME-bodese producton can be used. Dependng on the raw matera
used the greenhouse gas reducton from dwe to whee s typcay hgher than 75%, whch s sgnf-
canty hgher than for currenty used vegetabe os.
Goba resources of agrcutura resdues are hgh as can be estmated from crop producton sta-
tstcs from FAO. Aone sustanaby produced agrcutura based resdues are estmated to exceed
one bon tonnes annuay (Km and Dae 2004; FAO 2012.), whch coud, potentay, be suffcent
to cover a currenty used bofues.
Pilot scale
To further expore the possbty of ndustra mcroba o producton Neste O decded n ate 2011
to nvest nto a mcroba o pot facty to generate necessary data for estmatng the feasbty of
commerca scae producton of mcroba o and create data for process scae-up. The pot w
serve to optmze mcroba o technoogy from waste and resdue materas and generate mcroba
o and sde products for further studes. The pot pant conssts of raw matera fractonaton, m-
croba o producton and o recovery unts (Fgure 3).
A beneft of the concept s that technoogy for fermentaton s ready avaabe and aso the ex-
tracton of the o from the mcroba bomass s techncay rather straghtforward. After o extracton
the resdue dry bomass can be used as anma feed or for other appcatons whch adds to the
overa vaue generaton.

150

Figure 3. Mcroba o producton concept.
High quality applications
Renewabe NExBTL s a paraffnc HVO-type bofue, whch aows use of exstng nfrastructure,
ogstcs and engne technoogy wthout need for any modfcatons. It s a drop n souton wth no
bend was as t can be used even as 100% neat fue n exstng engnes.
Due to ts exceent propertes, ncudng cod propertes, NExBTL enhances the overa quaty of
fue and can be used n very demandng appcatons such as avaton. Neste O s very commtted
to be a forerunner n provdng hgh-quaty soutons for fueng ceaner traffc n a sustanabe way.
The target of utzng more than a mon tonnes of resdues, wastes and by-products for hgh-
quaty renewabe fue producton s worth strvng for.
References
1. Food and Agrcuture Organzaton of the Unted Natons (FAO). http://faostat.fao.org/ste/
567/defaut.aspx#ancor.
2. Km, S., Dae, B. 2004. Goba potenta boethano producton from wasted crops and crop resdues.
Bomass and Boenergy 26, pp. 361-375.
CHP-ntegrated bo-o producton demonstraton pant, pro|ect deveopment and current status

151
CHP-integrated bio-oil production demonstration plant,
project development and current status
Joakim Autio
1
, Jani Lehto
2
, Anja Oasmaa
2
, Yrj Solantausta
2
,
Jukka Heiskanen
3
, Sara Krki
3
, Pekka Jokela
4

1
Metso Power
2
3
Fortum Power and Heat
4
UPM-Kymmene Corporation
Abstract
The focus on fast pyroyss research n Fnand has been on fue o producton from bomass for
HFO-repacement appcatons. Experence has been ganed by producng bo-o from varous
feedstocks n bench and PDU scae unts at VTT and atey n an ntegrated pot scae unt Metsos
R&D facty n Tampere, Fnand. Charactersaton methods and fue o anayses have been deve-
oped, varous bo-os anaysed, and compared, and work has been done n order to obtan specf-
catons and standards for ths new type of bo-o.
The consortum, Metso, Fortum, UPM, and VTT, has been operatng a 7 tpd bo-o producton
unt In Tampere n whch a pyroyss reactor s ntegrated to a conventona fudzed-bed boer. The
concept enabes hgh overa effcency and hgh bo-o yeds. A by-product streams are utzed to
produce heat and eectrcty. Proof-of-concept has been carred out: over 100 tons of bo-o has
been produced and about 40 tonnes of bo-o combusted n 1.5 MW dstrct heatng pant wth hgh
effcency and ow emssons.
Metso s currenty budng a 30 MW bo-o demonstraton unt at the exstng Fortum combned
heat and power (CHP) pant n | oensuu, Fnand. The start-up for an ntegrated unt s schedued for
ate 2013. Process optmzaton and quaty contro through the whoe vaue-chan s crtca when
movng to commerca scae systems.
The focus of ths paper s to dscuss both on the chaenges and the potenta soutons for For-
tums bo-o demonstraton pant.
Background research
VTT has made, wth the support of Fnnsh ndustry and Tekes, techno-economc assessments, mar-
ket studes, and expermenta research on fast pyroyss for over 20 years and pubshed qute a num-
ber of papers. Bo-o s qute dfferent from conventona qud fues, and many chaenges reman to
be overcome. VTT has systematcay deveoped anaytca methods by whch the bo-o quaty can
be foowed both n aboratory and on-ne durng process. A stepwse market ntroducton s proposed:
bo o woud frst repace fue o n boers, where ts propertes woud not be prohbtve.
VTT has been deveopng an ntegrated concept, n whch fast pyroyss s ntegrated wth a fud-
zed-bed boer. In ths concept hot sand from the boer provdes heat for the pyroyss reactor. By-
products from pyroyss, such as char and non-condensabe gases are used as fue n the boer.
Usng the pyroyss by-product as fue to repace boer fue mproves the overa energy effcency of
the concept, because the by-products are used n the producton of power and heat n fudzed bed
boer operatng wth hgh steam parameters.
Expermenta work on fast pyroyss has been targeted at supportng ths concept. The ntegra-
ton s consdered to offer the foowng technca and economc advantages:
() hgh overa effcency
() reduced nvestment costs because of utzaton of exstng nfrastructure
() ow operatng costs due to exstng personne and operatons
(v) good operatng fexbty because of fu expotaton of the byproduct n man boer.


152
ndustrial movements
Pilot plant
The consortum, Metso, Fortum, UPM, and VTT, has been operatng a 7 tpd bo-o producton unt
n whch a pyroyss reactor s ntegrated to a conventona fudzed-bed boer. The concept ena-
bes hgh overa effcency and hgh bo-o yeds. A by-product streams are utzed to produce
heat and eectrcty. Proof-of-concept has been carred out: over 100 tons of bo-o have been pro-
duced and about 40 tonnes of bo-o combusted n 1.5 MW dstrct heatng pant wth hgh effcency
and ow emssons.
Demonstration plant
Metso s budng a bo-o producton unt at the exstng Fortum combned heat and power (CHP)
pant n | oensuu, Fnand (Fgure 1). The nomna output of the pant w be 30 MW (o producton)
and the panned annua producton w be 50 000 tons. The annua producton w equa to 210
GWh of energy, whch corresponds to the yeary heatng consumpton of more than 10 000 prvate
houses. The producton pant w utze n ts process 225 000 sod-m
3
of forest resdue and saw-
dust n a year. Integraton of bo-o producton nto the power pant process enabes to utze the
sde product from the producton process n the generaton of eectrcty and dstrct heatng. Utza-
ton of bo-o produced n the | oensuu pant heps reduce carbon doxde emssons by 59 000 tons
n a year.
The ntegrated technoogy has been deveoped nto commerca scae n cooperaton between
Fortum, Metso, UPM and VTT as part of Tekes BoRefne research programme. In the ntegrated
bo-o producton concept the heat for pyroyss s transferred from hot sand of a fudzed-bed boer.
The ntegraton of bo-o producton nto the power pant process enabes both hgh overa effcency
and hgh bo-o yed. Pyroyss by-products char and gases are used n the boer to partay re-
pace man fue n the generaton of eectrcty and dstrct heatng.
Metso w dever the pant to Fortum as a turn-key devery. The fu scope devery ncudes cv
and constructon works, fue handng and pretreatment, bo-o producton and storage equpment,
a Metso DNA automaton system, and E&I. Ths demonstraton venture w test and further deveop
ntegrated pyroyss technoogy, and the contro soutons of the Metso DNA system, whch w be
utzed n the pyroyss processes of arger-scae power pants n the future. The new bo-o produc-
ton pant s schedued for start-up n the autumn of 2013.

153

Figure 1. Industra-scae ntegrated bo-o pant n | oensuu, Fnand.
Challenges for commercialization
The most mportant chaenge s to make pyroyss o as a fue compettve for combuston appca-
tons. The whoe vaue-chan from the fue procurement to the end-use shoud be capabe of operat-
ng n the margn between the prce of the foss fue to be repaced and the prce of the feedstock.
Process optmzaton and quaty contro through the whoe vaue-chan s crtca. Demands for
pyroyss process nputs, such as the requrement of ow mosture content of feed wth very sma
partce sze are very chaengng and energy consumng. For exampe, utzaton of secondary
process heats for dryng and pyroyss process ntegraton to the fudzed bed boer whenever
possbe shoud be consdered. A bet dryer usng ow-grade process heat s economc and effcent
for dryng purposes. On-ne anayses provde up to date nformaton on process and save tme and
money. On-ne mosture anayser based on Metsos nventon has been successfuy used n pot
and a sods anayser s under testng at VTT. Standards and specfcatons both for pyroyss o
and combuston systems have been pushed forward. Comprehensve gudenes for transportaton
and MSDS are provded, standardsaton under CEN has been ntated, as we as data for REACH
regstraton gathered.
Properties of fast pyrolysis bio-oil
Fast pyroyss bo-os are hghy poar and hence competey mscbe wth poar fues ke methano
or ethano. About 80 wt-% of the bo-o s water-soube. They contan about 25 wt-% water whch
cannot be separated by physca means, ke centrfugaton. Another ma|or fracton s composed of
gnn-derved matera, whch s around 20 wt-% of the bo-o (pyroytc gnn).
Man snge compounds are acetc acd (35 wt-%) and evogucosan (410 wt-%). The rest of
the bo-o s composed of hundreds of varous oxygen-contanng compounds, most of them are
present at ow concentratons (beow 1 wt-%). Fast pyroyss bo-os are acdc TAN beng around

154
100 (pH 2.53), whch means that carefu seecton of proper contact materas s needed. Heatng
vaue s roughy haf from that of mnera os and density i s hi gher (1.2 kg/dm
3
).
Standardisation
Guidelines for transportation, handling and use of fast pyrolysis bio-oils
At the moment t seems that the product shoud be cassfed as Cass 8 (Corrosve) product. To
make a fna cassfcaton, a requred tests shoud be done accordng to reevant transport regua-
tons, referrng to UN Manua of Tests and Crtera, OECD test, and others as appcabe. It aso
appears that the varatons between dfferent products coud ead to dfferent cassfcatons. It s the
duty of each bo-o producer to prove that the cassfcaton suggested n ths paper s vad aso for
ther product. For boos there s no UN number assgned at the moment. If further testng shows
that the propertes for boos are mosty the same, t may be possbe to suggest a new UN number
for the product. Ths suggeston shoud be made to UN, normay by a competent authorty, or an
assocaton. A suggeston for transport cassfcaton s (Matera Safety Data Sheet, Secton 14
Transport Informaton):
UN NUMBER: 3265, PROPER SHIPPING NAME: CORROSIVE LIOUID, ACIDIC, ORGANIC,
N.O.S. (contans x, y*), CLASS: 8, PACKING GROUP: III, ENVIRONMENTAL HAZARDS: NO.
It s the o producers responsbty to show that ther bo-o meets the same cassfcaton as shown
here. More research s needed on matera testng usng a standard or we proven method at ree-
vant test condtons.
Table 1. Summary tabe of transportaton gudenes.

Property Transportaton
cassfcaton
Exstng test
methods
Lmt vaues Fast pyroyss bo-os Concuson
Fammabe Class 3,
flammable
liquids
Flashpoint

Sustained
combustibility
60C (closed
cup test)
Does not sustain
combustion
Does not apply to bio-oil

Does not sustain com-
bustion
f the product does
not sustain combus-
tion, it is not needed
to be classified as
flammable liquid
Corrosvty
corrosve
Class 8,
corrosive
substance
Full destruction
of skin tissue
Metal corrosion
of steel / Al
OECD tests

UN test manual
Slightly corrosive for
rabbit, pH>2,5
Not corrosive for steel,
corrosive for aluminium
Probably corrosive
(PG )
Toxc Class 6.1,
toxic sub-
stances
Rat testi ng LD
50
300 mg/kg
(oral )
>2000 mg/kg (oral, rat) Not classified as
toxic substance
Envronmentay
hazardous
Class 9,
misc.
dangerous
goods
Aquatic toxicity
Bioaccumulation
Degradation
10 mg/L
10 mg/L
OECD tests
Algae 72h:100 mg/L
Daphnia 48h: 100mg/L
Aerobic biodegradability
28 days: 42%
Not env. hazardous

Not class. as env.
hazardous
Reach registration
In the EU a new chemca reguaton system REACH (Regstraton, Evauaton and Authorsaton of
Chemcas) s beng apped. Regstraton under REACH has to be made f bo-o s produced or
mported to the EU. Ths paper descrbes fast pyroyss bo-o n detas and hghghts the ma|or

155
dfferences to other bo-os. It aso provdes nformaton on anaytca methods sutabe for fast
pyroyss bo-o and data needed for REACH regstraton of fast pyroyss bo-o.
References
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24. Oasmaa, A., Soantausta, Y., Arpanen, V., Kuoppaa, E., Sp, Ka. 2010. Fast Pyroyss Bo-
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26. http://www.bocoup.com/.

157
Thursday, 25 October:
R&D highl ights

Utzaton of hydroyss gnn n the Sovet Unon and Russa: What s appcabe n the wood
borefnery era?

159
Utilization of hydrolysis lignin in the Soviet Union and
Russia: What is applicable in the wood biorefinery era?
Mikhail L. Rabinovich
Bach nstitute of Biochemistry, Russian Academy of Sciences, Moscow, Russia

" We should focus on lignin applications in the areas inaccessi ble for the
oi l " fi redrake . Perhaps a time wil l come when oil and natural gas become
so expensi ve that we will be able to compete with thi s dragon i n its own
l and. However we should patientl y wai t for this at l east several decades
Mchae I. Chudakov. Industra gnn utzaton. In: Wood chemstry: Lgnn and
ts utzaton. Znatne, Rga, 1968

Abstract
Snce ts estabshment n the md 1930s and t the coapse by the end of 1990s, Sovet hydroyss
ndustry produced enormous amounts of the so caed hydroyss gnn as a ma|or by-product
(>40% of the tota consumpton of pant raw matera), whch has never been exacty accounted. In
the md 1980s ts annua producton n the former USSR reached roughy 1.5 mo. metrc tons. Ony
30-40% of ths amount was n fact utzed, whereas the ma|or part was usuay paced on the oca
dumps. The revew s focused on the composton of hydroyss gnn produced by Sovet ndustry
and ts ndustra utzaton. The foowng areas of gnn appcaton are brefy outned: gnn as a
domestc ndustra and househod fue, gnn carbonzaton, gnn humfcaton and utzaton n
varous fertzers, gnn dervatves as vscosty reducers by o drng, adsorbents from gnn,
gnn as a fng agent, gnn as a bnder, gnn n compostons for rust remova. Current state of
hydroyss gnn utzaton n the former Sovet repubcs and the envronmenta probems caused
by hydroyss gnn dumps are aso brefy addressed.
Lignin as a by-product and " the headache of Soviet hydrolysis plants
Most of the Sovet hydroyss pants, whch have been but after the Word War II, specazed on
the producton of furfura and/or fodder yeast rather than ethano. So caed hydroyss yeast pants
were pro|ected to amost competey utze the poysaccharde fracton of a feedstock, producng
hydroyss gnn smar to that of the oder ethano pants. Large and reatvey modern enterprses,
e.g., Krov bochemca pant, produced both furfura from the pre-hydroysates of wood chps or
sawdust and the fodder yeast from the acd hydroysates of resdua gnoceuose. In contrast wth
that, smaer furfura- or xyto-producng hydroyss pants n Karea, Sbera, Whte Russa,
Ukrane and the former Sovet Centra Asan repubcs have consumed mosty hemceuose frac-
ton of the renewabe feedstock (hardwood or agrcutura resdues), whereas the resdue, a so-
caed "ceognn" consttutng 60-65% of the nta raw matera, was often not utzed at a. For
exampe, acd-free producton of furfura from tan waste by Rechtsa hydroyss pant or Shumerya
chemca pant resuted n rapd accumuaton of ceognn dumps around these pants.
In 1950-1970s, dred softwood ceognn was consdered a promsng feedstock for gucose
producton by ow-temperature hydroyss wth sma amounts of 75% H
2
SO
4
(so caed Rzhsky
process tested n the end 1950s - begnnng of 1960s) or an excess of partay recyced 41% HC.
The atter, an anaog of Noguch Insttute and Udc-Rhenau processes, was deveoped by "VNII
gdroz" and has been operatona for about 16 years (1958-1974) n the Kansk pant, producng
annuay about 600 t of crystane gucose |1|. The resdua gnns after ow-temperature hydroyss
retaned more natve structure than hghy condensed gnn after percoaton hydroyss wth duted
H
2
SO
4
. They coud be converted nto some vauabe chemcas by hydrogenoyss wth hgher yeds

borefnery era?

160
and reveaed good propertes by modng. However, after cosng of the demonstraton pants n
| apan and Germany, producton of gucose from wood wth concentrated acds was aso stopped n
the USSR. At ow prces for wood and agrcutura resdues, ceognn, the by-product of furfura
pants, was no more consdered a vauabe feedstock, athough, ake that of steam-expoded wood,
ts ceuosc fracton coud be enzymatcay converted nto gucose wth hgh yed after neutraza-
ton of the ntrnsc acetc acd to pH 4, wthout substanta nhbton of ceuoytc enzymes wth
resdua furfura or HMF.
Even f hydroyss pants produced both furfura from hemceuosc fracton and hexoses for
subsequent fodder yeast manufacturng by a two-stage percoaton hydroyss of a feedstock, furfu-
ra as a "strategc" chemca was usuay a prorty product of the pants. It coud be obtaned more
easy and qucky than fodder yeast. Because of that arge bochemca pants, e.g., now aban-
doned Manturovo pant, coud smutaneousy depost n ther dumps both hydroyss gnn and
ceognn. Athough hydroyss gnn and ceognn substantay dffer from each other n the con-
tent of poysacchardes (<20 or >50% respectvey), the presence of sufurc acd, partce sze ds-
trbuton, degree of gnn condensaton, heat capacty, carbonzaton behavor, they were deposted
together and were never precsey accounted. Therefore, speakng about gnn resdues produced
by the former Sovet hydroyss ndustry we can not usuay strcty defne whether t was hydroyss
gnn or ceognn. In ths communcaton the appcatons of hydroyss gnn rather than ceognn
w be many addressed. However, the potenta reader shoud reaze that as a secondary re-
source, the rea gnn resdues of Sovet hydroyss pants may contan both gnn and ceognn n
dfferent ratos. The content of gnn tsef n (ceo)gnn dumps may vary from 40 to 88%, resns
and gnohumc substances consttute from 5 to 19% and ash contrbutes from 0.5 to 10% odm
dependng on storage condtons.
Characteristics of hydrolysis lignin
The amount of gnn resdues, produced by the Sovet hydroyss ndustry, ncreased from 0.5 to 1.5
mo. t/yr snce 1960s t the end of 1980s |2, 3|. Athough ths gnn was aways a mnor fracton of
tota Sovet gnn producton, whch grew from ca. 4 to ca. 10 mo. t/yr n ony 10 years snce 1960s
t 1970s, ths was the most condensed and dffcut for utzaton gnn by-product. It contaned
substantay ess functona groups (excudng -OCH
3
) and can not be easy dssoved n aka or
poar sovents. In contrast wth natve gnns, t contaned poynucear aromatcs, whch formed
benzenepoycarbonc acds by akane MnO
4
-
oxdaton |4, 5|.
Lgnn accumuated n the former Sovet Centra Asan Repubcs was mosty of the cotton pant
orgn (cotton hus, staks, etc.). Hydroyss gnn of South Russan and Ukranan pants was many
of agrcutura orgn, whereas that produced by Whte Russan, the North-European Russan, Ura,
Sberan and Far Eastern pants orgnated from soft- and hardwood.
Current amounts of gnn wastes n the Ukrane and Whte Russa are estmated as 5 to 15
mo.t, whereas Russan Federaton has accumuated an order of magntude greater amounts of
resdua gnn. For exampe, gnn waste stocks n Irkutsk obast, where Tuunsky, Bryusnsky,
Zmnsky and Ust-Imsky hydroyss pants are stuated, are estmated as >20 mo. t.
Hydroyss gnns of dfferent producers may strongy dffer from each other by the amount of re-
sdua reducng substances and nonhydroyzed poysacchardes, methoxys, ash, and acd content.
Ther composton depends on the type and granuometrc composton of the feedstock, tota
amount and concentraton of H
2
SO
4
at the hydroyss stage, sod/qud rato n the hydroyss appa-
ratus, ts constructon matera, temperature and duraton of hydroyss.

borefnery era?

161
Table 1. Yeds and content of dfferent hydroyss gnns |1-5|.
Feedstock Yield (% odm) Major Cont ami nants % ODM
Softwood 38 Poysacchardes 15-30
Hardwood 32 Resdua monosacchardes 2-10
Cotton hus 37 Lgnohumates (aka-soube) 5-15
Corncobs 24 Sufurc acd 0.5-2
Sunfower seed hus 32 Ash 2-10
Table 2. Average composton of softwood hydroyss gnn (eft) and ash of varous gnns.
Components (softwood gnn) % ODM A
s
h

c
o
mp
o
n
e
n
t
CaO,% 1.5-32.8
Sufurc acd 0.6-1.5 MgO,% 0.3-0.65
Reducng substances 1.5-3.0 Fe
2
O
3
,% 0-16.5
Nonhydroysed poysacchardes 15-20 A
2
O
3
,% 0-1.11
Ash <3 SO
2
,% 49.5-93.4
OCH3-groups 10-11 P
2
O
5
,% 0-1.5
Phenoc OH-groups <3 TO
2
,% 0-0.1
Resns (dchoroethane-soube) 7-12 Na
2
O+K
2
O,% 0.33-0.6
SO
2
,% 0-7.95

Varatons of ash composton are attrbuted to the presence of contamnants rather than the nature
of utzed pant feedstock.
Organc acds n the hydroyss gnn are represented many by formc and acetc acd. About
one haf (ca. 10%) of 20% tghty bound sugars (gucose) may be reeased by a treatment of hy-
droyss gnn (mosture 68%, H
2
SO
4
1.3%) at 300C n an autocave.
Granuometrc composton of gnn s far from unform because of smutaneous utzaton of df-
ferent ratos of wood chps and sawdust n the hydroyss reactors. Sze dstrbuton of hydroyss
gnn partces may vary n a wde range from 1 mm to >1 cm. The so caed commerca hydroyss
gnn for further ndustra utzaton shoud n prncpe contan mosture <65%, ash <4.5%, H
2
SO
4

<1,5%. The buk densty of gnn wth the mosture content <40% vary n the range 200-300 kg/m
3
,
whereas that of gnn contanng 65% mosture s about 700 kg/m
3
, 2/3 of whch contrbutes acdc
mosture. Ange of repose of the most gnn fas wthn 40-43o. A ths makes the transportaton of
hydroyss gnn expensve. A commerca ceognn shoud n prncpe contan mosture <52%, ash
<2.5%, organc acds (accounted as acetc acd) <3.5%. However, these standards were usuay
controed by further producton of granuated gnn (partce sze 20 mm for >90% granues, mos-
ture <20%, ash<7%, buk densty >550 kg/m
3
), whch was used for crystane S and A-S aoys
producton, or gnn four (mosture 10-20%, specfc surface area 200-300 m
2
/g), whch was con-
sumed as a fer n gues, pastcs, or noeum. The parameters of the ma|or part of gnn or ce-
ognn, whch was paced on oca dumps wthn 10-20 km around the producton facty were
usuay not controed at a.
borefnery era?

162
Hydrolysis lignin as a fuel
Athough burnng of produced gnn coud cover >25% of the overa energy consumpton by a
hydroyss pant, the use of unprocessed gnn as a fue n the usua boers was mted because of
hgh (50-70%) mosture content and the presence of H
2
SO
4
. Average heat capacty of the hydroy-
ss gnn strongy depends on ts mosture content, decreasng from 23-27 M| for 1 kg of the oven
dry matter to 20; 7.8; 6.2-6.9; or 5.7 M| /kg of gnn contanng 18-25; 60; 65; or 68% of mosture,
respectvey |2-4|. For the envronmenta reasons t was orgnay pro|ected that the new hydroyss
yeast pants burn >50% of gnn n ther boers and yeasts dryers. However, ony the demo Lenn-
grad pant at "VNII gdroz" burned -70% of gnn n ts boers. The other pants burned much ess
gnn, because ts mosture content shoud be ntay reduced to <45% for a stabe burnng wthout
back o or natura gas co-frng. Ths ncreased the expenses, makng gnn fue non-compettve
wth the cheap Sberan opencast coa, partcuary n the East of Russa.
Onezhsky, Krshsky, Kedanasky, Bratsky and some other hydroyss pants have used non-
med gnn of 60-65% mosture n the ow-temperature vortex combuston boers -50-24K NTV
or E-75-40K NTV equpped wth back-o torch. The boers were desgned by the char of steam
generators at the St. Petersburg Poytechnc Unversty |6|. The argest one consumed 32 t/h of
most gnn and produced 65-75 t/h of steam at 440C and the pressure of 4MPa wth the energy
converson effcency of 85-88%. It coud aso staby work wthout the use of back-o torch. How-
ever, after cosng of the hydroyss pants these boers do not burn gnn anymore. Attempts of the
use of three arge NTV furnaces at the Bratsky pant for combuston of non-med bark and sawdust
wthout the use of back o faed and the wood resdues are now ncnerated n the fudzed-bed
furnaces, whereas the od gnn boers are not n use.
Swrng-type ow-temperature furnaces for stabe gnn burnng wthout substanta feedng wth
back o were desgned by "Byskenergomash" for reatvey sma-scae boers. The arger boers
wth the capacty from 30 to 100 MWt for gnn, peat, or sawdust ncneraton, e.g. boer -75-3,9-
440DFT, are produced by Begorodsky pant for boers manufacturng (OAO ZKO) and utze fud-
zed-bed combuston prncpe. Authors of |7| aso propose a stabzed suspenson of coa dust and
most hydroyss gnn (1:1) as a qud fue. However, whether hydroyss gnn s actuay used
wthn the country for ncneraton at the current nterna prces for foss fue n Russa, s not cear.
In contrast wth Russan Federaton, Whte Russa strongy depends on exported fue. Ths mot-
vates oca authortes for gnn utzaton. Current annua producton of hydroyss gnn n Whte
Russa s equvaent to ca. 25 000 TOE or about 4.4% of the tota secondary energy resources
produced n the country. Commerca hydroyss gnn for energy producton n the Whte Russa
shoud contan mosture <60%, ash <23% odm,
137
Cs<18 Bq/kg at the eementa composton: 0.9%
S, 20.14% C, 2.31% H, 0.05% N, 13.88% O. Heat capacty shoud be wthn 8.51-11.76 M| /kg at the
owest vaue >6.2 M| /kg.
Estabshed n 1936, Bobrusky hydroyss pant (Whte Russa) has paced -2,5-3 mo. t of hy-
droyss gnn n the dumps, depostng up to 150-230 t day. Snce 2004 Bobrusky pant produces
fue brquettes from gnn. The pant has acqured abandoned turf brquette manufacture "Redk|
Rog" n the suburb Tugotsa together wth 8 ha and for gnn deposton. In the summer tme the
specasts of pant prepare gnn of 40% mosture content by a standard turf dryng and storage
technoogy for the whoe-year brquette producton. To avod undesrabe effects of H
2
SO
4
, freshy
obtaned gnn s neutrazed drecty n the hydroyss apparatus before ts unoadng. In 2005-2006
the state power generaton company "Mogevenergo" has ordered a pro|ect of a speca boer for
gnn ncneraton n the Bobrusk heat power staton TEC-1. Accordng to the pro|ect prepared by
BeNIItoppro|ect, 17 ha of the oca 34-ha gnn dump were adapted for gnn processng. The pant
together wth the natona Mnstry of natura resources has nvested $3.2 mo. n the necessary
machnes used n peatery and garbage separaton. The other $15 mo. were nvested by the oca
power staton and the Mnstry n the equpment, ncudng boer -30-3,9-440DF of the
Beoozersky energomechanca pant for gnn ncneraton. The boer produces 30-35 t/h of steam
at a pressure of 3.9 MPa, consumng 14 t/h of gnn (mosture 55-60%) wth the energy converson
effcency of 87-88%. In 2009, 68 000 t of gnn were consumed by ths boer of TEC-1, whereas
the other 40 000 t were used n the brquette producton for househod. Heat and eectrcty pro-
borefnery era?

163
duced by ths boer were twce as cheap as those from Russan natura gas. However, the exstng
gnn dump n Ttovka (7 km from Bobrusk) can contnuousy suppy the cheap fue (<20 $/t) for the
whoe expotaton perod (30 years) of ony one gnn-fueed boer, therefore no more such boers
w be nstaed.
Unfortunatey, ths successfu pro|ect seems to be unque. Indeed, deposted n Kazazaevka
(Gome obast, Whte Russa) (ceo)gnn resdues from Rechtsky furfura sem-ndustra pant are
no more used as a oca fue source snce the pant bankruptcy, athough the pant was equpped
wth a speca gnn-combuston for-chamber DE 24/25 wth a capacty of 10 MWt (Axs Industres,
Lthuana). A modern fuy automated mn-heat power staton of Rechtsa consumes ony peat and
sawdust but not gnn.
In 1980s, four Sovet pants have produced -17 000 t/yr of gnn brquettes as a domestc fue or
reductant for ferroaoys, usng press-machnes BPD-2 at a productvty of 0.5-2 t/h |3, 8|. At pre-
sent >20 manufacturers, mosty from Ukranan regons Zaporozhye (Teposntez, PeKo and 5 others),
Kharkov (Afa Tech, Svet Shakhtera), Lvov (Ecotec), Donetsk (Fart PR, Energetchesky brquette),
Novaya Kakhovka, Lugansk (Grandug), Vnntsa (Kamra); as we as at east 6 from Russan re-
gons Sverdovsk (Uak Chstaya energya), Vadmr (Trks), Yarosav (Yarnteres), Kropotkn Kras-
nodar kra, Eabuga Perm kra, Gukevch Krasnodar kra (Gre pant); and one from Whte Russa
(Bobruysk pant, Mogev obast) produce and se gnn brquettes or peets (Tabe 3).
Table 3. Manufacturers of hydroyss gnn peets and brquettes.
manuf act urer t/month $/t MJ/kg Ash, % H
2
O,% S,%
Gukevch,
Krasnodar kra
1 000, brquettes 18 19 6 0.4
Bobruysk pant
Mogev obast
1 200, brquettes
>25 mm
50-60 >13 (13.6) <20 (11.8) <22 (15.7) 0.4
Teposntez
Zaporozhye
>500, brquettes 24.7 20 8.7 0.45
Zaporozhye 2 500, brquettes
30 x 70 mm
120 22-23 10-15 10-12
Zaporozhye 1 000-5000
brquettes TBR-1
19 <15 <10 <0.56
Zaporozhye peets 18.9-25.6 20 20 0.6
Zaporozhye 300-500,
peets 6-8 mm
75-80
FCA
24.2 6.1 4.9 0.69

Some enterprses aso offer unprocessed hydroyss gnn/ceognn as a fue for oca heat power sta-
tons and for export nto Poand. Ukranan busnessmen from Zaporozhye offer 1 500-20 000 t/month
for 30 C/t FCA or 60 C/t DAF (Izov - Khrubeshov). Lnas Agro Group (Lthuana) panned to suppy
-50 000 t of gnn (standard EN 14961-1:2010) from the former Kedana hydroyss yeast pant for
C2.1 mo. n 2010. Loca authortes (Rechtsky Razhkomkhoz) n Gome obast offer a tender for 50-
225 thousand t of a gnn-ceognn mxture (mosture <70%, ash <10%, H
2
SO
4
<1.5%) from the
abandoned Rechtsa furfura pant on the condton of an estabshment of a gnn-processng enter-
prse, creaton of at east 5 new |obs, nvestment of $200-500 thousand at pace, and provdng a fre-
protectng measures for the rest of gnn dump. Startng prce s defned as 3.4 C/t of most gnn-
ceognn mxture.
borefnery era?

164
Lignin as a fertilizer and absorbent
Lgnn has obvous advantages over petroeum products n at east two features: as an absorbent and
a potenta source of humus. Swoen hydroyss gnn has hghy deveoped nterna surface area (760-
790 m
2
/g), athough after dryng t decreases amost 100 tmes. Large nterna surface area has stmu-
ated utzaton of the nsoube resdue of hydroyss gnn after akane extracton as o-coectng
absorbent |9| or as a matrx for preparaton of on-exchange absorbents of heavy, nobe or rare
metas. Charcoa from hydroyss gnn has aso found varous appcatons as the absorbent (Tabe 4).
Numerous studes have been devoted to the utzaton of gnn as a component of fertzers, potenta
source of humus, and so-structurng agent. Hydroyss gnn s aso a good carrer, stmuatng pro-
onged sustanabe reease of norganc nutrents or pant growth hormones |3-5|. A gnn-stmuatng
fertzer (LSU) was produced and used as growth stmuator of varous agrcutura cutures n Uzbekstan
(Tabe 4). However, hydroyss gnn shoud be neutrazed for agrcutura appcatons. For exampe,
compex organc-mnera fertzer for sandy or cay sos (90% of hydroyss gnn, NH
4
NO
3
, super-
phosphate, KC) contans 5% of me |10, 11|. Resdua H
2
SO
4
can aso be neutrazed wth phospho-
rte four Ca
3
(PO
4
)
2
whch forms gypsum and Precptate (CaHPO
4
) fertzer. In Sverdovskaya obast
three hydroyss pants (Lobva, Ivde, Tavda) have paced a ot of gnn n the dumps. At present, an
absorbent-fertzer Agrmus C (probaby an anaog of Agrmus fertzer manufactured by Agrfuran
n France from a ceognn-ke resdue) s produced from gnn (ca. 800 t n 2009) n ths regon.
Hydrolysis lignin in chemistry and other areas
The most mportant drawbacks of gnn as a feedstock for chemstry remaned reatvey ow yeds
of the desred products and competton wth petrochemstry. Foowng gnn hydrogenoyss stud-
es of Noguch Insttute n 1940-1960s, whch has succeeded n obtanng -50% of monophenoc
(o- and p-cresos, ethy- and propyphenos) from HC-gnn ake that produced by Kansk hydroyss
pant, smar studes were performed n the USSR. The man ob|ectve was an attempt of o-, m-
and p-cresos preparaton, whch were not supped by Sovet petrochemstry. Some attempts of
hydrogenoyss of resdua gnn after hgh-temperature hydroyss of wood or agrcutura resdues
wth duted H
2
SO
4
were made n Tashkent Insttute of Ceuose Chemstry and Technoogy, but
cheap and effcent hydrogenoyss catayst that coud provde hgh yeds of cresos was not found.
Hydroyss gnn of cotton hus was used for therma producton of cresos wth the tota yed up to
5%, ncudng >3% of m-creso, whereas gnn of sunfower husks produced 4.5 and 2.5% respec-
tvey. Contrary to that, gnn of corncobs produced amost excusvey o- and p-cresos (tota yed
3.2%). Tota yed of raw phenoc fractons from agrcutura hydroyss gnn reached 12%. The
other chemcas obtaned from hydroyss gnn wth ow yeds were DMS, DMSO (<10%) and py-
rometc danhydrde PMDA (<5%).
Nove exctng resuts of bomass nto dese converson by thermo-cataytc ow temperature hy-
drogenaton n qud medum (KDV) have aso nspred Sberan specasts n deveopng new
routes of hydroyss gnn hydrogenaton. Lquefacton and gasfcaton of 70-96% of hydroyss
gnn by Pt- or Pd-cataysts-drven hydrogenoyss was shown to proceed n supercrtca ,
EtOH, or n-BuOH, resutng n demethoxyaton and de-oxygenaton of gnn. As the fna products,
"gno-o" of an emprca formua
10-14
13-20
contanng three tmes ess oxygen than gnn, as
we as gaseous C
1
-C
4
hydrocarbons and CO
2
were obtaned. Fna sod resdue conssted of a
reduced catayst, ash (70-86%), whch, accordng to the new KDV technoogy can aso be used as
a hydrogenaton catayst, and a product contanng 11-21% C; 1.5-2.3% H and 0.4-1.0% S |12|.
Another nterestng approach was a co-pyroyss-hydrogenaton of hydroyss gnn wth moten
poyethyene or poypropyene wastes. Hydrogen-rch (>14% H) crackng fragments of poyoefnes
saturate gnn structures makng them more reactve. Hydrogenaton of qud products of co-
pyroyss resuts n the enrchment of qud fractons (b.p. 180-350) wth aphatc rather than
aromatc, heterocycc compounds or cycoakanes |13, 14|.
Lgnn has ong been consdered promsng for the appcaton n the budng ndustry |15-19|.
Brocen cemex (Latva) and Vorovsky cement pant (Lenngrad obast) used 0.3-0.4% gnn n
borefnery era?

165
cement m, whch ncreased the productvty of mng up to 20% |3-5|. Utzaton of 22 000 t/yr of
unprocessed (ceo)gnn (15-30% of ts producton by a hydroyss pant), as a burnng cay fer by
ceramc brcks producton woud be suffcent for a producton of 50 mo. brcks/yr |20|. Ths was
tested by Lenngrad brcks pant, whch utzed 9-12% most gnn n cay for producton of brcks.
Recenty, based on thermopastc propertes of hydroyss gnn, a new waterproof gnopastc
was obtaned from gnn four and 20-40% of poyethyene |21|. Ths can be an nterestng aterna-
tve to "qud wood" poymerc composton Arboform proposed n FRG.
Table 4. Industra hydroyss gnn appcatons tested n the USSR and CIS |1-5, 22-32|.
Pl ant location Product Technol ogy Yield,% Scale, t/yr Appli cations
And|an 1985

Krasnodar
Ntrognn
Igetan

Sun

Loxd
Chorognn
8-50% HNO
3
Ntrognn
saponfcaton
Ntrognn
suforeducton
H
2
O
2
-oxdaton
Chorne water
95-98
97-98
15 000
3 000
products
Surfactants, cay
quefers by o wes
drng
Tannn substtutes
Ore fotaton, rare
meta precptant
And|an 1985
Krasnodar,
Fergana1968
Coactvte
(charcoa
absorbent)
20%-oeum treatment
(carbonzaton)
70 5 000 prod.
1 500
1 500
Dscooraton of xyto
soutons
Nkoaev
Zaporozhye
2005
Lgnn rust
remover PRL-2
Mxng wth H
3
PO
4
vegetabe o, fat,
ethy scate, etc.
80-90 <1 000
product
Protecton from
corroson wthout
ceanng
Krasnoyarsk
1972
Granuated
coa
Pyroyss 35-40 coa,
10-20 setted
tar, 15-20 fue
gas
pan12 670
product
117 000
gnn use
CS
2
producton
(coa), fue
Krasnoyarsk
1972
Aka-soube
gnn
Akane cookng,
200C, 40% aka
70-80 pan10 000
product
Fer by rubber
vucanzaton
(soot substtute)
Pant ocaton Product Technoogy Yed,% Scae, t/yr Appcatons
Bryusnsk
2010
Granuated
charcoa
pyroyss 10 000
product
Absorbent
Khakasya
1968
ptch o, coke Fudzed bed pyroyss 12 ptch o, 30
coke, fue gas
pan25 300
dry gnn use
Herbcde (ptch o),
fue
Manutrovo
St. Petersburg
2005
Poyphepan
entero-
absorbent
Remova of md aka-
soube fracton
70-80 300
60
Medcne, veternary
And|an1972
Chmkent
1972
qunone-n-
tropoycar-
bonc acds
duted HNO
3
, 6h,
100
o
C, neutrazed
wth NH
4
OH
30 product,
7-10 oxaate
300, wth
gnn 1:10
pan50 000
Lgnn-stmuatng
fertzer, pant growth
hormone
St. Petersburg
1972
gnophenofor
madehyde
resn
Condensaton of
phenognn and
formadehyde
pot Press-powders
Fergana
1972
Lgno-
fberboard
1.9m
3
wood chps +1 t
most gnn
1 t (330 m
2
)
fberboard
pan20000
product
Budng matera
heat-nsuator
And|an
1972
formc, acetc,
succnc, mac,
gycoc acd
ar oxdaton n aka or
ammona
25-35 org.
acds, 25
ammona gnn
? Yeast bomass 0.1 t/t
gnn, fertzer (20%N)
0.25 t/t gnn
borefnery era?

166
Environmental issues and conservation of lignin dumps
The abandoned Zmnsky hydroyss pant (Irkutsk obast) has paced >11 mo t of hydroyss gnn
n a 25-ha dump currenty under management of the oca authortes. In 2003 oca dvson of the
Russan Mnstry of Emergency Stuatons has extngushed wth water the smoderng gnn t the
depth of 2 m on 13.3 ha wth 18 frefghtng cars and 305 frefghters for 1.5 months. However n a
short tme the extngushed fres appeared agan, snce the gnn ayer depth exceeds 15-18 m.
In 2005-2006 the Lmnoogy Insttute (Irkutsk) has tested for the recutvaton of Zmnsky gnn
dump ts conservaton technoogy |33|, whch was earer successfuy used for the preservaton of
the gnn dumps at Seengnsky ceuose and cardboard pant on Bayka. For ths purpose, 10 000 t
of the fy ash from the abandoned coa heat staton TEC-3 n Zma were spread on 1 ha of the gnn
dump t ts depth from 30 cm to 1-1.5 m (on the smoderng areas). Ths has protected the recut-
vated area from further smoderng fres. Loca authortes together wth the A/S Irkutskenergo
(owner of the abandoned coa staton) have panned to cover a the dump area wth 262 000 t of
the fy ash stored on the coa staton and nvest about 1 mo. USD n the gardenng of the dump
area, where ater a gof course or tenns courts can be arranged. The oca authortes beeve,
when a tme w come, the upper 1.5-m ayer of the dump can st be utzed for the producton of
porous brcks or cement, or by budng of roads, whereas the ma|or thck bottom ayer w be used
as a new source of peat.
In | une-October 2010, foowng persona request of Vadmr Putn, a smar technoogy was a-
so used to extngush the smoderng gnn of the Kansk hydroyss pant (Krasnoyarsk kra) near
the Trans-Sberan Hghway, route M-53: Krasnoyarsk-Irkutsk. The oca dump contanng 3 mo. t of
hydroyss gnn on 23 ha was covered wth a 30-cm ayer of a 2:1 mxture from cay (200 000 t)
and the fy ash (100 000 t) of the Kansk coa power staton. To provde gardenng, the dung from
oca chcken farm was then addtonay spread on the surface. Tota nvestment exceeded $1.5
mo. |http://www.arussa.ru/new/100720132130.htm|.
An aternatve souton of gnn dump probem was proposed by the management of Krov bo-
chemca pant ocated n the North-East of European Russa. Ths pant remans the ony hydroyss
enterprse st producng on a reatvey reguar bass ethano and dred fodder yeast (ca. 10 000 t n
2010) from wood resdues n Russa. In ts amost 40-years hstory ths argest pant has utzed ca.
100 mo m
3
of sod wood resdues. Its currenty avaabe capactes can consume up to 2 mo. m
3
/yr
of sod wood (sawdust and non-utzed wood). In the recent years the pant aso produces fue
peets from sawdust usng correspondng equpment of the German company Mnch-Edestah
GmbH, whereas hydroyss gnn s not utzed. The gnn dump near the pant occupes by varous
evauatons from 30 to 60 ha, where about 50 mo. t of hydroyss gnn and ceognn were paced
n the ast 39 years. Soon after ts openng, the pant has but a water pumpng staton wth a
800 mm ppene to pump 150-400 m
3
/h of water from Vyatka rver to the gnn dump. However, n
2000s the pump faed, and the gnn smoderng has become a nghtmare for the popuaton of the
cty. In 2010 water suppy was recovered and the smoderng gnn was converted nto a marsh.
The expenses exceeded 0.4 mo. USD n 2010, tota water consumpton n the recent few years
reached 0.6 mo. t. However, utzaton of the fy ash from the oca heat power staton was not
panned by the governments of Krov cty and obast responsbe for the gnn dump. Currenty
hundreds of seagus occupy n summer the marsh surface. Hopefuy, ther dung w aso convert
wth tme ths acdc marsh nto a ferte so.
Concl usi on
In the ong hstory of Sovet hydroyss ndustry many dfferent appcatons of hydroyss gnn were
proposed and successfuy tested on the arge- (gnn as a fue, absorbent, fertzer, fer) and
sma-scae ndustra appcatons (oxdzed akane extract of hydroyss gnn as an mmunostmu-
ator of a broad spectrum |34, 35|). However, gnn after bomass hydroyss wth duted H
2
SO
4
s
apparenty the worse type of gnn for further utzaton compared to other ndustra gnns. Utza-
ton of hydroyss gnn requres n every case a specay equpped facty and substanta capta
borefnery era?

167
nvestments at the producton or storage pace. Unfortunatey, n a appcatons, gnn s not a
unque and currenty not the cheapest feedstock compared to bomass or foss resources. There-
fore, if we are not sure that we can util i ze or prepare li gnin for further util i zati on immedi atel y
at place, should not we better l et it be conserved i n any envi ronmentall y friendly form as a
stock of sequestered CO
2
for the next generations as a future resource of fossil fuel or fertile soil?
References
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The Lignoworks Strategic Network a Canadian approach to value-added lignin products

169
The Lignoworks Strategic Network a Canadian
approach to value-added li gnin products
John Schmidt
1
, John Kadla
2

1
FPInnovations, Lignoworks Liaison Manager
2
Department of Wood Science, University of British Columbia, Lignoworks Scientific Director
Abstract
The Lignoworks Strategic Network is a five-year project whose mandate is to develop technology
platforms for conversion of forest-derived lignin to value-added chemicals and materials. Funding is
primarily from Canadas Natural Sciences and Engineering Research Council with additional cash
and in-kind resources provided by the four industrial partners: FPInnovations, Alberta-Pacific,
Lignol and Weyerhaeuser. A Lignin Users Forum provides an additional opportunity for potential
downstream users to interact with Network Investigators and Industrial Partners.
As befits a university-based network, the focus is on high value, second- and subsequent gener-
ation products. Projects in thermal and catalytic processing seek to disassemble lignin into platform
chemicals that are suitably functionalized for reassembly into novel and useful polymers and lignin-
based materials. Interesting developments in the first half of the Networks life include electromag-
netic carbon nanofibres, potential incorporation of lignin-based aldehydes into organic semiconduc-
tors, pyrolysis of kraft lignin in bubbling fluidized beds, purification of pyrolysis oils using green,
switchable solvents and the discovery of lignin-degrading bacteria.
Introduction
In the coming months and years significant new volumes of lignin will become available in North
America, either as a by-product from production of cellulose-based fuels or by precipitation from the
black liquor of kraft pulp mills. Many biorefinery schemes propose that this lignin should displace
fossil fuels to provide heat and power for the rest of the biorefinery operation or kraft mill. In the
current North American context of historically low natural gas prices and low or non-existent carbon
taxes, such schemes do not generally have a compelling business case. To create a robust and
diverse lignin industry, a suite of value-added, lignin-derived products must be developed.
While the use of lignin in phenol-formaldehyde resins is expected to be an important market,
commercial development of this technology has been underway for some time. Thus, as a universi-
ty-based network, Lignoworks is concentrating on the high-value second and subsequent genera-
tions of lignin-based products.
After a brief description of the structure of forest industry research in Canada, this paper will de-
scribe the mandate of the Lignoworks Network and present a few highlights that have emerged at
the halfway point of its existence.
National Forest Sector Innovation System
Since 2005, the major stakeholders in Canadian forest research individual companies, industry
associations, federal and provincial governments, FPInnovations and university researchers have
worked to develop what has become known as the National Forest Sector Innovation System. The
objective of the system is to improve communication and comprehension of the industrys most
critical needs, to ensure that limited research resources are aligned with these needs, to avoid
unnecessary duplication of effort and to ensure that the most effective solutions are moved rapidly
from the lab bench through pilot plant and demonstration scale testing and finally to commercialization.

The Lgnoworks strategc network - a Canadan approach to vaue-added gnn products

170
Strategic Research Networks
The prmary funder of unversty scence and engneerng research n Canada s the Natura Sc-
ences and Engneerng Research Counc of Canada (NSERC). NSERCs Research Partnershps
Program provdes a varety of ntatves for ndustra research, rangng from short pro|ects of a few
months duraton to compex Research Networks.
The Strategc Networks Program s targeted at ndustra probems whose scope and compexty
requres coaboraton across a number of scence and engneerng dscpnes. It s thus an dea
too to mpement an mportant component of the Natona Forest Sector Innovaton System - the
creaton of unversty networks to f strategc gaps, address unque opportuntes and compement
exstng research programs.
Strategc Networks are funded by NSERC at a eve of $1M/year for fve years. A crtca re-
qurement for a successfu Strategc Network s the engagement of ndustra partners, who provde
addtona cash and n-knd resources. Equay mportant, ther partcpaton vadates that the pro-
posed probem s n fact an mportant one. The ndustra partners partcpate actvey through Net-
work meetngs and, where approprate, drect coaboraton n ndvdua pro|ects. They aso provde
mportant feedback on the vabty of proposed soutons and the ndustra potenta of resuts that
may not be mmedatey obvous to academc researchers.
Informaton communcated at Network meetngs s confdenta to the partners unt such tme as
t appears n peer-revewed |ournas. Ownershp of arsng nteectua property s handed accordng
the poces of each ndvdua unversty; the ndustra partners have a rght of frst refusa to nego-
tate a cense to any nteectua property that arses from Network-funded research.
FBRE Forest nnovation by Research and Education
There are currenty seven NSERC Strategc Networks that serve the compete forest sector vaue chan -
from svcuture and harvestng through umber, engneered wood products and budng systems, bo-
materas and bomass-derved chemcas and fues. These Networks ncude over 100 prncpa nvestga-
tors, 400 graduate students and post-doctora feows and most of Canadas ma|or research unverstes.
FIBRE - Forest Innovaton by Research and Educaton - s an assocaton of the Scentfc D-
rectors of these seven Networks, who meet reguary to search for opportuntes to everage re-
sources across the Networks and to speak wth a snge voce to other stakehoders n the Natona
Forest Sector Innovaton System. FIBRE aso ncudes ArboraNano, who s payng an mportant
roe n deveopng nanotechnoogy n the forest sector, wth a partcuar focus on nanocrystane
ceuose. ArboraNanos structure and mandate dffers from the Strategc Networks, but t shares
the broad goa of deveopng new products form forest resources.
Lignoworks
The Lgnoworks Strategc Network was estabshed n | anuary, 2010, wth a mandate to create
technoogy patforms for nove materas and chemcas from forest-based gnn to repace foss-
fue based chemcas and products.
Currenty, Lgnoworks ncudes ffteen prncpa nvestgators, sxteen graduate students and
tweve post-doctora feows ocated n nne Canadan Unverstes. We are partcuary proud of
havng attracted many dstngushed researchers n dverse feds - catayss, mcroboogy, poymer
chemstry, materas scence, pyroyss and green chemstry - to brng a fresh perspectve to the
probem of convertng gnn to vaue-added materas. Three of our Network Investgators, Profes-
sor Franco Berrut, Professor Php | essop and Professor Tom Baker are recent recpents of the
Chemca Insttute of Canadas Green Chemstry Awards.
Lgnoworks ndustra partners are Aberta-Pacfc, FPInnovatons, Lgno and Weyerhaeuser. Addtona
ndustra partners are st wecome, partcuary those nterested n manufacturng gnn products. An add-
tona way to nteract s through a Lgnn Users Forum, whereby companes nterested n usng gnn as a
feedstock can receve reguar updates of Lgnoworks pubcy-avaabe research and nteract wth Network
Investgators and Industra Partners to communcate the performance requrements of products of nterest.

171
Structure and Organizati on
The sxteen pro|ects wthn the Lgnoworks Network are organzed nto three dscpne-based
themes, Poymerc Products, Thermochemca Processng and Cataytc Processng, each ead by a
theme eader. A st of the pro|ects, themes and theme eaders s shown n Tabe 1.
Each pro|ect s aso cassed accordng to ts contrbuton to the Networks two technoogy pat-
forms: Functonazed Aromatcs and Lgnn-based Materas. Most pro|ects n the Thermochemca
and Cataytc Themes w produce Functonazed Aromatcs, .e., ow moecuar mass patform
chemcas, whch can then be assembed nto Poymerc Products. In some cases, of course, cata-
ytc or therma processes may retan gnns poymerc nature and may produce a poymerc prod-
uct or gnn-based matera drecty.
Maj or nfrastructure
Severa Lgnoworks nvestgators beong to specazed research unts n ther respectve unvers-
tes and brng to the Network access to these factes.
Three partcpants n the Thermochemca theme are members of the Insttute for Chemcas and
Fues from Aternatve Resources (ICFAR, www.cfar.ca) at Western Unversty n London, Ontaro.
ICFAR focuses on pyroyss and hydrotherma processng of bomass and the best use of the re-
sutng bo-o, bochar and bogas. Ths 1 900 m
2
facty consodates ab and offce space for facu-
ty, staff and students, an array of anaytca equpment and hgh-bay pot pant space. A ths w
aow promsng pyroyss and hydrotherma technooges to move qucky from the ab to pot and
arge-scae commerca testng.
Professor Tom Baker eads the Lgnoworks Cataytc Processng theme and s aso the Drector of
the Unversty of Ottawas Centre for Catayss Research and Innovaton (www.catayss.uottawa.ca).
The Centre has state-of-the-art factes for automated hgh-throughput catayst screenng, ncud-
ng anayss of reacton products. For probems that are ess amenabe to drect experment, the
Centre aso has the atest toos for computatona chemstry. Fnay, heterogeneous cataysts can
be characterzed wth a compete array of anaytca equpment: transmsson and scannng fed-
effect eectron mcroscopes, X-ray photoeectron spectroscopy, snge-crysta X-ray dffracton,
therma anayss, surface area and porosty and eectrochemca anayss.
Table 1. Lgnoworks Themes and Pro|ects.
Polymeric Products, John Kadla (University of Briti sh Col umbia), lead
Mesophase materas from gnn for hgh performance carbon fbres | ohn Kada, UBC
Lgnn-based carbon nanofbres produced by eectrospnnng Frank Ko /| ohn Kada, UBC
Lgnn-based carbon aeroges and nanostructures | ohn Kada/Frank Ko, UBC
Renewabe green compostes Amar Mohanty, Gueph
Nove peptdc and conductng poymers Bruce Arndtsen, McG
Thermochemical Processing, Cedric Briens (Western University), lead
Fudzed bed pyroyss of gnn for the producton of aromatcs Franco Berrut/Cedrc Brens, Western
Converson of gnns to aromatcs Chares Xu, Western
Mcrowave pyroyss of gnn for the producton of aromatcs | ama Chauouk, Ecoe Poytechnque
Extracton of aromatcs from gnn pyroyss os Franco Berrut/Cedrc Brens, Western
Usng swtchabe sovents to extract aromatcs Php | essop, Oueens
Catalyti c Processi ng, Tom Baker (University of Ott awa), l ead
Lgnn oxdaton usng ar and base meta cataysts Tom Baker, Ottawa
Ruthenum compex-catayzed gnn converson Bran | ames, UBC
Cataytc upgradng of gnns to vaue-added chemcas Gregory Patence, Ecoe Poytechnque
Bactera transformaton of gnn Lndsay Ets, UBC
Cataytc gnn depoymerzaton n onc quds Robert Snger, Sant Marys
Cataysts for the functonazaton of monognos Doug Stephan, Toronto

172
Research Highlights
The remander of ths paper w gve a bref overvew of the ob|ectves of each of the three research
themes and a few hghghted resuts.
Theme 1: Polymeri c Products
Theme 1 s ead by | ohn Kada, Professor of Wood Scence at the Unversty of Brtsh Coumba
and the Networks Scentfc Drector. Pro|ects n ths theme are attemptng to convert gnns va
eectrospnnng nto carbon fbres and nanofbrous porous structures, to create thermopastc/kraft
gnn bends and to use functonazed aromatcs to create nove poymers.
Professor Kada and Professor Frank Ko (aso of UBC) have used eectrospnnng to create eec-
tromagnetc carbon nanofbre mats. Unke strength renforcement appcatons, where gnn-based
carbon fbre has sgnfcanty nferor propertes compared to poyacryontre (PAN)-based fbres,
eectrospun, gnn-based carbon fbres had comparabe eectromagnetc propertes (conductvty,
saturaton magnetzaton, remanence, coercvty) to PAN-based fbre. Potenta appcatons for
such gnn-based materas are for eectromagnetc shedng for the mcroprocessor-based devces
that are ubqutous n modern fe.
Professor Bruce Arndtsen and post-doctora feow Davd Letch have deveoped a one-pot syn-
thess for poy-Mnchnone conductng organc poymers |1|. These are constructed from carbon
monoxde, acy chordes and mnes; the atter two can be derved from gnn-based adehydes,
carboxyc acds or acohos. The band gap of such organc semconductors can be tuned over a
wde range, by varyng the substtuents on each monomer. However, synthetc procedures used to
date nvoved aborous mut-step syntheses. The one-pot procedure provdes a rapd way to
screen a arge varety of canddates and may aso provde an avenue for the use of gnn derva-
tves n organc eectroncs, a market estmated to be worth amost $33 bon by 2017 |2|.
Theme 2: Thermochemical Processing
Theme 2 s ead by Cedrc Brens, Professor of Chemca Engneerng at Western Unversty. The
two man thrusts n ths theme are: 1) therma breakdown of gnn to patform chemcas by fudzed
bed pyroyss, mcrowave asssted pyroyss and hydrotherma deoxygenaton, 2) extracton and
separaton of vaue-added chemcas from the resutng bo-o. A notabe achevement n the theme
has been the frst successfu pyroyss of unmodfed kraft gnn n a bubbng fudzed bed.
To purfy bo-os, Professor | essop s adaptng swtchabe-sovent technoogy orgnay deve-
oped to extract soy o |3, 4|. The essence of the technque s that a hydrophobc amne sovent
such as dmethycycohexy amne can be made hydrophc by passng CO
2
through t to generate
the correspondng amne bcarbonate sat. The crude soybean o s extracted nto the hydrophobc
form of the sovent. Water and CO
2
are added, causng the amne to "swtch" to ts hydrophc form
and separaton of the phases. After separaton of the purfed o, CO
2
s removed from the aqueous
ayer to regenerate the hydrophobc sovent and water, whch can be recyced.
Theme 3: Catal yti c Processing
Theme 3 s ead by Tom Baker, Professor of Chemstry at the Unversty of Ottawa. Pro|ects n ths
theme cover the gamut of catayss scence: enzymatc gnn degradaton, homogeneous oxdaton
and reducton cataysts, heterogeneous cataytc crackng, cataytc reactons n onc quds and
cataytc converson of monognos to vaue-added chemcas.
Professor Lndsay Ets s workng on deveopment of Rhodococcus jostii RHA1, a gnn-
degradng bactera |5, 6|. Whe there has been much research on funga degradaton of gnn over
the past three decades, few commerca appcatons have appeared, party because fung are often
dffcut to work wth on an ndustra scae. Bactera such as Rhodococcus, on the other hand, are
easy scaed to ndustra fermentaton. The sgnfcance of Professor Ets fndngs to the deveop-
ment of bo-based chemcas and fues has been recognzed by the |ourna Science |7|. The pro|ect

173
wthn Lgnoworks s compemented by addtona fundng for the metagenomc aspects of the work
from a Genome Canada Large-Scae Apped Research Pro|ect.
Summary
Lgnoworks, a NSERC Strategc Network comprsed of ffteen professors n nne Canadan unvers-
tes and four ndustra partners, was estabshed n 2010 to deveop a patform of technooges to
turn convert gnn nto vaue-added materas. The ong-term ob|ectve s to dversfy the tradtona
revenue streams of the forest ndustry by provdng bobased feedstocks for ndustra materas for
the pastcs, automobe and constructon sectors.
Lgnoworks s concentratng on the second and subsequent generatons of gnn-based prod-
ucts. Unque resources avaabe to Network Partners ncude pot-scae pyroyss apparatus at
Western Unverstys Insttute for Chemcas and Fues from Aternatve Resources (ICFAR) and
state-of-the-art factes for catayst deveopment and characterzaton at the Unversty of Ottawas
Centre for Catayss Research and Innovaton.
Eary technca successes ncude eectromagnetc gnn-based carbon nanofbres wth proper-
tes comparabe to PAN-based fbre, potenta ncorporaton of gnn-based monomers n organc
semconductors, the frst successfu pyroyss of unmodfed kraft gnn n a bubbng fudzed bed,
purfcaton of pyroyss os usng green, swtchabe sovents and the dscovery of gnn-degradng
bactera.
We ook forward to many more scentfcay and commercay nterestng deveopments durng
the Networks atter phase. Readers nterested n becomng Industra Partners or partcpatng n
the Lgnn Users Forum can contact ether of the authors through the Networks web ste:
www.gnoworks.ca.
References
1. Samak, A.R., Sakaauskas, M., Arndtsen, B.A. 2011. A Paadum-Catayzed Mutcomponent
Coupng Approach to p-Con|ugated Ogomers: Assembng Imdazoe-Based Materas
from Imnes and Acy Chordes. Angew. Chem. Int. Ed. 50, p. 6552.
2. Goba Eectroncs Market to Reach US$32.8 Bon by 2017 30-8-2012 http://www.prweb.com/
reeases/organc_eectroncs/OLED_dspays/prweb8953929.htm.
3. | essop, P., Phan, L., Carrer, A., Robnson, S., Drr, C., Har|an, | .R. 2010. A sovent havng
swtchabe hydrophcty. Green Chem. 12, p. 809.
4. | essop, P., Kozyca, L., Raham, Z.G., Schoenmakers, D., Boyd, A.R., Wechser, D., Hoand, A.M.
2011. Tertary amne sovents havng swtchabe hydrophcty. Green Chem. 13, p. 619.
5. Ahmad, M., Roberts, | .N., Hardman, E.M., Sngh, R., Ets, L.D., Bugg, T.D.H. 2011. Identfcaton of
DypB from Rhodococcus jostii RHA1 as a gnn peroxdase. Bochem. 50, p. 5096.
6. Roberts, | .N., Sngh, R., Grgg, | .C., Murphy, M.E.P., Bugg, T.D.H., Ets, L.D. 2011. Characterzaton
of DyP peroxdases from Rhodococcus jostii RHA1. Bochem. 50, p. 5108.
7. Chong, L.D. 2011. Edtors Choce. Scence, 332, p. 1483.
Lgnn-based sustanabe packagng soutons

174
Lignin-based sustainable packaging sol utions
Kristiina Poppius-Levlin, Eva-Lena Hult, Jarmo Ropponen,
Catharina Hohenthal, Tarja Tamminen
VTT Technical Research Centre of Finland, P.O. Box 1000, F-02044 VTT, Finland
Abstract
O-based barrer coatngs were repaced by gnn-based coatngs, and packagng materas made
of recyced fbers were renforced by gnn addton.
A sovent fractonaton method was deveoped to produce pure and homogeneous gnn frac-
tons wth ncreased thermopastcty compared to the startng matera.
Another way to successfuy ncrease gnns thermopastcty was chemca modfcatons by es-
terfcaton reactons. Lgnns esterfed wth fatty acds formed fms wthout any externa pastcz-
ers. Lgnn fatty acd esters coatngs on paper board reduced sgnfcanty water vapour and oxygen
transmsson rates. Barrer propertes aganst water vapour were as good as, or even better, than
those of commerca PLA (poy actc acd).
Unmodfed softwood and hardwood kraft gnns precptated on recyced fbers ncreased
strength, bondng and water resstance of packagng materas, e.g. corrugated boards. Accordng-
y, at east 20% of fbers can be repaced by gnns.
The carbon footprnt resuts for two new gnn-based products ndcated reductons n green-
house gas emssons by ncudng gnn ether n the furnsh to compensate fbres and gan ghter
weght or as barrer matera to repace o-based barrer coatngs.
ntroduction
Lgnn s one of the most abundant natura poymers, together wth ceuose and hemceuose.
Durng the annua producton of 130 mon tonnes of chemca pup, ca. 60 mon tons of kraft
gnn s annuay produced. However, ony 1-2% of that s soated for chemcas and matera ap-
pcatons. The rest of gnn serves as fue. The ony mportant producer of kraft gnn (and ts de-
rvatves) s the US Company MeadWestvaco, wth an estmated annua producton of ca. 50 000
tons. Metso has, however, started saes of commerca LgnoBoost soaton pants.
Most ndustray used kraft gnn s frst converted to water soube products, e.g. to sufonated
gnns, before varous uses |1|. The LgnoBond technoogy for renforcement of packagng mater-
as used hgh moar mass kraft gnn on fbres from varous sources |2|. A new appcaton s to use
gnn as a barrer matera n fber-based packages. The man products used n functona and bar-
rer coatngs on paper and board at the moment are extruson poymers and aumnum. The am of
the present work was to repace o-based barrer materas by gnn-based coatngs, and to ren-
force packagng materas made of recyced fbers by dfferent gnn addtons.
Experimental
The gnns used were softwood (SW) kraft gnn (Indun AT, MeadWestvaco) and hardwood (HW)
kraft gnn (PC13-60, MeadWestvaco) both obtaned as gft. Lgnn esters were acheved by the
standard acd chorde esterfcaton. Commerca paperboards (200g/m
2
) were coated wth gnn
esters n soutons usng an Erchsen coater. The sampes were apped as a snge or doube coatng
ayer.
The Oxygen Transmission Rates (OTR) were determned accordng to the standard ASTM
F2622-08. The tests were carred out at 23C and 50% reatve humdty. The Water Vapour
Transmission Rates (WVTR) were determned gravmetrcay accordng to a modfed ASTM E-96
procedure (wet cup method) at 23C and 50% reatve humdty.


175
Solvent fractionation
In efforts to mprove gnns thermopastc propertes a sequenta extracton method was deveoped
for softwood and hardwood kraft gnns (Fgure 1). The man soube fractons were the acetone
fracton; 23% and 39% for softwood and hardwood gnns, respectvey. The man part of gnns -
76% of softwood and 60% of hardwood gnns - remaned as nsoube resdue |3|.

Figure 1. Fractonaton of gnn by sequenta sovent extracton |3|.
The propertes of the acetone fractons were dfferent from those of the other fractons. The acetone
soube fractons had smaer weght average moar mass compared to the startng gnn or resdua
fractons, whereas the resdues had sghty hgher moar mass than the startng gnns. The soated
acetone fractons were rather homogenous wth narrow moecuar weght dstrbutons (Fgure 2).
They were aso chemcay dfferent and more hydrophc; .e. the phenoc hydroxy groups and
carboxy group contents were hgher. The gass transton temperature (Tg), determned by Dffer-
enta Scannng Caormetry (DSC), of the acetone soube softwood fracton was sgnfcanty ower
(83C) than that of the startng matera (148C), whch makes t potenta for matera appcatons
that requre thermopastc propertes.

176

Figure 2. Weght average moar masses of the gnn fractons and moar mass dstrbutons.
Esterifi cation by fatty aci ds
Both hardwood and softwood gnns were esterfed wth fatty acds havng dfferent carbon chan
engths. The fatty acds used were pamtc acd (C16), aurc acd (C12) and ta o fatty acd frac-
ton (TOFA). The TOFA used n the pro|ect was a gft from Forchem (Rauma, Fnand). It contaned
3.5% saturated fatty acds (C16 pamtc acd 1.2%, C18 stearc acd 1.5%, C20 arachdc acd
0.8%) and 86.3% unsaturated fatty acds (C18:1 oec acd 24.9%, C18:2 noec acd 52.4%, C18:3
noenc acd 9.0%). Dependng on the dosage of fatty acd (chorde) used the degree of gnn
esterfcaton can be ad|usted. Esterfcatons decreased sgnfcanty gnns gass transton tem-
perature. The hgher the degree of esterfcaton, the ower was the Tg observed for the ester. Lg-
nn TOFA ester n whch a hydroxys groups were esterfed had a Tg beow 0C.
Lignin fatty acid esters as coating and barri er materials
A the gnn ester coatngs mproved the water vapour and oxygen barrer propertes of the paper
board, .e. WVTR and OTR vaues decreased (Tabe 1). As expected, n most cases the doube
coatngs gave better resuts than the snge coatngs.
Lgnn pamtate coatngs provded better water vapour and oxygen barrer than the gnn aurate
coatngs |4|. HW gnn pamtate coatngs gave the owest OTR vaues. Ths can be expaned by
gnns ncreased thermopastcty and fm formng abty wth decreasng Tg due to the dfferent
chan ength of the fatty acds. Pamtc acd wth a onger carbon chan (C16) gave better resuts
than aurc acd wth the shorter chan (C12). It has been shown earer that the Tg of organosov gnn
esters decreased neary as the number of carbon atoms n the ester substtuent ncreased |5|.
Lgnn TOFA-ester (a hydroxy groups esterfed) coatng |6| gave as ow WVTR vaue as SW
gnn pamtate coatngs and sgnfcanty ower OTR vaues. The resuts thus show that the degree
of esterfcaton had a sgnfcant effect on barrer propertes. The water vapour barrer propertes of
the gnn ester coated paper boards were even better than those of the PLA (poyactc acd) extru-
son coated reference.

177
Table 1. WVTR and OTR of gnn pamtate (C16), aurate (C12) and TOFA-ester coated paper-
board normazed to coat weght of 10 g/m
2
. (TOFA-L-100: a hydroxy groups esterfed; TOFA-L-50:
50% of the tota hydroxy groups esterfed).
Sampl e WVTR (g/m
2
x24h) OTR (cm
3
/m
2
x24h)
Paperboard 740 >400 000
SW pamtate 122 24 200
SW aurate 238 62 900
SW pamtate, doube coated 156 31 400
SW aurate, doube coated 216 55 000
HW pamtate 118 1 500
HW aurate 243 59 100
HW pamtate, doube coated 42 1 800
HW aurate, doube coated 234 55 200
SW TOFA L-50 529 42 300
SW TOFA L-100 110 8 300
SW TOFA L-100, doube coated 101 9 200
PLA (extruson coated paperboard) 300 -

LignoBond Strength and water-resi stance
The LgnoBond technoogy was successfuy wdened for new gnn matera sources. Unmodfed
kraft gnns and VTT organosov gnn |7| (20% cacuated as dry/dry fbres) were added to recy-
ced fbers (.e. 50% magazne and 50% newsprnt). After the addton of gnn pH was ad|usted to
pH 4 wth suphurc acd n order to precptate the gnn on the fbres. The retenton was further
mproved by addng aum and a retenton agent. A the gnns ncreased paper sheets strength by
20-50% and water resstance by 90%. The remarkabe ncrease of ar resstance ndcates that the
addton of gnn has created barrer propertes to the sheet. A prerequste s that the gnn s con-
verted nto a soube form before addng t to the pup surry. Wth gnn addton the brghtness was,
however, decreased (Tabe 2).
Table 2. Change of sheet propertes as percentage compared to the reference pup.
Change as percent age SW li gni n HW li gni n Organosolv lignin.
Brghtness - 64 - 64 - 51
Ar resstance Gurey +165 +266 +318
Tense strength ndex +25 +21 +20
Tense stffness ndex +40 +40 +30
Compresson strength SCT +52 +52 +48
Water abs. Cobb60 - 92 - 90 - 91


178
Sustainabili ty evaluation Two new lignin-based cases
Our am was to drect the research of new products to a sustanabe drecton by envronmenta
evauaton usng fe cyce assessment (LCA), as we as economc and soca feasbty study and
SWOT anayss. Sustanabty evauaton was carred out for two reference products: 1) corrugated
cardboard box and 2) FBB (fodng board box) cerea package wth pastc bag nsde and for the
correspondng new gnn contanng products.
In the carbon footprnt, foss greenhouse gases (CO
2
, CH
4
and N
2
O) are ncuded and ex-
pressed as carbon doxde equvaents (CO
2
eq.). The carbon footprnt was cacuated from crade
to gate (corrugated board manufacturng) so the end of fe was not ncuded. In ths cacuaton, t
was assumed that gnn was extracted from back quor wth carbon doxde. The gnn was then
assumed to be added to the whoe corrugated board compensatng fresh fber 1:1. The added
amount of gnn DS / fber DS was here 20%. However, the amount coud aso be hgher. The n-
creased strength and thereby ower weght of the corrugated board was n ths case assumed to be
20%. So the reference board was 442 g/m
2
whe the board wth added gnn was 353 g/m
2
. Carbon
footprnt for the new gnn-based product s 20% ower than that for the reference. In case 2 the
gnn was added to test ner ony reducng test ner weght by 20% and tota weght reducton of
corrugated board was thus 10% (Fgure 3).
The LCA cacuatons n the cerea package case were done wth TOFA-gnn and wth gnn
pamtate (PA). The carbon footprnt of cerea package s 20% ower when TOFA-gnn s used as
barrer matera nstead of a pastc bag (HDPE). The carbon footprnt s, however, sghty hgher
wth gnn pamtate compared to the reference case (Fgure 3).

Figure 3. Carbon footprnt for the new gnn-based product compared to reference: 1) Corrugated
card box 2) fodng board box, e.g. cerea package wth pastc bag nsde and for the correspondng
new gnn contanng products.
The SWOT anayss ncuded the prces, costs, acceptance, markets, carbon and water footprnt
and end of fe anayss of the products.
As concuson, the gnn-based products ook promsng from the carbon footprnt pont of vew.
If the whoe vaue chan of the cerea packagng s consdered, the advantages of the new gnn
based products are the ghtness n the transportaton chan. Aso, gnn can compensate vrgn
fbre and o based products and can have ower envronmenta mpacts. Packagng aso meets the
greener demands of consumers n many ways. Opportuntes to acheve compettve marketng
advantage through water footprnt can aso be seen. In addton, the products have ght weght and
are thus ecoogca.


179
Conclusions
Lgnn esterfcaton by fatty acds and gnn fractonaton by sovents are potenta technooges
to prepare thermopastc gnn materas for varous appcatons.
Lgnn fatty acd esters are potenta materas for coatngs of fber based packagng materas,
reducng sgnfcanty water vapour and oxygen transmsson rates. Barrer propertes aganst
water vapour are comparabe to those of commerca PLA (poy actc acd).
LgnoBond technoogy s a smart and smpe process to mprove the compresson strength and
reduce the water absorpton for corrugated and fber board by gnn precptaton.
The new gnn-based products ook promsng from the carbon footprnt pont of vew, and the
products have ght weght and are thus ecoogca.
Acknowledgements
The study s part of two LgnVa pro|ects n the Tekes BoRefne program. Fundng to the
VTT/Industra consortum (Tekes, Stora Enso Oy|, UPM-Kymmene Oy|, Metstto Group, Myykosk
Oy|) and VTT/Unversty consortum (Tekes, Metso Power Oy, Oy Mets-Botna Ab, Stora Enso
Oy|, Roa Oy) s acknowedged.
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product. EP 0 355 041 B1, WO 8807 104.
3. Ropponen, | ., Rsnen, L., Rovo, S., Ohra-aho, T., Lt, T., van de Pas, D., Tammnen, T. 2011.
Sovent extracton as a means of preparng homogeneous gnn fractons. Hozforschung
65(4), pp. 543-549.
4. Hut, E.-L., Kovu, K., Wrgstedt, P., Ropponen, | ., Askkaa, | ., Sp, | ., Tammnen, T., Pop-
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Symposum on Wood, Fber and Pupng Chemstry, Tan|n, P.R. Chna, 1. P. 253.
5. Gasser, W.G., | an, R.K. 1993. Lgnn dervatves, I Akanoates. Hozforschung 47(3), p. 225.
6. Tammnen, T., Ropponen, | ., Hut, E.-L., Poppus-Levn, K. 2011. Functonazed gnn, US
Patent Fng date, 07.10.2011. Appcaton No 61/544303.
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Lgnn based carbon fbres - recent progress

180
Lignin based carbon fibres recent progress
Elisabeth Sjholm, Rickard Drougge
nnventia, P.O. Box 5604, SE-11486 Stockholm, Sweden
Abstract
Kraft gnn can be easy soated from back quor gvng a fary pure product sutabe as a bofue,
but t can aso be further vaorzed to provde new gnn products. Lgnn-based carbon fbres (CFs)
have been dentfed as the potentay most vaue-added product from a wood pup borefnery. Ths
new appcaton area has attracted great attenton, drven aso by the need to fnd aternatve raw
materas for CF to cover the demand on ght-weght compostes for structura appcatons. The
processng condtons for tradtona raw materas, many of petrochemca orgn, are taor-made
dependng on raw matera and target propertes. Thus, the optma processng condtons for gnn-
based CF are by far not gven and have aso proven to depend on the type of gnn ncudng the
processng condtons.
At Innventa research has been conducted to evauate the potenta for kraft gnn-based CF by
studyng the raw matera, the effect of dfferent treatments as we as the therma behavor of gnn
on the met-spnnng and the further transformaton nto a CF. The presentaton w gve an over-
vew of these resuts wth emphass on the stabzaton step.
ntroduction
Due to the ncreased competton among the producers of kraft pup t s mportant to evauate fu-
ture proftabe products from the wood raw matera ncudng vaorzaton of the sde streams to
transform the kraft m nto a borefnery. Besdes of the man fbre product, arge amounts of gnn
s dssoved the back quor durng kraft pupng. The deveopment of the LgnoBoost (1) process
has made t possbe to soate arge quanttes of gnn of hgh purty wthout dsturbng the chef
m operaton. The technoogy s now owned and commercazed by Metso. Currenty a LgnoBoost
nstaaton has been purchased (n the US) and two other nstaatons have been decded n two
European kraft ms. Ths gnn s conventonay used to generate heat but can aso party be used
as an externa energy product and/or for new vaue-added appcatons.
The potentay most vaue-added gnn product s carbon fbre (CF), whch consttutes the oad-
bearng component n poymer compostes. The raw materas used today are many derved from
petrochemca sources; poyacryontre (PAN, about 90%) or ptch (about 9%), but to a mnor ex-
tent aso regenerated ceuose. The fbres (or better; faments) are made by conventona tech-
nques such as wet spnnng and met spnnng, the atter apped to petroeum or tar derved ptch-
es. The carbon rch faments are then converted to CFs n consecutve steps to acheve a carbon
content of above 90%, but commony 96-98%, see Fgure 1. The processng of the so-caed green
fbres starts wth a ow temperature oxdatve stabzaton step whch s foowed by a hgh tempera-
ture carbonsaton step and sometmes aso a graphtzaton step at even hgher temperatures,
before t s surface treated through actvaton and szng. The condton of each of the producton
steps s taor-made dependng on the raw matera and the target appcaton.


181

Figure 1. Unt operaton steps of the carbon fbre process of PAN-, ptch- or rayon-based yarns. Specfc
condtons depend on raw matera and the graphtsaton step s apped for certan target quates.
Athough orgnay deveoped for the aerospace ndustry, the fna use of CF today ncudes mar-
kets such as automotve, energy converson (e.g. wnd turbne rotor bades) and sports equpment.
The tota goba demand, as estmated from the use of PAN-based CFs, s estmated to grow from
about 40 000 metrc tonnes n 2010 to 150 000 metrc tonnes n 2020, the drvng force beng the
ndustra appcatons. The expected ncrease n demand has aso put focus on deveopment of
aternatve startng materas due to the hgh costs of the conventona raw materas. In ths context
gnn, havng a carbon content of 61-66%, has been recognzed as an nterestng raw matera.
The sutabty of severa types of gnns for CF producton has been nvestgated throughout the
years, and the man emphass has been put on how to form a precursor fbre of good quaty. The
ony commerca CF derved from gnn, the Kayocarbon fbre made from gnosuphonate usng
poyvnyacoho (PVA) as pastczer, was marketed between 1967 and 1973 |2|. Besdes of the
Kayocarbon fbre, met-spnnng has been used to obtan gnn precursor fbre and amost a studes
have been aboratory scae studes of snge faments. It has been demonstrated that CF can be made
from hardwood gnn orgnatng from the steam exposon process after gnn modfcaton |3, 4|, orga-
nosov gnn such as acetosov gnn from hardwood or softwood |5, 6| and Ace gnn wth add-
ton of poyethyene oxde (PEO) as softenng agent |7|. After pretreatment, met-spnnng of hard-
wood kraft gnn (HKL) has been reported usng ether PEO or poyethyene terephthaate (PET) as
softenng agent and the obtaned fbres coud be further processed nto CFs. The so far best me-
chanca propertes of gnn-based CFs has been reported for bends of HKL/PET (75/25) |8|. Re-
centy, encouragng resuts regardng mutfament spnnng and CF producton of a HKL purfed
wth organc sovents has been reported |9|. Athough the mechanca propertes acheved were
ower than those reported for a HKL/PET combnaton t demonstrates promsng prospects for
contnuous producton of kraft gnn-based CF. In contrast, softwood kraft gnn (SKL) has for ong
been consdered unsutabe for met spnnng nto fbres |e.g. 6, 8|.
Research to evauate the potenta of makng kraft gnn-based CF has been gong on at Inn-
venta for about fve years. It has comprsed fundamenta characterzaton of kraft gnn as soated
by the LgnoBoost technoogy, studes on the therma behavor of kraft gnn, the met-spnnng of
kraft gnns, as we as the foowng converson nto gnn-based CF ncudng surface treatment.
Resuts from successfu met-spnnng of SKL nto fbres were reported ast year. These resuts
have consttuted a foundaton on deeper studes of the stabsaton of kraft gnn precursor fbres.
The presentaton w gve an overvew of these resuts, wth speca attenton on recent fndngs
regardng stabzaton.
Experimental
Detaed descrpton of the kraft gnns and condtons s gven n the correspondng terature refer-
ences.

182
Result and discussions
Maki ng precursor fibres from kraft lignin
Kraft gnn soated from back quor by the LgnoBoost process has a fary hgh purty wth respect
to carbohydrate and ash content, makng t sutabe to commercaze as a bofue. In order to make
t sutabe for processng nto CFs, the gnn fracton needs to be more homogeneous. Ths can be
accompshed through extended acd washng and/or fractonaton of the back quor pror to soa-
ton and/or modfcaton of the gnn. Other ways to mprove the processabty of kraft gnn s to
add a softenng agent.
In a comprehensve study |10| t was shown that ftraton wth ceramc membranes gves perme-
ate gnn fractons wth consderaby ower moecuar mass dstrbutons and dsperstes. The con-
comtant decrease n gass transton temperature (T
g
) aso ndcated a possbe postve nfuence
on the met-spnnabty of the studed fractonated gnns, .e. orgnatng from paper-grade pupng
of brch (HKL), eucaypt (E. globulus, EKL), spruce/pne (SKL) or hgh-yed pupng (ner) of
spruce/pne bends (LL). Usng PEO as softenng agent for HKL, contnuous fbres were obtaned
by met spnnng of unfractonated and permeate kraft gnns |11|. Later t was aso demonstrated
that, by usng a gnn-derved softenng agent (POL2), met spnnng of unfractonated SKL aso can
be performed renderng n precursor fbres of apparenty good quaty as reveaed by scannng
eectron mcroscopy (SEM) |12|. In Fgure 2, a gnn-based CF made from a bend of SKL/10%
POL2 precursor fbre s shown. The possbty to make SKL-based fbres, encouraged studes at
our aboratory on how to further process the precursor fbre nto CFs. In ths context studes on the
response to therma treatment under dfferent condtons have been studed on gnn powders and
precursor fbres.
Response to thermal treatment
The therma behavor of fractonated gnn powders (HKLP, EKLP, SKLP, LLP) was conducted n
the temperature range from 200 to 900C to determne the stabty of kraft gnns as we as the
composton of thermay nduced emsson |13|. The ma|or matera oss wth respect to pheno
products as detected by step-wse pyroyss GC/MS, was found n the temperature range 500-
600C where the domnant emtted products conssted of mono phenos wth akane and akene
sde-chans, and nuceus typca of guaacy- and syrngy gnns respectvey.

Figure 2. Lgnn-based carbon fbre based on softwood kraft gnn (SKL) and 10%POL2. The pre-
cursor fbre was oxdatvey stabsed at a heatng rate of 0.2/mn to 250C for one hour and car-
bonsed by heatng at 1/mn to 600C and thereafter 3/mn to 1 000C.

183
Prevousy |10| t was found that the man oss of matera, as observed by therma gravmetrc ana-
yss (TGA), s at around 400C for a gnn sampes and a tota yed of about 40% when treatng
the sampes to 1 000C under nert condtons. The ma|or weght oss observed n the temperature
range 200-300C wth the pyroyss-GC/MS anayss was attrbuted to guaaco and emnaton of
water from the sde-chan of the gnn moecue. Above 700C no pyroyss pheno products coud
be observed due to transformaton of the gnn to stabe structures. After oxdatve (ar) treatment at
250C, .e. condtons typcay used for oxdatve stabzaton of gnn fbres, the ma|or amount of
oxdzed and non-oxdzed pheno products reeased was shfted towards hgher temperatures
(600C), ndcatng an ncrease n stabty. Ths concuson was aso supported by the decrease n
the overa matera oss n the temperature range up to 800C. The greatest nfuence of oxdatve
treatment was observed for the softwood kraft gnns; the two hardwood kraft gnns appear to be
ess stabzed under the apped condtons. Ths refects that the CF process must be taor-made
dependng on kraft gnn orgn to acheve optma stabsaton and carbonzaton condtons.
Stabili sation of precursor fibre
The stabsaton step s mportant for the processng of CFs. The purpose s to transform the pre-
cursor fbre nto a thermoset whch w prevent the fbre from fusng n the foowng carbonzaton. It
s aso a tme consumng step, and thus needs to be carefuy optmzed. It has been reported that a
sow heatng rate s necessary to aow the shft n T
g
be hgher than the actua treatment tempera-
ture |14|. The type, presence and amount of a synthetc softenng agent nfuence the possbe
heatng rate (fna temperature 250C for one hour). Studes on powdered extrudates of HKL, nd-
cate that the heatng rate shoud be beow 0.06/mn |14|, for stabzaton of HKL/PEO fbres con-
tanng ess than 5%PEO a heatng rate of 2/C s possbe |7|, whereas for the oxdatve stabsa-
ton of HKL/PET (75/25) precursor fbres a heatng rate of 0.2/mn can be used |8|. A heatng rate
beow 0.1/mn was recenty reported necessary for oxdatve stabzaton of precursor fbres made
from HKL purfed by organc sovent extracton |9|.
The nfuence of heatng rate (0.2-1.0/C), fna temperature (230-280C) and treatment tme
0.5-2h) on the yed of fractonated gnn powders (HKLP, EKLP, SKLP) was evauated usng a
factora desgn |15|. The most mportant factor for ncreasng the yed after stabzaton was to
ower the hodng tme. On the other hand, the hghest yed (47-58%) for the hardwood kraft gnns
after carbonzaton at 1 000C was obtaned usng a heatng rate of 0.2/mn to 280C and two
hours treatment tme, but for the softwood kraft gnn ths was observed for the mdest condtons,
.e. at sowest heatng rate, owest temperature and shortest fna tme, gvng a yed of about 50%.
A consderabe ncrease, or even absence, of T
g
was observed for a stabzaton condtons, and
coud therefore not be evauated wth the factora desgn. Agan, a dfference n response towards
oxdatve stabzaton coud be observed between softwood kraft gnn and hardwood kraft gnn,
the former beng more easy stabzed and competey stabzed (no detectabe T
g
) when appyng
the sowest heatng rate. Furthermore t was found that oxdatvey stabzed precursor fbres made
from (unfractonated) HKL and 5% PEO became un-eveny oxdzed over the cross secton of the
fbre, as reveaed from sma spot anayss mode of X-ray photoeectron spectroscopy (XPS). Ths
can be expaned by the competton between the dffuson of oxygen nto the fbre and the oxdatve
reactons, the atter resutng n a skn-core structure whch aggravates the dffuson of oxygen nto
the fbre.
Recent resuts on stabzaton of precursor fbres made from unfractonated SKL and gnn-
derved softenng agent show that a fast stabzaton can be obtaned at non-oxdatve stabzaton
condtons as we, refectng the nherent structura dfference between guaacy and syrngy gnns
and the potenta to use SKL for makng gnn-based CFs of commerca cost per performance
soutons.

184
Conclusions
Despte the short perod of tme research actvtes reated to gnn-based CF has been gong on by
a mted number of research groups, promsng resuts have been acheved towards the under-
standng and optmzaton of the processng of gnns nto CFs.
Fndngs at Innventa show that precursor fbres can aso be made from softwood kraft gnn, be-
sdes of the prevous reports about ts hardwood kraft counterpart, provded that an approprate
softenng agent s used. The observed dfference n response to therma treatment s manfested as
a faster stabzaton of softwood kraft gnn as compared to hardwood kraft gnn.
Acknowledgements
The Swedsh Governmenta Agency for Innovaton Systems (Vnnova) and the Custer Borefnery II
at Innventa are acknowedged for fnanca support of the pro|ects LgnCarb and LgnCarb Add.
Former coeagues at Innventa; Ida Norberg, Gran Geerstedt and Yva Nordstrm, and Mare
Erntsson at the Insttute of surface Chemstry (YKI) are greaty acknowedged for ther contrbutons
n the named pro|ects.
References
1. hman, F., Theander, H., Toman, P., Axegrd, P. 2006. Method for separatng gnn from back
quor. Patent WO2006031175.
2. Otan, S. 1981. Carbonaceous mesophase and carbon fbers. Mo. Cryst. Lq Cryst. 63, pp. 249-264.
3. Sudo, K., Shmzu, K. 1992. A new carbon fber from gnn, | . App. Poym. Sc. 44(1), 127-134.
4. Sudo, K., Shmzu, K., Nakashma, N., Yokoyama, A. 1993. A new modfcaton method of ex-
poded gnn for the preparaton of a carbon fber precursor, | . App. Poym. Sc. 48,
pp. 1485-1491.
5. Urak, Y., Kubo, S., Ngo, N., Sano, Y. Sasaya, T. 1995. Preparaton of carbon fbers from orga-
nosov gnn obtaned by aqueous acetc acd pupng. Hozforschung 49(4), pp. 343-350.
6. Kubo, S., Urak, Y. Sano, Y. 1998. Preparaton of carbon fbers from softwood gnn by atmos-
pherc acetc acd pupng. Carbon 36(7-8), pp. 1119-1124.
7. Kada, | .F., Kubo, S., Vendtt, R.A., Gbert, R.D., Compere, A.L., Grffth, W. 2002. Lgnn-based
carbon fbers for composte fber appcatons, Carbon, 40, pp. 2913-2920.
8. Kubo, S., Kada, | .F. 2005. Lgnn-based carbon fbers: effect of synthetc poymer bendng on
fber propertes. | . Poym. Envron. 13(2), pp. 97-105.
9. Baker, D.A., Gaego, N.C., Baker, F.S. 2011. On the characterzaton and spnnng of an organc-
purfed gnn toward the manufacture of ow-cost carbon fber. | . App. Poym. Sc. 124,
pp. 227-234.
10. Brodn, I., S|hom, E., Geerstedt, G. 2009. Kraft Lgnn as Feedstock for Chemca Products.
The Effects of Membrane Ftraton. Hozforschung 63, pp. 290-297.
11. S|hom, E., Brodn, I., Drougge, R., Geerstedt, G. Carbon fbre - a new appcaton for gnn.
11
th
European Workshop on Lgnoceuoscs and Pup (EWLP). Hamburg, August 16-19,
2010. Pp. 1-4.
12. Nordstrm, Y., S|hom E., Brodn, I., Drougge, R., Geerstedt G. 2011. Lgnn for carbon fbres.
3
rd
Nordc Wood Borefnery Conference (NWBC). Stockhom, March 22-24, 2011.
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185
13. Brodn, I., S|hom, E., Geerstedt, G. 2010. The Behavour of Kraft Lgnn durng Therma
Treatment. | . Ana. App. Pyroyss 87, pp. 70-77.
14. Braun, | .L., Hotman, K.M., Kada, | .F. 2005. Lgnn-based carbon fbers: Oxdatve thermosta-
bzaton of kraft gnn, Carbon 43, pp. 385-394.
15. Brodn, I., Ernstsson, M., Geerstedt, G., S|hom, E. 2012. Oxdatve stabsaton of kraft gnn
for carbon fbre producton. Hozforschung 66, pp. 141-147.

Rapd refnng of gnoceuoscs to carbohydrates and gnn-based new materas (gnophenos)
and desgn of sustanabe ndustra network connectng forests and chemca ndustres

186
Rapi d refini ng of lignocellulosics to carbohydrates and
lignin-based new materials (li gnophenol s) and design
of sustainable industrial network connecting forests
and chemical industries
Masamitsu Funaoka
Department of Environmental Science and Technology, Mie University
1577 Tsu, Mie 514-8507, Japan
Abstract
In order to acheve the cascade-type fow of gnoceuosc components as functona materas n
human fe, a nove converson system (phase-separaton system) has been deveoped and a new
type of structure-controabe gnn-based poymers (gnophenos) has orgnay been desgned. A
key pont of the process s to set up two dfferent sovents whch are mmscbe each other for se-
ectve modfcaton and separaton of gnn and carbohydrates: hydrophobc sovent for hydrophobc
gnn and hydrophc sovent for hydrophc carbohydrates. Ths converson process works wthn
60mn wthout any heatng and pressng to gve gnophenos and soube sugars amost quantta-
tvey. The resutng gnophenos have unque functons, whch conventona gnns do not have:
hghy phenoc property, no con|ugated system, ght coor comparabe to natve gnn, structure-
varabe functon and sod-qud transformaton. The separated carbohydrates ncude water-
soube monomers, ogomers, and poymers. These are easy converted to vauabe chemcas
such as acohos, actc acd, furfura, xyto, etc. In order to create sustanabe human socety wth-
out petroeum, aphatc and aromatc types of ndustra raw materas must be derved sustanaby
from bomateras (gnoceuoscs). A new sustanabe ndustra network ntated from forests s
desgned.
Carbon flow in the ecosystem
The keywords, "Energy", "Materas", and "Envronment", are of mportance for sustanabe human
socety. Lgnoceuoscs are typca materas ncudng these three keywords. Lgnoceuoscs are
fundamenta materas, formng ong-term sustanabe carbon fow n the ecosystem through three
phases (Fgure 1): carbon doxdes are assembed by photosynthess to form bg compostes "trees"
|Moecuar assembng (potenta up) stage, Phase I|. The trees (concentrated carbons state) are
kept through the fe system for a ong tme (Potenta equvaent stage, Phase II) These assembed
moecues are graduay reeased fnay to gve carbon doxdes |Moecuar reeasng (potenta
down) stage, Phase III|. In order to create sustanabe human socety wthout dsturbng the ecosys-
tem, gnoceuoscs have to be utzed through cascade-type and ong term functonaty contro
system, foowng the eco-carbon fowng system ncudng Phase I, II and III. But n the present
human socety, after forest resources are utzed as wood and papers, the most of those are m-
medatey reconverted to carbon doxdes by burnng. Ths means that the moecuar eve potenta
of forest resources (Phase III actvty) s cut, dsturbng the ecosystem. The phase III actvtes n
moecuar eve after conventona forest and wood ndustres must be created n order to keep
sound eco-carbon fowng system. Lgnoceuoscs are composed of three poymers, ceuose,
hemceuose and gnn. Two breakthrough technooges are requred for achevng phase III actv-
tes: perfect refnng of gnoceuosc compostes and sequenta functonaty contro of the resut-
ng gnn and carbohydrate moetes.


187
LigninSustainable aromatic resource
Recenty bomateras have attracted the attenton because of ther sustanabty. There have been
ots of tras for gnoceuose utzaton n moecuar eve. However, the carbohydrate utzaton ony,
for exampe boethano producton, has been done a over the word. Lgnn has very mportant func-
tons: (a) Increase the mechanca strength for standng uprght on the earth, (b) Protect the body
aganst the attack of nsects and mcroorgansms, (c) Protect the body aganst strong UV rradaton,
(d) Sea fber ce was for water transportaton, (e) Combne fber ces to form the body, etc. Neverthe-
ess, gnns have been aways wastes n the prevous and present ndustra systems. There have been
ots of patents and research papers on gnn utzaton n the word. Ths stuaton means that the con-
ventona technooges ack some mportant factors for gnn. A new sght s now requred for gnn.

Figure 1. Schematc ustraton of eco-carbon fowng system.
Though carbohydrates and gnn both are bopoymers, the fundamenta moecuar desgns are totay
dfferent: carbohydrates have unversa desgn, same structures on the earth, whe gnn has env-
ronmenta desgn. Every gnn has dfferent structure, optmzed for the envronment. Envronmenta
factors are ncorporated n gnn structures. The combnaton of envronmenta and unversa desgns
(2:8) s a key for sustanabe matera desgns n next generaton because the most durabe bomater-
as are woods n the ecosystem. It s requred for us to understand the envronmenta desgn and
ncorporate t nto matera productons for the new generaton wthout dsturbng the ecosystem.
Lgnns are cassfed as phenoc poymers (poyphenos) because gnn precursors (confery
acoho, snapy acoho, p-coumary acoho) are phenoc monomers. However, gnn shoud be
cassfed as poyethers or poyacohos because of ow phenoc actvty (0.1-0.2/C9) and the pres-
ence of ots of aphatc OH and ether nkages. Furthermore, a gnn unts have reactve stes at
C1 (benzy) postons. Lgnns are atent phenoc poymers ncudng reactve ponts. The ma|or
envronmenta desgns ncorporated wthn gnn are as foows (Fgure 2): Varous functonaty at
C1 of sde chan, Hgh frequency of ary ether at C2 of sde chan, Bocked phenoc actvty, C-C
nked branched unts.
These features are optmzed for the envronment around gnn, mnmzng the nterna stress n
gnn. The fexbe reactvty qucky respondng to envronmenta change eads to ong term crcua-
ton of gnn n the ecosystem. On the other hand, these features of gnn ncorporatng envron-
menta factors prevent ts unversa use under every envronment such as petro-based materas.
How to sequentay reease the envronmenta factors ncorporated wthn gnn becomes a key for
effectve cascade-type gnn utzaton eadng to Phase III actvtes. Conventona ndustra process-
es ncudng hgh energy nput such as hydroyss, pupng or steam exposon destroy mportant struc-
tura unts nonseectvey, preventng the foowng functonaty contro (sequenta utzaton).
P
h
a
s
e

I
Phase II
Phase II
Phase II
Phase III
CO2
Time
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y

Life system
Supporting unit Lignocellulose
Potential Up
Potential Equivalent
Potential Down
Phase III
M
o
l
e
c
u
l
a
r

a
s
s
e
m
b
l
i
n
g

l
e
v
e
l
Carbon fl owing time
Phase I Molecular assembling stage
Phase II Trees
Molecular releasing stage
P
h
a
s
e

I
Phase II
Phase II
Phase II
Phase III
CO2
Time
P
o
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e
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CO2
Time
P
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e
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g
y

Life system
Supporting unit Lignocellulose
Potential Up
Potential Equivalent
Potential Down
Phase III
M
o
l
e
c
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a
r

a
s
s
e
m
b
l
i
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g

l
e
v
e
l
Carbon fl owing time
Phase I Molecular assembling stage
Phase II Trees
Molecular releasing stage

188

Figure 2. Dstrbuton of functona groups n gnn.
Selective transformation of native lignin and perfect refining of
lignocellulosics
Sequenta reeasng system of envronmenta factors wthn gnn has been desgned |2-8| (Fgure 3).
|Desgn I| Standardzaton of budng unts (C1 contro)
|Desgn II| Standardzaton of poymer structures (C1 contro)
|Desgn III| Standardzaton of poymer sze (C2 contro).

Figure 3. Seectve structura converson of gnn and carbohydrates.
O
OH
C2OAryl
OCH3
1 1
st st
Control Control
S
t
a
n
d
a
r
d
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a
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S
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s
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polymer size polymer size
OCH
3
Aryl-O-C1
HO-C1
2
1
- O C1
Open type
Control of Control of
polymer structure polymer structure
Control of Control of phenolic phenolic functionality functionality
C2=C1
O =C1
Aryl-O-C1
Cyclic type
C2Alkyl
C2Aryl
C2=C1
O
OH
C2OAryl
OCH3 OCH3
1 1
st st
Control Control
S
t
a
n
d
a
r
d
i
z
a
t
i
o
n

S
t
a
n
d
a
r
d
i
z
a
t
i
o
n

o
f

b
u
i
l
d
i
n
g

u
n
i
t
s
o
f

b
u
i
l
d
i
n
g

u
n
i
t
s
2 2
nd nd
Control Control
Standardization of Standardization of
polymer size polymer size
OCH
3
Aryl-O-C1
HO-C1
2
1
- O C1
Open type
Control of Control of
polymer structure polymer structure
Control of Control of phenolic phenolic functionality functionality
C2=C1
O =C1
Aryl-O-C1
Cyclic type
C2Alkyl
C2Aryl
C2=C1
C2Alkyl
C2Aryl
C2=C1
C2Alkyl
C2Aryl
C2=C1

189
Lgnn forms sem-nterpenetratng poymer network (IPN) structures wth carbohydrates wthn the
ce wa. The functonates of gnn and carbohydrates have to be controed seectvey and smu-
taneousy through snge treatment for drect synthess of gnn-based poymer from gnoceuose
compostes. Furthermore, both of gnn and carbohydrates must be converted to structure-
controabe functona materas for achevng sustanabe Phase III actvtes wthout dsturbng the
ecosystem. The precous reactvty contro, seectve functonaty contro and matchng of reacton
system are requred. Ths s the most mportant and dffcut breakthrough pont for cascade-type,
tota utzaton of gnoceuoscs.
The orgnay desgned process |2-8| ncudes the phase-separatve reacton system composed
of the organc phase (hydrophobc pheno dervatves) and the aqueous phase (concentrated acd),
whch are mmscbe each other under norma condton. The concentrated acd s a sovent for
carbohydrates, eadng to sweng carbohydrates, foowed by depoymerzaton by hydroyss, and
furthermore, works as a catayst for the fragmentaton and phenoaton of gnn. The pheno derva-
tves act as phenoaton agents for C1 standardzaton, a barrer to mnmze the attack of acd on
the gnn through sovaton, and a sovent for the gnn fractons.
Lgnoceuosc partces are sovated wth hydrophobc sovents (for exampe, akyphenos) frst,
and then, are contacted wth the acd at the nterface between both sovents. The carbohydrates
are swoen, partay hydroyzed, whe gnns are phenoated at reactve C1 postons seectvey to
gve 1,1-bs(ary)propane type structures. The ceavage of reactve C1 (benzy) ary ethers, foowed
by phenoaton resuts n the reease of network gnn to subunts. The hydrophc carbohydrates
reeased from IPN pass through the nterface to the aqueous phase, whe gnns aways stay n the
hydrophobc organc ayer, eadng to the perfect separaton of carbohydrates and gnn. Ths sepa-
raton process s acheved qucky (wthn 60mn for softwoods, 30mn for hardwoods, 10mn for
grasses) under norma condton wthout any heatng and pressng.
The resutng gnn-based materas (gnophenos) are of hgh brghtness comparabe to med
wood gnn, and qucky dssoved n sovents such as methano, ethano, acetone, doxane and
pyrdne. The amount of grafted phenos s about 25% (about 0.7 mo/C9) n softwood gnophenos
and about 30% (about 0.9 mo/C9) n hardwood gnophenos. The dfference between the speces
s due to both the fexbty of the moecue and the frequency of reactve functona groups n the
sde chans whch are caused by the baance of guaacy and syrngy unts wthn the moecues.
The TMA curves of gnophenos ndcate an apparent change of the phase at ca.130C n hard-
wood and at ca.170C n softwood, at whch those are transformed to cear qud state. That s,
natve gnns, three dmensona network poymers, are converted to branched near-type poymers
wth hgh frequency of 1,1-bs(ary)propane-2-O-ary ethers durng the process. The branched struc-
tures are formed many by coupng at guaacy C5. The moecuar weghts of softwood and hard-
wood gnophenos are 5 000-10 000 (Mw) and 3 000-5 000 (Mw), respectvey, refectng the sze
of subunts constructed by radca coupng.
It usuay takes a ong tme to perfecty swe and dssove ceuose wthn gnoceuoscs by the
acd treatment. Ths s due to the bet effect of gnn wth hghy rgd structures whch are formed
through the sef-condensaton n the eary stage of acd treatment. However, ths effect of gnn to
ceuose dsappears by the effectve phenoyss of gnn durng the phase-separaton treatment,
eadng to the rapd separaton of both consttuents. Furthermore, the rapd and seectve pheno
graftng of natve gnn s due to the gnn dstrbuton wthn the organc phase: natve gnns, whch
are rch n hydrophc functona groups, are dstrbuted near the nterface wth the aqueous phase,
resutng n frequent contact wth acd to gve rapd structura modfcatons. The resutng gnn
dervatves, whch are much more hydrophobc than natve gnns, are moved far from the nterface
area to escape from the frequent attack by the acd.
By the combnaton of pant speces (softwood, hardwood, grass) and process chemcas, the
functonaty of gnophenos are controed: thermopastcty, hydrophobcty, hydrophcty, moecu-
ar weght, recycabty, stabty, network formaton, near formaton, structure contro, functonaty
contro, compostes formaton, etc.
Ths process has been termed "Phase-separaton process". The system pants desgned specay
for tota utzaton of gnoceuoscs have been constructed n | apan: 1st (2001 n Me Unv. campus)

190
and 2nd (2003 n Ktakyushu) pants wth batch system, and 3rd (2008 n Wakayama) wth contnu-
ous system. The atest system pant (contnuous system) was constructed n Tokushma n 2012
(Fgure 4), ncudng the producton of gnophenos and soube sugars, foowed by acoho fermen-
taton, and the recovery of process chemcas.
1,1-Bs(ary)propane-2-O-ary ether unts formed frequenty n the gnn moecues through De-
sgn I can be used as swtchng devces for the structure contro (phenoc functonaty and moecu-
ar weght) |9-16|. The phenoxde ons of grafted phenos ready attack the eectron defcent C2
nuceophcay, resutng n the ceavage of C2-ary ether nkages wth the exchange of phenoc
functonaty from C1-grafted nuce to gnn nuce. Through ths swtchng treatment, moecuar
weghts of gnophenos are dramatcay decreased, whe tota phenoc actvty remans un-
changed. Snce ths type of neghborng group partcpaton s very quanttatve, the functonaty of
gnophenos can strcty be ad|usted by the frequency contro of C2-attackabe phenoc nuce
(swtchng devces) wthn the moecues. The swtchng devces are dvded nto two types: one s
the reactve devce wth a reactve pont on the nuceus, and the other s the stabe devce wthout
any reactve pont. The phenos nked to gnn sde chans through p-poston to phenoc hydroxy
group do not work as swtchng devces, due to the sterc factor and can be used as contro devces
for controng the frequency of swtchng devces wthn the moecue. There s a good correaton
between the controed moecuar weghts of gnophenos and the frequency of swtchng devces
wthn the moecue. The swtchng functon s controed by the structure of swtchng unt at C1.
The compact phenos wth hgh bascty work rapdy as swtchng devces. The rate of swtchng
functon gets sower wth the extenson of sde chans attached to swtchng unt. Usng reactve-
and stabe devces, network type- and near type poymers can be prepared, respectvey. By hy-
brdzng reactve- and stabe devces n the gnn moecues, the poymer network structures from
gnophenos can be controed. By the combnaton of orgna gnopheno unts, spacer unts and
termna unts, the structures of gnopheno-based poymers can be desgned so as to meet the
propertes requred. The resutng gnopheno poymers can be ready reeased to subunts usng
ntramoecuar swtchng unts and monomers-ogomers by the nuceus exchange technque |3|,
producng new raw materas for the next ndustra system.
Effective utilization of lignins
Lgnn s a natura poymer wth very compcated network structures. The compexty s due to the
combnaton patterns between budng unts, whch are controed by envronmenta factors. The C1 of
sde chan has a reactve substtuent (hydroxy group, carbony group or ether nkage). The seectve
pheno graftng at C1-postons eads to the formaton of new phenypropane unts between grafted
phenoc unts and gnn propane unts. Ths resuts n a dramatc change of the orgna gnn functons,
formng a new type of gnn-based poymers composed many of 1,1-bs(ary)propane type unts.
The appcatons of gnophenos are shown beow |17-48|.
(a) Recycabe compostes wth ceuose, bopoyesters, and norganc materas (gasses, metas)
(b) Raw materas for recycabe poymers
(c) Detachabe adhesves, Swtchng devces for matera recycng
(d) Eectromagnetc shedng materas
(e) Carbon moecuar sevng membranes
(f) Enzyme supports for boreactors and affnty chromatography
(g) Adsorbents for protens and metas
(h) Performance contro agents for ead-acd battery and enzymes
() Photoressts
(|) Antoxdants,
(k) UV barrers
() Hydroge
(m) Medca agents, etc.

191

Figure 4. Fourth system pant n | apan for refnng gnoceuoscs nto gnophenos and carbohydrates.
Concluding remarks
The carbon fow n the ecosystem s workng as the matera network from upstream (hgh potenta
stage) to downstream (ow potenta stage). The drect producton of post-petroeum (downstream
materas) from bomateras n the upstream dsturbs the eco-carbon fowng system wth "Energy",
"Functon" and "Tme" factors, eadng to the envronmenta destructon. That a bosystems are
baanced through sustanabe fow of energy and materas shoud be recognzed deepy. In order to
create sustanabe human socety wthout dsturbng the ecosystem, a nove desgn of human soce-
ty s requred, foowng the ecosystem and nkng the agrcutura- and ndustra feds through
functona materas.
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2. M. Funaoka I. Abe, Mokuza Gakkash 24 (1978) 256.
3. M. Funaoka, 6.6 *Nuceus Exchange Reacton, n S.Y. Ln and C.W. Dence Eds.), Methods n
Lgnn Chemstry, Sprnger-Verag, Bern Hedeberg, 1992, pp. 369-386.
4. M. Funaoka, Tapp | . 72 (1989) 145.
5. M. Funaoka, M. Matsubara, N. Sek, S. Fukatsu, Botechno. Boeng. 46 (1995) 545.
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7. M. Funaoka, Poymer Internatona 47 (1998) 277.
8. M. Funaoka, Macromo. Symp. 201 (2003) 213.
9. M. Funaoka, H. Ioka, T. Hosho, Y. Tanaka, | . Network Poymer | . 17 (1996) 121.
10. M. Funaoka, Poymer Processng 48(1999) 66.
11. Y. Nagamatsu, M. Funaoka, Trans. Materas Res. Soc. | . 26 (2001) 821.

192
12. Y. Nagamatsu, M. Funaoka, SenI Gakkash 57 (2001) 54.
13. Y. Nagamatsu, M. Funaoka, SenI Gakkash, 57 (2001) 75.
14. Y. Nagamatsu, M. Funaoka, SenI Gakkash, 57 (2001) 82.
15. Y. Nagamatsu, M. Funaoka, | . Adheson Soc. | . 37 (2001) 479.
16. Y. Nagamatsu, M. Funaoka, | . Advan. Sc. 13 (2002) 402.
17. M. Funaoka, H. Ioka, N. Sek, Trans. Matera Res. Soc. | . 20 (1996) 163.
18. M. Funaoka, M. Maeda, M. Matsubara, Trans. Matera. Res. Soc. | . 20 (1996) 167.
19. M. Uehara, Y. Nagamats, M. Funaoka, Trans. Mater. Res. Soc. | . 26 (2001) 825.
20. E. Ohmae, M. Funaoka, S. Fu|ta, Trans. Mater. Res. Soc. 26 (2001) 829.
21. | . Kadota, K. Hasegawa, M. Funaoka, T. Uchda, K. Kta|ma, | . Network Poymer, | apan 23
(2002) 142.
22. H. Kta, M. Hamano, M. Yoshno, K. Okamoto, M. Funaoka, Trans. Materas Res. Soc. | .
27(2002) 423.
23. Y. Nagamatsu, M. Funaoka, Matera Sc. Res. Internatona 9 (2002) 108.
24. Xao-S. Wang, T. Suzuk, M. Funaoka, Y. Mtsuoka, T. Yamada, S. Hosoya, Matera Sc. Res.
Internatona 8 (2002) 249.
25. H. Kta, K. Nanbu, T. Hamano, M. Yoshno, K. Okamoto, M. Funaoka, | . Poymers. Envron-
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26. Xao-S. Wang, N. Okazak, T. Suzuk, M. Funaoka, Chemstry Letters 32 (2003) 42.
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29. D. Para|u, H. Kawakta, K. Inoue, M. Funaoka, Ind. Eng. Chem. Res. 45 (2006) 8.
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32. M. Aoyag, M. Funaoka, | . Photochem. Photobo. A Chem. 181 (2006) 114.
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Bochemstry 348 (2011) 117.
Sugars and gnn from ceuosc source - hgh quaty, hgh vaue products - the "wet wood mng"
approach

194
Sugars and lignin from cellulosic source high quality,
high value products the " wet wood mill ing approach
Noa Lapidot
1
, Robert P Jansen
2
, Eran Baniel
1

1
Virdia, 6 Galgale Haplada St., Herzeliya, srael
2
Virdia, 228 Slayton Ave, Danville VA 24540 USA
noa.lapidot@virdia.com for correspondence

Hgh purty monosacchardes and gnn are obtaned from wood through a "wet wood mng" ap-
proach, that smary to corn mng optmzes a mut step process to extract maxma vaue of a
usefu components n the wood.

Figure 1. Scheme of the "wet wood mng" approach.
Cost effectve operaton of the wet wood mng s acheved by chemca and physca means. Ma|or
steps consst of szng the wood and extractng the organc extractves and ash as we as most of
the mosture, and at the same tme hydroyzng the hem sugars to monomerc C
5
and C
6
(compos-
ton depends on feedstock); the hem sugars are recovered and refned, whe the mpurtes are
separated; the cean wood chps foow to ceuose hydroyss, conducted smutaneousy wth the
separaton of the resutng hydroyzed sugars from the sod gnn; fnay, the products are recov-
ered and purfed: a sugar syrup (80% DS contanng C
5
& C
6
) havng -90% monomers of 99%
purty, and >99% purty gnn. The acd and sovents used n these processes are fuy recovered.
The sugar syrup has been successfuy fermented or chemcay converted wthout further purf-
caton by over 20 companes from Fortune 50 to technoogy startups, to obtan amno acds, bakers
yeast, carboxyc acds, p-xyene, dese, and ethano. In the framework of a BIRD GREEN pro|ect
the C
5
& C
6
mxture was used by Vrent Energy Systems to cataytcay produce hgh quaty |et
fue, whch was successfuy tested by the US Arforce to be compatbe wth petroeum fue.

Sugars and gnn from ceuosc source - hgh quaty, hgh vaue products - the "wet wood mng"
approach

195
The gnn product (Fgure 2). s soated as an odoress sod, contanng resdua ceuose (2%),
ow ash (<0.4%) and mnma sufur and chorde (<300 and <4 000 ppm respectvey). It can be
soubzed n water by a propretary process and refned further to the 99+% need for carbon fber
makng and other appcatons that requre hgh purty gnn.

Figure 2. SEM mage of gnn partce, x500.
Vrda s operatng ts Process Deveopment Unt at Denve, VA snce Apr 2012. Capacty of the
PDU s 300 pounds ds sugar and 160 bs dry gnn per day.
Ionc quds n wood and bomass dssouton and fractonaton

196
onic liqui ds in wood and biomass dissolution
and fractionation
lkka Kilpelinen, Jorma Matikainen, Pirkko Karhunen,
Arno Parviainen, Christoph Selg, Alistair W.T. King

Department of Chemistry, University of Helsinki,
P.O. Box 55 (A.. Virtasen Aukio 1), F-00014 Helsinki, Finland
Abstract

The effcent dssouton of ceuose, gnn and even wood n onc quds (ILs) has opened new
possbtes to fractonate, refne, dervatze, and generay process and utze gnoceuosc mate-
ras more seectvey and effcenty. We have screened fames of dfferent types of ILs for ther
effcency n the processng and fractonaton of wood to ts components. A new md method of
fbratng wood n neat onc qud meda has been dentfed and characterzed. These studes
have aso mproved our understandng of structure-property reatonshps concernng wood pro-
cessng n genera wth ILs. Ths study has aso provded new nsghts nto the connectvty of wood
components and wood archtecture. Ths presentaton summarzes recent deveopments, utzng
ILs for wood borefnng.
ntroduction
The nsoubty of wood n common moecuar sovents has severey hampered the deveopment of
new methods towards the effcent utzaton of wood and ts components. Today, the most com-
mon pathway for the utzaton of gnoceuosc materas s through chemca pupng, where the
gnn poymer s broken down by akane or acdc cookng to produce ceuose fbers. The re-
eased gnn s typcay burned to produce energy to fue the process.
The frst report to use moten sats for gnoceuose processng came from Graenacher |1| who
used akypyrdnum chordes to dssove ceuose, aowng for effcent chemca modfcaton. The
metng ponts of most akypyrdnum chorde sats are above 100C and as such, dont fa under
the tentatve defnton of onc quds. Oute some tme ater, Lu and Raph demonstrated that after
extensve ba-mng, wood becomes soube n dmethysufoxde-tertrabuty ammonum fuorde
(DMSO-TBAF) and dmethysufoxde-mdazoe (DMSO-Imdazoe) bnary sovent mxtures, |2|
whch may aready be consdered as onc reacton meda, for wood processng. Fnay, n 2002 the
work of Swatowsk demonstrated that some mdazoum-based onc quds, as pure moten sats
metng beow 100C, were hghy effcent sovents and reacton meda for ceuose. |3| Aong
these nes, we demonstrated that these same sovents are capabe of fuy dssovng fne sawdust
gvng homogenous soutons. |4|
Fractionation of wood using Ls
The gente and smpe dssouton process, provded by onc quds (ILs), as we as ther reatvey
nert nature provdes effcent means for the fractonaton of wood. As the whoe wood matera can
be essentay competey dssoved n ILs, a straghtforward approach for fractonaton s compete
dssouton foowed by seectve precptaton of the dssoved components. It has been demon-
strated that ceuose-rch and gnn-rch fractons can be recovered, and that the IL can be recyced
mutpe tmes. |5, 6| However, t seems on bass of terature and on our own experments that ths
knd of fractonaton ony eads to parta enrchment of some of the components.
An aternatve approach for wood fractonaton s to seek for ILs that are abe to seectvey ds-
sove some of the components. It has aready been demonstrated by MacFarene et al. that N,N-

Ionc quds n wood and bomass dssouton and fractonaton

197
dmethyammonum-N',N'-dmethycarbamate (DIMCARB), formed from the addton of dmethya-
mne to carbon doxde, s abe to effcenty extract tannns, from certan pant speces. |7| We have
aso recenty demonstrated that some mdazoum-based ILs can fbrate wood chps effcenty,
from the extracton of mnor components. |8|
Recycling and reactivity of Ls
So far, most of the pubshed terature concernng gnoceuose processng has been concentrated
on the appcaton of mdazoum-based ILs. However, the true sustanabty of prospectve pro-
cesses w depend on the chemca stabty of soutes and onc quds under process and recycng
condtons. There are aready some ndcatons that onc quds such as |emm||OAc| react chem-
cay wth gnoceuosc soutes. |9| Ths may ower the recovery of the meda upon recycng at-
hough, n the case of the reacton of C2 mdazoum postons wth C1 reducng end groups of ceu-
ose, |9| abe functonates may be ceaved by subsequent water treatments. A bgger concern s
the method of recycng to yed a pure onc qud. Hgh purty onc qud, for most processes, w
be requred to mantan effcency of dssouton and overa sustanabty of the process.
There aready exsts some exampes of truy recycabe ILs that have potenta for gnoceuose
processng. The DIMCARB approach s an exampe of a reversbe IL, whch can be purfed by
dstaton of the components. |8| We have aso recenty demonstrated that short-chan |TMGH|+
carboxyates are both capabe of rapdy dssovng ceuose and are techncay dstabe to hgh
purty (>99% purty, >99% yed), by temperature asssted dssocaton, vaporzaton and recomb-
naton of the component neutra speces. |10|

Figure 1. Dstaton of |TMGH|
+
Proponate n a short path dstaton apparatus (Kugerohr).
Ionic liquids in wood and biomass dissolution and fractionation

198
References
1. C. Graenacher, US 1943176, 1934.
2. Lu, F., Ralph, J . 2003. Plant J ournal 35(4), pp. 535544.
3. Swatloski, R.P., Spear, S.K.H., Rogers, R.D.J . 2002. Am. Chem. Soc. 124(18), pp. 49744975.
4. Kilpelinen, I., Xie, H., King, A., Granstrm, M., Heikkinen, S., Argyropoulos, D.S. 2007.
J . Agric. Food Chem. 55(22), pp. 91429148.
6. Sun, N., Rahman, M., Qin, Y., Maxim, M.L., Rodriguez, H., Rogers, R.D. 2009. Green Chem.
11(5), pp. 646655.
7. Lee, S.H., Doherty, T.V., Linhardt, R.J ., Dordick, J .S. 2009. Biotechnology and Bioengineering
102(5), pp. 13681376.
8. Tan, S.S.Y., MacFarlane, D.R., Upfal, J ., Edye, L.A., Doherty, W.O.S., Patti, A.F., Pringle,
J .M., Scott, J .L. 2009. Green Chem. 3, pp. 339345.
9. Chowdhury, S., Vijayaraghavan, R., MacFarlane, D.R. 2010. Green Chem. 12, pp. 10231028.
10. a) Liebert, T., Heinze, T. 2008. BioResources 3, pp. 576601; b) Ebner, G., Schiehser, S.,
Potthast, A., Rosenau, T. 2008. Tetrahedron Lett. 49, pp. 73227324; c) etinkol, .P.,
Dibble, D.C., Cheng, G., Kent, M.S., Knierim, M., Auer, D.E., Wemmer, J .G., Pelton, Y.B.,
Melnichenko, J .R., Simmons, B.A., Holmes, B.M. 2010. Biofuels 1, pp. 3346.
11. King, A.W.T., Asikkala, J ., Mutikainen, I., J rvi, P., Kilpelinen, I. 2011. Angewandte Chemie 50,
pp. 63016305.

Ethano-based organosov borefneres: feedstock-fexbty & economc evauaton

199
Ethanol-based organosolv biorefineries:
feedstock-flexibility & economic evaluation
Raimo van der Linden, Wouter J.J. Huijgen, Johannes H. Reith
Energy research center of the Netherlands (ECN)
+31-224-564755, vanderlinden@ecn.nl
Abstract
An economc anayss was made to nvestgate the economc potenta of dfferent feedstocks n an
organosov borefnery, producng ceuose, gnn and furfura. Cacuatons were based on an ex-
permenta optmzaton study to fnd the best reactor condtons for the process.
Resuts show that brch s economcay the most attractve feedstock wth an expected payback
tme of about 6 years. It mght aso be economcay nterestng to have a feedstock-fexbe pro-
cess, aowng the choce of the cheapest feedstock. Despte a hgher nvestment, reduced feed-
stock costs make ths opton economcay nterestng too.
ntroduction
Borefnng s the sustanabe processng of bomass nto a spectrum of marketabe products (food,
feed, materas, chemcas) and energy (fues, power, heat). ECN s deveopng an organosov-
based borefnery technoogy sutabe for converson of hardwoods and herbaceous crops nto 2
nd

generaton bofues and chemcas |2|. Athough the motvaton for the deveopment of borefneres
fnds ts orgn n targets for the reducton of greenhouse gases and a decreased dependence on
foregn energy sources, the prmary drver for the successfu mpementaton of such a borefnery s
ts proftabty.
The organosov borefnery s abe to fractonate gnoceuosc bomass nto ts man compo-
nents by extractng gnn nto an ethano/water mxture at eevated temperature and pressure. Sm-
utaneousy, the hemceuose s hydroysed and ts monomerc components and degradaton prod-
ucts dssove nto the same sovent. Ths enabes the remova of the ceuose fracton from the
mxture by ftraton. The gnn s subsequenty removed from the hemceuose hydroysate by
remova of the ethano from the mxture. Ths owers the gnn soubty, so that the gnn precp-
tates. A second ftraton step s then used to recover the gnn.
The process produces three man products: a sod hydroysabe ceuose fracton whch can be
used for e.g. ceuose ethano producton, a hgh purty gnn product for use n performance mate-
ras and chemcas, and furfura, whch s a sutabe patform chemca for bobased chemcas and
fues producton.
ECN has performed aboratory experments on four dfferent types of feedstock: wheat straw |1|,
rce straw, brch and popar. The goa of these experments was to fnd those organosov process
condtons that gve the best fractonaton. The best fractonaton s defned by the combned vaue
of the man products, .e. ceuose and gnn. The process temperature, resdence tme, the etha-
no:water rato and amount of catayst (H
2
SO
4
) were vared n a parametrc study to fnd the optma
condtons for the four bomass feedstocks.
A conceptua process desgn, based on earer work |3|, was constructed usng Aspen Pus
smuaton software. The goa of ths conceptua process desgn was to nvestgate the economc
dfferences between the dfferent types of feedstock, whch s caused by the dfferent product yeds
as we as the dfferent feedstock prces. In addton, t was nvestgated whether t s economcay
nterestng to have a feedstock-fexbe process, whch can use mutpe types of feedstock.


200
Process description
Secton 1, Organosov
Secton 2, Ceuose
Secton 4, Furfura Secton 3, Lgnn
Organosov
Ceuose
Strpper
1
2
3
4
5
6
Washer
Fter
Make up
(ethano, water)
Ceuose
Ceuose
Recyce
Furfura /
Ethano
Dstaton
Recyce
Ethano / Water Recyce
Fter
Wet
Lgnn
(to anaerobc dgester)
Furfura (aq)
Make up
(water)
Bomass
Vacuum
Lgnn
Precptator Lgnn Dryer
Lgnn
Steam
Compressor, condenser,
Pump, heater
Mosture
Furfura
purfcaton
Furfura
Water

Figure 1. Process fow sheet of the organosov borefnery.|3|

The organosov borefnery s dvded nto four sectons: the organosov secton, and three sectons
for the three products: the ceuose, gnn and furfura sectons. The organosov secton ncudes a
sze-reducton (not ncuded n the fgure), the organosov reactor where the bomass s fractonated,
and a fter where the sod ceuose pup s separated from the qud phase.
In the ceuose secton, frst the ceuose s washed to remove undesrabe components from the
adherng qud, such as dssoved gnn. The ethano s then removed from the ceuose by steam
strppng so t can be recyced.
The gnn secton contans the gnn precptator, where gnn precptates because the ethano
s removed from the souton to be recyced. The ethano vapour s compressed and recyced. The
remanng qud s removed from the sod gnn n a fter and a subsequent dryer. The qud thus
obtaned contans some sugars and other organc components, and ths can be used n an anaero-
bc dgester to produce bo-gas. However, ths s outsde the scope of the current study.
In the furfura secton, furfura and a few other sma components such as acetc acd are re-
moved from the recyce. Of those components, furfura s the ony one that s consdered a product,
and t s therefore purfed. Other components eave the process n the waste water stream.
Results
The optma process condtons, as found n the screenng for the four gnoceuosc feedstocks are
presented n Tabe 1. These optma process condtons are used as nput for the conceptua pro-
cess desgn.

201
Table 1. The optma process condtons for the four gnoceuosc feedstocks.
Feedstock Birch Wheat straw Rice Straw Popl ar
Temperature (C) 190 200 210 190
H
2
SO
4
(mM) 30 50 15 5
EtOH:H
2
O (w/w) 60:40 60:40 60:40 50:50
CGCE (% wt)
(
*
)
98% 89% -100% 99%
Lgnn recovery (% wt)
(
*
)
79% 86% 95% 80%
(
*
)
CGCE (cellulose to glucose conversion efficiency) and lignin recovery are based on the raw dry weight biomass material
Conceptual process design
Tabe 2 presents the mass baances of the four conceptua process desgns. The products from the
four types of feedstock are dentca: ceuose, furfura and gnn. The product yeds of ceuose,
gnn and furfura as shown n Tabe 2 are the actua expermenta resuts. The other resuts (mosture
contents, as we as the waste water streams) orgnate from of the process modeng. In a cases,
ceuose s the man product. Lgnn s the second product, and furfura s the smaest product
stream.
Table 2. Weght ratos of raw materas and products requred for the organosov process (bomass
nput =1).
N Birch Wheat straw Rice Straw Popl ar
Bomass (dw) 1 1 1 1
Bomass (most.) 0.116 0.116 0.116 0.116
Ethano 0.004 0.004 0.004 0.004
Water (tota ) 1.54 1.56 1.55 1.56
OUT
Ceuose (dw) 0.545 0.457 0.531 0.465
Ceuose most. 0.774 0.649 0.754 0.660
Lgnn (dw) 0.156 0.177 0.113 0.172
Lgnn mosture 0.038 0.043 0.027 0.042
Furfura (pure) 0.012 0.040 0.067 0.039
waste water 0.333 0.320 0.320 0.320
CO
2
0.018 0.018 0.018 0.018
To dgester 0.788 0.973 0.840 0.960
Economi c analysis
In ths anayss, fve scenaros are ncuded: four borefneres usng ony a snge type of feedstock,
and a ffth concept where a borefnery has the fexbty to change ts feedstock, aowng the
choce of the cheapest feedstock. The assumed costs of the feedstock are shown n Tabe 3. It s

202
assumed that the four borefneres usng a snge feedstock w pay the year average feedstock
prce, whe the feedstock-fexbe borefnery w pay the ower vaues.
It s aso assumed that the process s ocated n Western Europe. Wheat straw, brch and popar
are grown ocay, and rce straw s mported. Transportaton costs are ncuded. The scae of the
factory s 150 kton/yr. The process runs for 8 000 hrs/yr.
Table 3. Feedstock prces.
Bi omass Year average (C/ton dw)
Low val ue
(C/ton dw)
Brch 60 45
Wheat Straw 70 55
Rce Straw (mported) 70 55
Popar 60 45

Beow, the economc anayss of the feedstock-fexbe borefnery s shown as an exampe. In ths
anayss, t s assumed that the feedstock-fexbe borefnery uses equa amounts of a four types of
bomass. The amounts and costs of the raw materas are shown n Tabe 4.
Table 4. Raw materas costs of the feedstock-fexbe borefnery.
n Scale (kton/yr) price (C/ton dw) MC/yr
Brch (dw) 37.5 45 1.69
Wheat straw (dw) 37.5 55 2.06
Rce Straw (dw) 37.5 55 2.06
Popar (dw) 37.5 45 1.69
Ethano 0.525 750 0.39
Water 234 1.75 0.41
Sub Tota 8.30

The process s fuy heat ntegrated. It s assumed that steam producton s outsourced, and a prce
of 27 C/ton s assumed for steam. The waste water stream s assumed to cost 5 C/ton, even though
t contans vauabe organc components whch can be used to produce bo-gas n an anaerobc
dgester. The uttes are sted n Tabe 5.


203
Table 5. Uttes of the feedstock-fexbe borefnery.
tem
Amount
(kton/yr)
Pri ce
(C/ton)
Costs
(MC/yr)
Steam (heatng ony) 183.6 27 4.96
Coong water 10 903.3 0.05 0.55
Waste water treatment 174.6 5 0.87
kWh/yr Prce (C/kWh) MC/yr
Eectrcty 9 440 000 0.1 0.94
Tota 7.32

The operatng costs are estmated usng a standard terature method |4|. The man tems are the
raw materas (8.30 MC/yr, Tabe 4), uttes (7.32 MC/yr, Tabe 5) and mantenance (6.55 MC/yr, or
7.5% of the capta nvestment costs). Other tems such as abour, pant overhead and taxes brng
the tota operatng costs to 32.8 MC/yr.
The pant ncome s the sum of the revenues from the three man products. Ceuose s the pr-
mary product, both n quantty as we as economcay. It shoud be noted that ceuose quaty was
optmzed for enzymatc hydroyss, not for paper producton.
Table 6. Income of the feedstock fexbe borefnery concept.
Product Producti on (kton/yr) Pri ce (C/ton) ncome (MC)
Pup (Ceuose) 74.9 350 26.2
Lgnn 23.2 750 17.4
Furfura 5.9 625 3.7
Tota 47.3

The capta nvestment was estmated usng a standard terature method |4|, and was based on the
modeng resuts. The tota fxed capta nvestment of a fve borefnery cases are shown n Tabe 7.
The varaton n the costs of the sectons n the dfferent scenaros depends on the dfferent fow
rates, whch resut from dfferent product yeds n the organosov reactor. It was assumed that the
sze reducton (e.g. mng) s 50% more costy n the case of a fexbe feedstock.
In a cases, the organosov secton s the most expensve, accountng for about a thrd of the to-
ta CAPEX. The organosov secton s aso the process secton where the uncertanty about the
nvestment costs s hghest.
The payback tme s cacuated usng the ncome, operatng costs (OPEX) and capta costs
(CAPEX) as nput. Tabe 7 shows that the organosov borefnery usng brch as feedstock s the
most proftabe, whch s argey due to the expected ower costs of the feedstock. The fexbe-
feedstock borefnery s aso economcay nterestng, despte beng the concept wth the hghest
nvestment costs.


204
Table 7. Overvew economcs of the organosov borefnery concepts.
Birch Wheat straw Rice Straw Popl ar Mixed feed
Income (MC/yr) 47.3 47.7 46.9 47.4 47.3
OPEX (MC/yr) 33.2 35.9 35.7 34.2 32.8
CAPEX (MC/yr) 81.7 82.0 80.0 81.8 87.3
Payback tme (yr) 5.78 7.00 7.15 6.19 6.04
Concl usi on
The process condtons of the organosov process were optmzed for four types of gnoceuosc
feedstock. These optmzed process condtons, and the resutng product yeds were used as nput
for a conceptua process desgn and an economc evauaton. The economc evauaton shows that
brch s the most economcay nterestng feedstock, because t s expected to be cheaper than for
exampe straw, whe amost the same amount of ncome can be generated.
It mght aso be economcay nterestng to have a feedstock-fexbe process, aowng the
choce of the cheapest feedstock. Despte a hgher nvestment, reduced feedstock costs make ths
opton economcay nterestng too.
The study has shown that a sgnfcant addtona nvestment can be made wthout any penates
regardng the economc payback tme of the process. Payback tmes of around 5-7 years seem
feasbe.
Acknowledgement
The work reported here has been performed n the framework of the EC Integrated Pro|ect
BIOCORE (http://www.bocore-europe.org/), wth fundng from the European Communtys Seventh
Framework Programme (FP7/ 2007-2013) under grant agreement nFP7-241566.

References
1. Wdschut, | ., Smt, A.T., Reth, | .H., Hu|gen, W.| .| . 2012. Optmsaton of ethano-based orga-
nosov fractonaton of wheat straw for the producton of gnn and enzymatcay dgestbe
ceuose. (Submtted.)
2. Hu|gen, W.| .| ., Smt, A.T., Reth, | .H., den U, H. 2011. Cataytc organosov fractonaton of
wow wood and wheat straw as pretreatment for enzymatc ceuose hydroyss. | ourna
of Chemca Technoogy & Botechnoogy 86(11), pp. 1428-1438.
3. van der Lnden, R. 2011. Conceptua Process Desgn and Senstvty Anayss of an Organosov
Based Wheat Straw Borefnery, XIX ISAF conference, Verona, Itay.
4. Snnott, R.K. 1983. Couson & Rchardsons Chemca Engneerng, Voume 6, Butterworth
Henemann, Oxford.
Bobutano from forest resdues - a process utzng SO2-ethano-water fractonaton and ABE
fermentaton

205
Biobutanol from forest residues a process utilizing
SO
2
-ethanol-water fractionation and ABE fermentation
Minna Yamamoto
1
, Evangelos Sklavounos
1
, Shrikant Survase
2
, German Jurgens
2
,
Tom Granstrm
2
1, 3
1
Department of Forest Products Technology, Aalto University, F-00076 AALTO, Finland
2
Department of Biotechnology and Chemical Technology, Aalto University, F-00076 AALTO, Finland
3
Department of Chemical and Biological Engineering,
University of Maine, 5737 Jenness Hall, Orono, ME 04469-5737 USA
Abstract
A process for the producton of bobutano from forest resdues, such as branches, tree tops and
stump wood, s presented. Target of the process s to utze ceuose and hemceuose derved
wood sugars as a feedstock for bofue producton by ABE (acetone-butano-ethano) fermentaton
technoogy. The presentaton concentrates on the bomass fractonaton technoogy and enzymatc
hydroyss to obtan sugars from bomass. Addtonay, a summary s provded of the resuts ob-
taned from spent quor condtonng and subsequent fermentaton of sugars to butano.
It s demonstrated that the SO
2
-ethano-water (SEW) fractonaton technoogy (whch s used by
API n a patented Borefnery process caed AVAP
TM
|1|) effcenty fractonates both softwood and
hardwood bomass n ony 30 mn at 150C temperature. Hemceuose sugars are dssoved n
hgh yed (80%) n the spent fractonaton quor and of these up to 50% are n monomerc form.
Sugar degradaton products are not formed n notabe quanttes due to the short treatment tme.
Degnfcaton s effcent, beng 89% for HW bomass and 64% for SW bomass after ony 20 mn
treatment. The spent quor s condtoned for the recovery of cookng chemcas and to mprove ts
propertes for fermentaton.
Ceuose remans as sod resdue whch therefore s enzymatcay hydroysed to obtan gu-
cose. Gucose yeds up to 95% are acheved for HW ceuosc resdues utzng a commerca
enzyme mxture at 3% enzyme dosage on substrate whereas the SW resdues are shown to re-
qure hgher enzyme dosages. The dfferences n enzymatc dgestbty are partay expaned by
the chemca characterstcs of these feedstocks.
Fermentaton of condtoned spent fractonaton quor has been successfuy carred out usng a
patent pendng fermentaton coumn technoogy where wood pup s used as ce mmobzaton
matera. ABE sovent mxtures were produced by a Clostridium acetobutylicum stran wth produc-
tvty of 4.86 g/L/h and tota yed of 0.27 g/g sugars wth condtoned quor from spruce chps frac-
tonaton. We are aso deveopng a metabocay engneered Costrdum stran whch s producng
sopropano nstead of acetone n the ABE mxture.
ntroduction
Goba demand for bofue s ncreasng fast. It s cear that n the future bofues w be produced
from gnoceuosc bomass such as agrcutura and forest resdues, energy crops and waste pa-
per. Nevertheess, there are severa obstaces to overcome n deveopng an economcay vabe
process for the converson of these feedstocks nto bofue. Cost effectve fractonaton and conver-
son technooges have to be deveoped. Ideay those shoud be abe to treat varous dfferent types
of bomass ocay avaabe.
Ths study presents a promsng process where forest resdues (tree tops, branches, stumps) are
converted nto a bofue consstng of a mxture of sopropano, butano and ethano. The fow da-
gram of the process s presented n Fgure 1. In the frst stage of the process forest bomass s
fractonated usng the SO
2
-ethano-water (SEW) fractonaton technoogy to dssove hemceuoses
and gnn n the spent quor |2, 3|. The method s hghy sutabe for borefneres snce contrary to
acd suphte treatment t s omnvorous, does not requre an mpregnaton stage or cause oxdaton

fermentaton

206
of sugars. Addtonay, t aows more economca scae due to the smpe recovery of ethano and
SO
2
by evaporaton and condensaton/absorpton.
After evaporaton to recover cookng chemcas, the spent quor s condtoned through steam
strppng, mng and cataytc oxdaton to mprove ts propertes for fermentaton |4, 5|. SO
2
has to
be fuy removed and recovered due to ts toxcty to the ABE bactera, as we as due to the eco-
nomca vabty of the process. Other nhbtors ncudng gnn, furanc compounds and formc acd
must aso be removed.
Ceuose s preserved n the sod resdue and undergoes enzymatc hydroyss for the recovery
of gucose from ceuose and mannose and xyose from resdua hemceuoses n the pup |6|. The
target of our studes was to determne the rate of hydroyss, gucose yeds and the effect of pup
propertes on enzymatc dgestbty.
In the fna stage of the process, sugar streams are sub|ected to acetone-butano-ethano (ABE)
fermentaton by Costrda to produce bochemcas sutabe as drop-n fue |7, 8|. A metabocay
engneered C. acetobutylicum stran whch s producng sopropano nstead of acetone s aso
under deveopment |9|. In ths presentaton, we revew the most mportant outcomes of ths re-
search pro|ect.
SEW fractonaton
(pupng)
Evaporaton and
condtonng
Fermentatonand
separaton
Butano
Acetone/Isopropano
Ethano
Make-up Ethano
+SO2
Bomass/
wood
Lgnosufonates
Ethano
+SO2
Gucose
Xyose
Mannose
Hemceuose
monosugars,
gnosufonates
Enzymatc
hydroyss
Recyced fbres
Sod
resdue
(pup)
"Organosov"gnn
Dssovng/
papermakng
pup

Figure 1. Fow dagram of the process.
Experimental
The raw materas used n the fractonaton experments were ar dred screened hardwood (HW)
and softwood (SW) bomass resdues consstng of oggng resdues such as branches. The bo-
mass was fractonated usng the SEW fractonaton method at the foowng condtons: temperature
150C, SO
2
concentraton 12%, ethano concentraton 55% (v/v), quor-to-wood rato (L:W) 6:1 L/kg
and fractonaton tme 20/30/60 mn. Experments have aso been demonstrated at a ower L:W
rato (3:1) more sutabe for commerca practse |5|. Mass baances of fractonaton were deter-
mned by anaysng the chemca composton of raw materas, sod resdues of fractonaton
(pups) and spent quors. More detas about the fractonaton method and the anayss methods
used have been pubshed earer |2, 3|.
fermentaton

207
Enzymatc hydroyss experments were carred out accordng to NREL technca report |10|. The
commerca enzyme mxture Cec CTec2 from Novozymes was used.
The spent quor was condtoned by frst evaporatng t under vacuum unt about 70% weght
reducton to remove SO
2
and ethano. Subsequenty, steam strppng was done where resdua SO
2

was amost totay removed. Overmng wth Ca(OH)
2
was done to remove some nhbtors and to
make quor sutabe for fermentaton |11|. Fnay, the quor was cataytcay oxdzed to convert
resdua sufte ons to sufate and fuy emnate the remanng SO
2
. The ron catayst aso func-
toned as a mcronutrent source to Costrda bactera. |5|
At ab scae, batch as we as coumn fermentaton experment were performed usng spent q-
uor as a substrate for Clostridia acetobutylicum DSM 792. The batch experments were carred out
n 125 m screw cap bottes wth 50 m producton medum. It was purged wth ntrogen and auto-
caved at 105 Pa (121C) for 20 mn and cooed. It was nocuated (5% v/v) wth 20 h actvey grow-
ng seed cuture and ncubated for 96 h at 37C. The effect of duton of SEW quor was studed on
producton of sovents. The SEW spent quor was duted as 2-fod, 4-fod and 8-fod wth water to
make t sutabe for growth and fermentaton of costrda. The effect of suppementng extra gucose
(15, 25 and 35 g/) to the 4-fod duted SEW quor was aso studed to smuate the addton of
gucose derved from the pup. The medum composton obtaned was tested for contnuous opera-
ton. The effect of duton rate on sovent producton, productvty and yed was studed n coumn
reactor consstng of mmobzed Clostridium acetobutylicum on wood pup.
The resuts obtaned and pubshed |2-8, 12| n ths pro|ect have reveaed the hgh potenta of ths
process as a future borefnery patform durng the past four years. Here, we shorty dscuss the
man fndngs obtaned wthn each stage of the process.
Fracti onation of biomass
SEW method has been shown to fractonate dfferent types of bomass very rapdy and the knetcs
of fractonaton are smar for dfferent speces |2, 3|. Aso HW and SW bomass derved from forest
resdues are effcenty fractonated by ths method. For exampe, 30 mn treatment (ncudng the
heat-up tme) at 150C temperature dssoves 80% of hemceuose sugar n the spent quor wth-
out notabe degradaton of the dssoved sugars. About haf of the dssoved hemceuoses are
present n monomerc form and the share ncreases durng subsequent condtonng. Ceuose
remans n the sod resdue. Acety groups and uronc acds from the hemceuose sde chans are
amost fuy dssoved wthn the frst 30 mnutes. However, f fractonaton tme s extended, uronc
acds and hemceuose sugars start to graduay degrade formng products such as CO
2
and furfu-
ra, respectvey.
Degnfcaton s rapd especay for HW bomass snce 90% of gnn s removed wthn 20 mn
treatment. SW bomass degnfcaton s notaby sower; ony 64% gnn s removed wthn 20
mnutes. Reasons reated to the sow degnfcaton are suspected to be the hgher ash and extrac-
tves content n SW bomass.
Fgure 2 presents the mass baances of HW and SW fractonaton based on the components ds-
trbuton n the raw matera, sod resdue and spent quor.
fermentaton

208

Figure 2. The dstrbuton of wood components n sod resdue and spent quor durng HW (eft)
and SW (rght) bomass SEW fractonaton at 150 and 12% SO
2
concentraton.
Enzymatic hydrolysis of the solid resi dues of fractionation
The resuts obtaned on enzymatc hydroyss have reveaed that SEW resdues can be effcenty
hydroysed as ong as ther gnn content s ow |6|. In our studes, the man nhbtor for effcent
hydroyss was found to be the resdua gnn n the sod resdues. Thereby, HW pups wth ow
gnn content (4-6%) gave 95% gucose yeds wth 3% enzyme dosage on pup (4.8 FPU/g ceuose),
whereas SW pups (gnn content 17-21%) requred 10% dosage on pup (19.2 FPU/g ceuose) to
reach 85% gucose yeds. Nevertheess, the enzymatc dgestbty of SEW SW pups s comparabe to
that reported n the terature for a varety of dfferent pretreated SW bomass feedstocks. We aso
found that hydroyss yeds of SW pups can be mproved and enzyme dosage reduced by optmzng
the enzyme mxtures. We are aso workng on mprovng the degnfcaton of SW bomass snce
ths was found to be crtca for successfu enzymatc hydroyss.
Spent liquor conditioning
The condtonng resuts of the SW spent quors |5| show that the fna treated quor s sutabe for
fermentaton. The amount of fermentaton nhbtors n the quor s very ow and about 70% of the
sugars are present n monomerc form. Sugar concentratons of 62.0 g/L or 13.0 g/ 100 g OD SW
bomass have been obtaned for the fna condtoned quor. However, there s st room for m-
provement snce about 30% of the sugars are ost durng the entre condtonng process. Addton-
ay, a more compete remova of gnn from the spent quor may be necessary to ncrease the
quor fermentabty.
ABE fermentation
The ABE fermentaton technoogy has been optmzed for the producton of commodty chemcas
from SEW condtoned spent quors. Wthn ths pro|ect a patent pendng fermentaton coumn,
whch factates effcent fermentaton wth hgh sovent productvty, has been demonstrated |12|.
ABE fermentaton tests show that the condtoned and resn treated spruce chps quors are fer-
mentabe by C. acetobutylicum DSM 792 upon 4-fod duton and suppementaton wth gucose. In
batch experments, the maxmum concentraton of tota ABE was found to be 8.79 g/ usng 4-fod
duted SEW quor suppemented wth 35 g/ of gucose. In contnuous coumn experments, ABE
sovents are produced at a tota yed of about 0.27 g/g sugars and wth productvty of 4.86 g/L/h |8|.
fermentaton

209
Further mprovements n productvty and yeds of sovents are expected as part of present work to
scae-up the coumn technoogy.
We are aso workng on the metabocay engneered Costrdum stran whch produces sopro-
pano nstead of acetone. Addtonay, a contnuous sovent recovery system w be deveoped.
Conclusions
The SO
2
-ethano-water method s an attractve opton for the fractonaton of gnoceuosc bo-
mass. Lgnn and hemceuoses rapdy dssove n the spent fractonaton quor whereas ceuose
fracton fuy remans n the fbers as a source of gucose obtaned n hgh yed by enzymatc hy-
droyss.
Ethano and SO
2
are recovered from the spent fractonaton quor, and then the quor s cond-
toned to form an aqueous souton contanng a hgh concentraton of hemceuose monosugars.
The fna condtoned quor s fermentabe by Costrda bactera to sopropano, butano and ethano
wth or wthout suppementaton by gucose obtaned from the enzymatc hydroyss. Further optm-
zaton and mprovement of a process steps of ths Borefnery patform are ongong.
Acknowledgements
Fnanca support of Tekes (Fnnsh Fundng Agency for Technoogy and Innovaton) and ndustra
pro|ect members (ABB, Amercan Process Inc., Andrtz, Kemra, Neste O, Ruukk Group, St1 Bo-
fues, Stora Enso, UPM) through the BoRefne program s greaty acknowedged.
References
1. Retsna, T. et a. Method for the producton of fermentabe sugars and ceuose from gnoceu-
osc matera, U.S Patent No. 8,030,039, October 4, 2011.
2. Iakovev, M. 2011. SO
2
-Ethano-Water (SEW) Fractonaton of Lgnoceuoscs. Doctora dsser-
taton, Aato Unversty, Fnand.
3. Yamamoto, M., Iakovev, M., Van Henngen, A. 2011. Tota mass baances of SO
2
-ethano-water
(SEW) fractonaton of forest bomass. Hozforschung 65(4), pp. 559-565.
4. Skavounos, E., Iakovev, M., Yamamoto, M., Tersvuor, L., | urgens, G., Granstrm, T., Van
Henngen, A. 2011. Condtonng of SO
2
-ethano-water spent quor from spruce for the
producton of chemcas by ABE fermentaton. Hozforschung 65(4), pp. 551-558.
5. Skavounos, E., Iakovev, M., Van Henngen, A. 2012. Study on condtonng of SO
2
-ethano-
water spent quor from spruce chps/softwood bomass for ABE fermentaton. European
Workshop on Lgnoceuoscs and Pup (EWLP), Espoo, Fnand, August 27-30.
6. Yamamoto, M., Iakovev, M., Van Henngen, A. 2012. Enzymatc hydroyss of hardwood and
softwood bomass fbers reeased by SO
2
-ethano-water fractonaton. European Work-
shop on Lgnoceuoscs and Pup (EWLP), Espoo, Fnand, August 27-30.
7. | urgens, G., Survase, S., Berezna, O., Skavounos, E., Lnnekosk, | ., Kurk|rv, A., Vkev, M.,
van Henngen, A., Granstrm, T. 2012. Butano producton from gnoceuoscs. Botech-
noogy Letters 34(8), pp. 1415-1434.
8. Survase, S.A., Skavounos, E., | urgens, G., van Henngen, A., Granstrm, T. 2011. Contnuous
acetone-butano-ethano fermentaton usng SO
2
-ethano-water spent quor from spruce.
Boresource technoogy 102(23), pp. 10996-11002.
fermentaton

210
9. Lee, | ., | ang, Y.-S, Cho, S.| ., Im, | .A., Song, H., Cho, | .H., Seung, D.Y., Terry Papoutsaks, E.,
Bennett, G.N., Lee, S.Y. 2012. Metaboc Engneerng of Costrdum Acetobutycum
ATCC 824 for Isopropano-Butano-Ethano Fermentaton. Apped and Envronmenta M-
croboogy 78(5), pp. 1416-1423.
10. Seg, M., Wess, N., | , Y. 2008. Enzymatc Saccharfcaton of Lgnoceuosc Bomass. NREL
Laboratory Anaytca Procedure (LAP).
11. Ouresh, N., Saha, B.C., Den, B., Hector, R.E., Cotta, M.A. 2010. Producton of butano
(a bofue) from agrcutura resdues: Part I - Use of barey straw hydroysates. Bomass
Boenergy 34, pp. 559-565.
12. Survase, S.A., van Henngen, A., Granstrm, T. 2012. Contnuous bo-cataytc converson of
sugar mxture to acetone-butano-ethano by mmobzed Costrdum acetobutycum DSM
792. Apped Mcroboogy and Botechnoogy 93(6), pp. 2309-2316.
Upgradng pup m waste streams for ntegraton wth fsh farmng

211
Upgrading pulp mill waste streams for integration
with fish farming
Adj prof Nippe Hylander
1
, Dr Ragnar Johannsson
2
,
Christer Svanholm
3
, Liselotte Uhlir
4
, Clas Engstrm
4

1
F Pulp&Paper, SE-169 99 Stockholm, Sweden
2
Matis ohf celand, Vnlandslei 12, 113 Reykjavk, celand
3
Eurocon Engineering, SE-891 26 rnskldsvik, Sweden
4
Processum Biorefinery nitiative, SE-891 22 rnskldsvik, Sweden
The Processum pre-study
Background
Processum Borefnery Intatve has, fnanced by Vnnova, made a pre-study of the technca and
economca potenta to ntegrate a pup m wth and based fsh farmng n recrcuated systems.
The nvestgaton was performed by F n coaboraton wth Eurocon. A reference group wth ex-
perts from the Doms| m and connected ndustres, fsh handng and dstrbuton companes,
experenced fsh farmers, regona organsatons wth nterests n fsh farmng and researchers from
SLU, were consuted durng the pro|ect. The man purpose of the pre-study was to assess the po-
tenta synerges n utzng waste heat from the ndustry for warmng, cross utzaton of waste
water nutrents and fermentaton of sugars nto fsh feed protens.
The concept has a potenta to decrease the envronmenta mpact from fsh farmng and pro-
mote more sustanabe fsh producton by mnmzng water effuents both from pup ms and fsh
breedng and smutaneousy avodng arge scae "vacuum ceanng" of oceans for scrap fsh con-
verted nto fsh feed.
Wth the Doms| suphte m as the case studed, the nvestment and operatng costs have been
assessed for a pant producng 300 t/y of Tapa. The technca concept evauated n ths study s
based on experence from Dr. Ragnar | ohannsson and the pot pant for producton of tapa whch
has aready been n successfu operaton on Iceand for severa years. Eurocon has modfed the
concept to be appcabe for the northern Swedsh condtons and ntegraton wth the Doms| M.
Results and conclusions
The Processum pre-study resuts n a desgn of a possbe fsh breedng pant ntegrated wth the
Doms| m paced n an avaabe budng. The pre-study aso shows a frst nvestment- and proft-
abty cacuaton and mportant connectons have been made wth possbe partners regardng fsh-
handng and dstrbuton.
The pre-study concudes that 300 t/y s a too sma producton but that a 10 tmes arger scae
may have the potenta to be economcay vabe, provded that "sustanabe grown fresh fsh fets"
can be marketed at prce eves comparabe to hgh quaty samon or perch fets.
The vaues of the synerges are tentatvey estmated and the concuson s that the argest po-
tenta s n ntegrated proten producton from dssoved and hydroyzed sugars n the spent back
quor and waste streams. The fermentaton of these nto sutabe hgh quaty protens are presenty
under study by Processum Borefnery Intatve n a coupe of pro|ects.
Issues that need to be further nvestgated, besdes fndng a ocaton whch makes a ten tmes
arger pant possbe, are to evauate the dentfed synerges for ths arger scae pant, for exampe:
Possbtes to use ntrogen and phosphorus from the fsh pant waste water to reduce
chemca costs n the m externa ceanng pant.


212
Possbtes to repace the most expensve protens n the commerca fsh feed wth protens
produced from the m waste streams.
Evauaton of the advantages wth ocay produced fsh feed.
Production of tropical fish and fish feed experience from celand
Background
Constant nnovaton has made t possbe to farm tropca and subtropca fsh n cod cmates.
Famng cose to the target markets has a beneft for producers and proftabe unts can be but to
bend the course of nature and produce fresh products that otherwse woud have to be mported
from esewhere to meet market demands.
The performed Processum pre-study s based on severa years of experence regardng produc-
ton of the tropca fsh tapa n a pot pant on Iceand.
Tapa grows very fast at 28C and s not prone to scknesses and easy to farm. Tapa has
been farmed a over the word for centures - as far back as ancent Egypt. In fact, many beeve
tapa s the fsh | esus used to feed the 5 000. Tapa s one of the top fve most popuar fsh n the
USA. Tapa fets are whte and frm wth md favour. The producton per unt s much hgher than
n trout or char per unt area whch makes tapa more productve n a sustanabe way than produc-
ng trout or arctc char. As an omnvorous speces (eat both pant and anma matera as ther pr-
mary food sources) tapa feed formuaton can ncude more varetes of raw materas than carn-
vores fsh ke trout.
Recirculation systems and Benefits of Closed Culture Systems
Recrcuaton systems are aquacuture systems (RAS) n whch the ma|orty of water s reused fo-
owng the remova of sods and the boogca converson of dssoved ammona to ntrate. Water
quaty and chemstry s often modfed before the water s returned to the fsh. Reguatons of water
suppes (quaty and quantty), waste dscharges and heath reguatons are becomng more and
more onerous for the ndustry. The Ma|or system components are the foowng:
Sods Remova: The frst step n recrcuaton of water s the remova of sods. Inadequate
sods remova can resut n eevated ammona eves, ow oxygen eves, ower system carry-
ng capacty, reduced water carty, hgher aeraton/oxygenaton costs and a poorer quaty
fsh product. Sods remova s very mportant because t dramatcay reduces the organc
content of the water. For sods remova drum fters wth 100 m fter are used.
The next step s bo-ftraton. Bo-ftraton s the use of naturay occurrng bactera to con-
vert toxc ammona to non-toxc ntrate through the toxc ntermedate ntrte. Ths process
s often caed ntrfcaton or ammona oxdaton. Two genera (or groups) of bactera ac-
compsh ths process. The group of bactera that convert ammona to ntrte s named N-
trosomonas and the group of bactera that convert ntrte to ntrate s named Ntrobactera.
Crcuar tanks are used to ensure good hydrauc propertes and proper sef-ceanng of the
tanks. Aeraton and Oxygenaton: Foowng bo-ftraton, the water requres further water
quaty or chemstry modfcaton before returnng to the fsh. As prevousy mentoned, n-
trfyng bactera remove dssoved oxygen and ower pH. Therefore, water has to be aerated
to remove CO
2
from the water and oxygenated before returnng to producton tanks.
Benefi ts of fish farmi ng close to pul p production si te
Water exchange n a RAS farm pro|ected s n the range of 5-15% athough ower exchange can be
acheved. The water demand of a 500 ton farm woud be n the range of 3-5 ters per second of
new cod water. The water needs to be heated to 28C. Freshwater of suffcent quaty for farmng

213
of tapa and ow temperature heat s usuay avaabe on pup producton stes. The waste water
from the farmng can be processed n the waste water treatment system of the pant and n some
cases dependng on characterstcs of recevng water bodes, be drecty sent away after n-house
sods remova n farm.
How to continue?
Athough the Processum pre-study concudes that the scae studed here s too sma to be profta-
be, possbe future potenta s dentfed for arger scae producton. For dfferent reasons the
Doms| M today do not have the possbty to prortze workng wth these ssues. However, there
are a coupe of contractors nterested n budng and runnng a pant, f, the rght m and the rght
ocaton can be found.
In order to move towards reazaton of the dea wth an ndustray ntegrated fsh pant a coupe
of questons need to be answered before a sharp nvestment cacuaton can be made.
Inta key questons are:
Locaton, are there sutabe budngs or areas avaabe?
Do you have access to warm waste water, what amounts and temperatures?
Is t possbe to use the exstng boogca treatment pant? (Are there room for extra oad today?)
Wecome to uncondtona nta dscussons!
References
1. Dey, R. 2012. Comng from the Cod. Fsh farmng Internatona | anuary 2012, p. 23
http://www.ntrafsh.com.
2. Mutter, R. 2012. The Tropcs come to Engand. Fsh farmng Internatona August 2011, p. 34.
http://www.ntrafsh.com.
3. Dey, R. Poes apart. Fsh farmng Internatona Apr 2012, p. 28. http://www.ntrafsh.com.
FPInnovatons nove fractonaton process for gnoceuosc bomass

214
FPnnovati ons' novel fracti onation process
for lignocellulosic biomass
Changbin Mao, Zhirun Yuan, David Wong, Waleed Wafa Al Dajani, Thomas Browne
FPnnovations, 570 Boul. St-Jean, Pointe-Claire, QC, Canada H9R 3J9
Abstract
Despte tremendous research efforts around the word, the recactrance of ceuosc bomass re-
mans a crtca chaenge for the gnoceuosc bomass-based borefnery. Due to the nature of
many pretreatment technooges that generate varous nhbtors, many sugar streams produced
from gnoceuosc bomass have dffcuty to be drecty fermented nto the target bo-products.
FPInnovatons has deveoped a mechanca fractonaton process (MFP) whch converts ceuo-
sc bomass nto varous vaue-added bo-products. The process ncudes bomass pretreatment,
enzymatc hydroyss and gnn extracton technooges. The pretreatment of bomass conssts of a
md chemca treatment and a mechanca refnng stage that can be easy retroftted nto an exst-
ng pup m nfrastructure at a arge scae. Based on commerca enzymes, we successfuy deve-
oped an enzyme formuaton whch can acheve smutaneous hydroyss of both gucan and xyan
wth yeds above 90% at hgh sods oadng. Our resuts aso show that the cean and hghy-
concentrated sugar stream (140 g/L) from ths process can be drecty fermented to butano, etha-
no, succnc acd, and actc acd at yeds of 33%, 47%, 76%, and 84%, respectvey.
ntroduction
The poysacchardes (hemceuose and ceuose) present n natve gnoceuosc bomass are
hghy resstant to enzymatc hydroyss. Ths s many attrbuted to: 1) a hgh degree of poymerza-
ton and crystanty of the ceuose; 2) the cose assocaton and compexty of the gnn-
carbohydrate compexes (LCC); and 3) gnn and hemceuose both actng as barrers preventng
the access of ceuase enzymes to ceuose. Besdes, gnn aso appears to reduce enzyme hy-
droyss effcency by actng as an attractant to enzyme protens resutng n non-productve bndng.
To overcome the recactrance of the ceuosc bomass, parta remova of hemceuose and gnn
are beeved to be essenta to mprove dgestbty of bomass. Durng the ast two decades, tre-
mendous efforts have been made n deveopng the bomass pretreatment technooges and nu-
merous pretreatment methods have been deveoped. These pretreatment technooges are gener-
ay categorzed as mechanca, physco-chemca (e.g., autohydroyss, qud hot water, steam
exposon), chemca (e.g., aka, acd, organc sovents, oxdzng agents) and boogca (e.g., fun-
g) processes or combnatons of these approaches |1, 2|.
Despte the tremendous efforts, pretreatment remans a crtca step n the process for convertng
gnoceuosc bomass to bo-fue and other vauabe chemcas. It s st one of the most costy
steps and has a ma|or nfuence on the cost of both pror (e.g., sze reducton) and subsequent
(e.g., enzymatc hydroyss and fermentaton) operatons |3|. Among the exstng technooges,
steam exposon s the cosest to commercazaton, and there are severa pot and pre-commerca
pants based on steam exposon pretreatment technoogy (e.g., Iogen, Chemtex, and Mascoma).
However, steam exposon s expensve to scae-up to ndustra scae; other mtatons of ths tech-
noogy aso ncude parta degradaton of hemceuoses, ncompete dsrupton of the bomass
structure, and generaton of nhbtors (furfura and 5-hydroxymethy furfura (HMF) etc.) for subse-
quent fermentaton processes |4, 5|.
FPInnovatons has deveoped a patent-pendng nove Mechanca Fractonaton Process (MFP) for
gnoceuosc bomass. The technoogy produces a hghy dgestbe bomass from whch a cean,
concentrated sugar stream and a hgh-quaty, sufur-free gnn can be generated on arge scaes. The
MFP technoogy opens the door for producng varous bofues and bochemcas from a renewabe
non-food gnoceuosc bomass. The paper w dscuss the resuts on aspen wood chps.


215
Novel Fractionation Process for Lignocellulosic Biomass
FPInnovatons patent-pendng bomass fractonaton process many ncudes three technooges: 1)
a unque bomass pretreatment technoogy; 2) a robust enzymatc hydroyss technoogy; and 3) a
gnn extracton technoogy. As ustrated n Fgure 1, gnoceuosc bomass w frst be pretreated
to produce a hghy dgestbe bomass. After enzymatc hydroyss, the bomass w be separated
nto tow streams: 1) a mxed C5/C6 sugars; and 2) hydroyss gnn whch contans about 55-65%
gnn dependng on the carbohydrates converson yed n the enzymatc hydroyss process. A hgh
purty, suphur-free gnn (E-gnn) can aso be extracted from the hydroyss gnn. A process
streams w be used to generate varous boproducts.

Figure 1. Mechanca Fractonaton Process.
Unique biomass pretreatment technology
The pretreatment technoogy conssts of a md chemca treatment and a mechanca refnng.
Compared to current pretreatment technooges such as steam exposon, hot water-extracton,
ammona and me pretreatment, our pretreatment process has many advantages, and can utze
the exstng ded/cosed pup & paper factes n scang up. The process empoys ow-pressure
mechanca refnng usng mnmum energy nput to dsntegrate the gnoceuosc feedstock. Ths
factates the separaton and fractonaton of hemceuose, ceuose and gnn n the subsequent
processes. Due to the md pretreatment condtons, ony a sma porton of hemceuoses and
gnn are removed n the pretreatment process. The resutng bomass has very smar chemca
composton as the orgna bomass as shown n Tabe 1. We beeve under such desgned md
pretreatment condtons, the chemca nkages between xyan and gnn are modfed or ceaved,
but the degradatons of these two components are mnma.
Table 1. Chemca components n percentage of aspen before and after pretreatment.
Glucan Xylan Lignin Others Carbs. Extractives Total
Orgn bomass 47.07 16.68 23.62 5.60 1.61 94.58
Pretreated bomass 54.71 14.37 23.10 2.91 0.35 95.44

216
As shown n Fgure 2, for grounded aspen coarse partces, the gucose yed from subsequent
enzymatc hydroyss can ony reach 14% even at a very hgh enzyme dosage (60 FPU/g gucan).
By refnng, gucan converson can be mproved to 31%. Furthermore, by combnng a chemca
treatment wth refnng, the gucose yed can be sgnfcanty mproved to 82%, whch s about 5
tmes hgher than that of untreated bomass. The hgh gucan converson yed ceary ndcated that
our pretreated bomass s hghy accessbe to enzymes. Further optmzaton of enzyme formuaton
to match the characterstcs of the pretreated bomass has been conducted and a robust enzymatc
hydroyss technoogy has been deveoped.

Figure 2. Effect of pretreatment methods on bomass dgestbty wth Ceucast 1.5L. Enzymatc
hydroyss condtons: 2% sod oadng at 60 FPU/g of gucan for 72 hours, 50C, 150 rpm n shak-
ng ncubator, 50 mM sodum acetate buffer at pH4.8, 100g tota reacton mass n 250m fasks.
Robust Enzymatic Hydrolysis Technology
Detaed studes of the enzymatc hydroyss profes for both gucan and xyan ndcated that the
converson of gucan s the botteneck of the whoe enzymatc hydroyss process, as shown n
Fgure 3 (A). Wth the fact that amount of hgh gnn and hemceuose presented n our pretreated
bomass, we beeve that smutaneousy hydroyzng both gucan and xyan s the key to mprove
the effcency of the enzymatc hydroyss. By suppementng wth other enzymes and addtves, we
deveoped a set of enzyme formuatons based on three key enzymes from Novozymes, namey,
Ceucast 1.5L, Novozymes 22C, and Cec Ctec1. A three formuatons worked qute we resut-
ng n carbohydrate converson yeds above 85% n 3 days at an enzyme charge of 20FPU/g of
gucan. The most promsng formuaton (Ctec 1 based F3) can smutaneousy hydroyze both gu-
can and xyan wth carbohydrate converson cose to 100% n three days, as shown n Fgure 3 (B).
14
31
82
0
20
40
60
80
100
G
l
u
c
o
s
e

Y
i
e
l
d

(
%
)
No refi ning
Refini ng
Chemical treatment + Refining

217

Figure 3. Wth the enzyme formuaton F3 at 20 FPU/g gucan, enzymatc hydroyss botteneck s
emnated wth gucan and xyan beng smutaneousy hydroyzed. A: Ceucast 1.5L aone at 20 FPU/g
of gucan; B: the Cec Ctec1 based formuaton at 20 FPU/g of gucan wth other suppement en-
zymes and an addtve. Other condtons are the same as n Fgure 2.
The statstca mode was but to further optmze the enzyme formuaton. The addtves we dent-
fed works extremey we wth the pretreated bomass, especay at ow enzyme dosage. As shown
n Fgure 4, an ncrease of 50% n gucan converson yed can be acheved at 5 FPU/g of gucan.
Ths s equvaent to an enzyme charge of 2% on the bomass. At ths ow enzyme dosage, carbo-
hydrate converson reached 61% and 78% after 3 days and 6 days of hydroyss, respectvey. We
beeve there s st potenta to further mprove the hydroyss effcency wth Novozymes new Cec
Ctec 3 enzyme formuaton.
In the ndustra appcatons, enzymatc hydroyss at hgh sods oadng s essenta for opera-
tona and economc reasons. However, much pror research has ndcated that ncreased sods
oadng w resut n a dramatc decrease n the carbohydrate converson yed. For exampe, Hen-
nng et a. |4| showed that the carbohydrate converson yed decreased from 90% to beow 60%
when sods oadng ncreased from 2% to 20%, and stated that ceuose and hemceuose con-
verson decreased amost neary wth ncreasng sods oadng. Our research has ndcated that
bomass quefacton s the key n hgh sods oadng hydroyss, and t vared greaty wth dfferent
hydroyss reactors. Some reactors requred up to 5 days for quefacton, whe other reactors
needed ony a few hours. We successfuy deveoped a 60-ter reactor abe to run enzymatc hy-
droyss at up to 20% sods oadng. As shown n Fgure 5, bomass can be quefed wthn 5 hours
n genera, and carbohydrate converson can reach greater than 85% n three days at 18 FPU/g of
gucan. Ths ndcated that our enzyme formuaton and addtves aso work very we at hgh sod
oadng.

218

Figure 4. Robust enzyme formuaton (F3) and addtve towards ow enzyme dosage. The enzymatc
hydroyss condtons are the same as n Fgure 2.

Figure 5. Hgh sod oadng enzymatc hydroyss wth F3 enzyme formuaton. Hydroyss cond-
tons: 15% sod oadng (6kg of bomass n 40kg of surry) at 18 FPU/g of gucan, 50C, 50 mM
sodum acetate buffer at pH4.8, 20 rpm/mn (ntermttent mxng).
Value-added Products form Lignin and Sugars
Mechanca Fractonaton Process generates a cean, concentrated sugar stream due to the md
pretreatment condtons and the hgh sods enzymatc hydroyss technoogy. The sugar stream
was free of most nhbtors and ony contaned a sma amount of acetc acd, as showed n Tabe 2.
Wthout any pre-condtonng of the sugar stream, we further evauated varous fermentaton path-
ways to dfferent sugar products. As summarzed n Tabe 3, the sugar stream from our process can

219
be drecty fermented to butano, succnc acd, actc acd, and ethano wth yeds of 33%, 76%,
84%, and 47%, respectvey. These resuts were obtaned wth ony a few tras under typca fer-
mentaton condtons; optmzaton w most key further mprove the effcences of the fermenta-
ton for these products.
In addton, we are aso workng towards deveopng vaue-added products from the sod product
stream from enzymatc hydroyss. The md bomass pretreatment process aong wth hgh enzy-
matc converson of carbohydrate produces a sod stream enrched n gnn. A pure gnn can be
ready extracted from ths sod stream wth a very md sovent extracton process. The soated
gnn chemcay resembes natve gnn, and s of hgh purty havng ow carbohydrate, ow ash
content and sufur free. Ths gnn has potenta to be used n hgh vaue products such as carbon
fbre precursor, poyo substtute n poyurethane foams, and pheno substtute n resns etc.
Table 2. Sugar compostons from mechanca fractonaton process (20% sod oadng n EH).
Component Glucose Xylose
Oli go-
sacchari des
Furfural,
HMF
Levuli nic
aci d
Lactic, Formi c
aci d Aceti c acid
Conc. (g/L) 90.9 29.0 10.2 0 0 0 3.3
Table 3. Pathways to varous vaue-added sugar products.
Sugar products Starti ng Sugar conc., g/L Consumed sugar Yield, % Product conc., g/L
Ethano 74 Gucose 47 34
Butano 79 Gu/Xy 33 15
Lactc acd 88 Gu/Xy 84 69
Succnc acd 77 Gu/Xy 76 37
Conclusions
FPInnovatons has deveoped a nove mechanca fractonaton process (MFP) for gnoceuosc
bomass that can produce hghy dgestbe bomass for enzymatc hydroyss. The process can be
easy scaed up for arge ndustra appcaton. Based on commerca enzymes, we successfuy
deveoped an enzyme formuaton whch can acheve smutaneous hydroyss of both gucan and
xyan wth yeds above 90% at hgh sods oadng. Our resuts aso showed that the cean and
hghy concentrated sugar stream from ths process can be drecty fermented to ethano, butano,
actc acd and succnc acd wth yeds of 47%, 33%, 84% and 76% respectvey.
Acknowledgement
The fnanca support from NRCAN, MRNF and our member companes are hghy apprecated.
We woud ke to thank our techncans, Dane Gbert, Davd Gampaoo, Mchae Hestern, Sy-
ve Renaud, Wen|uan On and many other staff for ther exceent work and support.
We aso woud ke to gratefuy thank Novozymes for provdng us Cec seres enzymes, and
the ARS Natona Center for Agrcutura Utzaton Research, USDA for provdng us the Bacillus
coagulans MXL-9 stran for actc acd fermentaton.

220
References
1. Hendrks, A.T.W.M., Zeeman, G. 2009. Pretreatments to enhance the dgestbty of gnoceuosc
bomass. Boresource Technoogy 100, pp. 10-18.
2. Wyman, C.E., Dae, B.E., Eander, R.T., Hotzappe, M., Ladsch, M.R., Lee, Y.Y. 2005. Coordnated
deveopment of eadng bomass pretreatment technooges. Boresource Technoogy 96,
pp. 1959-1966.
3. Langan, P., Gnanakaran, S., Rector, K.D., Pawey, N., Fox, D.T., Cho, D.W., Hamme, K.E.
2011. Exporng new strateges for ceuosc bofues producton. Energy. Envron. Sc. 4,
pp. 3820-3833.
4. | rgensen, H., Vbe-Pedersen, | ., Larsen, | ., Feby, C. 2007. Lquefacton of Lgnoceuose at
hgh-Sods Concentratons. Botechnoogy and Boengneerng 96(5), pp. 862-870.
5. Cantarea, M., Cantarea, L., Gafuoco, A., Spera, A., Afan, F. 2004. Effect of nhbtors re-
eased Turng steam-exposon treatment of popar wood on subsequent enzymatc hy-
droyss and SSF. Botechno Progr 20, pp. 200-206.
6. Garca-Aparco, M.P., Baesteros, I., Gonzaez, A., Ova, | .M., Baesteros, M., Negro, M.| .
2006. Effect of nhbtors reeased durng steam-exposon pretreatment of barey straw on
enzymatc hydroyss. App Bochem Botechno 129, pp. 278-288.

Co-producton of renewabe poymers and ethano from eucayptus-based pup ms

221
Co-production of renewabl e polymers and ethanol
from eucalyptus-based pulp mills
Niklas Berglin, Anna von Schenck, Christian Hoffstedt
nnventia AB, P.O. Box 5604, 114 86 Stockholm, Sweden
Abstract
As borefnery producton pants start to dever products on a arger scae t s becomng cearer
what vaue chans can be expected to be reazed frst. One such chan s poyethyene producton
va ethano, whch s aready beng commercazed n Braz on a scae of severa hundred thou-
sand tonnes per year. Sugarcane ethano prevousy used many as a bofue s thus fndng ts way
nto a new market as a chemca ntermedate, makng t an nterestng product both for stakehod-
ers that have the potenta to produce cean sugar streams on a arge scae and for downstream
producers of chemcas that currenty rey on foss raw materas.
Ethano producton from lignocellulosic raw materas w generate mutpe streams, snce ony a
certan fracton of the matera can be converted nto sugars and then fermented to ethano. Ths
requres a poy-generaton approach, where by-products aso must have hgh vaue (e.g. gnn,
sugars from hemceuose). To reach the arge scae requred for proftabty, t s proposed that the
best way s to ntegrate the new processes wth exstng ndustres, preferaby those that aready
operate bomass-to-materas or bomass-to-fues pants. The two argest ndustry branches n ths
respect are the pup and paper and the sugar cane ethano ndustres. In a coaboratve pro|ect,
POLYNOL, between Swedsh and Brazan companes, research nsttutes and unverstes these
opportuntes w be expored.
ntroduction
The demand for materas, chemcas and fues produced from renewabe raw materas s ncreas-
ng rapdy, n ne wth a decreasng suppy of foss resources and ncreasng costs for these. In-
dustry needs to repace an ever arger share of the non-renewabe raw materas, and at the same
tme ensure that producton processes and vaue chans are as resource effcent as possbe. Ths
s a great chaenge, snce the forest and agrcutura products that are possbe raw materas de-
mand very arge scae handng of arge voumes of sod matera that needs to be grown, harvest-
ed, transported and processed n an effcent way.
The forest ndustry s today the eadng producer of renewabe materas, many n the form of
paper and board, whe the agrcutura sector s responsbe for a ma|or share of the qud fues that
are produced from renewabe raw materas today. Both sectors have a arge potenta for growth n
a shft to a more sustanabe socety, but to acheve ths party new processes are needed. A cha-
enge n the deveopment of these processes s that the vaue chan conssts of many steps, where
each one needs to be deveoped n reaton to the prevous one. There s aso a need to aready at
an eary stage fnd buyers for products and ntermedate products. From a pure busness econom-
cs perspectve ths hnders many ntatves, because the rsk for one snge actor n the vaue chan
becomes too great. A centra dea n the pro|ect s therefore to te actors n the borefnery vaue
chan together.
The POLYNOL concept
Sweden and Braz are two of the words argest producers of paper pup wth consderabe
knowhow reated to wood as a raw matera. Braz s n addton a word eader n the producton of
frst generaton ethano from sugar cane |uce. Producton of second generaton ethano (or other
products) va sugars from gnoceuosc materas ncudes a reatvey costy pretreatment of the


222
raw matera n order to separate the gnn from the ceuose. Severa technooges have been
deveoped for ths purpose, some of whch are beng demonstrated on pot scae n e.g. Sweden,
Denmark, Itay and the Unted States. Ths separaton of the wood components aready takes pace
n the chemca pup m, and the ong proven technoogy n pup producton known as soda cookng
(pretreatment under akane condtons) has aso shown postve resuts as a pretreatment method
when producng ethano |1|. The process has been tested n m-scae tras and has a great ad-
vantage n the fact that t can be drecty ntegrated nto the recovery of chemcas and energy n the
pup m. The pup ms are aready very arge scae pants to process bomass, and an ntegrated
producton of sugars that can be turned nto hgh vaue products can therefore reatvey qucky
gve a consderabe contrbuton to the suppy of e.g. green chemcas or second generaton etha-
no. The smpfed ntegraton of the two processes s a centra dea to the pro|ect. The concept has
been evauated by | ansson et al. |2| for a theoretca pup m converson to ethano producton.

Fi gure 1. An ustraton of how the "Poyno" concept can be ntegrated wth a pup m and dever
mutpe products n severa vaue chans.
Process integration
Athough converson of an od pup m to a borefnery shows some potenta, the ma|or advantage
n economy of scae wth the POLYNOL concept es n process ntegraton wth arge, modern fac-
tes. A greenfed eucayptus-based kraft pup m s abe to produce on the order of 1.5 mon
tonnes of pup per year and w have an energy surpus correspondng to more than haf of the
bomass nput |3|.
Heat ntegraton opportuntes n a borefnery consstng of a modern eucayptus kraft pup m
and a gnoceuosc ethano process have been studed by Innventa and Chamers and reported
by Forne et al. |4, 5|. Resuts show that ths combnaton gves rse to arge opportuntes of m-
provng the energy effcency n the borefnery f heat ntegraton s consdered (Fgure 2). The costs
and net annua savngs have aso been cacuated for severa dfferent aternatve desgns of the
Ethanol & lactic acid
Hydroyss &
fermentaton
Lgnn
separaton
Electricity
CO
2
Fuels for
heavy-duty
vehicles
Polyethylene
& PLA
Kraft
pupng
Paper/
board
producton
Pulp wood
Liquid
packaging
board
Renewable
packaging
Sulfur-free lignin
Energy and
chemicals recovery
Akane
fractonaton
Forestry residues,
energy wood, bagasse

223
ntegrated processes, and the resuts ndcate short payback perods (beow 3 years) and substan-
ta annua savngs (2 MC/year) compared to the base case process.

Figure 2. Grand Composte Curve ndcatng the avaabty of heat at a hgh temperature (>100C)
n the ntegrated pup m hot and warm water system of a 4000 ADt/d eucayptus-based pup m.
Raw materials
There are arge amounts of gnoceuosc materas avaabe n or near exstng pup or sugar ms,
many n the form of resdues from harvestng (bagasse, forestry resdues) and resdues from the
process (e.g. woodyard re|ects). These materas contan sgnfcant amounts of ceuose and hem-
ceuose that can be converted to sugars, but aso up to 30% gnn that can be processed sepa-
ratey. One ma|or probem wth ow-cost resdues s that they contan much ash. In a chemca pro-
cess the ash components w tend to accumuate and cause process dsturbances due to precpta-
ton of sats and aso ead to ncreased consumpton of chemcas. Annua crops and woody mater-
as can dspay arge dfferences n ash composton wth respect to, e.g., scon, phosphorus, po-
tassum and chorne. One way to overcome ths probem s to ntroduce an acdc pre-hydroyss
step pror to the akane fractonaton. It has been showed that ths step can reduce process "ds-
turbng" substances such as meta ons, ash etc. An acdc pre-hydroyss step can aso mprove the
condtons n the foowng hydroyss and fermentaton step due to a reducton of meta ons and
unreactve C5 sugars, whch when present can have a negatve effect on the hydroyss yed. A
reduced meta on content s aso an advantage n the further upgradng of the gnn.
Avaabty of bomass resdues n Braz has been assessed by Ferrera-Letao et al. |6|. Sugar-
cane resdues consttute the argest share, amountng to more than 415 mon tonnes per year
(195 mon tonnes of bagasse and 220 mon tonnes of straw and eaves). The contrbuton from
corn and cassava resdues s aso sgnfcant, whereas wheat and rce resdues are sma n com-
parson. Forestry resdues were estmated to about 39 mon tonnes per year, (59% fed resdues
and 41% ndustra waste). Tota crop and and panted forests consttute about 67 mon hectares
of Brazan and use (Fgure 3).

224

Figure 3. Current and use n Braz as presented by Sparovek et al. |7|.
Products
Recenty, a technoogy has been deveoped amed at extractng gnn from akane quors and turn
t nto a purfed and we defned product that can be used as a fue or as an ntermedate for chem-
cas producton |8|. Ths technoogy can be used aso for extracton of gnn n the new ntegrated
concept. The kraft cookng process that s the most currenty used separaton method n the pup
ms today gves a gnn contanng suphur. However, f the separaton of the wood components s
performed usng the soda cookng process there s aso a possbty to obtan a gnn that s suphur
free. Ths s an advantage n some future possbe appcatons of the gnn as a hgh-vaue added
product, e.g. carbon fbers.
Other exampes of potenta products for the gnn are actvated carbon, dspersants, bnders
and phenos.
The studed process w aso gve the possbty to separate the hemceuoses of the wood as a
thrd product besdes the sugars and gnn. The hemceuoses can be used as fbre addtve, gas
barrers and hydroges.
A part of the sugar cane conssts of bagasse, a raw matera that s not yet used n commerca
ethano producton, snce t s smar to wood n composton, e.g. contanng gnn. It s of great
mportance to utze aso ths part of the sugar cane n an effcent way. Integraton wth a pup m
where the bagasse s processed together wth forestry resdues to produce sugars (that can be
turned nto green chemcas or bofues) at the same tme as a pure gnn s produced gves good
optons for a cost-effectve producton.
Potenta products from sugars ncude actc acd, acryc acd, ethy acetate, ethy actate, pro-
pyene gyco, pyruvc acd, and snge ce proten.
Market deveopment for fues, chemcas and materas made from renewabe sources s predcted
to be rapd n the comng decade, wth growth rates many tmes that of pup and paper products (cf.
tabe 1). By voume, boethano s the product wth the hghest producton rate today |9|.
Co-production of renewable polymers and ethanol from eucalyptus-based pulp mills

225
The biomass products can substitute for fossil fuel based products. Chambost et al. [10] point
out that a distinction can be made between replacement and substitution products. Replacement
products are identical in chemical composition to existing products, but are based on renewable
resources, e.g. bioethanol. Substitution products have a different chemical composition to existing
products, but have a similar functionality, e.g. lactic acid to produce PLA (polylactic acid) which
could substitute PET (polyethylene terephthalate) in the production of e.g. plastic bottles.
Table 1. Estimated annual growth rate and global market value of some products from renewable
raw materials. Compiled by FPAC [11].
Products Annual growth rate
20092015 (%)
Global value 2015
(billion USD)
Green chemicals 5.3 62.3
Alcohols 5.3 62.0
Bioplastic and plastic resins 23.7 3.6
Platform chemicals 12.6 4.0
Wood fibre composites 10.0 35.0
Glass fibre market 6.3 8.4
Carbon fibre 9.5 18.6

Acknowledgements
Much of the experimental work leading up to this project was initiated by Leelo Olm and Disa
Tormund, and we would like to acknowledge their contribution. We also wish to thank Rickard For-
nell and Thore Berntsson for valuable discussion, as part of our collaboration funded by the
Chalmers Energy Initiative. Other funding has been provided by Fibria, Klabin and Parsons & Whit-
temore within the Innventia Cluster Energy and biofuels, and by Stora Enso and Sekab in projects
also supported by the Swedish Energy Agency (Project numbers P30478-1P30478-3).
References
1. von Schenck, A., Berglin, N., Uusitalo, J . 2011. Ethanol from Nordic wood raw material by simpli-
fied alkaline soda cooking pretreatment. International Symposium on Alcohol Fuels XIX,
Verona, Italy, October 1014, 2011.
2. J ansson, M., Berglin, N., Olm, L. 2010. Second generation ethanol through alkaline fractionation
of pine and aspen wood. Cellulose Chem. Technol. 44(13), pp. 4752.
3. Berglin, N., Lovell, A., Delin, L., Trml, J . 2011. The 2010 Reference Mill for Kraft Market Pulp.
TAPPI PEERS Conference, Portland, Oregon, October 25, 2011.
4. Fornell, R., Berntsson, T. 2012. Process integration study of a kraft pulp mill converted to an
ethanol production plant Part A: Potential for heat integration of thermal separation
units. Applied Thermal Engineering 35, pp. 8190.
5. Fornell, R., Berntsson, T., sblad, A., von Schenck, A. Heat integration opportunities for a com-
bined lignocellulosic ethanol and kraft pulping process. (Submitted for publication.)

226
6. Ferrera-Leta, V., Gottschak, L.M.F., Ferrara, M.A., Nepomuceno, A.L., Monar, H.B.C., Bon, E.
2010. Bomass Resdues n Braz: Avaabty and Potenta Uses. Waste Bomass Vaor 1,
pp. 65-76.
7. Sparovek, G. 2012. Persona communcaton, February 2012.
8. Axegrd, P., Bergn, N., Lndgren, K., Toman, P., hman, F. 2011. The kraft pup m borefn-
ery patform. 5th Internatona Cooquum on Eucayptus Pup, Porto Seguro, Baha, Braz
May 9-12, 2011.
9. Socco, C.R., Vandenberghe, L.P., Mederos, A.B., Karp, S.G., Buckerdge, M., Ramos, L.P.,
Ptareo, A.P., Ferrera-Leto, V., Gottschak, L.M., Ferrara, M.A., da Sva Bon, E.P., de
Moraes, L.M., Ara|o | de, A., Torres, F.A. Boethano from gnoceuoses: Status and
perspectves n Braz", Boresource Technoogy 101(13), pp. 4820-5025.
10. Chambost, V., McNutt, | ., Stuart, P. 2008. Guded tour: Impementng the forest borefnery
(FBR) at exstng pup and paper ms. Pup and Paper Canada 109(7-8), pp. 19-27.
11. http://www.fpac.ca/pubcatons/BIOPATHWAYS II web.pdf.
Lgnn remova from dfferent back quors

227
Lignin removal from different bl ack li quors
Per Tomani, Peter Axegrd, Lars Norberg, Lars-Erik kerlund
NNVENTA AB, P.O. Box 5604, SE-11486 Stockholm, Sweden
per.tomani@innventia.com
Abstract
Pup m borefnng s st a reatvey young area n modern pupng R&D drven by megatrends
such as ncreased costs for foss o and wood, but aso ncreased competton on the pup market.
The need for new revenues s obvous f the pup and paper ndustry s to mantan ts strong pos-
ton. Borefnng can smpfed be defned as the efforts to reach as compete utzaton of wood raw
matera as possbe n a pup m to reach as hgh revenues as possbe. A pup m producng
chemca pup s for severa reasons an exceent an ndustra patform for borefnng. The chemca
pup m s abe to produce reatvey pure ceuose, hemceuose and gnn. The focus n ths
paper s on separaton of gnn from dfferent types of back quors, the behavor of these back quors
when they are treated accordng to the LgnoBoost concept and propertes of the separated gnn.
Lgnn remova from kraft/soda back quors has been deveoped (the LgnoBoost process) n
cooperaton between Innventa and Chamers. The technoogy was sod to Metso Power 2008 and
s now commercay avaabe. Lgnn separaton, purfcaton, modfcaton and appcatons have a
hgh prorty n R&D work at Innventa.
ntroduction
Severa back quors (from dfferent wood speces, annu pants) have been studed n the Lgno-
Boost concept by Innventa for about a decade. Informaton from ths database s used to pont out
smartes and dfferences n behavor and the fna gnn propertes. One exampe of ths s the
chaenge we have had to separate gnn from certan hardwood back quors. The chaenge s n
ths case a hgh ftraton resstance n the separaton of precptated gnn. We propose a souton n
ths paper.
In the LgnoBoost process a stream of back quor s taken from the evaporaton pant, Fgure 1.
The gnn n the stream s precptated by acdfcaton (preferred acd s CO
2
) and ftered ("Cham-
ber press fter 1" n Fgure 1). Instead of washng the gnn drecty after ftraton the fter cake s
re-dspersed and acdfed ("Cake re-surry" n Fgure 1). The resutng surry s ftered and washed
usng dspacement washng ("Chamber press fter 2" n the Fgure 1).


228
Washtank
CO
2
30-45 % DS
To "ate"evap.
To "eary"evap.
H
2
SO
4
H
2
SO
4
+ warmH
2
O
Scrubber
Chamber
press
fter 1
Chamber
press
fter 2
Back quor
storage tank
Coong
Precptaton
& maturaton
Cake
re-surry
Ftrate tank 1
Ftrate tank 2
Heatng
Conveyor
bet 2
Whte Lq.
WarmH
2
O
Acdc, but owbuffer capacty
pH 9.5-10.5
Conveyor
bet 1

Figure 1. A genera ayout of the LgnoBoost gnn remova process, LgnoBoost (post-treatment
such as dryng & puverzng s excuded).
It shoud be noted that the ftrate from chamber press fter 1 (a ftraton and dewaterng stage),
Fgure 1, shoud be recyced to the m evaporaton pant after the pont at whch the feed stream to
LgnoBoost s ocated. Ths to avod a decrease n the gnn concentraton n the stream fed to the
LgnoBoost operaton, whch woud be the resut f the ftrate were recyced to the begnnng of the
evaporaton pant. The ftrate from chamber press fter 2 (a ftraton, washng and dewaterng
stage) shoud be recyced to the weak back quor.
Results
Different bl ack liquors
Many back quors have been tested over the years usng the LgnoBoost concept. We have tested
quors from pup ms as we as from aboratory tras. The mportance of m quor tests s that
they gve a gmpse of the ndustra reaty, whch not aways s easy to nterpret snce you not a-
ways have the compete background - wood speces, steady-state producton or not etc. Some
ms aso run campagns where they swtch between SW and HW, and ths w affect the compos-
ton of back quor and the behavor n gnn separaton. The chemca composton of the hardwood
back quors we have studed seem to be more heterogeneous than the softwood back quors we
have studed, Tabe 1. Ths can be shown as arger varatons n acd soube gnn and carbohy-
drates.

229
Table 1. Chemca composton of ndustra aboratory produced back quors.

These back quors, together wth some addtona quors, have been studed n the LgnoBoost
process and the resuts are summarzed beow.
Yield and chemical consumption in the LignoBoost process
A summary of gnn yeds for precptaton to approxmatey pH 10 for a number of back quors
from dfferent ms s shown n Fgure 2. The yed was measured gravmetrcay over the frst ftra-
ton stage. Ths assumpton s reasonabe snce the yed s normay very hgh n the LgnoBoost
process (and sometmes even above 100% snce addtona gnn can precptate from the carry-
over ftrate n the re-surryng stage). The precptaton temperature (fna temperature) s normay
65-70C for softwood and 55-60C for hardwood back quors.
The precptaton step n our demonstraton pant s normay conducted at a pH sghty hgher
than 10 and the varaton s between approxmatey pH 10,1 to 10,4. Ths can expan the ower
gnn producton rates n the eft part of Fgure 2.

230

Fi gure 2. Lgnn yed for dfferent back quors when pH s ad|usted to about 10.
The behavour of gnn n aqueous souton s controed many by the pH, onc strength and tem-
perature. The man chemca reactons that partcpate n owerng the pH durng CO
2
absorpton n
akane soutons are descrbed n reactons (1) and (2):

(1)

(2)
The CO
2
consumpton has been estmated from ttratons on back quor wth 1M HC to determne
the acd consumpton, and the consumpton of CO
2
was estmated from equbrum cacuatons.
These expermenta and cacuated CO
2
consumptons per tonne gnn for precptaton at pH 10
are gven n Fgure 3.
CO
2
(g) CO
2
(aq) CO
2
(g) CO
2
(aq)
CO
2
(aq) +2OH
-
CO
3
2-
+H
2
O CO
2
(aq) +2OH
-
CO
3
2-
+H
2
O

231

Figure 3. Carbon doxde (CO
2
) consumpton for dfferent back quors when pH s ad|usted to
about 10 and gnn precptates.
The domnant component that determnes the consumpton of CO
2
s the resdua aka n back
quor, Fgure 4, but neutrasaton of e.g. phenoc groups n gnn and sugar acds aso consume
CO
2
. The chemca consumpton for the soda back quor process was sgnfcanty hgher than for
back quor from the Kraft process. The resdua akanty n ths specfc case s regarded as beng
very hgh. Typca vaues for owerng pH of back quor to vaues used n the LgnoBoost process s
about 50 kg CO
2
/BLDS.

232

Fi gure 4. Consumpton of CO
2
as a functon of resdua akanty n the back quor.
The H
2
SO
4
consumpton has been estmated from ttratons on fter cakes and ftrates from ether
m tras n bench-scae or aboratory tras wth a sma chamber press fter, Fgure 5. A genera
assumpton s that the gnn concentraton n the fter cakes from the frst ftraton stage can be
ncreased to 50-55 %-w, when the fter operaton s scaed up to arger fters where hgher pres-
sures are used and "edgng effects" are mnmsed. Ths concentraton has been reached n a num-
ber of studes even wth a pot fter press wth a fter area of 0.1 m
2
. If ower concentratons were
obtaned (e.g. n the aboratory fter), the H
2
SO
4
consumpton was re-cacuated to a gnn concen-
traton of 50-55%. The back quors are generay extracted at ether 40% DS (varaton between
37-44% DS) or 30% DS (27-30 % DS). Ths means dfferent amounts of carry over whch needs to
be neutrased.

233

Fi gure 5. Suphurc acd (H
2
SO
4
) consumpton for dfferent back quors when pH s ad|usted n the
re-surry stage from about 10 to pH about 2-2,5.
Filterability in the LignoBoost process
The specfc ftraton resstance s a scentfcay not a very cear way to express how easy or dff-
cut t s to separate the gnn by ftraton. One way to expan ths coud be to show the reaton
between specfc ftraton resstance and the weght produced gnn expressed as kg gnn/m
2
fter
area. Ths s shown n Fgure 6 for the frst ftraton step (after addton of CO
2
to back quor). Pre-
cptated back quor from fve dfferent ms usng softwood or a mxture of softwood and hardwood
has here been used to vsuase ths correaton. Correaton for hardwood back quors s generay
smar n the begnnng of ftraton phase, but n some cases there are more than one specfc ftra-
ton resstance durng ftraton of some hardwood gnns. The specfc ftraton resstance for gnn
precptated from hardwood back quor often ncreases when thcker cakes are made rapdy (from
a magntude of 1E10 to 1E11 or even 1E12). Ths ndcates that the ater parts of the ftraton de-
mands arger ftraton area.

234

Figure 6. The reatonshp between specfc ftraton resstance and bud-up of kg precptated
gnn/m
2
fter area.
Severa tras were made where dute carbon doxde was used as the acd for gnn precptaton.
Fue gases from for exampe the me kn was smuated by feedng the bottom of a sma adsorp-
ton tower wth a duted carbon doxde at room temperature. The gas mxture then reacted wth
back quor, crcuatng through the tower from the top. Percentage of carbon doxde n gas net,
dry sod of back quor and contact matera nsde the tower was vared, aso dfferent mass fows
through the tower was tested. The resuts showed sgnfcant ncrease n ftraton rate (ower specf-
c ftraton resstance) when gnn was precptated sowy n the carbonsaton (absorpton) tower
compared to reference back quor precptated n the demo pant at the same temperature and to
the same pH, Fgure 7. The mprovement of ftraton rate n the absorpton tower was about 150%.

235

Fi gure 7. Improvements n fterabty when duted CO
2
s used n the acdfcaton of back quor.
There are dfferent ways to hande poor fterabty of some hardwood gnns. One way s to n-
crease the dry sod content of the ncomng back quor. The gnn concentraton w by that be
ncreased whch factates an effectve ftraton. However a too hgh dry sod content n the back
quor ncrease the rsk to form Na
2
CO
3
when CO
2
s added to precptate gnn. Ths can be pos-
tve and ower the ftraton resstance but ths w cause ncreased carry-over of carbonate to the
re-surry stage and the acdfcaton whch resut n ncreased consumpton of H
2
SO
4
. However,
there are ways to avod sove ths, Fgure 8, by such as addton of sat and/or recrcuated precp-
tated gnn nstead of ncreasng dry sod content.
Fgure 8 shows that duton of orgna hardwood back quor (Aspen 43% DS) w ncrease the
ftraton resstance. Addton of gnn and sat to the duted surry before precptaton resuted n a
ower ftraton resstance. The argest effect was obtaned when both sat and gnn cake were
added. Addton of gnn and/or sat (Na
2
SO
4
) was made to ncrease the dry sod content and/or
mantan the onc strength. Experments made wth duted back quor (34% DS) and addton of
gnn and/or sat (Na2SO4) to 47% DS had postve nfuence on the fterabty. Ths ndcates that
t s possbe to mprove fterabty when the gnn content to the precptaton s sghty ow.

236

Figure 8. Average specfc ftraton resstance at dfferent tota dry sod content of the ncomng
back quor acheved n dfferent ways.
Properties of the produced lignin
Lgnn from the kraft process contans more carbon compared to most other bo-fues (torrefed
wood s bascay smar) and correspondngy hgher heat vaue. The heatng vaue of gnn fue
sampes has been determned as hgher heatng vaue (HHV) n a bomb caormeter. The ower
heatng vaue (LHV) s cacuated based on the HHV and the eementa anayss. The HHV (mean
vaue) for softwood gnn was n our studes about 27 M| / kg dry gnn, Tabe 2. Ths shoud be
compared wth 18-20 M| / kg for wood chps.

237
Table 2. Characterzaton of dfferent gnn sampes produced by the LgnoBoost concept.


238
Heatng vaues for hardwood gnn was n our studes |ust sghty ower (-26 M| /kg) than for soft-
wood gnn (-27 M| /kg). Lgnn from hardwood seemed to contan more acd soube gnn. Most
hardwood gnn sampes n our study contan carbohydrates on the same eve as equa to soft-
wood or softwood/hardwood mx. The soda gnn s an excepton and 10% carbohydrates are n
ths specfc case amongst the hghest vaue we have seen.
Hardwood gnn seems to have ower amount of carbon, but hgher amount of oxygen. Oxygen
s not anaysed as such, but cacuated from what s eft after other components. A gnns contans
traces of chorne, but very ow eves (0,01-0,02%). Suphur content n gnn ranges from 1.3 to 3.4
for kraft gnns, wth a typca vaue of 2.4%. Excepton s the hardwood soda gnn where the pro-
cess s suphur free and by that t resut n about 0,3% suphur n the gnn. The suphur added n
the LgnoBoost process (H
2
SO
4
) s effectvey washed out from the gnn before t eaves the fna
chamber press fter. The suphur content measured n the kraft gnn s bonded nto the gnn struc-
ture durng the kraft cookng operaton and t s wth todays knowedge reatvey costy and not
effectve to remove ths suphur.
Summary
Innventa has a ot of knowedge about gnn remova from many dfferent back quors
The LgnoBoost concept resuts n qute pure gnns
There are some dfferences n how dfferent back quors behave n the LgnoBoost process.
Innventa has toos for handng of these dfferences.
Lgnn s an exceent bo-fue and severa fue appcatons are ready for use aready today
Lgnn has a great potenta to be converted nto hgher vaue products, e.g. to carbon fbers,
bnders etc.
Acknowledgements
Many peope have been nvoved at Innventa to coect the data for these resuts. The author wants
to acknowedge the whoe gnn team at Innventa for ther hgh quaty work, great atttude and
contrbuton n many dfferent ways.
The Swedsh Energy Agency, Fortum Vrme, Metso, Stora Enso and Sdra Ce are acknow-
edged for ther fundng and engagement n the LgnoFue Program whch s one mportant ong-term
patform for our work on process deveopment.
Recovery of bobased ght carboxyc acds from dute aqueous soutons

239
Recovery of biobased light carboxyli c acids from
dilute aqueous solutions
Jukka Hietala
Kemira Oyj
Abstract
Therma, chemca and botechnca treatments of bomass can degrade components ke hemceu-
ose, ceuose and starch to smaer moecues that ncude water soube carboxyc acds.
These acds are commercay usefu but ther recovery from bomass processes s generay not
consdered feasbe because they are normay present as compex mxtures n very dute aqueous
soutons.
We have studed qud-qud extracton foowed by dstaton or back extracton as methods to
soate C
1
-C
4
acds from dute aqueous soutons. Many crtca parameters were dentfed. In
some cases even 98% recovery yeds were obtaned from soutons that contan 2-3 wt-% of the
desred acd. However, each partcuar feed s a case of ts own. Varous techncay workng, safe
and ndustray feasbe concepts shoud be deveoped sde by sde and at the end et the tota
costs decde.
ntroduction
Biomass as source of light carboxyl ic acids
Durng the past years severa thermo-chemca bomatera converson processes have been deve-
oped for renewabe fue and chemca producton. In these processes some ceuose, hemceuose
and starch dsntegrates to acds. Usuay t happens as unwanted sde reactons but there are
some on-purpose concepts aso. One of them s the co-producton of formc acd and evunc acd
by acd cataysed decomposton of ceuose. |1| Formc acd has many appcatons as natura,
easy controabe pH reguator or mcroba contro agent and ts sats are used for exampe as
bodegradabe ant-cng agents. Levunc acd s a patform chemca and ts esters are renewabe
fue oxygenates.
When one ton of pup s produced n Kraft process, 100-200 kg of ght carboxyc acds are
formed. |2| Ths woud mean goba producton of 13-26 mon tons of these acds, now burnt as
an nsgnfcant contrbuton to the process heat. In addton to these, potentay vauabe sugar
acds are formed (10-15% of the dry mater).
A typca fast pyroyss o unt produces annuay 50-150 kt bo o for heatng and transportaton.
The composton vares on the feed and process condtons but t ncudes 4-5 wt-% water soube
carboxyc acds. |3| Seectve remova of them woud not affect much to the heatng vaue but
woud decrease corrosvty of the o.
Many mcroorgansms are capabe of convertng ow vaue organc matera, even muncpa
waste, to carboxyc acds. In one of our pro|ects technca gycero comng from bodese produc-
ton as sde stream was converted to a mxture of proponc, acetc and succnc acd. These acds
have appcatons n poymers, and acetates and proponates are aso mportant food preservatves.
Organc acds are aso formed durng pre-treatment of ceuosc matera for boethano fermen-
taton. The acds are nhbtors of the fermentaton yeast and ther remova have shown to boost
boethano producton sgnfcanty. |4|
Wth a these bomass based sources of ght carboxyc acds the man technca chaenge s
the very dute soutons. Concentraton of the desred acd s usuay 0.1-5 wt-%. Therma separa-
ton woud nvove evaporaton of ot of water, whch s a very energy consumng process. On the


240
other hand, proftabe borefneres shoud make the best possbe use of a chemcas that are
formed n the process.
Extractants for qud-qud extracton are n ths case often ether neffcent, poory separatng
from water or too strongy bndng. Many reactve extractants are aso abeed toxc or they are
avaabe ony as ab chemcas. Accumuaton of acds on sod adsorbents from arge water vo-
umes, foowed by ther soaton and purfcaton from the surface s not very effcent. Membranes
have dffcutes to separate sma poar moecues from each other (ke formc acd from water) and
n contnuous operaton ther foung by other bomass components s a probem.
Liquid-liquid extraction as the method of recovery
Wth some earer experence and teachngs of the terature n our mnd we set a target to fnd
feasbe extracton methods to recover acds from very dute (ca. 1-3 wt-%) aqueous soutons. The
man target processes were formc acd separaton from evunc acd producton and recovery of
proponc acd and acetc acd from gycero fermentaton. Extracton foowed by dstaton or aka-
ne back extracton were seected as the separaton methods. Some of the systems were tested
aso n feeds comng from back quor and pyroyss o fractonaton and from sugar fermentaton to
gycoc acd.
The extractants used n the terature n soaton of organc acds from dute aqueous soutons
can be dvded nto three groups |5|:
organc tertary and quaternary ntrogen compounds
traky phosphne oxdes
organc oxygen compounds wth ow reactvty (acohos, ketones, esters, ethers).
Experimental
Most of the extractons were run n 100-200 m scae batches n a strred vesse; a exampes here
are from these experments. In addton, some arger tras were done n agtated or fxed bed ex-
tracton coumns wth contnuous co-current feeds. Acds were recovered from the extracts by dst-
aton or by back extracton wth hot water or wth akane souton. Some product sats were soat-
ed as precptates.
Lab grade chemcas were used, except the ndustra Aamne sovents from BASF, Cyanex 923
from Cytec and hydrocarbon mxtures from ExxonMob Chemcas, ncudng Isopar H.
When ony one acd component was present, ke synthetc formc acd soutons, both extracts
and raffnates coud by anaysed by ttraton. In many cases exceent mass baances and agree-
ment wth HPLC anayss were be obtaned. In more compcated cases the acd dstrbutons were
based on the raffnate anayss (HPLC and n some cases CE) and on the ttraton of the tota acds
n a phases. Water n organc phase was determned by Kar-Fscher ttraton. FT-IR, NMR (
1
H,
13
C,
31
P) and GC-MS were used to characterze other components and the nteracton between the
extractant and acds.
Extractant-acid complexes
Fgure 1 shows extracton yeds of 3 wt-% and 25 wt-% formc acd souton wth a hydrocarbon
sovent (touene), an ether, an amne and a mxture of traky phosphne oxdes. It can be seen that
the sovents from the groups mentoned n the ntroducton are hghy actve extractants to formc
acd. Interestngy, often more than one moecue of acd can be bound per actve ste of the ex-
tractant. For exampe n ths experment the more concentrated acd souton was used wth the
rato acd (mo)/amne (mo) =2.8.

241

Figure 1. Comparson of the effcency and capacty of varous types of extractants n formc acd (FA)
extracton. Feed 3 w-% or 25 wt-% formc acd souton n water, feed (g)/extractant (g) =1.0 (=w/o), 20C.
E-1 an ether
Aamne 304 traky amne (trdodecy amne)
Cyanex 923 traky phosphne oxdes ((aky =C
6
, C
8
).
Bndng of carboxyc acd to the extractant can be seen as change of C =O absorptons n FT-IR
(Fgure 2). Dependng on the strength of the nteracton, varous proporton of sat character can be
seen. For phosphne oxdes, shft n
31
P-NMR can be used to compare the strength of bndng.

242

Figure 2. Carbony absorptons (A) n FT-IR of some formc acd - amne compexes. The peaks at
1 717 cm
-1
come from free or oosey bound acd, the peaks at 1595-1580 cm
-1
are reated to formate
sats. The sampes contaned 2 wt-% formc acd and moar equvaent of amne n dchoromethane.
I Trs(2-ethyhexy) amne
II Trs(so-octy) amne
III Trocty amne
IV Dmethydecy amne

Strong bndng gves hgh dstrbuton constant (K
D
) but can aso cause probems n the acd recovery
step (Tabe 1).
Tabl e 1. Correaton of the ength and branchng of the amne carbon chans to extracton effcency
and behavour n dstaton. Sat character n IR ncreases I II III IV (see Fgure 2). Dstaton
wth 20 wt-% formc acd n amne, the maxmum bottom temperature was 140C n order to avod
formc acd decomposton.
No Carbon chains in amine K
D
Di stil lation

I 3 x CH
3
-(CH
2
)
3
-CH(CH
2
CH
3
)-CH
2
- 0.19 A part of formc acd dsts out at 1 bar, dsts fuy
under vacuum
II 3 x (CH
3
)
2
-CH-(CH
2
)
5
- 3.8 A part of formc acd dsts out at 1 bar, dsts fuy
under vacuum
III 3 x CH
3
-(CH
2
)
7
- 4.6 Formc acd does not dst out at 1 bar but dsts
under vacuum
IV 1 x CH
3
-(CH
2
)
9
-
2 x CH
3
-
syrup Sodfes, formc acd does not dst out even under
vacuum
K
D
=|HCOOH|
extract
/|HCOOH|
raffnate
, |HCOOH|
feed
=0.65 modm
-3
(3 wt-% souton)

243
The compexes are formed ony between free acd and extractant, whch means that n most fer-
mentatons a separate acdfcaton step s needed before extracton. Fermentatons that can be run
near or beow pKas of the product acds woud have an advantage.
Co-solvents
Extractant-acd compexes can have so strong sat character that they do not dssove we n the
buk extractant but separate as thrd qud phase. Remova of the resdua water n dstaton can
cause formaton of sod sat. The organc phases can be homogenzed by addton of certan hy-
drocarbon co-sovents. We have notced that n formc acd extracton acoho co-sovents that are
often used n terature cause sgnfcant ester formaton. Formate esters were found to be poor acd
extractants.
Co-sovent affects aso the extracton seectvty and can be a too to fne tune the extractant
propertes n a certan appcaton. For exampe co-extracton of furfura wth acds was be ncreased
by addton of poar cycohexanone to amne and decreased by addton of non-poar akanes.
Uptake of water
The sovent system s preferaby seected so that mnma amount of extractant s dssoved n the
aqueous phase (hgh purty of the process waste water) and mnma amount of water s dssoved
n the extract (soaton and purfcaton of the product wth mnma evaporaton of water).
We found that formaton of acd-extractant compexes ntroduce some poarty (see Fgure 2) that
can change the propertes of the qud. Water soubty can ncrease sgnfcanty (Fgure 3), as we
as extractant soubty to water. Ths can nterfere wth phase separaton. If the acd s recovered by
dstaton, t s key that azeotropes wth water changes the dstaton pattern n some extent.

Figure 3. Effect of formc acd, acetc acd and furfura on the dssovaton of water n an ether type
of extractant. Indvdua contrbutons are addtve. Extractons wth w/o =1.1, 45C.

244
Recovery of the acid and regenerati on of the extractant
There are hardy any ow bong pont extractants that woud have ow enough water soubty,
toxcty and fammabty to be usefu. Thus, n practse the compex formng extractants are usuay
hgh bong pont quds that are not feasbe to regenerate by dstaton. If the products are hy-
droxy acds, they are easy decomposed or dmerzed durng dstaton.
A dstatons may be avoded f aqueous concentrated base s added to the extract and the ac-
ds are back-extracted as sats. Ths s especay convenent f the acd s aso used n sat form n
the fna appcaton. The remanng organc phase s washed and recyced back to extracton. Suc-
cess of ths procedure depends naturay on the bndng of non-acdc mpurtes.
Interestngy, the base does not need to be very strong or we soube to be effectve. The gyc-
ero fermentaton product extracted wth amne based sovent contaned 5.00 wt-% proponc acd,
0.21 wt-% acetc acd and 0.16 wt-% succnc acd. When back extracted wth extremey poory
water and organc sovent soube cacum bases; CaCO
3
and Ca(OH)
2
(as aqueous suspensons,
w/o =0.4, 20% Ca excess), cacum proponate yeds up to 90% were obtaned. Cacum sats of
ght carboxyc acds are water soube, so they are easy to separate from the unreacted base.
Carbonate and hydroxde have dfferent bascty and so they tend to gve dfferent cacum sat
dstrbuton from a mxture of acds. In ths case the weaker base Ca(CO)
3
gave a arger porton of
acetate n the product.
Conclusions
Therma, chemca and botechnca treatments of bomass can degrade sugar ogomers and poy-
mers to smaer moecues that ncude water soube carboxyc acds. In some speca cases aso
fats and os, gnn, poypeptdes etc. coud be the startng pont n the converson. These reactons
are normay run n aqueous envronment and the acds end up usuay n very dute soutons con-
tanng many components. Ther recovery s chaengng.
We have studed qud-qud extracton foowed by dstaton or back extracton as methods to
soate C
1
-C
4
acds from bomass based dute aqueous soutons. Varous crtca parameters and
prerequstes were dentfed. In some cases even 98% recovery yeds were obtaned from sou-
tons that contaned 2-3 wt-% of the desred acd. However, each partcuar feed s a case of ts
own where many varabes, not east the composton of the extractng sovent and the method of
recovery from the extractant shoud be carefuy optmzed. After the screenng phase, where the
basc understandng of the system s obtaned, the work shoud contnue wth feed from the rea
process so that the effect of a the components n actua concentratons can be seen.
After fndng techncay workng arrangements, where a the chemcas are ndustray avaabe
and safe to use, t s mportant to ncude tota energy consumpton, waste water purfcaton, sovent
regeneraton, purfcaton of the product etc. n the studes. A fows n the process are modeed.
Varous concepts shoud be deveoped sde by sde and at the end put the tota nvestment and
operaton costs to comparson.
In genera, our experence has shown that qud-qud extracton foowed by dstaton or back
extracton can provde an attractve route for carboxyc acd recovery from ndustra sde streams.
Acknowledgements
Antero Latnen, Satu Sundqvst (VTT); Ikka Turunen, Arto Laar, Abayneh Demesa, Ida-Kasa
Kempp and | uho Uustao (Lappeenranta Unversty of Technoogy); Mnna Westersund and Krs-
tan Bragge (Metropoa Unversty of Apped Scences, Hesnk) and Esko Trronen, Martna
Tomnen and Ra|a Pukknen (Kemra) are acknowedged for ther essenta contrbuton, together
wth many others n these ocatons for vauabe supportve work.
Out Kovstonen (VTT), Tuomo Sano and Sanna Hesten (Lappeenranta Unversty of Tech-
noogy) and | uhana Ahoa (Kemra) are acknowedged for provdng chaengng sampes.

245
The work was supported by Tekes as part of the Kemra-VTT SWEET program, whch has been
apprecated.
References
1. Ftzpatrck, S.W. 2006. A "Bo-Refnery" Concept Based on Thermochemca Converson of Ceuo-
sc Bomass. Feedstocks for the Future, ACS Symposum Seres, 921, Chapter 20, p. 271.
2. Kk, | ., An, R., Pakkanen, H., Matanen, R., Laht, K.| . 2007. Ouanttatve Determnaton of
the Man Aphatc Carboxyc Acds n Wood Kraft Back Lquors by Hgh-Performance
Lqud Chromatography-Mass Spectrometry. Chromatography A 1139(2), p. 263.
3. Oasmaa, A., Peacocke, C. 2010. Propertes and Fue Use of Bomass-derved Fast Pyroyss
Lquds. VTT Pubcatons 731.
4. Arksson, B., Cavka, A., | nsson, L.| . 2011. Improvng the Fermentabty of Enzymatc Hydroy-
sates of Lgnoceuose Through Chemca In-stu Detoxfcaton wth Reducng Agents. Bo-
resour. Techno. 102, p. 1254.
5. Kertes, A.S., Kng, C.| . 1986. Extracton Chemstry of Fermentaton Product Carboxyc Acds.
Botechno. Boeng. 28, p. 269.
Some xyan ethers for coatng appcatons

246
Some xylan ethers for coating applications
Christiane Laine, Ali Harlin, Jonas Hartman, Sari Hyvrinen, Kari Kammiovirta,
Bjrn Krogerus, Heikki Pajari, Hille Rautkoski, Harri Setl, Jenni Sievnen,
Johanna Uotila, Mika Vh-Nissi
Abstract
Hemceuoses and ceuoses are the most abundant natura poymers and ther avaabty out-
ranges practcay the current voumes of pastc producton. Ths paper demonstrates opportuntes
of xyan ether dervatves n matera appcatons as deveoped for wood-based xyan. Routes to
chemcas and materas usefu for coatng and packagng - ncudng barrer materas and coatng
bnders - was demonstrated for whte and pure xyan from beached brch kraft pup resutng n
materas wth mproved pastczaton, processabty, and barrer propertes. Ths patform, taorng
of chemcas and materas, enabes further deveopment for specfc appcatons.
ntroduction
Hemceuoses are non-crystane heteropoysacchardes casscay defned as aka soube mate-
ra after remova of pectc substances |1|. They are composed of varous sugar unts and are
branched. Hemceuoses have a degree of poymerzaton of 80-200. The backbone of hemceu-
oses can consst of ony one unt e.g. xyose n xyans, or of two or more unts n e.g. gucoman-
nans. Hemceuoses are qute easy hydroyzed by acds to ther monomerc components consst-
ng of D-xyose, L-arabnose, D-gucose, D-gaactose, D-mannose, uronc acds and sma amounts
of other sugar unts. Hemceuoses and n partcuar xyan can be produced from dfferent knds of
wood or agro-based materas usng dfferent knd of extracton methods |2, 3, 4|.
For xyan soaton, gnn s usuay frst removed from pup foowed by beachng. After that, the
xyan s easy extractabe from wood and agro-based matera n akane condtons |6, 7|. Typcay,
akane extracton ceaves the natve acety substtuents of the xyan and markedy affects soubty.
Dependent on the source of xyan, the coor can vary from brown (gnn-contanng) to whte.
Xylan isolation from bleached birch kraft pulp
The xyan content n hardwood and hardwood pups s between 20 and 30 w-% for eucaypt and
brch as shown n Fgure 1. Due to the hgher xyan content, brch s favored over eucaypt as raw
matera for xyan.
A producton process for pure and essentay near xyan has been deveoped and upscaed at
Keskusaboratoro (KCL), Fnand and VTT Technca Research Centre of Fnand. The process
ncudes akane extracton of beached brch kraft pup and purfcaton by e.g. utraftraton, precp-
taton or a combnaton of the methods |10, 11, 12|. The xyan extract composton from an ndustra
beached kraft pup s shown n Tabe 1 showng that the ma|or component s very pure xyan (.e.
free from other hemceuose components). Ony 1-2% of the tota sugars are other than xyose.
Mannose and gaactose contents were beow 5 mg/. The product s a mky, whte dsperson after
e.g. utraftraton (see Fgure 2). Ths xyan s used as dsperson n non-dred form for the further
modfcaton.


247

Figure 1. Xyan content, %, n hardwood and hardwood pup for brch and eucaypt |1, 8, 9|.
Tabl e 1. Sugar content as monosacchardes after acd hydroyss and xyan content of akane
extract from beached brch pup; vaues of two parae extractons.
NaOH,
mol /l
Xylose, mg/l Arabi nose,
mg/l
Glucose,
mg/l
Total sugars,
mg/l
As xyl an,
mg/l *
Extracted xylan,
% of ori ginal pul p
0.5 5 000-6 100 9-10 13-15 5 100-6 200 4 400-5 400 8-9
1.0 9 900-11 000 5 16-25 9 900-11 000 8 710-9 680 15-17
* As acety-free, gucuronc acd-free, poymerc xyan.
Modification
The non-dred xyan was etherfed n akane condtons usng epoxde reagents12, 13 to dfferent
dervatves as shown n Scheme 1. The products, hydroxypropyated xyan (HPX), buty-ayated
xyan (X-BA) and hydroxypropyated and buty-ayated xyan (HPX-BA), have thermopastc prop-
ertes e.g. fm formng propertes. Some characterstcs and anayss data s coected n Tabe 2.
Table 2. Characterstcs of the xyan ether dervatves HPX, XBA and HPX-BA (see text for abbre-
vatons). The degrees of substtuton were cacuated from the peak areas after peak ntegraton of
1H-NMR spectra.
Sampl e code DS (HP) DS (A) DS (B) Fil m forming properti es T
g
(C)
HPX 1.5 No no Transparent fexbe fm 66
X-BA No 0.3 0.5 Transparent fexbe fm 58
HPX-BA 0.6 0.2 0.3 Sghty opaque fm 64

248

Scheme 1. Etherfcaton routes usng epoxy reagents n akane condtons. () xyan s hydroxy-
propyated usng propyene oxde; () xyan s ony etherfed usng buty and ay gycdy ethers; ()
hydroxypropyated xyan s further etherfed usng buty and ay gycdy ethers |1|. Hydroxypropyated
(HPX); |2| buty-ayated (X-BA) and |3| hydroxypropyated and buty-ayated (HPX-BA) xyans.
Application tests
Barrier coati ngs on board
The growng demand for repacng exstng barrers, such as aumnum and synthetc non-
renewabe poymers (e.g. poyethyene, poyvny acoho, poyvnydene chorde etc.) wth b-
obased materas, has ed to an acceerated deveopment of bopoymer barrer ayers for food
packagng systems. Barrer coatngs have been desgned to protect and preserve the product from
harmfu externa nfuences. Such externa nfuences can range from oxygen, carbon doxde and
water n consumer commodty packages to trace eves of meta ons n state-of-the-art mcroeec-
tronc devces. In 2007, the market for barrer coatngs for paper and board was 3 778 MC and s
expected to cmb to 4 552 MC by 2014 |14|.
The prepared xyan ether dervatves were evauated as barrer coatng materas n packagng
for oxygen, water vapor and grease barrer propertes. It was found that chemcay cross-nked
water-soube xyan dervatves show promsng barrer propertes on precoated board (Tabe 3).
The non-dred xyan and precoated board coated wth HPX are shown n Fgure 2 as an exampe.
The key to success es n the water soubty and partce dmenson as we as the structure of the
board substrate. The ntroduced nterna pastczaton mproved fm formaton of xyan, snce un-
modfed xyan from akane extracton of kraft pup s not fm formng. Cross-nkng was used as a
technque to further mprove the barrer propertes of the xyan ether dervatves and ther coatngs.
The best oxygen permeabty (OP) at 23C and 0% RH was exhbted by cross-nked hydroxyprop-
yated xyan (HPX 2+CA) and was three tmes better than the best reference, that beng PET-
coated board. Water vapor permeabtes of the xyan coatngs were 50-100% of that measured for
the commerca bopoymer coatng. In addton, the barrer coatngs showed grease barrer propertes.

249
Tabl e 3. Normazed oxygen permeabty (OP), normazed water vapor permeabty (WVP) and
grease resstance vaues for xyan dervatve coatngs on precoated board |12|.
Sampl e OP
23C, 0% RH
(cm
3
m/d,m
2
,kPa)
WVP
23C, 50% RH
(gm/m
2
,d,kPa)
Grease
barri er
KT grease
resi stance
SE Cupforma Cassc PE 1 141 37 1.3 0.8 - 12
SE Cupforma Natura Bo 202 22 13 0.3 >24 h NA
SE Trayforma Performance PET 41 0.1 2.3 0.9 NA NA
SB-atex +tac 9 405 8 0.4 NA NA
Xyan - - - -
HPX* +5% CA 15 1 7 1 >24 h >12
X-BA+5% CA 150 28 6 1 >24 h >12
X-BA+20% G:S 1:1+5% CA 181 8 8 1 >24 h >12
HPX-BA +20% G:S 1:1 1 487 84 13 2 >24 h >12
SE-Stora Enso; G-Gycero; S-Sorbto; CA-Ctrc acd; *20% sods; 11% sods; NA-Not Anayzed

Figure 2. Xyan soated from beached brch kraft forms a whte dsperson after utraftraton or
precptaton from the akane extract (eft). Barrer coatng of HPX on pre-coated board (rght).
Pigment coating binder for offset grade printing grades
Another mportant convertng process s pgment coatng whch s apped for prntng papers as we
as board to mprove prntng propertes and the appearance of uncoated paper and board. Coatng
coors contan mnera pgments, bnders, rheoogy modfers (thckeners), and water and are ap-
ped on the base matera. Repacement of o-based atex bnders wth bo-based poymers s of
nterest n the coatng coor to decrease the dependence synthetc poymers. Currenty, synthetc
atexes are preferred to commercay avaabe bo-based, soube starch bnders, because the
surface strength of the coated paper s normay hgher and prntng propertes are better wth atex
than wth starch formuatons. Dspersed xyan acetate has been tested earer as coatng bnders
|15| but some chaenges were observed e.g. n fm formng propertes. Introducton of nterna
pastczaton to xyan dervatves as performed here s a too to address these chaenges.

250
Xyan ether dervatves were tested as bnders n pgment coatng appcatons for offset grade
papers |12|. Good surface strength of coated paper coud be demonstrated wth butyated and
ayated xyan(X-BA) and t performed n the tests amost as we as the reference atex (Fgure 3).
The performance of hydroxypropyated xyan (HPX) was not as good as that of X-BA. Some deve-
opment s needed as e.g. shear vscostes of the coatng coors wth xyan dervatve bnders were
generay consderaby hgher than that of the atex coor.

Figure 3. Coated paper sampes after Prfbau wet pck test. The abes descrbe the bnder type
and the bnder amount (pph) n the coatng coors. Aso mxtures of bnders were tested.
Conclusions
Xyan provdes a good startng poymer for modfcaton of potenta chemcas n fm, coatng and
barrer appcatons. Good barrer propertes were demonstrated for the xyan ether dervatves n
oxygen, water vapor and grease barrer. The tested dervatves demonstrated reasonabe perfor-
mance as pgment coatng bnders for offset prntng papers, as ndcated, for exampe, by the rea-
tvey good surface strength. By further optmzaton and taorng, even better propertes are ex-
pected. Currenty, there s no ndustra producton of hemceuoses for product deveopment.
However, xyan and other hemceuoses may become ready avaabe n case the producton of
dssovng pup ncreases sgnfcanty. Ths woud be the case, f the demand to use wood-based
fbers to repace e.g. synthetc texte and cotton fbers woud grow sgnfcanty. In addton, the
deveoped modfcaton routes can be apped and ad|usted for new sources of poysacchardes n
agrcutura or marne borefneres.
Acknowledgements
The ma|orty of the work was performed wth parta fundng by Forestcuster Ltds program Future
Borefnery (FuBo) whch s acknowedged. Stora Enso, M-rea, KCL, Mets Fbre Oy are thanked
for ther co-operaton. The contrbuton of Hannu Mkkonen, VTT, to ths work s acknowedged n
memoram.
References
1. S|strm, E. 1993. Wood chemstry-fundamentas and appcatons. Academc, London.
2. Ebrngerov, A., Henze, T. 2000. Xyan and xyan dervatves - bopoymers wth vauabe prop-
ertes, 1 Naturay occurrng xyans structures, soaton procedures and propertes. Mac-
romo. Rapd Commun. 21, pp. 542-556.
3. Gasser, W.G., Kaar, W.E., | an, R.K., Seaey, | .E. 2000. Isoaton optons for non-ceuose
heteropoysacchardes (HetPS). Ceuose 7, pp. 299-317.

251
4. Wfr, S., Rehn, P., Sundberg, A., Sundberg, K., Hombom, B. 2003. Recovery of water-soube
acety-gaactogucomannans from mechanca pup of spruce. Tapp | . 2, pp. 27-32.
5. Wfr, S., Sundberg, A., Pranovch, A., Hombom, B. 2005. Poysacchardes n some ndustray
mportant hardwood speces. Wood Sc. Techno. 39, pp. 601-617.
6. Buchanan, C.M., Buchanan, N.L., Debenham, | .S., Sheton, M.C., Wood, M.D. Corn fber for the
producton of advanced chemcas and materas: arabnoxyan and arabnoxyan derva-
tves prepared therefrom. US Patent appcaton 2001020091 A1.
7. Gasser, W.G., | an, R.K., S|stedt, M.A. Thermopastc pentosan-rch poysacchardes from
bomass. US Patent 5430142.
8. Fuhrmann, A., Rautonen, R., Tokkanen, L. 1999. Karterng av en TCF-b|rkvedssufatmassa-
fabrk, Survey of a TCF brch kraft m, SCAN Forsk report 715. 54 p.
9. Lane, C., Tammnen, T. 2002. Orgn of carbohydrates dssoved durng oxygen degnfcaton of
brch and pne kraft pup. Nord. Pup Pap. Res. | . 17(2), pp. 168-171.
10. Pekkaa, O. Method of producng paper and cardboard, WO2007065969 A1.
11. Krogerus, B., Fuhrmann, A. 2009. Isoaton and use of pure xyan from beached kraft pup, The
2nd Nordc Wood Borefnery Conference, NWBC 2009. Hesnk, Fnand, Sep 2-4, Pro-
ceedngs, Posters, Voume 2. Pp. 198-202.
12. Lane, C., Harn, A., Hartman, | ., Hyvrnen, S., Kammovrta, K., Krogerus, B., Pa|ar, H.,
Rautkosk, H., Set, H., Sevnen, | ., Uota, | ., Vh-Nss, M. Hydroxyakyated xyans
- ther synthess and appcaton n coatngs for packagng and paper, Ind. Crop. Prod.
(Accepted for pubcaton.)
13. | an, R.K., S|stedt, M., Gasser, W.G. 2001. Thermopastc xyan dervatves wth propyene
oxde. Ceuose 7, pp. 319-336.
14. | enkns, S. 2009. The Future of Functona and Barrer Coatngs for Paper and Board, Leather-
head, PIRA Internatona Ltd.
15. Lane, C., Petonen, S., Hyvrnen, S., Krogerus, B., Mkkonen, H., Pa|ar, H., Vh-Nss, M.
Producton of nove dspersons based on hemceuose ester poymer n water, WO
2008145828 A1.


253
Posters

Actvtes of IEA boenergy task 42 "borefnery" on wood based boenergy drven borefneres -
cassfcaton, sustanabty assessment, compexty ndex and nternatona perspectves unt 2025

255
Activities of EA bioenergy task 42 " biorefinery
on wood based bioenergy dri ven biorefineries
classification, sustainability assessment, complexity
index and international perspectives until 2025
G. Jungmeier
1
, R. Van Ree
2
, E. de Jong
3
, H. Jrgensen
4
, N.S. Bentsen
4
, A. Departe
4
, C. Philips
4
,
J.C. Pouet
4
, . Skiadas
4
, P. Walsh
4
, M. Wellisch
4
, K. Piquette
4
, T. Willke
4
, . de Bari
4
, M. Klembara
4
,
G. Bullock
4
, J. Tomkinson
4
, O. Atac
4
, G. Garnier
4
, M. Mandl
4

1
JOANNEUM RESEARCH Graz/Austria
2
Wageningen UR, Bio-based Products, Wageningen, The Netherlands
3
Avantium Technologies BV
4
National delegates of the 12 participating countries in EA Bioenergy Task 42 "Biorefinery

IEA Boenergy Task 42 "Borefneres" has formuated the foowng defnton: "Borefnng s the
sustanabe processng of bomass nto a spectrum of bo-based products (food, feed, chemcas,
materas) and boenergy (bofues, power and/or heat)". "Energy-drven" borefneres and "product-
drven" borefneres are dstngushed. A cassfcaton system for borefnery was deveoped to
descrbe each borefnery by the foowng four features (Fgure 1, Fgure 2): 1) patform, 2) feed-
stock, 3) products and 4) processes, e.g. "A 3-patform (gnn, C6&C5 sugar, eectrcty&heat,)
borefnery usng wood chps for boethano". Based on the actvtes of the 11 partcpatng countres
(A, AUS, CA, DK, FR, G, I, IR, NL, T, US) the task dentfes and assesses the current status and
deveopment potenta of "energy-drven" borefneres and "product-drven" borefneres based on
wood. The assessments are based on a "Fu Vaue Chan Approach", coverng raw matera ssues,
converson processes and fna product use n an ntegrated approach and assessng economc,
soco-economc, envronmenta and soca aspects n comparson to conventona processes and
products. As a frst step the 6 most nterestng "energy-drven" borefnery concepts based on wood
unt 2025 and ther vaue chans, ncudng the ntegraton and depoyment optons n ndustra
nfrastructures, are anaysed. These concepts based on wood (e.g. wood chps, saw m resdues)
produce road transportaton bofues: boethano, FT-bofues, bomethane and hydrogen (Fgure 3):
1. "2-patform (syngas, eectrcty&heat) borefnery usng wood chps for FT-Bofues, eectrc-
ty, heat and waxes wth steam gasfcaton"
2. "3-patform (pyroyses o, syngas, eectrcty&heat) borefnery usng straw for FT-bofues
and methano wth oxygen gasfcaton"
3. "3-patform (pup, syngas, eectrcty&heat) borefnery usng wood chps for FT-bofues,
eectrcty, heat and pup"
4. "3-patform (C6&C5 sugar, gnn, eectrcty&heat) borefnery usng wood chps for boetha-
no, eectrcty, heat and phenos"
5. "4-patform (hydrogen, bomethane, syngas, eectrcty&heat) borefnery usng wood chps
for bomethane (SNG), hydrogen and carbon doxde"
6. "4-patform (C6&C5 sugar, gnn&C6 sugar, eectrcty&heat) borefnery usng saw m res-
dues, wood chps and sufte quor for boethano, pup&paper, eectrcty and heat".
In a next step for these seected concepts "Borefnery Fact Sheets" w be made wthn the actv-
tes of IEA Boenergy Task 42 "Borefneres" (Fgure 4). Based on the mass and energy baance of
these energy drven borefneres n these "Borefnery Fact Sheets" a sustanabty assessment
based on whoe vaue chan ncudng envronmenta, economc and soca aspects w be docu-
mented. In addton a so caed "Borefnery Compexty Index" s under deveopment based on the


256
cassfcaton, whch s deveoped for these borefneres smar to the "Neson`s compexty ndex"
for o refneres. Further nformaton see: http://www.ea-boenergy.task42-borefneres.com/.

Figure 1. The 4 features to characterse a borefnery system.

Figure 2. Appcaton of cassfcaton system and namng.

257

Figure 3. Energy drven borefneres usng wood n context to borefneres usng other feedstocks.

Figure 4. The "Borefnery Fact Sheet".
Immobzaton of ceuases on magnetc partces enabes enzyme re-use durng hydroyss of
pretreated spruce

258
mmobilization of cellulases on magnetic particles
enables enzyme re-use during hydrolysis of
pretreated spruce
Johan Alftrn, Timothy Hobley
nstitute for Food, Technical University of Denmark, Denmark
ntroduction
Boethano produced from gnoceuosc bomass s currenty one of the most promsng aterna-
tves due to the great avaabty and ow cost of ths raw matera. An mportant step for the produc-
ton of gnoceuosc derved ethano s the converson of ceuose to gucose whch can be
acheved enzymatcay, by the combned acton of endogucanases, exogucanases and beta-
gucosdases. However, enzyme cost s one of the man obstaces for enabng an economcay
vabe arge-scae process of gnoceuosc ethano. Consequenty, dfferent approaches for de-
creasng the cost of the enzymatc step are beng consdered. Enzyme mmobzaton coud reduce
the enzyme cost by mprovng operatona stabty of the enzyme and aowng enzyme re-use.
Recycng of the enzyme may however be dffcut when treatng crude partcuate contanng gno-
ceuosc feedstocks. One approach to overcome the dffcuty n recycng woud be to use en-
zymes mmobzed on sma magnetcay susceptbe partces (Fgure 1).

Figure 1. Schematc ustraton of ceuose hydroyss usng enzyme mmobzed on magnetc partces.
The am of ths study was to evauate the possbty of covaenty mmobzng ceuases on mag-
netc partces. The magnetc partces used were mcron-szed, non-porous sca based ones, act-
vated wth poygutaradehyde and cyanurc chorde groups. Immobzaton was conducted by
usng one pure -gucosdase preparaton and two dfferent commerca ceuase mxtures from
Novozymes; Ceucast 1.5L and Cec Ctec2.
The resuts demonstrate that t s possbe to mmobze and retan actvty of ceuases on magnet-
c partces (Tabe 1). Cec Ctec2 gave hgher mmobzed -gucosdase and ceuase actvty
compared to Ceucast 1.5L. Purfed -gucosdase resuted n hghest mmobzed -gucosdase
actvty. The bead reated actvtes shown n Tabe 1 are based on magnetc partces actvated by

Immobzaton of ceuases on magnetc partces enabes enzyme re-use durng hydroyss of
pretreated spruce

259
cyanurc chorde. These partces were n a cases superor, n terms of mmobzed actvty, com-
pared to partces actvated wth poygutaradehyde.
Table 1. Immobzed enzyme actvty on magnetc partces usng dfferent enzyme preparatons.
The PNPG-assay was empoyed for determnng -gucosdase actvty. Ceuase actvty was de-
termned by measurng berated reducng sugar usng mcrocrystane ceuose as substrate (1h,
pH4.8 at 50C).
Enzyme preparation -glucosidase act ivity
(Units / g parti cles)
Cellulase activity mol e reducing sugar /
(min*g parti cles)
Pure -gucosdase 104.7 -
Ceucast 1.5L 5.5 18.2
Cec Ctec2 22.8 61.0

The performance and recycabty of mmobzed -gucosdase (BG) on more compex substrate
(pretreated spruce) was studed. It was shown that addng mmobzed BG to free ceuases n-
creased the hydroyss rate of pretreated spruce (Fgure 2). Furthermore, t was possbe to recyce
the mmobzed BG and retan actvty for at east four hydroyss campagns. The mmobzed en-
zyme thus shows promse for gnoceuose hydroyss.

Figure 2. Hydroyss yed of pretreated spruce usng Ceucast 1.5L n combnaton wth mmob-
zed -gucosdase (BG). No BG =Ony Ceucast 1.5L. One hydroyss cyce was performed for 24 h
usng 1.5% (w/v) DM spruce, pH4.8 at 50C. Amount of added Ceucast 1.5L and mmobzed BG
was 8 FPU/g DM and 16 U/g DM, respectvey.
0
20
40
60
80
100
No BG 1 2 3 4
H
y
d
r
o
y
s
s

y
d

(
%
)
Hydroyss cyce
Contrast of Eschercha co KO11 and Saccharomyces cerevsae ATCC96581 n fermentng Pnus
patua hydroysate pretreated at severe steam exposon condtons

260
Contrast of Escherichia coli KO11 and Saccharomyces
cerevisiae ATCC96581 in fermenting Pinus patula
hydrolysate pretreated at severe
steam explosion conditions
Nyangi Chacha
1
, Nils Dyrset
2
, Godliving Mtui
1
, Jamidu Katima
3
, Godwill Mrema
3

1
Department of Molecular Biology and Biotechnology, College of Natural and Applied Sciences,
University of Dar es Salaam, Dar es Salaam, Tanzania
2
The Foundation for Scientific and ndustrial Research (SNTEF), Trondheim, Norway
3
Department of Chemical and Mining Engineering, College of Engineering and Technology,
University of Dar es Salaam, Dar es Salaam, Tanzania
Abstract
Boconverson of wood resdues to bofues such as ethano s one of the feasbe ntatves towards
producton of renewabe energy. Ths work compares the effectveness of Escherichia coli KO11
and Saccharomyces cerevisiae ATCC96581 n fermentng Pinus patula (pne) hydroysate pretreat-
ed by acd-catayzed steam exposon. The resuts showed no sgnfcant dfference n terms of the
ethano yed when E. coli KO11 and S. cerevisiae ATCC96581 were used. The maxmum ethano
concentraton obtaned n test tubes fermentaton was 18.30g/ and 19.41g/ for E. coli KO11 and S.
cerevisiae ATCC96581 from sampes pretreated at 0.5 and 3% SO
2
, respectvey. The ethano
yeds obtaned usng 3L Appcon fermentors for sampes pretreated at 225C and 0.5% SO
2
for
5mn. were 21.30g/ and 19.63g/ for E. coli and S. cerevisiae, respectvey. Overa, ethano yeds
were hgher n Appcon fermentors than n the test tubes for both strans. In comparson, S. cere-
visiae consumed the substrate faster than E. coli, thus makng S. cerevisiae the most preferred
stran n fermentaton of hydroysates from steam pretreated P. patula.
Background
Saccharomyces cerevisiae has been wdey used as a fermentng organsm. Presence of 5-HMF,
evunc acd and formc acd n fermentaton hydroysate affect ce growth, eadng to ow ethano
yed. Researchers have deveoped recombnant organsm to ferment sugar substrate that are not
fermentabe by S. cerevisiae and toerance to gnoceuosc nhbtors. Among other deveoped
strans, Escherichia coli KO11 has been reported by many researches (Trnh et a., 2010) to fer-
ment both 5-carbon and 6-carbon sugars n gnoceuosc bomass n the presence of nhbtory
compounds resutng from steam exposon pretreated processes (G et a., 2009).
Material and methods
Pinus patula wood chps were steam pretreated usng gaseous suphur doxde (SO
2
) (0.5-3% on
water) as acd catayst. The acd cataysed steam pretreatment was carred out at extensve cond-
tons by usng hgh (225C) temperature. The pretreated materas were washed and sub|ected to
enzymatc hydroyss carred out by enzymes (ceuacast 1.5L and Novozyme 188) at 50C and
200 rpm for 72 hours. The enzymatcay hydroysed hydroysate was ftered usng Whatman fter
paper (O 110mm). The supernatant were used as a substrate n precedng fermentaton process
optmsaton experment. The fermentaton experments were done n test tubes for both three set of
pretreated sampes whe n fermentors ony sampes pretreated at (0.5% SO
2
, 225C, 5mn) were
used. The fermentatons were performed at nocua eve of 10%v/v (test tube) and 30%v/v (fermentors)
for both strans but dfferent pH and temperature, for S. cerevisiae pH 5.5, temperature 30C were
apped whe for E. coli pH were 5.5 (test tube) and 6 (fermentors), and 37C temperature.

Contrast of Eschercha co KO11 and Saccharomyces cerevsae ATCC96581 n fermentng Pnus
patua hydroysate pretreated at severe steam exposon condtons

261
Results
The maxmum ethano concentratons obtaned were 18.30 g/ (87%) and 19.410 g/ (88%) for
E. coli KO11 and S. cerevisiae obtaned from the sampe pretreated at acd concentraton of 0.5%
and 3%, respectvey (Fgure 1). The resuts ndcate that a sampes were fermented by the two
strans. However, unt the termnaton of the experment, E. coli fermentaton broth remaned wth
some amount of gucose. In comparng test tubes and boreactors, at 0.5% SO
2
, 225C and 5 mn,
the maxmum ethano concentratons were 18.30 (87%) and 21.30 g/ (91%) for E. coli KO11; and
17.29 (82%) and 19.63 g/ (82%) for S. cerevisiae respectvey. These resuts ndcate that the theo-
retca maxmum ethano yed s the same for test tubes and boreactors n case of S. cerevisiae but
they are not the same n case of E. coli KO11.

Figure 1. Maxmum gucose utzed and ethano concentraton produced by tube fermentaton of S.
cerevisiae and E. coli at dfferent SO
2
concentraton.
Acknowledgements
The authors acknowedge wth grattude the fnanca support from the NUFU to the ESEPRIT Pro-
|ect that factated ths study. PFI and SINTEF, Norway, are thanked for grantng permsson to use
ther aboratores to carry out part of the experments for ths work. The departments of Moecuar
Boogy and Botechnoogy and Chemca and Mnng Engneerng at UDSM are acknowedged for
ogstca support.
References
1. Trnh, C.T., Huffer, S., Cark, M.E., Banch, H.W., Cark, D.S. 2010. Eucdatng Mechansms
of sovent toxcty n ethanoogenc Eschercha co. Botechnoogy and Boengneerng 106(5),
pp. 721-30.
2. G, T.R., Ms, T.Y., Sandova, N.R. 2009. Ceuosc hydroysate toxcty and toerance
mechansms n Eschercha co. Botechno. for bofues 2(26), pp. 1-11.
Smutaneous producton of ethano and softwood kraft pup: pretreatments and effects of nhbtors
on fermentatons

262
Si multaneous production of ethanol and softwood
kraft pulp: pretreatments and effects of inhibitors
on fermentations
Christine Chirat, Jrmy Boucher, Dominique Lachenal
Grenoble NP PAGORA, France
Christine.Chirat@pagora.grenoble-inp.fr
ntroduction
The ob|ectve of ths pro|ect s to deveop a process for the parae producton of ethano and ceu-
ose n the same pup m, by appyng a prehydroyss step to softwood chps to extract hexose
sugars for ther subsequent fermentaton n ethano.
In a prevous work t was shown that prehydroysates from prehydroyss treatment carred out
wth the addton of suphurc acd, coud be fermented drecty nto ethano (Chrat, 2009). However,
the overa yed was sgnfcanty ower than the contro kraft process, and the fna DPv was aso
sgnfcanty decreased. By appyng an autohydroyss treatment, pups of better propertes coud
be obtaned (Chrat et a., 2009, 2011). However, the drawback of the autohydroyss stage per-
formed at 160C was that the hydroysate contaned a ma|orty of ogomers, whch s not sutabe
for a drect fermentaton nto ethano. The ob|ectve of the present study was to compare a prehy-
droyss wth the addton of 1% suphurc acd on wood, wth an autohydroyss foowed by a
posthydroyss of the hydroysate, n terms of sugars content and nhbtors concentraton. The ef-
fect of the nhbtors on ethano producton was studed n a second part.
Effect of a post-hydrolysis on hydrolysate produced from an autohydrolysis
To ncrease the rate n monomers after the autohydroyss treatment, a post acd hydroyss was
performed on the resutng hydroysate. Fgure 1 shows the concentratons n hexoses, HMF, furfu-
ra and acetc acd after secondary hydroyss run under dfferent condtons. Some treatments a-
owed the hydroyss of amost a the ogomers nto monomers, whe mnmzng the producton of
degradaton products: 140C durng 30 mn wth 0.5 and 4% of H
2
SO
4
and 120C durng 60 mn
wth 2.25% of H
2
SO
4
. The fna concentratons n hexoses were ower than after an acd hydroyss
(23.6 g/L compared to 33.1 g/L) but wth concentratons n acetc acd, HMF and furfura respectvey
1.5 tmes, 4 tmes and 2 tmes ower.
Effect of inhibitors on fermentation
The effect of three nhbtors, HMF, furfura and acetc acd was studed on synthetc meda of fer-
mentaton contanng sugars and nhbtors at the same concentratons as those measured after the
hydroyss carred out wth 1% suphurc acd. The fermentatons of sugars aone, sugars wth one
nhbtor and sugars wth the smutaneous presence of the three nhbtors were compared.
Gay-Lussac yeds of fermentatons were cacuated from the nta amount of hexoses after 4,
24 and 48 hours of fermentaton. The yed after 4 hours gves the productvty of the fermentaton
before reachng the fna yed. The measurement after 24 or 48 hours ensures that the fna yeds
are reached before 24 hours, when no sgnfcant dfference s observed between 24 and 48 hours
(Fgure 2). The presence of ony one nhbtor had no sgnfcant effect compared to the fermenta-
ton wthout any added nhbtor. The smutaneous presence of the three nhbtors however ow-
ered the productvty, but the fna yed was not affected. Inhbtors are known to potentay de-
crease the ethano yed (Ameda et a., 2007), but can aso reduce the productvty.

on fermentatons

263
These resuts show that the concentratons of nhbtors found n the hydroysates from the pre-
hydroyss carred out wth 1% of suphurc acd shoud not be a probem for ethano producton.
Ths pont was verfed by carryng out a fermentaton of the "rea" hydroysate obtaned from wood.
Nevertheess, ncreasng the hydroysate concentraton pror to the fermentaton coud be neces-
sary to have a proftabe dstaton. An autohydroyss woud be advantageous n ths case, as t
was shown that autohydroyss foowed by a post-hydroyss of the hydroysate yeded very ow
concentratons of nhbtors.

Figure 1. Concentratons n hexoses, acetc acd, furfura and HMF n hydroysates resutng from
secondary hydroyss. Comparson wth the hydroysate from the prehydroyss carred out wth the
addton of 1% of suphurc acd.

Figure 2. Gay-Lussac yeds of fermentatons after 4, 24 and 48 hours.
Acknowledgements
The authors wsh to thank the TUCK foundaton (ENERBIO programme) for the fundng of ths study.
0
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Time of fermentation (h)
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a
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%
)
Sugars aone Compete HMF Furfura Acetc acd
on fermentatons

264
References
Ameda, | .R.M. et a. 2007. Increased toerance and converson of nhbtors n gnoceuosc hy-
droysates by Saccharomyces cerevisiae. | ourna of chemca technoogy and botechnoogy
82, pp. 340-349.
Chrat, C. et a. 2009. Hemceuoses extracton from eucayptus and softwood wood chps: pup
propertes and ethano producton n ISWFPF, Oso, Norway.
Chrat, C. et a. 2011. Beachng abty of pre-hydroysed pups n the context of a borefnery m,
Internatona Pup Beachng Conference, Tapp Proceedngs, October 5-7, 2011, Portand,
USA.
Sustanabe bofue: nnovatons n boethano producton technooges (SusBoFue)

265
Sustai nabl e biofuel: innovati ons in bi oethanol
production technol ogies (SusBioFuel )
Nils Dyrset
1
, Karin yaas
2
, Timothy John Hobley
3
, Johan Alftrn
3
, Gudmundur Hreggvidsson
4
,
Jaana Uusitalo
5
, Anna von Schenck
6
, Esther Ochoa-Fernndez
7
, Jrn Einen
8

1
SNTEF, Norway
2
PF, Norway
3
DTU, Denmark
4
Matis-Food, celand
5
VTT, Finland
6
NNVENTA, Sweden
7
Statoil, Norway
8
Weyland, Norway

Abstract
The am of the pro|ect s to deveop bochemca technooges for sustanabe ethano producton
from gnoceuosc matera (spruce and straw). Ionc qud pretreatment ndcates a reducton n
ceuose crystanty gvng a more effectve enzymatc hydroyss. Immobzed -gucosdase on
cyanurc acd partces has been shown functona after repeated recycng operaton. A doube
mutant of the thermophc anaerobe Thermoanaerobacter islandicum (ace
-
lac
-
) has been deve-
oped wth ncreased ethano yed and abe to ferment pentoses, hexoses and the dsaccharde
ceobose.
ntroduction
SusBoFue (2010-2014) s a pro|ect n the Top-Leve Research Intatve (TRI) party funded by
Nordc Energy Research. Ma|or barrers for bochemca converson of gnoceuosc materas and
to ther utzaton as bofues are hgh costs for physca pretreatment, enzyme hydroyss of ceu-
oses/hemceuoses and fermentaton of sugars to ethano. Reductons n ceuose crystanty
and/or gnn content by onc/organc sovents pretreatment are expected to mprove the enzymatc
hydroyss yed of ceuose. A new recycng method for enzymes, based on magnetc partces and
mmobzaton, may reduce the cost of enzymatc hydroyss. Hgh ethano yed and hgh produc-
ton rate are requred for an optma producton of ethano. Thermophc anaerobc bactera are
robust mcroorgansms and wd types are known for drect ethanoogenc fermentaton of poysac-
chardes contanng both hexoses and pentoses. However, the yeds of ethano for known strans
on sugar bass are ow and need to be mproved by genetc methods. Anaerobc thermophc
strans soated from geotherma habtats n Iceand, such as Thermoanaerobacter spp are used for
knock-out mutatons to reduce by-product formaton and ncrease yed.
Results
mproved pretreatment process using ionic liquids
Pretreatment process has been optmzed for Norway spruce usng the onc qud EMIM-OAc
(1-ethy-3-methymdazoum acetate). The spruce raw matera used was treated by the newy
deveoped Advanced Thermo Mechanca Pupng (ATMP) process whch shows sgnfcanty ower
energy consumpton than tradtona TMP processes (up to 40% reducton). The onc qud pre-
treatment process was optmzed wth respect to tme and temperature, usng enzymatc saccharf-
caton potenta of the pretreated bomass as the man optmzaton parameter. Pretreatment wth
EMIM-OAc gave effectve dssouton of the spruce ATMP, gvng 90% enzymatc dgestbty of
spruce gucans under optma condtons (100C, 12 hrs). Lgnn dssouton n EMIM-OAc was,
however, ow at these condtons.

Sustanabe bofue: nnovatons n boethano producton technooges (SusBoFue)

266
Enzyme recycling process
-gucosdase has been covaenty mmobzed on non-porous magnetc partces whch were act-
vated by dfferent functona groups. Partces actvated wth cyanurc chorde and poygutarade-
hyde gave the hghest bead reated mmobzed enzyme actvty. Added mmobzed -gucosdase
to free ceuases (Ceucast 1.5L) ncreased the hydroyss rate of pretreated spruce. In addton,
the mmobzed -gucosdase was re-used and the actvty retaned for at east 4 cyces. In another
approach of mmobzaton, botn-tagged -gucosdase has been expressed by usng in vivo bot-
nyated n E. coli strans. Immobzaton of ceuase mxture (Ceucast 1.5 L and Cec Ctec2) has
aso been performed. The resuts showed that the mmobzed ceuases coud hydroyse mcro-
crystane ceuose and pretreated spruce. The next w be to study whether the mmobzed ceu-
ases can be recyced and determne how many hydroyss cyces the ceuases can be used.
Combining lac
-
and ace
-
mutations in one strain of T. islandicum
The ma|or obstaces to genetc manpuaton of thermophc bactera are the ack of avaabe func-
tona genetc markers and dffcutes wth transformaton. Inserton of kanamycn and erythromycn
resstance genes nto T. islandicum AK17 was successfuy acheved through eectrotransformaton
and both genes conferred antbotc resstance at 55C, makng t possbe to genetcay manpuate
T. islandicum. Two T. islandicum mutants were constructed, knockng out a actate dehydrogenase
gene (lac
-
) and acetate knase and acetadehyde dehydrogenase genes (ace
-
), respectvey, for
reduced by-product formaton. The lac
-
mutant produced amost undetectabe amounts of actc
acd, whe acetc acd producton was smar to what was observed n the wd type stran, and
ethano yeds were ncreased. The ace
-
mutant showed reduced acetc acd producton, ncreased
actc acd producton, and reduced ethano producton. The knockouts were subsequenty com-
bned nto one doube mutant (lac
-
ace
-
) whch produced ethano as the man by-product, and a-
most undetectabe amounts of acetc and actc acd.
Optimizing of fermentation process for double mutant strain of
T. islandicum
The deveoped doube mutant (lac
-
ace
-)
of T. islandicum AK 17 has been characterzed for sugar
fermentaton and product formaton. The stran ferments the gnoceuosc hexoses (gucose, ga-
actose and mannose), the pentoses (xyose and arabnose) and the dsaccharde ceobose, but
not the poysacchardes ceuose or xyan. As expected, the strans produce ethano as the man
product, and amost undetectabe amounts of acetc and actc acd was observed. In batch fermen-
taton, 17 g ethano/ was obtaned wth a yed of 0.41 g/gucose consumed, a specfc growth rate
of 0.12 h
-1
n the exponenta growth phase, and a voumetrc ethano producton rate of 0.34 g/h n
the man ethano producton perod.

Oxidative pretreatment of CCA-treated wood for bioethanol production

267
Oxidative pretreatment of CCA-treated wood
for bioethanol producti on
Maija Hakola, Markku Leskel, Timo Repo
University of Helsinki, Department of Chemistry, Laboratory of Inorganic Chemistry,
P.O. Box 55, FI-00014 University of Helsinki, Finland
maija.hakola@helsinki.fi
Abstract
The waste management of chromate copper arsenite treated wood is challenging due to the toxic
chemicals it contains. Catalytic and alkaline pretreatments are effective methods for separating
carbohydrates from lignin in lignocellulosic materials. Here these pretreatments are applied to CCA-
treated wood in order to produce easily hydrolysable carbohydrate rich material.
Introduction
Chromated copper arsenite (CCA) has been one of the most widely applied preservative for over
60 years around the world. Although it is not used anymore as preservative the challenge of waste
management and recycling continues as the lifetime of CCA-treated wood is approximately 30
years. The waste management is complicated due to the toxic chemicals it contains. Primarily
CCA-treated wood is disposed within landfills, but the leaching of copper, chromium and arsenic to
the environment is a problem. On the other hand, the possible vaporization of toxic arsenic com-
pounds is a matter of concern in thermal treatment of CCA-treated wood.
Here we present an interesting method that enables the use of treated wood as a raw material
for bioethanol production. Earlier studied catalytic (CatOx) and alkaline (AlkOx) oxidation pretreat-
ments can be used to isolate cellulose also from CCA-treated wood. [1, 2] During the treatments
lignin is dissolved and some of the metal ions are removed. The obtained material can be enzymat-
ically hydrolyzed.
Experimental
CatOx and AlkOx were carried out at 120C for 20 hours in alkaline water solution (0.25 M Na
2
CO
3
)
and under 10 bar oxygen pressure. In CatOx 1,10-phenanthroline was used as a catalyst ingredi-
ent. The reactions proceeded well; lignin was solubilized and the solid carbohydrate fraction was
filtrated. The hydrolysis experiments were done for the carbohydrate rich materials as such and
after additional extraction with mild sulfuric acid for 22 hours at room temperature.
The pretreatments proceeded well; lignin was solubilized and after CatOx 76% of copper, 50% of
chromium and 45% of arsenic were removed. After AlkOx the amounts were 82%, 36% and 39%
respectively.
The cellulose from CatOx was hydrolyzed slightly better than the cellulose from AlkOx (Figure 1).
However both samples when treated also with mild sulfuric acid were almost completely hydrolyzed
already in 24 hours.

Oxdatve pretreatment of CCA-treated wood for boethano producton

268

Figure 1. Enzymatc hydroyss of carbohydrate fracton after cataytc and akane oxdaton reac-
tons wthout extracton (CatOx and AkOx) and after addtona sufurc acd extracton (CatOx
H
2
SO
4
and AkOx H
2
SO
4
).
Conclusions
CatOx and AkOx together wth sufurc acd extracton are effcent methods for pretreatng CCA-
treated wood for ceuosc ethano producton. Athough some of the meta ons remaned n the
matera the ceuose fracton s we hydroyzed by enzymes aso wthout addtona extracton after
the oxdatons.
Acknowledgements
The authors thank Demote Oy for provdng the raw matera, Anne Kaonen, VTT Technca
Research Centre of Fnand, for the hydroyss experments and | uhan Vrkanen, Unversty of
Hesnk, for ICP anayss.
References
1. Hakoa, M., Kaonen, A., Keme, M., Lahtnen, P., Lanknen, E., Leske, M., Repo, T., Rekkoa, T.,
Ska-aho, M., Uustao, | ., Vuorea, S., von Weymarn, N. 2010. Lberaton of Ceuose
from the Lgnn Cage: A Cataytc Pretreatment Method for the Producton of Ceuosc
Ethano. ChemSusChem 3, pp. 1142-1145.
2. Rovo, S., Kaonen, A., Tammnen, T., Hakoa, M., Leske, M., Ska-aho, M. 2012. Cataysed
Akane Oxdaton as a Wood Fractonaton Technque. BoResources 7(1), pp. 756-776.
Improvement of enzymatc hydroyss condtons of Sax vmnas poysacchardes

269
mprovement of enzymatic hydrolysis conditions
of Salix vimi nalis polysacchari des
Karolina witek, Magdalena witek, Magorzata Lewandowska, Wodzimierz Bednarski
Chair of Food Biotechnology, University of Warmia and Mazury in Olsztyn
karolina.swiatek@uwm.edu.pl
Abstract
Research evauatng the effect of used enzyme preparatons on the effectveness of hydroyss of
Salix viminalis poysacchardes s presented. The used enzyme preparatons ncuded: two ceuase
preparatons - Ceucast 1.5L and ceuase from Trichoderma longibrachiatum, two xyanase prepara-
tons - Pentopan Mono BG and xyanase from Trichoderma longibrachiatum, and ceobase. The hgh-
est hydroyss effcency was obtaned when poysacchardes of pretreated Salix viminalis were hydro-
yzed usng the enzyme compex composed of: ceuase and xyanase from T. longibrachiatum and
ceobase.
ntroduction
The ncreasng consumpton and decreasng suppes of crude o have ed to a search for aterna-
tve energy supports. The abundance and ow prce of gnoceuosc materas make them attrac-
tve as a feedstock for fue ethano producton |2|. Fast-growng energy crops, such as Salix and
swtchgrass, are consdered to be a possbe source of boethano. A process based on pretreat-
ment of matera, enzymatc hydroyss of poysacchardes and fermentaton s regarded as a prom-
sng aternatve n convertng the carbohydrates n gnoceuosc materas nto ethano wth hgh
yeds and reatvey ow producton costs |1|.
Experimental
Salix viminalis bomass ground to a partce sze of 1-2 mm was aka pretreated wth the use of
expermentay fxed condtons: the proporton of aka - 0.1 g NaOH/g d.m. of substrate, temperature
121C, tme 3 h. After pretreatment, the pH of the suspenson (10% d.m.) was ad|usted to 5.0 and
sodum azde was added to avod mcroba contamnaton. In the next step, numerous attempts at
hydroyss of the pretreated matera were performed, wth the use of: two ceuase preparatons -
Ceucast 1.5L and ceuase from Trichoderma longibrachiatum, two xyanase preparatons - Pen-
topan Mono BG and xyanase from Trichoderma longibrachiatum. In a the hydroyss experments,
ceobase (Novozyme 188) was used n order to convert ceobose to gucose. The effects of 72-
hour hydroyss were estabshed on the bass of the amount of reeased reducng sugars, meas-
ured wth DNS reagent. The experments of hydroyss of untreated matera were aso conducted.
The hghest hydroyss effcency was obtaned when poysacchardes of pretreated Salix viminalis
were hydroyzed usng the enzyme compex composed of: ceuase and xyanase from T. longi-
brachiatum and ceobase. Under these condtons, the concentraton of reeased reducng sugars
(expressed as gucose) after 72 hour hydroyss was 48.5 g/dm
3
(69.05% of theoretca vaue (on
the bass of ceuose and hemceuose content n raw matera). The owest amount of reeased
reducng sugars was obtaned for the enzyme compex composed of Ceucast 1.5 L and ceob-
ase, wthout xyanase. As s shown n the Fgure 1, xyanase from T. longibrachiatum s cruca n
the process of enzymatc hydroyss of Salix poysacchardes. Furthermore, t was confrmed that
the pretreatment step sgnfcanty affects the enzymatc hydroyss yed (approx. a 3-fod ncrease).

Improvement of enzymatc hydroyss condtons of Sax vmnas poysacchardes

270

Figure 1. The effects of 72 h hydroyss of Salix viminalis poysacchardes wth the use of dfferent
compostons of enzymes.
Conclusions
The resuts of the conducted research show that hydroyss effcency s strongy determned by the
type of enzyme compex used. Moreover, usng a xyanase n combnaton wth ceuase sgnfcanty
mproves process yed. It was aso found that pretreatment of gnoceuosc substrate s an essenta
step n obtanng a hgh hydroyss yed.
The strategc program of the Natona (Posh) Centre for Research and Deveopment (NCBR):
"Advanced Technooges for Energy Generaton. Task 4: Eaboraton of Integrated Technooges
for the Producton of Fues and Energy from Bomass, Agrcutura Waste and other Waste Ma-
teras."
References
1. Sassner, P., Gabe, M., Zacch, G. 2008. Techno-economc evauaton of boethano producton
from three dfferent gnoceuosc materas. Bomass Boenergy 32, pp. 422-430.
2. Stephenson, A.L., Dupree, P., Scott, S.A., Denns, | .S. 2010. The envronmenta and economc
sustanabty of potenta boethano from wow n the UK. Boresource Technoogy 101,
pp. 9612-9623.
Producton of fermentabe sugars by enzymatc hydroyss of pretreated waste texte

271
Production of fermentable sugars by enzymatic
hydrolysis of pretreated waste textile
Elahe Gholamzad
1
, Kheikhosro Karimi
1
, Mahmood Masoomi
1
, Vahid Jafari
2
1
sfahan University of Technology,
Department of Chemical Engineering sfahan 84156-83111, ran
2
Abstract
Ceuose (cotton) and poyester based texte wth contrbuton of 27 and 39 mon tons per year,
respectvey, has the hghest share of the texte market n the word. Ceuose recovery and degra-
daton to smpe sugar n order to use for other appcatons, such as bofue producton, s the best
way to acheve envronmenta goas at the owest cost. In ths study, NaOH/urea aqueous souton
was used for recovery of ceuose from cotton-poyester waste textes. The treatment wth the
aka sovent resuted n effcent separaton and purfcaton of poyester and a hgh yed of gucose
recovery out of the hghy crystane cotton after an enzymatc hydroyss.
ntroduction
A huge amount of fbre producton creates mon tons of waste textes. On the other hand, one of
the serous probems of coth ndustry s waste textes dsposa. Envronmenta probems wth and-
fng and ncneraton force us to fnd procedures for texte recycng and new appcatons for
these recyced textes |1|. Cotton composes of 88-96% ceuose, therefore t s possbe to hydro-
yse these textes and produce fermentabe sugars for bofue producton |2|. A separaton can be
obtaned by enzymatc hydroyss of the ceuose n the textes. However, the cotton structure s
hghy crystane resutng to deprved hydroysed by the hydroytc enzymes. The current study,
nvestgate the effect of dfferent treatment procedures for havng effcent separaton of cotton and
atey fermentabe sugar producton.
Experimental
The waste texte used n ths work was 35/65 poyester/cotton bend (Poya Baft factory, Isfahan,
Iran). Two enzymes, ceuose (SIGMA, C2730) and -gucosdase (SIGMA, G0395) were used for
enzymatc hydroyses.
Texte souton (4%) was prepared by mxng 2 g texte wth 48 g NaOH/urea aqueous souton
(7:12 n wt.%) at dfferent temperatures -20, 0, 20 and 100C for 1 h and manuay mxed every
10 mn usng a gass rod. The chemcay treated fbers were then washed wth extensve amounts
of dsted water to obtan pH 7 and kept n the refrgerator unt hydroyss. The treated and un-
treated textes were sub|ected to 72 h enzymatc hydroyss at 45C and pH 4.8 n 50 mM sodum
ctrate buffers wth 3% (w/v) sod substrates, usng 30 FPU ceuase and 60 IU -gucosdase per
gram ceuose. After 72 h hydroyss, the resdua sod (poyester) was separated by centrfugaton
at 4 000 rpm and 10 mn.
The effcency of texte dsntegraton after treatment at -20-100C was between 95-99%. The best
resuts were obtaned at the hghest temperature n whch ceuose separaton acheved by 99%,
whe effcency of untreated process was ony 54%.
Tabe 1 shows the resuts of enzymatc hydroyss of NaOH/urea treated texte at dfferent
treatment condtons. The resuts ndcate a sgnfcaton mprovement n gucose producton from

Producton of fermentabe sugars by enzymatc hydroyss of pretreated waste texte

272
the texte after pretreatment compared to untreated sampe. The best gucose concentraton was
ganed by 20.5 g/L at the hghest temperature (100C) after 72 h of hydroyss.
Table 1. Gucose producton from the texte by the aka pretreatment (g/L).
Alkali pretr eat ment 24h 48h 72h
-20C 14.4 15.5 19.3
0C 10.5 12.9 18.7
20C 17.7 19.2 19.7
100C 17.6 18.8 20.5
Untreated 6.1 7.4 8.1

Conclusions
NaOH/urea treatment eads to a remarkabe enhancement n fber separaton over 90%. Aso, tem-
perature rse has a notabe effect on the process effcency after 48 hours whe t sghty ncreases
the sugar producton after 72 hours.
References
1. | ehanpour, A., Karm, K., Nkasson, C., Taherzadeh, M.| . 2010. A nove process for ethano or
bogas producton from ceuose n bended-fbers waste textes. Waste Management 30,
pp. 2504-2509.
2. | ehanpour, A., Taherzadeh, M.| . 2009. Ethano producton from cotton-based waste textes.
Boresource Techno 100, pp. 1007-1010.
Monosaccharde producton from gnoceuosc bomasses va concentrated acd hydroyss

273
Monosaccharide production from li gnocellul osic
biomasses via concentrated acid hydrolysis
Jari Heinonen
1
, Anu Tamminen
2
, Jaana Uusitalo
2
, Tuomo Sainio
1

1
Lappeenranta University of Technology, Laboratory of ndustrial Chemistry,
Skinnarilankatu 34, F-53850 Lappeenranta, Finland
2
VTT Technical Research Centre of Finland, P.O. Box 1000, F-02044 VTT, Finland
ntroduction
Monosacchardes are vauabe and versate patform chemcas that can be obtaned by hydroyz-
ng ceuose and hemceuoses n gnoceuosc bomasses |1, 2, 3|. Hydroyss wth concentrated
sufurc acd as catayst eads to 80% or hgher monosaccharde yed. Ony a ow amount of by-
products s formed |2, 3|.
The hydroyss acd must be removed pror to downstream processng of monosacchardes. Trad-
tonay neutrazaton wth Ca(OH)
2
has been used. Ths resuts n hgh chemca consumpton and
generaton of waste gypsum. In addton, fresh sufurc acd s needed for every hydroyss |2, 3|.
In order to ower the chemca costs of the concentrated acd hydroyss process, the hydroyss
acd shoud be recyced. Ths can be accompshed by usng chromatography: the hydroysates are
fractonated nto sufurc acd fracton, monosaccharde fracton, and by-product fractons |2|.
In ths work, batchwse chromatographc fractonaton of wood based concentrated acd gnoce-
uosc hydroysates was studed. Effectveness of the chromatographc purfcaton was evauated
by nvestgatng ethano producton from the purfed monosaccharde soutons usng S. cerevisiae.
Results
Chromatographi c fractionation
An euton chromatogram of a batchwse chromatographc fractonaton of a concentrated acd
spruce hydroysate usng sufonated strong acd poystyrene-dvnybenzene caton exchange resn
n acd form as adsorbent s shown n Fgure 1A. Sufurc acd has a co-operatve effect on the sorp-
ton of the other components. Ths co-operaton eads to some pecuar shapes of the monosaccha-
rde euton profes: the profes have eongated front parts under the sufurc acd profe and focus-
ng of the monosacchardes occurs at the rear of the sufurc acd profe (Fgure 1A). The co-
operatve effect of sufurc acd on the euton of the other components s not ceary seen due to
eary separaton.
The performance of the chromatographc fractonaton was nvestgated by smuatons. Both
stand aone chromatographc separaton and a process consstng of concentrated acd hydroyss
unt, chromatographc fractonaton unt, and sufurc acd concentraton unt were nvestgated.
Coumn oadng and hydroyss acd concentraton have strong effects on the performance of the
chromatographc separaton. Yed and productvty of the process wth respect to the monosaccha-
rdes decreases rapdy as hydroyss acd concentraton n the feed souton ncreases. Ths s due
to stronger overappng of the sufurc acd and monosaccharde profes. Increase n coumn oadng
eads to decrease n the monosaccharde yed, whe the productvty goes through a maxmum.
Strong overappng of sufurc acd and monosaccharde profes resuts n ow monosaccharde
yed n the stand aone separaton: a arge part of the monosacchardes end up to the sufurc acd
fracton. Due to the recycng of the sufurc acd fracton, the process performance shoud be evau-
ated n steady state condtons whe takng nto account the surroundng unt operatons.
In the nvestgaton of the effect of the coumn oadng on the separaton, the oadng gvng the
maxmum productvty was found to be consderaby hgher wth the recycng (18 vo%) than wth-
out t (13 vo %). Aso the maxmum productvty was found to be 2.6 tmes arger. However, the
recycng has the argest effect on the monosaccharde yed: the yed n stand aone separaton

Monosaccharde producton from gnoceuosc bomasses va concentrated acd hydroyss

274
wth the optma oadng was as ow as 32.0% whereas wth the recycng t was 90.6%. Wth recy-
cng of sufurc acd fracton, ess than 10% of fresh sufurc acd s needed n the hydroyss.

Figure 1. A: Outet profe of concentrated acd spruce hydroysate on strong acd PS-DVB resn n
acd form (50C). Coors: back =H
2
SO
4
; green =gucose; bue =combned xyose gaactose, man-
nose, arabnose; red =acetc acd; pnk =HMF; cyan =furfura (FF); shaded area =monosaccha-
rde fracton. B: Fermentaton of chromatographcay purfed (back) and Ca(OH)
2
neutrazed (red)
spruce hydroysates wth S. cerevisiae.
Fermentation
Fermentaton of chromatographcay purfed and Ca(OH)
2
neutrazed concentrated acd hydroy-
sates was studed usng genetcay modfed S. cerevisiae. Ethano productvty from chromato-
graphcay purfed and Ca(OH)
2
neutrazed hydroysates were comparabe (Fgure 1B). Chroma-
tographc purfcaton removes a HMF and furfura from the hydroysates and ony a sght amount
of acetc acd remans n the purfed souton. Ths s not the case wth Ca(OH)
2
neutrazaton. Ths,
however, has a very mted effect on the S. cerevisiae. Athough the ethano productvtes were
comparabe, chromatographc separaton provdes a sgnfcant ncrease for the ethano yed
(74.3% of the theoretca vaue 0.51 g(EtOH)/g(sugar)) over the Ca(OH)
2
neutrazaton (61.3%).
References
1. Burk, M.| . 2010. Sustanabe producton of ndustra chemcas from sugars. Int. Sugar. | . 112,
pp. 30-35.
2. Henonen, | ., Tammnen, A., Uustao, | ., Sano, T. 2012. Ethano producton from wood va
concentrated acd hydroyss, chromatographc separaton, and fermentaton. | . Chem.
Techno. Botechno. 87, pp. 689-696.
3. Farone, W.A., Cuzens, | .E. 1995. Strong acd hydroyss of ceuosc and hemceuosc materas.
US Patent No. 5,597,714, | une 7.
Process schemes for chromatographc fractonaton of gnoceuosc concentrated acd
hydroysates

275
Process schemes for chromatographic fractionation
of lignocell ulosic concentrated acid hydrolysates
Jari Heinonen, Sanna Hellstn, Tuomo Sainio
Lappeenranta University of Technology, Laboratory of ndustrial Chemistry,
ntroduction
Chromatography s we suted for dffcut arge scae bomass hydroysate fractonatons. However,
often cassca batch process does not gve suffcent productvty and may become a botteneck n
a forest borefnery. In such cases more advanced chromatographc separaton process schemes
are requred.
One advanced process opton for chromatographc separatons s the steady state recycng
chromatography (SSR) whch has been shown to provde better process performance than batch
chromatography n dffcut separaton (e.g. |1|). In SSR, a recyced (mxed) fracton s fed to the
coumn wth fresh feed. Eventuay, a perodc steady state s obtaned |1|.
Smuated movng bed chromatography (SMB) aso often provdes better performance than the
batch process (e.g. |2|). However, conventona SMB cannot dever mutpe fractons as s often
desred, and more advanced SMB schemes are needed. One opton s the | apan Organo SMB
(| O-SMB), whch s used n sweeteners ndustry. On the contrary to the basc SMB, the feed to | O-
SMB s not contnuous whch enabes the separaton of three or even more components aready
wth four coumn system |2|. A perodc steady state s eventuay reached aso wth | O-SMB.
In ths work, SSR and | O-SMB are compared wth the cassca batch process n the chromato-
graphc fractonaton of concentrated acd gnoceuosc hydroysates. Effectve fractonaton of
these hydroysates s essenta for the producton of monosacchardes va concentrated sufurc acd
hydroyss. The hydroysates are chromatographcay fractonated nto sufurc acd fracton, mono-
saccharde fracton, and by-product fractons. The sufurc acd fracton s recyced back to the hy-
droyss reactor whe the other fractons are ed to downstream processng.
Results
Steady state recycling chromatography
Use of steady state recycng chromatography for the fractonaton of concentrated acd gnoceu-
osc hydroysates was nvestgated wth a bnary mode system of sufurc acd and gucose. A arge
scae system (h
bed
3 m, d
bed
1 m) was used and both fow rate and coumn oadng (% of resn bed
voume) were optmzed. Steady state was acheved n sx cyces.
Hghest productvty of the separaton process wth respect to the monosacchardes was ob-
taned wth a hgh fow rate of 250 mL/mn and 6.5 vo % coumn oadng. The productvty was
approxmatey 33% arger than wth the batch process. Mnmzaton of euent consumpton whe
keepng the productvty constant was aso nvestgated: SSR provded equa productvty as the
batch process wth amost 50% smaer euent consumpton.
Pareto sets ustratng the process performance for dfferent purty requrements are presented
n Fgure 1A. Pareto fronters show the hghest productvty that can be acheved wth certan euent
consumpton. Operaton above the nes s not possbe, and euent consumpton can be owered
ony at the expense of productvty. Decrease n the productvty wth ncreasng purty s greater
wth the batch process: the beneft of SSR s pronounced when hgh product purty s desred.

Process schemes for chromatographc fractonaton of gnoceuosc concentrated acd
hydroysates

276

Figure 1. A: Pareto fronters for sufurc acd-gucose separaton usng batch (crces) and SSR (nes)
chromatography wth varous gucose purty

constrants: 90% (red), 95% (bue), and 99% (back).
Purty of H2SO4 fracton =98.7%. B: Spata profes of H2SO4 (back), gucose (green), xyose (bue),
and acetc acd (red) n | O-SMB n steady state at the end of cyce.
Japan Organo SMB chromatography
Ternary fractonaton (sufurc acd, monosaccharde, and acetc acd fractons) usng a fve coumn
| O-SMB (h
bed
2 m, d
bed
2 m) was aso nvestgated. Euent consumpton was omtted.
15 cyces were needed for the system to reach perodc steady state. Good separaton between
monosacchardes and acetc acd was obtaned (Fgure 1B). However, overappng of sufurc acd
and monosaccharde profes was caused by nteractons between these components |3|. Due to
the nteractons, focusng of the monosacchardes was observed at the rear of the sufurc acd
profe. Ths s benefca for the productvty of the process.
| O-SMB was found to provde approxmatey 50% arger productvty than batch process. Wth
the operatng condtons gvng the maxmum productvty the purtes of sufurc acd, monosaccha-
rde, and acetc acd outet streams were 89.0%, 88.7%, and 100%, respectvey. Accordngy, the
recoveres were 97.3%, 61.7%, and 93.5%, respectvey. The recovery of the monosacchardes s
rather ow due to overappng of the sufurc acd and monosaccharde profes (Fgure 1B). However,
the monosacchardes n sufurc acd outet stream are not ost product because they are recyced
back to the hydroyss reactor.
References
1. Sano, T., Kasperet, M. 2009. Anayss of steady state recycng chromatography usng equbrum
theory, Sep. Purf. Techno. 66, pp. 9-18.
2. Kurup, A.S., Hda|at, K., Ray, A.K. 2006. Optma operaton of a pseudo-SMB process for ternary
separaton under non-dea condtons, Sep. Purf. Techno. 51, pp. 387-403.
3. Henonen, | ., Sano, T. 2012. Modeng and performance evauaton of chromatographc mono-
saccharde recovery from concentrated acd gnoceuosc hydroysates. | . Chem. Techno.
Botechno. Do: 10.1002/|ctb.3816.
Potenta expanson of second generaton Fscher Tropsch bodese producton n Fnand

277
Potential expansi on of second generation Fischer
Tropsch biodiesel production in Finl and
Karthikeyan Natarajan
1
, Sylvain Leduc
2
, Paavo Pelkonen
1
, Erik Dotzauer
3
,
Erkki Tomppo
4
, Matti Katila
4
, Kai Mkisara
4
, Jouni Persaari
4

1
University of Eastern Finland (UEF), F-80101 Joensuu, Finland, karthikeyan.natarajan@uef.fi
2
nternational nstitute for Applied System Analysis (ASA), A-2361 Laxenburg, Austria
3
Mlardalen University, SE-72123 Vsters, Sweden
4
Finnish Forest Research nstitute (METLA), F-01301 Vantaa, Finland
Abstract
The Fnnsh bofue ndustry s undergong a ma|or change n partcuar second generaton Fscher
Tropsch (FT) bodese producton. However, effcent geographca energy pannng s essenta to
optmay aocate the mted natura resources between bomass based ndustres. Therefore, a
decson too was formuated whch ncudes three dfferent modes: (1) a spata mode that est-
mates the amount of bomass suppy and ndustra resdues avaabe for energy producton, (2) an
energy demand mode cacuates the amount of heat and transport fue that can be devered to the
customers, (3) an optmzaton mode that mnmzes the compete costs of bodese suppy chan
from bomass suppy to bodese devery at the fue statons to determne the optma ocaton, sze
and confguratons of FT bodese producton pants n Fnand. Mode resuts show that fve cost-
optma bodese producton pant ocatons of 390 MW
feedstock
are needed to be but to meet the
2020 renewabe energy share n transport (25.2 P| ). The unt cost of FT bodese produced n
Fnand coud range between 1.1 and 1.4 C/
2011
wthout heat saes.
Optimization modeling
Gven a set of feedstock suppy ponts, energy demand regons, exstng ndustra ocatons and
canddate FT bodese producton pant stes, the MILP mode mnmzes the costs of compete
suppy chan from bomass suppy to bodese dstrbuton to determne a cost-optma FT bodese
pant ocatons, number, sze and confguratons (Fgure 1). The mode soves the optmzaton prob-
em by aocatng the feedstock resources effcenty to new FT bodese pants consderng the
demand from the exstng bomass based ndustres ke pup and paper ms, peet pants, and
Combned Heat and Power (CHP)/Dstrct Heatng (DH). The mode provdes souton to whch type
of feedstock (forest bomass, sawm resduas and bomass mport) can be effectvey used and
from whch regon sha t be procured consderng the transportaton dstance, prce of feedstock
and ts avaabty. Moreover, the mode aso anayses the potenta to se the produced by-
products, heat and eectrcty to ncreases the proftabty of the pant as a whoe. Detaed descrp-
ton of the mode can be found n |1, 2|.
Plant locations and costs
Fve cost-optma FT bodese pant ocatons seected ndcate that the spata dstrbuton of bo-
mass suppy and energy demand pays a domnant roe n optmzng the ocatons of bodese

Potenta expanson of second generaton Fscher Tropsch bodese producton n Fnand

278

Figure 1. Outne of the optmzaton mode. Figure 2. Optma pant ocatons.
pants. Out of fve, three were ocated at Rovanem, Kauhava and Rauma whe the other two were
ocated cose to bomass resources. Spata extenson of sawms whch are another potenta
source of feedstock aso pay a sgnfcant roe n determnng the bodese pant stes. The resuts
of the senstvty anayss show that the most nfuencng parameters on the bodese cost are found
to be nvestment costs, bodese converson effcency and operatng hours, and then foowed by
bomass cost and heat prce. The bomass avaabty, bomass transportaton and bofue transpor-
taton costs are east nfuenta parameters on the bodese cost. Ths s due to the reason that the
gven optma ocatons are ndeed rch n bomass resources and aso sted cose to hgh energy
demand regons where the excess heat coud be sod to potenta customers.
The conceptua and mathematca modeng framework contrbutes greaty to an understandng
of the feasbty, constrants, and potenta for the expanson of a bodese ndustry n Fnand. More
recenty, renewabe transportaton fues have become the top prorty for Fnnsh Government and
prvate nvestors, and therefore t s mperatve to dentfy the optma ocatons for bo-refneres n
order to start up the arge scae commerca bodese producton. Thus, ths study heps to provde
a vauabe study for government and prvate stakehoders to determne the most sutabe strategy
regardng the cost optma ocatons and confguraton of new bodese pants.
References
1. Leduc, S. 2009. Deveopment of an optmzaton mode for the ocaton of bofue producton
pants, Dvson of Energy Engneerng, Department of Apped Physcs and Mechanca
Engneerng, Lue Unversty of Technoogy.
2. Natara|an, K., Leduc, S., Pekonen, P., Tomppo, E., Dotzauer, E. 2012. Optma Locatons for
Methano and CHP Producton n Eastern Fnand: BoEnergy Research, Do:
10.1007/s12155-011-9152-4.
Bofues and chemcas from gnoceuosc materas - a scheme for condtonng SO2-ethano-
water spent quor for ABE fermentaton

279
Biofuels and chemicals from lignocellulosic materials
a scheme for conditi oning SO
2
-ethanol-water
spent l iquor for ABE fermentation
Evangelos Sklavounos
1
, Mikhail akovlev
1
1, 2
1
Aalto University, School of Science and Technology, Department of Forest Products Technology,
P.O. Box 16400, F-00076 AALTO, Finland
2
University of Maine, Department of Chemical and Biological Engineering,
5737 Jenness Hall, Orono, ME 04469-5737 USA
Abstract
We are presentng a process for condtonng spent quor produced by SO
2
-ethano-water (SEW)
fractonaton of dfferent gnoceuosc materas .e. spruce chps, mxed forest softwood bomass
and Empty Frut Bunches (EFB) for fermentaton to bofues and chemcas by ABE (acetone-
butano-ethano) fermentaton technoogy utzng Costrda bactera.
ntroduction
SEW fractonaton s a we proven, gnoceuosc fractonaton technoogy that s heren empoyed
to reease hemceuose derved sugars and ceuosc fbers from dfferent feedstocks n ony 30
mn at 150C. However, the dssoved sugars cannot be drecty utzed for producton of butano by
ABE fermentaton, and further processng and condtonng s requred. For nstance, t s necessary
to ad|ust the pH of SEW spent quor to neutra eves to avod kng the bactera. Moreover, fer-
mentaton nhbtors such as ethano and SO
2
must be fuy removed and recovered to obtan an
economca and envronmentay bengn process. Lgnn and any other fermentaton nhbtors such
as furanc compounds and formc acd must aso be removed.
Experimental
SEW fractonaton for a gnoceuosc materas tested s performed n 30 mn at 150C wth a 50%
(w/w) ethano-water souton contanng 12% (w/w) SO
2
at a quor-to-wood rato of 3:1 L/kg. In
addton, ony n the case of EFB, the ash content of the feedstock s reduced by eachng before
SEW fractonaton. The produced pup after SEW fractonaton s effcenty washed to aow for hgh
sugars recovery. Pup washngs are added to SEW spent quor and the dute mxture s then
evaporated under ow pressure to remove the ma|or fermentaton nhbtors .e. SO
2
and ethano.
Ethano remova s amost compete and any SO
2
eft after vacuum evaporaton s amost totay
removed by subsequent steam strppng. Neutrazaton by mng wth Ca(OH)
2
s then empoyed to
brng the souton to a pH eve sutabe for fermentaton by Costrda bactera. The quor s then
cataytcay oxdzed to convert any resdua sufte ons to sufate. Fnay, the quor s treated wth
resns to further remove gnn. Fgure 1 presents the overa condtonng scheme and carfes the
names of the quors after each condtonng step.

Bofues and chemcas from gnoceuosc materas - a scheme for condtonng SO2-ethano-
water spent quor for ABE fermentaton

280

Figure 1. SEW spent quor condtonng scheme.
The mass baance n Tabe 1 shows that 76 to 88% of the mass of the orgna feedstock s ac-
counted for n the combned CATOX quor and pup fbers. The sugars n the CATOX quor of the
Spruce and softwood bomass feedstocks are mosty monomerc n nature, whe they are mosty
poymerc (tota mnus monomerc) n the EFB CATOX quor.
Table 1. Mass baance on sod phase (pup) and condtonng quors.

IC anayss resuts show that SO
2
s fuy removed from condtoned quors. Resuts from fermentaton
tras confrm that a condtoned quors are fermentabe by Costrda bactera.
Conclusions
An effectve method to fractonate and condton SEW spent quor from dfferent gnoceuoscs s
presented. Further optmzaton of the condtonng scheme s underway to aow more effcent
handng of feedstocks of wdey dfferent composton.
References
1. Skavounos, E., Iakovev, M., Yamamoto, M., Tersvuor, L., | urgens, G., Granstrm, T., van
Henngen, A. 2011. Condtonng of SO
2
-ethano-water spent quor from spruce for the
producton of chemcas by ABE fermentaton. Hozforschung 65(4), pp. 551-558.
Opportuntes and chaenges n emergng boenergy busness: Case of Fnnsh sawmng ndustry

281
Opportuni ties and chall enges in emerging bioenergy
busi ness: Case of Fi nnish sawmilli ng industry
Minli Wan
1*
, Katja Lhtinen
2
, Anne Toppinen
3
, Matti Toivio
3

1*
First author and corresponding author, Department of Forest Sciences,
P.O. Box 27, 00014 University of Helsinki, Finland (minli.wan@helsinki.fi)
2
Finnish Environment nstitute (SYKE), P.O. Box 111, 80100 Joensuu, Finland
3
Department of Forest Sciences, P.O. Box 27, 00014 University of Helsinki, Finland
Abstract
The resources of currenty domnant foss fues are mted, and ther use causes greenhouse gas
emssons. Consequenty, the pubc nterest wthn the European Unon has changed toward usng
renewabe energy. Fnands forest ndustry s one of the word eaders n producng and utzng
wood-based boenergy. Hence, t s of nterest to evauate new vaue-creaton opportuntes and the
consequent chaenges that face the Fnnsh sawm ndustry. In order to dentfy the strategc re-
sources that enabe deveopng compettve advantages n the emergng boenergy fed, we apped
the natura resource-based vew of strategy to the sawm ndustry. In the emprca part, quatatve
sem-structured ntervews wth managers of 23 sawms based on the Deph methodoogy were
conducted n two phases. We dentfed partnershps wth oca communty heat pants as a strategc
resource for provdng new busness opportuntes, apart from raw matera avaabty and exstng
technooges. Athough the Fnnsh sawms have a ong tradton n energy producton, most ener-
gy-reated nvestments have been made ony durng the past decade, and the sawms woud be
keeny nterested n ncreasng the effcency of usng ther by-products through new nvestments. In
concuson, the Fnnsh sawm ndustry beng the oca producer of wood-based boenergy can
support meetng the ambtous natona target for renewabe energy producton for 2020. However,
the voate boenergy pocy changes act as a ma|or factor of uncertanty n predctng the future
deveopment of the busness envronment and further ncrease the rsk eve for future nvestments.

Keywords: Opportuntes, chaenges, boenergy, Fnnsh sawm ndustry
ntroduction
Drven by gobazaton, ndustrazaton, economc growth, and expandng popuaton, the demand
for goba energy has grown rapdy. Snce the resources of currenty domnant foss fues are m-
ted and ther use causes greenhouse gas emssons, renewabe energy usage has ganed popuar-
ty as a way to address these concerns. Bofues have been regarded as the most vabe aternatve
to foss fues (Bauen et a., 2009).
Fnands forest ndustry s one of the word eaders n producng and utzng wood-based bo-
energy, and sawmng s the odest ndustry n the Fnnsh forest-based sector. To create a sus-
tanabe compettve advantage (SCA), the Fnnsh sawm ndustry needs to deveop new vaue-
creaton strateges (Lhtnen and Toppnen, 2008), for exampe, by usng ther by-products to pro-
duce boenergy. The purpose of ths study s to expore the sources of SCA, the vaue-creaton
opportuntes and the consequent managera chaenges that face the Fnnsh sawm ndustry.
Theoretical background
In the theoretca background, we apped natura resource-based vew to the sawm ndustry to
dentfy the strategc resources that enabe mantanng and deveopng SCA n the emergng boenergy
busness.


282
Materials and methods
In ths study, the focus n data gatherng was on the Fnnsh non-ntegrated medum-szed sawms
whose core busness s sawn wood manufacturng, and the focus n data anayss was on the man-
agera perceptons of the man resources for boenergy busnesses of the Fnnsh sawms and the
factors that factate or hnder future deveopment n boenergy producton of sawms. In the empr-
ca part, quatatve sem-structured ntervews wth managers of 23 sawms based on the Deph
questonnare methodoogy were conducted n two phases.
Results
Accordng to the two-rounds of ntervews, the share of boenergy n the Fnnsh sawm vaue crea-
ton ranged from 0 to 10%. The ntervewed sawm managers unformy stated that raw materas,
technoogca know-how, personne know-how, coaboraton and servces were the most mportant
resources for boenergy producton, and suffcent and stabe demand for boenergy, governmenta
energy poces and fnanca support were the most mportant factors that affect the future of boen-
ergy busness for the Fnnsh sawms. In addton, prces of raw materas, prces and subsdes of
boenergy, prces and taxaton of foss fues, vcnty of potenta markets, quaty of customer reaton-
shps and avaabe outbound ogstcs aso payed mportant roes n deveopng the boenergy busness.
Based on the resuts mentoned above, we summarzed the most promsng vaue-creaton op-
portuntes and the consequent managera chaenges for deveopng boenergy busness at the
Fnnsh sawms, as shown n Tabe 1.
Table 1. Opportuntes and chaenges for boenergy busness of the Fnnsh sawms.
ndustry
fact ors
Opportuniti es Chall enges
Market
demand
1) A boom n renewabe energy demand;
2) Potentay frutfu opportuntes for sawms
for ntatng vaue-creaton busnesses by pro-
ducng boenergy n coaboraton wth the energy
ndustry.
Due to the cyccaty of the sawm ndus-
try, reance of the boenergy producton on
sawms as raw matera suppers mpes
that the boenergy busness aso becomes
vunerabe to downturns n demand n
busness cyces.
Poces
1) Renewabe energy pocy s the man drver of
the growth n renew-abe energy use;
2) Fnands ong-standng government pocy
support for boenergy (envronmenta taxes,
nvestment support and subsdes);
3) A new feed-n scheme ntroduced n Fnand n
2011 supports the wood-based power generaton
(MEE, 2011).
1) In Fnand, envronmenta taxes on foss
fues are eved ony n the heatng sector;
2) Fnands potca decson, such as
"renewabe energy package", s a factor of
dstortng the competton among energy
producers;
3) The voate boenergy pocy changes
woud pose chaenges for predctng the
deveopment of the busness envronment
and ncrease the rsk of nvestments.
Avaabty
of raw
matera
1) Interna suppy of wood fues for sawms at a
compettve prce w factate processng nto
energy products (Mke et a., 2011);
2) The structura change of the forest ndustry n
reducng the demand for sawm by-products n
tradtona appcatons coud promote the use of
by-products n boenergy producton and thus
open up coaboraton opportuntes between the
sawm ndustry and the energy ndustry.
1) Uncertanty n the sawn wood markets
has ncreased due to Russas potca
decson to mt ts round wood exports;
2) Uncertanty of peet prces prevents the
expanson of the tradtona sawm ndus-
try nto Fnands peet markets (Mke et
a., 2011).

283
Techno-
ogca
know-how
Fnand s one of the word eaders n usng
wood-based fues n energy producton, wth
gobay recognzed technoogca and ogstca
know-how.
The same technoogca and ogstca
soutons mght be repcated by compet-
tors outsde Fnand;
Forms of
coabora-
ton
Partnershps wth dstrct heatng pants of the
oca communty were emphaszed as a strategc
resource to create compettve advantages for
boenergy busness of sawms.
A smar coaboraton form mght be
repcated by compettors outsde Fnand.
Impacts on
profts
Athough the share of boenergy n Fnnsh
sawm vaue creaton s sma, t w affect the
fnanca performance of sawms overa.
Low share of boenergy mght make some
sawms ose ther nterest n ncreasng
boenergy producton.
Invest-
ments
1) The Fnnsh forest ndustry has nvested
heavy n boenergy, and the share of boenergy
s pro|ected to ncrease (Kao et a., 2007);
2) Fnnsh muncpates have a ong tradton n
nvestng n wood fue pants;
3) The Fnnsh non-ntegrated sawms have
made arge nvestments n boenergy producton.
Some sawm managers are nterested n nvest-
ng n new boenergy branches and enargng
boenergy busness by usng by-products to n-
crease effcency and proftabty.
1) Investments n boenergy are rsky and
capta ntensve;
2) Reatvey hgh nvestment costs are an
obstace for sma-scae CHP and peet
producton
Discussion and conclusion
Producng wood-based boenergy s regarded n both the ong term and the short term as a sus-
tanabe energy provson aternatve. Fnand s one of the eadng countres for utzng wood-
based boenergy, and the forest ndustry s the argest producer of wood-based boenergy n Fn-
and. Some Fnnsh sawms have nvested n boenergy producton to dversfy ther busness and
ncrease the frm-eve vaue added. Athough t s commonpace that producng boenergy s em-
phaszed as a new busness opton for sawms n dscussons, t s not a new ssue for the Fnnsh
sawms and there are aready many unutzed vaue-creaton opportuntes n ths emergng boen-
ergy busness.
Faced wth the ambtous natona targets for renewabe energy for 2020, the Fnnsh sawm n-
dustry coud strongy support meetng ths target by provdng a oca-eve contrbuton for renewa-
be energy producton. Nevertheess, ncreasng boenergy producton to meet arger demands n
the energy markets and managng both nterna resources and externa nvestment rsks aso brngs
new chaenges for management. For nstance, as raw matera suppers for boenergy producton,
sawms have an nterna suppy of wood fues, but uncertanty n the sawn wood markets and the
cyccaty of the sawm ndustry makes the boenergy busness vunerabe to sawm busness
cyces. Moreover, the voate boenergy pocy changes were consdered a ma|or factor of uncer-
tanty that poses chaenges for forecastng the future deveopment of the busness envronment
and further ncreases the rsk eves of nvestments n boenergy capacty.
References
1. Bauen, A., Berndes, G., | ungnger, M., Londo, M., Vue, F. 2009. Boenergy - a sustanabe and
reabe energy source. Executve Summary. IEA Boenergy: ExCo: 2009:05. Retreved
December 23, 2011, from http://www.eaboenergy.com/MedaItem.aspx?d=6360.

284
2. Kao, K., Erkk, A., Rata, | . 2007. Fnnsh frewood markets (D2). | yvsky. VTT. Ouaty
Wood Pro|ect Report WP2.1/2007, Pro|ect EIE/06/178/SI2.444403.
3. Lhtnen, K., Toppnen, A. 2008. Fnanca performance n Fnnsh arge- and medum-szed
sawms: the effects of vaue-added creaton and cost-effcency seekng. | . Forest Econ.
14(4), pp. 289-305.
4. Mke, M., Lntunen, | ., Kangas, H.-L., Uusvuor, | . 2011. Peet promoton n the sawm ndustry:
the cost-effectveness of dfferent pocy nstruments. | . Forest Econ. 17(2), pp. 185-196.
5. Mnstry of Empoyment and the Economy (MEE) 2011. Fnand takes concrete steps to promote
renewabe energy. Retreved December 23, 2011, from http://www.energy-envro.f/
ndex.php?PAGE=2&PRINT=yes&ID=3475.

Premnary spectra characterzaton of the caorfc vaue of pyrotc products from wood bomass

285
Preliminary spectral characterization of the calorific
value of pyrolitic products from wood biomass
K.V. Kulikov
1
, D.A. Ponomarev
1
, A.A. Spitsyn
1
, H.D. Mettee
2
, Y.V. Maksimuk
3
, A.V. Levdanski
4
,
D.S. Sharova
1
, O. Yu. Derkacheva
1
1
St. Petersburg State Forest Engineering University (Russia, St. Petersburg)
2
Youngstown State University (USA, Ohio)
3
Belarus State University (Belarus)
4
Siberian Branch of Russian Academy of Sciences (Russia, Krasnoyarsk)
Abstract
Heats of combuston of pne, spruce, brch and aspen pyrotcay produced os correate we wth
proton type abundances gven by ther NMR spectra n the aphatc (0.6-3.5 ppm), unsaturated and
oxygenated (3.5-6.0 ppm) and aromatc (6.1-8.0 ppm) regons. Premnary resuts usng the ptch
(hghest bong) fractons show a correaton R vaue of 0.999 for predcted vs. measured heats of
combuston, the atter determned by oxygen bomb caormetry. The equaton O =Aa +Bb +Cc was
used for varous os, where O was the measured heat of combuston, the A, B, and C were "sens-
tvty factors" determned by east squares fttng procedures usng the NMR ntegras a, b, and c for
the three proton regons.
ntroduction
Snce foss fues are growng ncreasngy scarce, boogcay renewabe fues such as pyrotc os
based on waste wood have receved ncreasngy more attenton. Tradtonay such os have been
dvded nto fractons based upon ther bong ponts - summary o (ow and mdde bong frac-
tons), mdde bong fracton, and ptch, the hghest bong fracton. Each fracton contans severa
hundred compounds, wth 95% of the os composed of at east 50 compounds, many partay oxy-
genated. For the purpose optmzng the energy yeds of these fractons and ther sub-fractons, t s
convenent to correate ther overa heat of combuston (O) as a compex mxture wth a straght-
forward set of ndces, much as the Duong formua s based on eementa composton: O =
340.6(%C) +1431(%H - (%O/8)) |k| /kg|. An aternatve possbty coud reate O to the ntegrated
ntenstes of NMR sgnas n the mxtures n the aphatc, unsaturated and aromatc proton regons,
correspondng to C-H bonds of dfferent energes.
Experimental
Severa 10-30 g sampes of mature pne, brch, aspen and spruce were dred at 115C for 24 hrs

and pyroyzed n a cosed reactor wth an ext stream passng through a |acketed water coectng
condenser and burn off vapor exhaust n a fume hood. The process requred 2.5 hours n a temper-
ature-controed oven heated at a 2.0C/mn

temperature ramp termnatng at a fna temperature near
600C. The bong pont range for the summary os was 125-220, the mdde fractons 160-220,
and the ptch from 220-260C.
Once the NMR data were acqured (Bruker Advance III 400 MHz at YSU) the spectra were nte-
grated n the 0.3-3.0, 3.0-6.0 and 6.0-10.0 ppm regons (vs TMS) and normazed so the tota
proton area was 1.0 and the fractona areas are a, b and c.
The set of equatons O
= Aa
+ Bb
+ Cc
for the four ptch sampes was soved for usng the meas-
ured heats of combuston O
by standard near regresson technques to yed the optma vaues of

Premnary spectra characterzaton of the caorfc vaue of pyrotc products from wood bomass

286
A, B and C. Once these senstvtes were determned, a predcted O
cac
from the normazed nte-
grated areas was cacuated to see f there was a correaton between O
cac
and O
msd
. Fgure 1
shows the resuts of ths correaton, and Tabe 1 contans the reevant vaues. Further work contn-
ues wth other fractons and os to fnd more wdey appcabe senstvty vaues.

Figure 1. Correaton of measured and cacuated heats of combuston of four ptches. Unts: k| /kg.
Table 1. Expermenta and cacuated heats of combuston for ptch fractons of four pyrotc os
wth ther
1
H NMR area fractons (a, b, c) and cacuated senstvty coeffcents (A, B, C).
Ptch() O
exp
(k| /kg) O
cac
(k| /kg) a

b
c

Senstvty Coeff.
Pne 2392556 23930 0.7533 0.2054 0.0413 A = 22656144
Spruce 2564646 25629 0.6371 0.2279 0.1351 B = 25351495
Brch 2567992 25740 0.5729 0.2961 0.1310 C = 40106818
Aspen 2543623 25408 0.5645 0.3285 0.1070
Concl usi on
From the reasonabe correaton above the concuson coud be drawn that the caorfc vaues of
ptches from varous wood speces strongy depend on the chemca structure of ther consttuents.
For other fractons ther characterstcs coud be obtaned from ther NMR spectra.
Acknowledgements
The authors gratefuy acknowedge the fnanca support of the Russan Foundaton of Basc Re-
search Grant 10-03-92500 and the US Cvan Research and Deveopment Foundaton Grant
RUC1-2989-ST-10.

An ndustra pant (25,000 m3/yr) for wood utraoxypyroyss by the formed ayer process

287
An industrial plant (25,000 m
3
/yr) for wood
ultraoxypyrolysis by the formed layer process
V.V. Litvinov
1
, H.D. Mettee
2
, V.. Shirshikov
3
, V.N. Piyalkin
1

1
St. Petersburg State Forestry Engineering University (Russia, St. Petersburg)
2
Youngstown State University (USA, Ohio)
3
Vyborg Coal Company (Russia, St. Petersburg)
ntroduction
A technoogy for obtanng bo-os s presented here whch s based on the utraoxypyroyss of
waste wood bomass. Presenty the quantty of ths bomass exceeds 700 M m
3
per year n the
Russan Federaton. We have deveoped a resource conservng, ecoogcay cean thermochemca
technoogy for the converson of waste wood bomass, whch ncudes waste forest cuttngs,
chopped waste, sawdust, and processed wood, nto qud boer fues (some of whch may be used
as dese fue) and energetc bocharcoa.
Technology
The perspectve technoogy for the boer fues and bocharcoa accordng to our desgn empoys
the technque of "formed ayers" of wood chps n counter-current fow wth hot gases consstng of
ar and recyced pyroyss gases n the pyrotc reactor. The method s characterzed by thermay
equbrated matera baances and a mnma apparatus sze for varous feedstock processng. Our
qud products have hgh energy densty (30-32 G| /m
3
) consstent wth a boboer fue. The sma
sze means that these thermochemca conversons can be produced by mobe unts at the ponts
of wastewood producton, rather than by coectng the waste wood and processng t at a centra
ocaton, thereby savng both transportaton costs for the waste wood and aternatve fue costs for
pant operaton.
Distinguishing features
The speed of advancement of the raw materas aong the auger bed and reactor ength s strcty
controed so as to permt the approprate product dstrbuton of unform quaty and quantty. Com-
pact formed ayers of waste wood chps st permt a sgnfcant ncrease n feedstock permeabty
by hot gases, thus aowng for a more rapd ncrease n the pyrotc temperature and mass n the
reactng zone. Ths ncreased coeffcent of fng the reactor resuts n the abty to decrease ts
dmensons and ts massveness, thus gvng the unt ts added mobty. The formed ayer structure
aso ncreases the utzaton of heat and thus the effcency of thermochemca converson, whch n
turn strongy ncreases the specfc producton of the apparatus.
Mobile installation
Foowng the research resuts on the smaer unt, a technca-economc anayss was performed.
Ths evauaton showed the most promnent (proftabe) operatona features of the unt are: (1) ts
mobty (saves fue transportaton costs); (2) t s ecoogcay cean (recyced exhaust gases are
combusted eventuay to CO
2
and H
2
O); (3) t produces 3 200 t/y boer fues and 3 800 t/y energetc
bocharcoa; and (4) ts produces derved specaty products, ncudng domestc and ndustra br-
quettes (for cookng and smetng of sca to semconductor quaty scon) and road surface coat-
ngs. We are n the fna stages of constructon of ths arger nstaaton.

An ndustra pant (25,000 m3/yr) for wood utraoxypyroyss by the formed ayer process

288
Figure 1. The current mode for the mobe utraoxypyroyss producton unt set for 1,5 t/hr from dry
wood chps.
Conclusions
We consder the practca pyrotc converson of waste wood chps nto boer fues and bocharcoa
n a process that s ecoogcay cean and economcay effcent. Addtona appcatons ncude
owerng the toxcty of gasone and dese exhaust, reducng fue transportaton costs to workstes,
smokehouse food preparatons, and food favorng agents. Energetc bochar may be used to pre-
pare ar and water fters as we as brquettes for everyday fe and ndustra semconductor scon.
List of patents and sponsors
1. Charcoa producton unt Patent RF N2001127158/20 (Russa) 08.10.2001;
2. Retort for contnuous therma processng of wood chps Patent RF N 75657 (Russa)
20.08.2008;
3. Method for wood chps processng nto bo-os and charcoa; a dryng modue desgned for
wood chps processng nto bo-os and charcoa Patent RF N 2338770 (Russa) 20.11.2008;
4. Method of purfcaton of pouted water Patent RF N 2344997 (Russa) 27.01.2009;
5. The adsorbent for ead ons Patent RF N 2351390 (Russa) 10.04.2009;
6. Contnuous therma processng of chpped wood Patent RF N 2351390 (Russa) 22.05.2009.
The authors gratefuy acknowedge the |ont fnanca support of the Russan Foundaton of Basc
Research (Grant 10-03-92500) and the US Cvan Research and Deveopment Foundaton (Grant
RUC1-2989-ST-10).
Measurement methods for physca propertes of the pyroyss o components

289
Measurement methods for physical properties of
the pyrolysis oil components
Juho Autio, Erlin Sapei, Piia Haimi, Ville Alopaeus
Aalto University, School of Technology and Science
Abstract
Fast wood pyroyss os are consdered as an aternatve energy resource for foss fues. Thermo-
dynamc data of the components of the os are needed to mode ther behavour n processes and
borefneres. Ths data ncudes vapour pressure and heat of combuston, whch can be measured
wth Knudsen effuson and bomb caormeter, respectvey. A new Knudsen effuson apparatus has
been assembed and tested wth organc chemcas havng a vapour pressures of 0.1-1 Pa. A
commerca hgh precson combuston caormeter Parr-6200 s tested and used for measurng the
heat of combuston.
Background
The nevtabe prospect of the depeton of foss fue resources has ncted the research for aterna-
tve and renewabe sources of os and fues. Especay o recovered from fast wood pyroyss s
seen as one of the most potent aternatves to satsfy the ever ncreasng goba demand for energy
and fue. |1|
The producton and upgradng processes of pyroyss os are rather new technques and they
are not yet competey understood. The profound understandng of the processes and subsequent
optmzaton of borefneres requre accurate thermodynamc modes of the compounds formed
durng pyroyss. These modes rey on the accurate data of the physca propertes of the pyroyss
os components. Aso, the stabty and storabty of pyroyss os s a matter of nterest. Our revew
of the thermodynamc data avaabe n terature reveaed a arge gap on expermenta data of
physca propertes such as vapour pressure and enthapes of vaporzaton. The vapour pressure of
the pyroyss o components has an nfuence to the separatng process, storabty, transport, ds-
trbuton, mpact on the envronment, and safe use of the product.
Measurement of physical properties
Our research concentrates on measurng reabe physca propertes, ncudng vapour pressure
and energy of combuston, of the components most commony found n bo-os. These data sets
w be used to create reabe predctve thermodynamc modes, whch are needed to desgn pro-
ducton and upgradng processes of pyroyss os. The Knudsen effuson s used to obtan enthapy
of vaporzaton and heats of combuston can be measured usng bomb caormeter. Hgh purty of
the compounds s essenta to obtan reabe physca propertes data. The purty shoud e n the
99.9 % range and compounds of such a hgh purty are commercay scarce. Thus the compounds
must be purfed onste before the measurements. For ths purpose we have but a submaton
apparatus wth sx ces.

Knudsen effusion
The Knudsen effuson method s one of the best ways to evauate vapour pressures of sod organc
compounds havng vapour pressure beow 1 Pa. |2-4| Aso, the Knudsen effuson method aows
the measurements to take pace n ow temperatures thus avodng the decomposton of thermay
abe pyroyss o components.

Measurement methods for physca propertes of the pyroyss o components

290
A new Knudsen effuson apparatus has been but n our aboratory and has been tested wth
basc organc compounds such as anthracene and benzoc acd wth temperature ranges 340-360 K
and 299-317 K, respectvey.
Bomb calori metry
A commerca bomb caormeter Parr-6200 has been tested and used for measurng the heat of
combuston of sod and qud organc compounds. In terature there are penty of data about the
hgh accuracy of commerca bomb caormeters. |5-7| Benzoc acd has been used to determne
the energy equvaent of the caormeter and to test precson and accuracy of the equpment. The
heat of combuston of anthracene has been measured. From the vaue of the standard specfc
energy of combuston the standard moar enthapy of combuston and the standard moar enthapy
of formaton n the qud state can be derved.
Future measurements
The work on estabshng the vapour pressures and heats of combuston of pyroyss o compo-
nents s expected to get underway n mmedate future.
References
1. Mohan, D., Pttman, | r., C.U., Steee, P.H. 2006. Pyroyss of wood/bomass for bo-o: a crtca
revew. Energy & Fues 20, pp. 848-889.
2. Knudsen, M. 1909. The aw of the moecuar fow and vscosty of gases movng through tubes.
Ann. Phys. 28, p. 75.
3. Knudsen, M. 1909. Effuson and the moecuar fow of gases through openngs. Ann. Phys. 28,
p. 999.
4. Knudsen, M. 1909. Expermenta determnaton of the vapor pressure of mercury at 0 and at
Hgher Temperatures. Ann. Phys. 29, p. 179.
5. Verevkn, S.P., Emeyanenko, V.N., Hentz, A. 2009. 1,2-Propanedo. Comprehensve exper-
menta and theoretca study. | . Chem. Thermodynamcs 41, pp. 1125-1131.
6. Ferro, M.L.C.C.H., Pcher, | . 1987. Enthapes of combuston of the three bromobenzoc acds
by rotatng-bomb caormetry. | . Chem. Thermodyn. 19, pp. 543- 548.
7. Rbero da Sva, M.A.V., Ferro, M.L.C.C.H., Lopes, A.| .M. 1993. Enthapes of combuston of
each of the two bromonaphthaenes. | . Chem. Thermodyn. 25, pp. 229- 235.
Effect of pastcs on the co-quefacton of ceuosc bomass and pastcs to qud fue

291
Effect of plastics on the co-liquefaction of cellulosic
biomass and plastics to li quid fuel
Katsumi Hirano
1
, Yusuke Kakuta
1
, Takuya toh
1
, Koji Yoshida
1
, Shouzo tagaki
2
, Masahiko Kajioka
2
,
Hideki Yamada
2
, Toshihiko Okada
2
1
Nihon University
2
JFE Techno-Research Corporation
Abstract
Co-quefacton of ceuosc bomass and poypropyene(PP) n the presence of sovent at 400C
was carred out. It was confrmed that the co-quefacton of ceuosc bomass and PP gave the
hgher converson than the cases of ceuosc bomass or of PP. O was aso obtaned n the co-
quefacton wth varous pastcs (Poystyrene(PS), Poyethyene terephthaate(PET)) and the ac-
ceeraton of decomposton of pastcs by ceuosc bomass was observed.
ntroduction
Deveopment of an effcent technoogy for convertng ceuosc bomass to qud fue s an m-
portant research area. New technoogy for convertng ceuosc bomass and waste pastcs to hgh
quaty ght o at ow pressure and ow temperature usng a sovent wth quefyng pants of sma
and smpe process s beng deveoped. The effects of pastcs on the yed and on the quaty of the
quefed o n the co-quefacton of ceuosc bomass and waste pastcs were nvestgated.
Experimental
Co-quefacton of ceuosc bomass and pastcs n the presence of sovent was conducted by
300mL-autocve or by a sma extruder wth two axes (25 kg/h) at 678-693K for 15-60 mn. Ceuo-
sc bomass(| apan cedar puverzed and dred) was used and peet of poypropyene(PP) or of
poystyrene(PS), fake of Poyethyene Phthaate(PET) were used as pastcs. Mnera o and wood
tar were used as a sovent. The rato of sovent to bomass and the rato of pastcs to bomass were
1/3 to 1/6 and 2/8 to 5/5, respectvey.
Co-quefacton of ceuosc bomass and pastcs n the presence of mnera o conducted by
300mL-autocve at 678K for 60 mn. gave quefed o of 60 wt% aong wth gas and water. It was
found that the co-quefacton of ceuosc bomass and PP gave hgher converson (73 wt%) than
the cases of ceuosc bomass or of poypropyene, whch was ascrbed to the acceeraton of de-
composton of pastcs by radcas derved from the decomposton of ceuosc bomass. In the co-
quefacton by a sma extruder wth two axes desgned as quefacton pants of sma and smpe
process, quefed o was obtaned wth a smar converson of ceuosc bomass wth the case of
the autocave. It was aso found that the quefed o was obtaned n the co-quefacton wth var-
ous pastcs (PP, PS, PET), and the acceeraton of decomposton of pastcs n the presence of
ceuosc bomass occurred.
The adaptabty of the quefed o as an aternatve fue for dese engnes was carfed by the
anayss of the quefed o prepared by the co-quefacton. Anayss of three knds of o (fracton
190 to 290C dvded by fractona dstaton) prepared by the co-quefacton of PP, PP/PS, PS
wth ceuosc bomass showed that the o prepared by the co-quefacton wth pastcs had better
propertes for dese engnes than that wth the quefacton of ceuosc bomass.

Effect of pastcs on the co-quefacton of ceuosc bomass and pastcs to qud fue

292
Conclusions
It was found that the co-quefacton of ceuosc bomass and pastcs gave quefed o, whch was
ascrbed to the acceeraton of decomposton of pastcs by radcas derved from the decomposton
of ceuosc bomass.
Acknowledgement
Authors wsh to thank NEDO for the permsson of ths presentaton.
AFORE - Forest Borefneres: Added-vaue from chemcas and poymers by new, ntegrated
separaton, fractonaton and upgradng methods

293
AFORE Forest Biorefineries: Added-val ue from
chemicals and polymers by new, integrated separation,
fracti onation and upgrading methods
Anna Suurnkki
VTT Technical Research Centre of Finland, Espoo, Finland
Abstract
A arge EU pro|ect AFORE deveops new sustanabe technooges for the separaton, fractonaton and
prmary upgradng of wood-based poymers and vauabe ow moecuar weght compounds present n
forest resdues and process sde streams. These technooges can be apped by the wood processng
ms of today and the future wood borefneres to turn sde streams nto proftabe busness.
Background of the AFORE project
Today, ony part of the vauabe wood bomass ends up n hgh-vaue appcatons (paper and card-
board), whst a sgnfcant part s channeed nto dfferent "sde-streams", such as oggng resdues,
debarkng resdues and pupng quors. A of these sde-streams contan chemcay appeang and
reactve consttuents that coud be further refned to vaue-added chemcas, poymers, materas,
and fues aongsde wth the sustanabe forestry and paper fbre producton. The utzaton of the
wood refnng sde-streams has been wdey studed durng the past century. Now, aong wth the
market chaenges n the pup and paper ndustry and rsng o prces, the nterest towards effcent
expotaton of process sde-stream components has rased agan.
Durng the past 100 years, ta o and turpentne have become we-estabshed man by-products so-
ated durng kraft pupng of wood raw materas. Recenty, gnn separated from the kraft back quor has
aso gan nterest prmary as an energy component. Substanta amounts of other unharnessed, poten-
tay usefu by-products ncudng hemceuose, hydroxy acds and certan ow moecuar mass com-
pounds are, however, aso known to be formed to sde-streams at a wood kraft pup ms. Furthermore,
wood resdues and aternatve pupng processes as we as totay new wood matrx openng methods
are potenta sources for vauabe wood based poymers and chemcas.
AFORE project
The man am of the AFORE pro|ect s to deveop new, ndustray adaptabe and techno-economcay
vabe and sustanabe methods and technooges for the separaton, fractonaton, and prmary upgrad-
ng of wood poymers and ow moecuar mass compounds from forest resdue or process sde-streams.
AFORE strongy targets to demonstraton of most potenta separaton, fractonaton and upgradng tech-
nooges whe concurrenty nove process and product openngs are search for. The research supports
the European wood processng ndustry and ts ndustra vaue chan n ther am of deveopng new
busness from forest borefneres accordng to the prncpes of sustanabe deveopment.
The AFORE pro|ect s a arge European Commsson Framework program FP7 NMP area fund-
ed pro|ect. It w run for four years and t has a budget of EUR 10.9 mon. The pro|ect w end n
2013. There are 19 partcpants n tota: VTT as the coordnator, 17 other European partcpants and
one partcpant from the USA. Corporatons (8 n tota), research nsttutons and unverstes form
the mutdscpnary consortum to acheve the chaengng targets of ths pro|ect.
AFORE research examples
Pease vst AFORE web ste www.eu-afore.f to earn more about the pro|ect and to see the re-
search exampes from the recent newsetter.

Boconverson of prmary sudge from Portuguese pup and paper ms to fermentabe sugars

294
Bioconversi on of primary sludge from Portuguese
pulp and paper mills to fermentable sugars
Ctia V.T. Mendes, M. Graa, V.S. Carvalho, Jorge M.S. Rocha*
CEPQPF, Department of Chemical Engineering, Faculty of Sciences and Technology, University of
Coimbra, Plo , Rua Slvio Lima, 3030-790 Coimbra, Portugal
*jrocha@eq.uc.pt

Prmary sudge, generated n pup and paper ms, conssts of ceuosc fbers ost aong the pup-
ng and papermakng process and ash (mosty CaCO
3
). Ths gnoceuosc waste s a potenta
attractve raw matera for the bosynthess of fermentaton products. However, prmary sudge bo-
converson s chaengng because ceuose s tough to chemca and boogca degradaton, and
moreover, the hgh ash content affects negatvey the producton of fermentabe monosacchardes
from the carbohydrate fracton of the prmary sudge. CaCO
3
s responsbe for the akane pH of
prmary sudge |7-10| and t aso may mt the sod oadng capacty n the boreactor, thus affect-
ng enzymatc hydroyss pH and yed |1, 2|. A prevous treatment may be necessary to remove the
exstng ash n order to ensure good yeds of sugars from both ceuose and hemceuose. The
am of ths research s to study the bochemca processes to convert the prmary sudge to fer-
mentabe sugars to be used as substrate to produce boethano, as a case study, by fermentaton.
Prmary sudge and unbeached pup (cean reference matera) were coected from a Portuguese
Kraft pup m, whch uses Eucalyptus globulus as raw-matera. Tabe 1 shows the organc, ash
(tota norgancs) and CaCO
3
contents for both materas. Untreated prmary sudge and unbeached
pup were submtted to enzymatc hydroyss wth ceuase Cec
CTec2, from Novozymes, usng

an nta carbohydrate (CH) content of c.a. 2.5% w/v and an enzymatc dosage of 35 FPU per gram
of carbohydrate (FPU g
CH
-1
). After 24 h of hydroyss, 90% of the carbohydrates from the un-
beached pup were converted to gucose and xyose, whst sugar yeds reached ony 20% for
prmary sudge wth no treatment |3|. Severa acds were used to neutraze CaCO
3
n the prmary
sudge (H
2
SO
4
, HC, HNO
3
and CH
3
COOH). HC was the most effcent acd to treat prmary sudge
as shown n Tabe 1. To avod the undesrabe CO
2
reease n the acd neutrazaton, aternatve
technques conssted n washng prmary sudge wth dsted water for severa tmes (resuts from
2, 6 and 12 washng cyces are shown n Tabe 1) were aso tested. Accordng to Tabe 1, CaCO
3

was effcenty removed when prmary sudge was washed for 6 or more tmes. These water-based
technques may be a good substtute to acd neutrazaton n the pre-treatment of prmary sudge.
Inta carbohydrate concentratons of c.a. 2.5% and 5% w/v of prmary sudge pre-treated wth HC
were used n enzymatc hydroyss experments. The sugar yeds obtaned after 24 h of reacton
are shown n Tabe 2. Hydroyss yeds of 79% and 88% were reached when usng nta carbohy-
drate concentratons of 2.5% and 5% w/v, respectvey (Tabe 2); t confrms the hydroyss m-
provement when a pre-treatment s apped. The enzymatc extracts from the dgestbty of prmary
sudge wth an nta 5% w/v carbohydrate content comprsed 82% of gucose and 18% of xyose
and were used as cuture meda n ethanoc fermentaton processes wth Pichia stipitis (co-
ferments gucose and xyose) and Saccharomyces cerevisiae (ferments chefy gucose). In genera,
P. stipitis showed a better overa performance, producng boethano wth hgher ethano yed and
producton rate, accordng to Tabe 2. Prmary sudge, prevousy treated, represents a potenta
resource to be used n order to obtan vaue-added products by fermentaton.

Boconverson of prmary sudge from Portuguese pup and paper ms to fermentabe sugars

295
Table 1. Composton of unbeached pup (reference) and prmary sudge (untreated and pre-treated).
Lignocell ulose/Treatment Content, % w/w (dry weight basi s)
Organc Ash CaCO
3

Unbeached pup 98.9 1.1 0.9
Prmary sudge 65.2 34.8 26.7
Pre-treated prma-
ry sudge
H
2
SO
4
89.2 10.8 0.7
HC 98.2 1.8 0.5
HNO
3
97.9 2.1 1.9
CH
3
COOH 98.1 1.9 1.9
2 washng cyces 86.5 13.5 6.9
6 washng cyces 95.9 4.1 0.1
12 washng cyces 96.2 3.8 0.5
Table 2. Enzymatc hydroyss and ethanoc fermentaton of prmary sudge pre-treated wth HC.
Enzymatc hydroyss
Cec
CTec2
Inta CH conc., % w/v 2.5 5.0
Sugar yed, % 79 88
Sugar conc.*, g
sug
L
-1
20.3 40.4
Ethanoc
Fermentaton
P. stipitis EtOH conc., g
EtOH
L
-1

-

11.1
EtOH Yed, g
EtOH
g
sug
-1
0.49
Productvty, g
EtOH
L
-1
h
-1
0.24
S. cerevisiae EtOH conc., g
EtOH
L
-1

-

8.3
EtOH Yed, g
EtOH
g
sug
-1
0.48
Productvty, g
EtOH
L
-1
h
-1
0.18
*Sugar concentraton n the enzymatc extracts before sterzaton; (-) Not performed.
References
1. Kang, L., Wang, W., Lee, Y.Y. 2010. Boconverson of kraft paper m sudges to ethano by SSF
and SSCF. App. Bochem. Botechno. 161, pp. 53-66.
2. Wang, X., Song, A., L, L., L, X., Zhang, R., Bao, | . 2011. Effect of cacum carbonate n waste
offce paper on enzymatc hydroyss effcency and enhancement procedures. Korean | .
Chem. Eng. 28, pp. 550-556.
3. Mendes, C.V.T., Rocha, | .M.S., Carvaho, M.G.S.V. Enzymatc hydroyss of pretreated prmary
sudge from a Portuguese pup and paper m. 11th Int. Chemca and Boogca Engneerng
Conference, Lsbon, Portuga, 2011.
Investgatng anaerobc dgeston of pup washng effuent usng bench-scae UASB reactors

296
nvestigating anaerobic digestion of pul p washing
effluent using bench-scale UASB reactors
Minqing vy Yang, Torsten Meyer, Mike Lacourt, Liqun Zheng, Angie Tse,
Elizabeth Edwards, Honghi Tran, D. Grant Allen
University of Toronto, Department of Chemical Engineering and Applied Chemistry,
200 College St., Toronto, ON, M5S 3E5, Canada
Abstract
Pup m wastewater streams such as pup washng effuent often contan hgh concentratons of
compounds, such as resn acds (RAs) and fatty acds (FAs) that adversey affect the anaerobc
dgeston process (see refs n Rntaa and Puhakka, 1994). The mpact may ncude dmnshed
bogas producton and dsntegraton of anaerobc sudge granues. Two bench-scae upfow anaer-
obc sudge bed reactors have been constructed to nvestgate the mechansms behnd those pro-
cesses, whch utmatey w assst n deveopng strateges to mnmze the adverse mpact of pup
washng effuent and other recactrant n-m streams on anaerobc sudge granuaton and dgester
performance. After an adaptaton phase of two months, one reactor (test reactor) has been fed wth
a sowy ncreasng fracton of pup washng effuent (PEW) obtaned from a suphte pup m. The
other reactor (contro reactor) s beng fed wth artfca and easy dgestbe wastewater. The m-
croba communty, the RA/FA composton, as we as the physca propertes of the granues n the
reactors are cosey montored usng pyrosequencng technoogy, qud chromatography - mass
spectrometry (LC-MS), and granue anayss methods. So far, the test reactor fed wth PEW exhb-
ts sgnfcanty ower chemca oxygen demand (COD) remova rates as we as bogas producton
rates, compared to the contro reactor.
Methods
The anaerobc reactors were made from acryc and each has a workng voume of 5.4 L (Fgure 1).
Mesophc condtons wth a temperature of 37C wthn the reactor are ensured by means of a
water |acket and a crcuatng pump. The bogas producton s measured usng a bubbe counter
setup. Mxng, necessary to mantan we functonng sudge granues, s provded by recrcuatng
headspace gas nto the bottom of the reactor through a porous ceramc dsc. The generated fne
bubbes provde upft and turbuence of the granues. Granuar seed sudge for both reactors was
taken from a fu-scae anaerobc IC reactor at a suphte pup m n Canada. The PEW used to
feed the test reactor contans approxmatey 19 g L
-1
COD, 100 mgL
-1
RAs and 20 mgL
-1
FAs, and
s generated durng hgh apha specaty pups producton at the m, where t s for the most part
excuded from anaerobc treatment because of ts detrmenta mpact on process performance. The
contro reactor s beng fed wth artfca wastewater, whch resembes the composton of easy
dgestbe pup m wastewater and contans substrate and mnera nutrents. The feed COD of the
contro reactor conssts of acetate, methano, ethano, xyose, gucose, and sodum carboxymethy
ceuose. Over the course of the experment the organc oadng rate has been kept at approx-
matey 25 g COD per Ltre of reactor per day, and the hydrauc retenton tme s approxmatey 12
hours. Frequent, routne anayss ncudes measurements of effuent pH, oxdaton-reducton poten-
ta, bogas producton, voate acds - akanty rato, voate suspended sods / tota suspended
sods, COD, as we as granue strength and sze. For most of these anayses, effuent sampes are
coected severa tmes per week. Furthermore, weeky samped effuent s stored at -20C for ater
anayss usng tme-resoved LC-MS. Sampes of dgester sudge are taken every 3 to 4 weeks from
sudge sampng ports n order to anayze granue strength and sze. Addtona sudge sampes
have been stored at -80C for subsequent DNA extracton and communty composton anayss by
454 pyrosequencng of ampfed 16SrRNA genes.

Investgatng anaerobc dgeston of pup washng effuent usng bench-scae UASB reactors

297

Fi gure 1. Bench-scae reactors.
The test reactor nfuent currenty contans 60 mgL
-1
RAs and 15 mgL
-1
FAs. The remova rate of
soube COD n the test reactor s dmnshed by approxmatey 30% compared to the contro reac-
tor. The bogas producton rate s aso ower n the test reactor by a smar percentage. Premnary
resuts from LC-MS anayses ndcate that of a the nvestgated chemcas, dehydroabetc acd s
the east degradabe compound. At the same tme ths RA s one of the most abundant and nhbto-
ry substances present n pup m effuents (Serra-Avarez and Lettnga, 1990; Rntaa and Puhak-
ka, 1994). The resuts of ths study are expected to notaby enhance our understandng on how
RAs and FAs nfuence the anaerobc communty dynamcs as we as the physco-chemca proper-
tes of anaerobc sudge granues.
References
1. Rntaa, | .A., Puhakka, | .A. 1994. Anaerobc treatment n pup- and paper-m waste manage-
ment: a revew. Bores. Techno. 47, p. 1.
2. Serra-Avarez, R., Lettnga, G. 1990. The methanogenc toxcty of wood resn consttuents. Bo.
Wastes 33, p. 211.
From brch to Soda-AO pups, pure xyan and fractons thereof - HemEx pro|ect overvew

298
From birch to Soda-AQ pulps, pure xylan and
fractions thereof HemiEx project overview
Lidia Testova, Annariikka Roselli, Luciana Costabel, Herbert Sixta
Department of Forest Products Technology, Aalto University School of Chemical Technology,
P.O. Box 16300, Vuorimiehentie 1, Espoo, F-00076 AALTO, Finland
Abstract
In ths research pro|ect hemceuose-soatng pretreatments and pupng operatons were opt-
msed and the papermakng propertes and sutabty for vscose process of the resutng pups
were evauated. Akane pre-extracton process produced hgh moecuar weght xyan (20kDa) and
paper pup wth exceent papermakng propertes. Prehydroyss pups had nferor strength, how-
ever, the sampes wth more extensve xyan remova were we suted for vscose producton.
ntroduction
The HemEx pro|ect amed at seectvey extractng hemceuoses from brch wood n the course of
soda-anthraqunone (SAO) fractonaton, foowng the borefnery prncpe. Three dfferent methods
for separatng xyan were nvestgated, ncudng water (AH) and oxac acd (PH(OA)) prehydroyss
as we as akane extracton (E) pror to akane pupng.
Optmsaton experments demonstrated that at dfferent pretreatment ntenstes desred amounts
of xyan coud be soated by both acdc and akane pretreatments |1, 2|. Smutaneousy, sma
amounts of gnn were co-extracted whe ceuose remaned argey preserved (Fgure 1). Optma
pretreatment condtons seected for further experments are sted beow.
AH P200 150 C, L:S=4 L/kg, 90 mn PH(OA) 120 C, L:S=4 L/kg, 0.05 M OA, 70 mn
AH P1000 170 C, L:S=4 L/kg, 94 mn E 95 C, L:S=9.3 L/kg, 2.4 M NaOH, 60 mn

Figure 1. Mass baances of the seected pretreatments.


299
The weght-average moar masses of the extracted xyans were 20 kDa, 2.1 kDa and 0.4 kDa for E,
AH P200 and AH P1000 pretreatments, respectvey. As expected, addng oxac acd as a catayst
n prehydroyss consderaby ncreased the share of monomerc xyose n the hydroysate wth a
50% share after 0.05 M OA treatment at 120C for 70 mn.
Akane pupng after renforced autohydroyss as we as md oxac acd prehydroyss and
strong akane pre-extracton was targeted towards dssovng and paper-grade pup producton,
respectvey. Pupng of pre-treated brch chps (EA 22%, AO 0.1% L:S=3.5) requred ower pupng
ntenstes as compared to the SAO reference (Tabe 1). The yeds of the pretreated paper pups
were notaby ower (up to 4% and 7% osses based on raw wood for akane pre-extracton and
pre-hydroyss, respectvey) compared to the reference pup. Ths s due to the ower hemceu-
oses content and, n the case of acdc prehydroyss, to susceptbty towards peeng reactons n
akane pupng due to ncreased content of carbohydrate reducng end groups. Attempted stab-
saton of carbohydrates aganst akane peeng wth sodum borohydrde (B), AO and anthraqu-
none monosufonate (AOS) resuted n a yed gan of 1-4% based on raw wood. It was observed,
however, that not ony ceuose but aso hemceuoses were stabsed by oxdatve and reductve
addtves, whch s benefca for paper pups but s not desred for hghy pure dssovng pups.

Figure 2. Papermakng propertes.
Fgure 2 reveas exceent papermakng propertes of aka pre-extracted paper pups. Prehydroy-
ss pups had nferor strength, but stabsaton wth BH, resuted n acceptabe strength propertes.
The sampes wth more extensve xyan remova had hgh aka resstance (Tabe 1) and were we
suted for vscose producton, havng fter vaues of 417 and 332 for AH P1000-SAO and AH
P1000-SAO BH, respectvey.

300
Table 1. Propertes of pups obtaned by SAO pupng.

S
A
Q

p
u
l
p

E
-
S
A
Q

P
H
(
O
A
)
-
S
A
Q

P
H
(
O
A
)
-
S
A
Q
-
A
Q

P
H
(
O
A
)
-
S
A
Q
-
A
Q
M
S

P
H
(
O
A
)
-
S
A
Q

B
H

A
H

P
1
0
0
0
-
S
A
Q

A
H

P
1
0
0
0
-
S
A
Q
B
H

Unbl eached
H-factor 800 550 400 350 450 700 350 300
Yed, % of o.d. wood 50.4 46.6 42.7 44.3 45.5 46.3 36.9 38.3
Kappa number 19.8 17.9 19.8 15.6 16.0 16.1 8.3 8.2
Intr. vscosty, mL/g 1051 1123 1321 1342 1291 1221 1305 1309
Oxygen delignifi ed Bleached
Yed, % of o.d. wood 49.6 44.7 41.9 43.3 44.6 46.0 34.1 36.2
Kappa number 14.0 12.1 12.9 10.6 11.3 9.0 0.78 0.80
Intr. vscosty, mL/g 945 878 1147 1112 1153 1014 507 572
Zero-span ndex, Nm/g 0.63 0.54 0.55 0.55 0.55 0.57 - -
Xyan content, % 21.0 17.5 13.3 14.0 13.8 15.6 4.5 5.7
Aka resstance R18, % - - - - - - 95.8 95.5
Conclusions
Akane and acdc hemceuoses-soatng pretreatments were best suted for producng paper and
dssovng-grade pups, respectvey. However, the economc feasbty of the studed processes s
hghy dependent on the added vaue of the products derved from hemceuoses to compensate
for the oss of pup yed.
References
1. Testova, L., Vonen, K., Pynnnen, H., Tenkanen, M., Sxta, H. 2009. Isoaton of hemceuoses
from brch wood: dstrbuton of wood components and premnary tras n dehydraton of
hemceuoses. Lenz. Ber. 87, pp. 58-65.
2. Costabe, L., Testova, L., Aekhna, M., Ruuttunen, K., Sxta, H. 2011. Akane pre-extracton of
brch wood pror to akane pupng. 3rd NWBC. Stockhom, Sweden. Pp. 305-306.
Impementaton of gnn-based borefnery wthn a Canadan kraft m: Impact on utty system and
soutons toward optma operaton

301
mplementation of lignin-based biorefinery within a
Canadian kraft mill: mpact on utility system and
sol uti ons toward optimal operation
Abdelaziz Hammache, Etienne Ayotte-Sauv, Zo Prin-Levasseur,
Marzouk Benali, Luciana Savulescu
Natural Resources Canada, CanmetENERGY,
ndustrial Systems Optimization, Varennes, Quebec, Canada
marzouk.benali@nrcan.gc.ca
ntroduction
Kraft pupng ms contnue to expore borefnery opportuntes that create boenergy, bochemcas
and bomateras. One of theses opportuntes offers suppementary revenues through the recovery
of gnn contaned n the back quor stream and the ncrease of pup producton by debotteneckng
the recovery boer. However, mpementng such a market transformatve souton affects sgnf-
canty the resources demand (.e., wood bomass, process energy, utty, water and chemca reac-
tants). To dentfy and mnmze such mpacts, severa technca and economc chaenges need to
be addressed va a ste-wde approach dentfyng the compex nteractons between the processes
of gnn recovery and kraft pupng. Ths shoud prortze effcent use of the resources and optma
strategy desgn for utty system. Thus, an assessment of expoted resources s performed on a
Canadan softwood kraft pupng m producng up to 400 tonne/day (dry bass). The maxmum
gnn recovery rate s fxed at 50 tonne/day (dry bass) whe the hgher heatng vaue of back quor
vares from 13.8 G| /tonne to 12.7 G| /tonne durng gnn recovery process. The evauaton of the
utty system focuses on the potenta pathways to generate and dstrbute the steam from the fue
system and suppy t to the end user. The optma operatng condtons are estabshed to mnmze
the tota cost wthn certan technca and operatona constrants. To estabsh the optma operatng
condtons for the exstng utty system, a modeng, smuaton and optmzaton of the m utty
system has been deveoped usng a GAMS patform |1|. Three scenaros have been consdered:
scenario #1 as a reference case n whch the utty system s optmsed for basene oad condtons of
the m; scenario #2 corresponds to the ntegrated gnn recovery wthn the m; scenario #3 con-
forms to the ntegrated gnn recovery wthn the m, ncudng process ntegraton measures.
Methodology
The utty system s many composed of fve boers (one bomass boer burnng hog fue and bun-
ker o, three natura gas power boers and a back quor recovery boer) that generate medum
pressure steam. Ths steam s then dstrbuted to severa users at both ow and medum pressures.
Low pressure steam s obtaned through etdown expanson vaves consderng that there s no
power generaton capabty on the m ste. A reference scenaro was frst modeed, smuated and
optmsed wth respect to the m energy demands and reated costs. Afterwards, the mpact of the
gnn-based borefnery mpementaton on the utty system operaton was evauated. The nfu-
ence of energy savngs pro|ects on the optma utty system was aso assessed. The economc
vabty of a scenaros has been estabshed based on one ma|or operatng constrant: the mn-
mum back quor fow rate for steam generaton was set at 346 tonne/day (dry bass).
Tabe 1 shows the optma condtons for scenario #1. The recovery boer was set at ts current
basene oad. Due to hgh cost of bomass and bunker o, the bomass boer shoud operate at ts
mnmum oad. The power boers burnng natura gas are makng-up for the remanng dfference n


302
steam demands. As there s enough nstaed power boers capacty, about 32% tota cost savngs
coud be acheved f the kraft m shuts down the bomass boer.
Table 1. Optma condtons for scenaro #1.
tem Fuel consumpti on, MW Steam generation, tonne/h Operat ing Costs, M$/year
Bomass Boer
Bomass 8.8
13.7
1.69
Bunker O 5.0 2.47
Power Boers Natura Gas 54.9 70.6 5.53
Recovery Boer Back Lquor 89.1 67.3 0
Tota cost, M$/year 9.84

Tabe 2 presents the optma condtons for scenari o #2 n whch the cost of chemca reactants
requred for effcent gnn recovery are ncuded.
Table 2. Optma condtons for scenaro #2.
tem Fuel consumpti on, MW Steam generation, tonne/h Operat ing Costs, M$/year
Bomass Boer
Bomass 8.8
13.7
1.69
Bunker O 5.0 2.47
Power Boers Natura Gas 95.5 122.4 9.62
Recovery Boer Back Lquor 62.2 46.8 0
Lignin recovery process, 50 tonne/day
Chemcas 2.13
Annuased Investment 1.91
Revenues 12.50
Tota cost, M$/year 5.51

The current average seng prce s consdered as 750 $/tonne for both gnn and beached kraft
pup |2|. As ustrated n Fgure 1, t s more proftabe to ncrease the pup producton to the max-
mum aowabe mt and use a excess back quor for gnn recovery. Fgure 1 provdes optma
condtons for gnn recovery rate, tota cost and payback perod (PBP) as a functon of pup pro-
ducton ncrease. The PBP s shorter than one year for a optma condtons. As expected for sce-
nari o #3, the PBP s shfted up by about 11% due to extra capta nvestment correspondng to the
ncreased heat exchange area needed for a energy savng pro|ects (.e., cumuatve savngs of
11.3 MW). Scenario #3 s economcay vabe snce the PBP remans about one year. The poten-
ta to produce power was assessed and was n the order of 0.7 MW for the current utty topoogy.
Thus, t was not ncuded n the optma condtons for a scenaros.

303

Fi gure 1. Optma condtons for scenaros #2 and #3 wth ther correspondng PBP.
Concl usi on
A rea kraft m utty system was assessed for optma management n the context of an ntegrated
gnn-based borefnery. For ths case study, the optma mpementaton s acheved wth a reduced
tota cost by up to 55% usng process ntegraton measures. The PBP, whch s n the order of one
year, ponts towards the economc vabty of the gnn recovery process. The extra revenues from
gnn and beached kraft pup exceed the capta expenses assocated wth the gnn recovery
technoogy and the process ntegraton measures.
References
1. Rosentha, R.E. 20129.GAMS - A users gude; GAMS Deveopment Corporaton: Washngton.
http://www.gams.com/dd/docs/bgdocs/GAMSUsersGude.pdf.
2. Prn-Levasseur, Z., Savuescu, L., Bena, M. 2012. Techno-economc evauaton of a gnn-
based borefnery mpementaton wthn a Canadan Kraft pup m, 2
nd
Internatona Forest
Borefnery Symposum, PaperWeek Canada, Montrea, Ouebec, Canada.
Pup producton ncrease (%)
12 14 16 18 20 22 24 26
P
a
y
b
a
c
k

p
e
r
o
d

(
y
e
a
r
s
)
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Scenaro #3
Scenaro #2
Pup producton ncrease (%)
12 14 16 18 20 22 24 26
L
g
n
n

m
a
s
s

f
o
w
r
a
t
e

(
t
o
n
n
e
/
d
a
y
)
0
10
20
30
40
50
60
T
o
t
a

c
o
s
t

(
M
$
/
y
e
a
r
)
4
5
6
7
8
9
10
11
12
Scenaro #2 and #3
Scenaro #2
Scenaro #3
Opportuntes for energy upgradng by means of an absorpton heat pump n an ntegrated forest
borefnery

304
Opportuni ties for energy upgrading by means of
an absorption heat pump in an integrated
forest biorefinery
Olumoye Ajao, Tatiana Rafione, Mariya Marinova, Robert Legros, Louis Fradette, Jean Paris
Department of Chemical Engineering, cole Polytechnique de Montreal, Canada
Abstract
The purpose of ths study s to evauate the technca feasbty of mpementng an absorpton heat
pump (AHP) nto an ntegrated forest borefnery for furfura producton n order to reduce ts energy
requrement. An AHP confguraton s proposed for ntegraton nto the man dstaton coumn of the
borefnery. The resuts show that the heatng requrement of the borefnery s reduced by 4.2 MW
(31%) and the coong requrement by 9.9 MW (24%). Ths w factate the mpementaton of the
borefnery unt nto a Kraft pupng m wthout requrng added steam and hot water producton
capacty.
ntroduction
The man process steps of the furfura borefnery are ustrated n Fgure 1 wth heatng (O
H
) and
coong (O
C
) requrements for each operaton. About 65% of the tota heatng requrement for pro-
ducng 58 t/d of furfura comes from the separaton and purfcaton of furfura by dstaton. Ths
requrement can be reduced by means of heat pumpng between the refux condenser and the
reboer of the man dstaton coumn. AHPs are heat drven devces that upgrade free heat avaa-
be from a process to a hgher temperature. In an AHP (Fgure 2), drvng heat s supped to the
evaporator (E) and generator (G), at an ntermedate temperature eve, whe usefu heat s berated
by the absorber (A) at a hgher temperature and by the condenser (C) at a ower temperature |1, 2|.
The ob|ectve of ths work s to evauate the potenta for energy reducton from an AHP mpemen-
taton n a borefnery process.

Figure 1. Process dagram of the furfura borefnery.
Methodology
Operatng parameters for the heat pump (temperature, pressure and LBr concentraton) were de-
termned by pottng the cyce on a H
2
O/LBr phase dagram (Fgure 2). The work was supported by
Q
H
: 16.3 MW
Q
C
: 43.7 MW
Q
C
=16 MW
Q
C
= 10.7MW
Q
C
= 9.9MW
Q
H
= 10.2 MW
Q
H
= 0.24 MW
Q
C
= 3.0 MW
Q
C
= 0.11 MW
Q
H
= 5.8 MW
Q
C
= 3.3MW

Opportuntes for energy upgradng by means of an absorpton heat pump n an ntegrated forest
borefnery

305
Aspen Pus
smuatons of the borefnery and AHP to determne the energy oads and coeffcent
of performance (COP). An optmzed heat exchanger network was deveoped by pnch anayss
before the AHP nstaaton producng a heat requrement and coong requrement reducton of 15
and 6% respectvey. The methodoogy for postonng an AHP s descrbed by Bakhtar et a. |2|.
Results and conclusion
A snge stage AHP wth H
2
O/LBr as workng fud was seected and mpemented as shown n Fgure 3.
The seected concentraton of the H
2
O/LBr strong souton (0.4/0.6) and the operatng pressures (4.5 kPa /
65 kPa) prevent crystazaton n the heat pump cyce. The operatng temperatures ensure a mnmum
dfference (T
MIN
) of 10C between the coumn and the AHP; the COP of the heat pump s 0.42.

Figure 2. AHP representaton n H
2
O/LBr phase dagram. Figure 3. AHP ntegraton.
The condenser duty of the coumn s competey satsfed as 9.9 MW s transferred to the AHP va
the evaporator-generator par. Usefu heat s recovered at a hgher temperature from the AHP ab-
sorber and fed to the coumn reboer; ths reduces the heatng requrement by 4.2 MW (41%). The
reboer duty s partay satsfed eavng a heatng requrement (O
H
) of 6 MW. The heat from the
AHPs condenser s sutabe for preheatng freshwater streams n the receptor m.
Impementng an absorpton heat pump n the ntegrated borefnery s techncay feasbe. The
AHP upgrades heat from the dstaton coumn condenser to be used at a hgher temperature n
the reboer, thus reducng the steam and coong water requrement. However, nstang an AHP
w requre the deveopment of an adapted contro strategy for effcent operaton of the dstaton
coumn wth the ntegrated heat pump |3|.
References
1. Costa, A., Bakhtar, B., Schuster, S., Pars, | . 2009. Integraton of absorpton heat pumps n a
Kraft pup process for enhanced energy effcency. Energy 34(3), p. 254-260.
2. Bakhtar, B., Fradette, L., Legros, R., Pars, | . 2010. Retroft of absorpton heat pumps nto man-
ufacturng processes: Impementaton gudenes. Can. | . Chem. Eng. 88(5), p. 839-848.
3. Aarcn-Pada, D.C., Garca-Rodrguez, L., Banco-Gvez, | . 2010. Expermenta assessment
of connecton of an absorpton heat pump to a mut-effect dstaton unt. Desanaton
250(2), pp. 500-505.
The LgnoForce System for the recovery of gnn from back quor

306
The Li gnoForce System for the recovery of lignin
from black liquor
Lamfeddal Kouisni
1
, Michael Paleologou
1
, Peter Holt-Hindle
2
, Kirsten Maki
2

1
FPnnovations Pulp, Paper & Bioproducts Division, Pointe-Claire, Quebec, Canada
2
FPnnovations Pulp, Paper & Bioproducts Division, Thunder Bay, Ontario, Canada
Abstract
To mprove gnn fterabty, FPInnovatons deveoped a patent-pendng process caed LignoForce
n whch the back quor (BL) s oxdzed under controed condtons pror to the acdfcaton step.
Based on the data obtaned, BL oxdaton was found to mprove the fterabty of the acd-
precptated gnn by provdng sutabe condtons wth respect to pH, and temperature for the for-
maton of partces that are easy to fter and wash. In addton, BL quor oxdaton was found to
mnmze or emnate the tota reduced suphur (TRS) compounds n BL thereby eadng to reduced
TRS emssons durng a steps assocated wth a processng steps. Furthermore, BL oxdaton ed
to reduced acd requrements durng gnn precptaton from BL by oxdzng sufde to sufate and
organcs to organc acds, whch consume the resdua effectve aka (sodum hydroxde) n BL.
ntroduction
Lgnn can be recovered from kraft back quor through the addton of an acdfyng agent such as
carbon doxde, foowed by coaguaton, ftraton and washng. Durng ths process, however, severa
researchers have prevousy observed a hgh ftraton resstance whch, utmatey, affects gnn
purty, productvty and cost. One approach for addressng ths probem s a process deveoped by
STFI (now caed Innventa) and censed to Metso |1|

whch empoys a frst fter for the ftraton of
gnn n the sodum form foowed by suspenson of the gnn cake n dute suphurc acd before
ftraton n a second fter. Another approach for addressng ths probem s a patent-pendng pro-
cess deveoped by FPInnovatons and currenty commercazed by NORAM under the trade name
"LignoForce Systems
TM
" |2| (Fgure 1). The purpose of ths paper s to descrbe ths new process.

Figure 1. LgnoForce system for gnn recovery from back quor.


307
Experimental
For the purpose of mprovng the gnn ftraton propertes, the BL was oxdzed under controed
condtons. The oxdzed BL was then acdfed, coaguated, ftered, and the gnn washed and
dred amost n the same way as n other processes. Snce the LignoForce process mproves gnn
fterabty, ony one fter press was requred.
The ftraton rate was measured as the number of kograms of recovered gnn ftered per unt
surface area per hour. The recovered gnn sampes were anayzed for dry sods, UV-gnn, and
ash content. The resuts are presented n Tabe 1.
Table 1. Ftraton rate and gnn characterzaton n the case of oxdzed & unoxdzed BL.
Without oxi dation With oxidation
Ftraton rates (kg of gnn/h.m
2
) 0-80 100-200
Tota sods (%) 30-58 60-62
Ash content (%) 0.2-15 0.1-0.7
UV gnn (%) 50-98 97-98
Lgnn partce sze (m) 0.2-1 5-10

Tabe 1 shows that hgher ftraton rates, hgher purty, hgher gnn sods content and arger gnn
partce sze were obtaned when the BL was oxdzed usng the LignoForce process compared to
the absence of BL oxdaton.
Durng the oxdaton step, sugars are converted to organc acds and tota reduced sufur (TRS)
compounds are oxdzed to non-voate compounds such as suphurc acd, methane suphonc acd
and dmethy suphone, thereby: 1) reducng odour durng a subsequent processng steps, 2) gen-
eratng and dstrbutng heat n a homogeneous fashon, and 3) reducng the pH of BL by consum-
ng the resdua sodum hydroxde. The extent of pH reducton was found to be reated to the extent
of BL oxdaton and the rate of pH decne was found to sow down sgnfcanty as the carbonate-
bcarbonate bufferng effect became sgnfcant |3|. At the hgh pH of typca BLs, the repusve forc-
es between the onzed hydrophc groups (many phenoc hydroxy and carboxyate groups), sta-
bze the cooda gnn and keep t n souton, thereby preventng gnn aggomeraton and precp-
taton |3|. However, as the pH of the BL decnes (as a resut of the oxdaton of sugars to organc
acds and the TRS to non-voate compounds), the dssocated phenoc hydroxy groups on the
gnn begn to accept protons resutng n a decne n the repusve forces and the aggomeraton of
gnn to arger partces |3|. As shown n Tabe 1, the arger gnn partces were found to fter much
faster than the smaer gnn partces obtaned durng acd precptaton of unoxdzed back quor.
Conclusions
The LignoForce system was shown to ncrease the ftraton rate, the purty, and the sods content
of gnn durng ts separaton from BL. Ths system was aso found to reduce the acd requrements
of the process by oxdzng sufde to sufate and organcs to organc acds whch consume the re-
sdua effectve aka n back quor.

308
Acknowledgements
The authors wsh to acknowedge the technca assstance provded by Pak-Yan Wong of FPInno-
vatons and the fnanca support provded by Natura Resources Canada (NRCAN) and the Centre
for Research and Innovaton n the BoEconomy (CRIBE).
References
1. hman, F., Theander, H., Toman, P., Axegrd, P. 2012. Method for separatng gnn from
back quor. European Patent, EP1794363B1.
2. Kousn, L., Paeoogou, M. 2011. Method for separatng gnn from back quor. US Patent Ap-
pcaton 2011/0297340A1.
3 Hermans, M.A. 1984. Hgh ntensty back quor oxdaton. PhD. Thess, Lawrence Unversty, 1984.
Infuence of the use of hgh shear rate modue n membrane ftraton performance n utraftraton of
back quor

309
nfluence of the use of high shear rate module in
membrane filtration performance in ultrafiltration
of black liquor
Jussi Lahti, Mari Kallioinen, Mika Mnttri
Laboratory of Membrane Technology and Technical Polymer Chemistry,
Department of Chemical Technology, Lappeenranta University of Technology,
P.O. Box 20, F-53851 Lappeenranta, Finland
ntroduction
It has been shown that the use of hgh shear rate modues decreases foung and ncreases ftra-
ton capacty n treatment of pup and paper m process and waste waters |1, 2|. Foung and de-
cne of ftraton capacty are chaenges aso n utraftraton of back quor and these phenomena
are wdey studed. However, the research has been many focused on the nfuence of membrane
choce on foung or on the nfuence of operatona condtons on foung and ftraton capacty n
one modue type. The am of ths study s to fnd out f the use of hgh shear rate modues s advan-
tageous n utraftraton of back quor.
Experimental
The hgh shear rate modues used n the experments were the cross-rotatona modue CR-250
from Metso Paper and the vbraton enhanced modue (VSEP) from New Logc Inc. The resuts
acheved wth these modues were compared wth the resuts acheved wth the ow shear rate
modue DSS LabStak
(Afa Lava). The ftraton experments were performed wth soft wood back
quor wth two dfferent poyether suphone (PES) membranes: 1000 g/mo (NP010 Nadr) and
10 000 g/mo (UP010 Nadr) utraftraton membranes.
The resuts ceary demonstrated that the ncreased shear rate mproves ftraton capacty n the
treatment of back quor. Sgnfcanty hgher ftraton capactes were measured wth the hgh shear
rate modues than wth the ow shear rate modues (Fgure 1., NP010 membrane). The magntude
of the hgh shear rate on the ftraton capacty coud be notced especay at ower recovery vaues.
The hghest ftraton capacty was acheved wth the CR-fter, n whch turbuence s caused on
the membrane surface by rotors (Fgure 1.). Ftraton capacty ncreased ceary when rotaton
speed of the rotors ncreased from 600 to 1200 RPM. The ncrease of rotaton speed to the vaues
hgher than 1200 RPM seemed to have reatvey sma nfuence on ftraton capacty. Compared to
the ow shear rate DSS fter, hgher ftraton capacty coud aso be acheved wth the VSEP fter,
n whch the turbuence on membrane surface s caused by vbratng the fter ce. The resuts
showed the mportance of the vbraton amptude choce. The VSEP fter produced ceary hgher
ftraton capacty than the DSS fter ony when the hgher vbraton amptude (3.8 cm) was used.
The gnn retentons acheved wth the dfferent fter modues were between 67 and 84%. It
seemed that modue type had a sgnfcant nfuence on retenton. The owest retenton vaues were
measured wth the CR-fter.

Infuence of the use of hgh shear rate modue n membrane ftraton performance n utraftraton of
back quor

310

Figure 1. Permeate fux when the ow shear (DSS) and hgh shear rate (CR & VSEP) ftraton
modues have been used to concentrate gnn from 10 w% back quor wth the NP010 membrane
(1 000 g/mo). Ftraton temperature was 60C and pressure n the VSEP experments 19 bar.
Concl usi ons
The comparson of the hgh and ow shear rate ftraton modues n the treatment of soft wood back
quor reveaed that sgnfcanty hgher ftraton capactes can be acheved when the hgh shear
rate modues are used. However, at hgh recovery vaues the dfferences n the capactes were
decreasng. Based on the resuts gnn retenton seemed to be affected by the used modue type.
Thus t can be concuded that advantageous of the use of the hgh shear rate fter modues depends
on the appcaton and ts requrements for the permeate quaty and voume reducton needs.
Acknowledgements
The authors are gratefu to the Future Borefnery Research Program FuBo 2 for fnanca support.
References
1. Huuho, T., Vsnen, P., Nuorta-| oknen, | ., Nystrm, M. 2001. Infuence of shear on fux n
membrane ftraton of ntegrated pup and paper m crcuaton water. Desanaton
141(3), pp. 245-258.
2. | nsson, A.S. 1993. Infuence of shear rate on the fux durng utraftraton of cooda substances.
| . Membr. Sc. 79(1), p. 93-99.
0
50
100
150
200
0 20 40 60 80 100
F
l
u
x
,

k
g
/
(
m
h
)
Volume reduction, %
VSEP, vbraton 3.8 cm VSEP, vbraton 1.3 cm
CR-250, 9 bar, 1000 RPM DSS, 16 bar
Impact of gnn extracton on the recovery oop of the Kraft process: Measures to mnmze the
consumpton of chemcas

311
mpact of li gnin extracti on on the recovery loop of the
Kraft process: Measures to minimize the
consumpti on of chemicals
Miyuru Kannangara, Carmen Liebich, Mariya Marinova, Louis Fradette, Jean Paris
Department of Chemical Engineering, cole Polytechnique de Montreal, Canada
Abstract
Impacts of gnn extracton by acd precptaton on Kraft m chemca recovery cyce have been
quantfed n ths study. Evaporator demand ncrease, recovery boer steam producton decrease
and dsrupton of Na and S baance have been evauated accordng to two scenaros reated to
spent quor and washng ftrates recyce. The consumpton of make-up caustc was mnmzed
when spent quor and frst 25% of washng ftrates are recyced back to the process.
ntroduction
Lgnn, a ma|or component of the back quor whch s currenty burnt n the recovery boer of the
Kraft process, can be extracted and converted nto a broad spectrum of bo-based products. An
acd precptaton process s used to recover gnn. In ths process, back quor s extracted from the
evaporator tran and treated wth CO
2
to reduce the pH and precptate gnn. Precptated gnn s
then washed wth dute H
2
SO
4
to remove the remanng mpurtes. Spent back quor and washng
ftrates have to be recyced back to the chemca recovery oop of the Kraft m n order to recover
organc and norganc materas that they contan |1, 2|. Lgnn extracton and recyce fows change
the composton and fow rates of the chemca recovery cyce and dsrupts ts Na and S baance. In
ths study these mpacts are quantfed and mtgaton measures are proposed.
Methodology
The studed m s a representatve Canadan Kraft pup m whch has a pup producton capacty
of 750 adt/d. Mass and energy baances have been performed for chemca recovery cyce usng
Cadsm Pus process smuator. Na and S baance of mode m has been estmated. Lgnn extrac-
ton process requres 0.21 kg CO
2
, 0.2 kg H
2
SO
4
and 8 kg water per kg of gnn output. It was mod-
eed n Aspen Pus patform usng eectroyte approach to predct the onc composton changes. In
order to exchange data between the two smuators a common exce nk has been used. Acd pre-
cptaton was mpemented n the mode m and spent quor and washng ftrates were recyced
accordng to the foowng two scenaros. |1|. Ony the spent quor after ftraton s recyced back to
the Kraft m; |2|. Spent quor and ftrates from washng step are recyced back to the Kraft m as
we. Changes n evaporator steam demand and recovery boer steam producton have been est-
mated. Dsrupted Na and S baance was brought to orgna vaues by varyng the amounts of sat
cake and caustc addton and precptator dust purge.

Impact of gnn extracton on the recovery oop of the Kraft process: Measures to mnmze the
consumpton of chemcas

312

Figure 1. (a) Lgnn extracton mpementaton scenaros: (1) - Weak back quor tank, (2) - Evapo-
rator tran, (3) - Precptator, (4) - Fter and (5) - Washer. Fgure 1(b) - Na and S baance of the
reference m (wthout gnn extracton).
Table 1. Impacts on evaporators, recovery boer and chemca make-up and purges.
Parameter Refer ence mi ll
(No li gni n extracti on)
With lignin extraction
Scenari o 1 Scenari o 2
Evaporator steam demand 25 MW 28 MW 36 MW
Recovery boer steam producton 88 MW 72 MW 78 MW
Sat cake addton 13 t/d 24 t/d 0
Caustc addton 8 t/d 12 t/d 26 t/d
Precptator dust purge 8 t/d 0 30.5 t/d

Accordng to Tabe 1 evaporator steam demand s sgnfcanty ncreased for scenaro 2 due to the
recyce of water used n washng. On the other hand, the recovery boer steam producton s de-
creased for the scenaro 1 as the organc components of ftrates are ost. The Na and S baance
can be mantaned by ncreasng sat cake addton to make-up Na ost wth gnn and ftrates. In
scenaro 2, where addtona S s brought nto the cyce by H
2
SO
4
, ncreasng amounts of precpta-
tor dust have to be purged to mantan S baance. Ths, however, ncreases the caustc requrement
up to 26 t/d. Excess S addton can be controed by recycng ony the frst 25% of ftrates, whch
resuts n mnmzaton of make-up caustc requred.
References
1. Toman, P., Axegard, P., Bergn, N., Love, A., Nordgren, D. 2011. Integraton of gnn remova
nto a Kraft pup m and use of gnn as a bofue. Ceuose Chemstry and Technoogy
45(7-8), pp. 533-540.
2. Kousn, L., Fang, Y., Paeoogou, M., Ahvaz, B., Hawar, | ., Zhang, Y., Wang, X.. 2011. Kraft
gnn recovery and ts use n the preparaton of gnn-based pheno formadehyde resns
for pywood. Ceuose Chemstry and Technoogy 45(7-8), pp. 515-520.

Black
liquor
(1) (2)
(3)
(4)
To recovery
boiler CO2
(5)
Sulfuric
acid
Water
Lignin
Spent liquor recycle
Filtrates recycle
Evaporators
Recovery
boer
Dgester
Whte
quor
storage
Caustszng
Dssovng
tank &
Saker
Weak back
quor
storage
Salt cake
make-up
Precipitator
dust
Caustic
make-up
Washng
Na: 243
S: 55.5
Na: 243
S: 55.5
Na: 239
S: 55
Na: 239
S: 55
Na: 4.2
S: 2.9
Na: 239
S: 55.5
Na: 4.6
S: 0
Na: 2.9
S: 1.4
Na: 238.7
S: 55.5
Na: 238.4
S: 55.5
(a) (b)
Unt: t/d
Bo-methano producton from kraft pup m condensates

313
Bio-methanol producti on from kraft pul p
mill condensates
Naceur Jemaa, Michael Paleologou
FPnnovations, Quebec, Canada
Abstract
Kraft pup ms have the potenta of producng and recoverng a consderabe amount of methano.
We demonstrated the technca feasbty of removng TRS compounds from the fou condensate
feed to the steam strpper or from steam strpper off gas (SOG) condensates usng hoow fber
contactor (HFC) technoogy. HFCs, whch are exceent mass transfer devces, can remove TRS
compounds from condensate at hgh effcency by usng a gas stream as a strppng medum. We
have shown that the man TRS compounds can be removed from condensates wth an effcency as
hgh as 99% wth neggbe methano and terpene osses. We aso demonstrated the technca
feasbty of usng the sufur-free, methano-rch SOG condensate as a reducng agent n the cho-
rne doxde generator. Any excess bo-methano n the SOG condensate has to be further purfed
and concentrated usng dstaton n order to produce hgh grade bo-methano for the market.
ntroduction
Evaporator and dgester condensates generated at kraft pup ms contan severa voate organc
compounds (VOCs), tota reduced suphur (TRS) compounds, and traces of back quor. The man
tota reduced suphur (TRS) compounds reported are hydrogen suphde (H
2
S), methy mercaptan
(CH
3
SH), dmethy suphde (CH
3
SCH
3
), and dmethy dsuphde (CH
3
SSCH
3
) |1, 2|. The TRS
compounds have an offensve odour and ther drect dscharge to the ambent ar or to an effuent
treatment system can rase odour concerns from the communtes near the m and/or may cause
the m to exceed ts emsson mts wth respect to these compounds. A kraft hardwood m can
generate 10-15 kg/tp of methano whe a softwood m typcay generates 7-10 kg/tp |3|. The amount of
methano generated depends on the pupng tme, temperature, and hydroxde concentraton.
Approach
Steam strppng s the domnant condensate treatment approach n the pup and paper ndustry. A
sgnfcant amount of methano can be present n the fou condensate whch ends up n the (SOGs.
These gases are commony burned n the recovery boer, power boer, me kn, or n a dedcated
ncnerator. No ma|or attempt has prevousy been made to recover or to further purfy the methano
content n these streams for use wthn the m or for sae for specfc appcatons. The ob|ectve of
ths work was to devse a cost-effectve approach to purfy the fou condensate and to recover
methano for use on ste (e.g., n the chorne doxde generator as a reducng agent). Ths w aow
kraft pup ms to stop purchasng methano from externa sources. Ms wthout steam strppers
can use ths technoogy to reduce odour around the m resutng from the sewerng of the untreat-
ed condensate. The proposed approach s based upon the use of (HFC technoogy to remove TRS
compounds from condensate ahead of the steam strpper. These contactors contan severa hoow
fbers. The condensate s aowed to fow around the fbers whe an acceptor fud, or a strppng
agent, for exampe another aqueous souton or a gaseous carrer, s aowed to fow on the nsde
of the fbers. These contactors can provde fast mass transfer wthout foodng or oadng snce the
acceptor fud and the aqueous feed souton fow on dfferent sdes of the hoow fber thereby a-
owng better contro. The HFC unt used n ths work had a dameter of about 100 mm, a heght of
about 330 mm (4 by 13 nches) and a membrane surface area of about 8.1 m
2
. Snce these fbers
are hydrophobc, ony hydrophobc compounds can dffuse nto the hoow fber membrane pores.
Water moecues as we as other hydrophc compounds are mosty excuded. The condensate at

Bo-methano producton from kraft pup m condensates

314
50C was frst ftered to remove suspended sods and then passed through the HFC unt at a fow
rate of about 5 L/mn. The ar or ntrogen fow rate was about 16 L/mn.
Results
Usng ths technoogy, as much as 99% of the TRS compounds n pup m fou condensates was
removed. The contamnated gas stream generated from the HFC system can be burned n the
recovery boer or n a power boer. The oss of methano and terpenes durng fou condensate
treatment was qute ow (about 5%). Once the TRS compounds are removed, the condensate can
be fed to a steam strpper thereby obtanng a suphur- free SOG condensate composed mosty of
methano and water (40-70% methano souton). The terpene phase can easy be separated from
the SOG condensate usng a decanter. Aternatvey, the SOG condensate whch represents a much
ower voume than the fou condensate can be treated usng an HFC to remove TRS compounds.
The recovered methano can be used for nstance as a reducng agent n the chorne doxde
generator or sod for some specfc appcatons. For hardwood pup ms, a terpene-free methano
stream can be generated. To produce pure methano for sae, the SOG condensate w have to be
dsted. The use of methano-rch soutons n the generator was evauated usng the FPInnova-
tons pot pant. A souton contanng 20-40% methano and traces of TRS compounds was em-
poyed. The terpene content was ess than 1.0 g/L and most of the terpenes were terpene acohos.
Premnary resuts ndcated that the treated SOG condensate generated as much chorne doxde
as the contro souton (20-40% pure methano souton). No ssues wth the contamnants present
n the methano-rch souton were observed durng the run.
References
1. Backwe, B.R., Mackay, W.B., Murray, F.E., Odham, W.K. 1970. Revew of kraft fou conden-
sates. Tapp | . 62(10), p. 33.
2. Neme, K. 2004. Sufur and ntrogen compounds n rectfed methano from fou condensate
strppng, TAPPI Internatona Chemca recovery Conference, TAPPI Press, Atanta,
pp. 471-482.
3. Zhu, | .Y., Yoon, S.H., Lu, P.H., Cha, X.S. 2000. Methano formaton durng akane wood pupng.
Tapp | . 83(7), pp. 65-78.
Utzaton of byproduct streams treated by wet oxdaton

315
Uti lization of byproduct streams treated by
wet oxidation
Kristian Melin, Sarada Kuppa, Raja Muddassar, Jukka Koskinen, Markku Hurme
Department of Biotechnology and Chemical Technology
Aalto University School of Chemical Technology, Espoo, Finland
Kristian.Melin@aalto.fi
Abstract
In ths work a two stage process for recovery of fue gas components from back quor s presented.
Treated back quor decomposed nto a vapor phase and a sod resdue. The vapor phase contans
vauabe organc components such as methane, acetone, carbon monoxde, besdes steam and
carbon doxde. The sods contans sodum carbonate and some char resdue. Accordng to mater-
a baance for treated back quor and carboxyc acd sats mxture vauabe fue components such
as carbon monoxde, acetone, methano, methane etc. are produced. In the experment the yed of
fue components for treated back quor was fary ow.
ntroduction
Byproduct streams such as back quor or other byproduct streams contanng a hgh amount of
organc matera are attractve due to ow cost. Both n the Nordc countres and Asan non wood
pup ms back quor s avaabe n huge amounts. Normay the byproducts are ony for energy
producton. Fues or chemcas are usuay more vauabe products than energy. The process of wet
oxdaton was at frst empoyed n pup and paper ndustry n order to oxdze waste gnn present n
back quor nto carbon doxde and water (Strehenert, 1915). When the converson s not compete
carboxyc acd sats such as acetates, formates and actates are obtaned. In addton gnn mght
precptate due to ower soubty of gnn at ower pH (Devn and Harrs, 1984). The acds sats can
be decomposed when heated to approxmatey 300-500C. Ether as sods or n aqueous souton
at hgh pressure nto fue gas contanng for exampe methane, hydrogen and other voate organc
components (| ude and Pau, 2010). Aso a sod carbonate resdue and some char are obtaned.
Experimental
Suphur free back quor evaporated to approxmatey 30 w-% sod conc. was wet oxdzed n a
mcro reactor to convert sugars and gnn to carboxyc acd sats whch decompose at a ower
temperature than gnn. The partay wet oxdzed back quor was dred and heated n the mcro
reactor from room temperature up to a temperature of 470C wthout strrng. The formed gases
were anaysed usng FTIR anayss each 20 seconds. Based on the anaysed gas composton n
the apparatus the average gas composton durng the run was cacuated. For comparson a carbox-
yc acd sampe wth composton shown n Fgure 2 was decomposed wth the same procedure.
The gas compostons, chemca oxygen demand etc. are shown n Fgure 1 and 2.


316

Fi gure 1. Therma decomposton matera baance for partay wet oxdzed back quor.

Figure 2. Therma decomposton matera baances for the carboxyc acd mxture.
Conclusions
The chemca oxygen demand has been sgnfcanty reduced and usefu fue components are
formed. However for the back quor case the yeds of fue components are ow and char remans
n the sod resdue. A the gaseous components (hydrogen and some hydrocarbons coud not be
quantfed so fue components yeds mght be underestmated.
Acknowledgements
Tekes, Aato Unversty, Fortums and Gasums foundatons are acknowedged for fundng.
wt-% g
tota mass 100,0 10,5
water 72,1 7,6
CO2 16,9 1,8
CO 7,4 0,8
Acetone 1,6 0,2
Methano 1,8 0,2
formadehyde 0,2 0,0
Baances IN OUT DIFF %
wt-% g Tota 27,6 24,3 -12,0
tota mass 100,0 27,6 ASH 11,7 9,2 -22,0
sodum acetate 6,6 1,8
sodum formate 9,4 2,6
sodum actate 4,9 1,4
sodum gycoate 4,0 1,1
Ash TG 800 C 42,5 11,7
g/g sodsg tota wt-% g
COD 1,0 28,1 tota mass 100,0 13,8
TOC 0,34 9,5 Ash TG 800C 66,3 9,2
Inorganc carbon g/g g
COD 0,7 9,9

Therma decomposton
upto temperature of 470 \C

317
References
1. Devn, H.R., Harrs, I.| . 1984. Mechansm of the oxdaton of aqueous pheno wth dssoved
oxygen, Ind. Eng. Chem. Fundam. 23(4), pp. 387-392.
2. | ude, A.O., Pau, T.W. 2010. Hydrotherma reactons of sodum formate and sodum acetate as
mode ntermedate products of the sodum hydroxde-promoted hydrotherma gasfcaton
of bomass, Green Chem. 12, pp. 2214-2224.
3. Strehenert, R.W., U.S: Patent No. 1,149,420, Aug, 1915.
Borefnery and energy savngs

318
Biorefinery and energy savings
Anna Slobodenyuk
1
, Esa Vakkilainen
2

1
Lappeenranta University of Technology, Energy Department, PhD student
2
Lappeenranta University of Technology, Energy Department, Supervising Professor
Abstract
Fnand s a country of very hgh energy consumpton per capta and ack of natura resources.
Because of rapd ncrease of fue prce, the eectrcty prce s growng too. Therefore, Fnand has
strong energy potcs forcng adopton of energy savng technooges. Improvement of technoogy,
pouton montorng, fue consumpton deveopment and reguar contro from responsbe organza-
tons coud be mechansms to acheve stabty, ndependence and proft.
Envronmenta-orented governmenta programs force research to be focused on transportaton
fues. Growng o prces affect sustanabty of economcs. Foss resources from outsde of Fnand
coud be party repaced n near future wth own second generaton bofues.
Borefneres based on exstng pup and paper ms s obvous decson for Fnand. UPM-
company s gong to bud a borefnery n South Carea, Fnand. Innovatons used n UPM pant
bud scentfc patform and methodoogy for other pro|ects n ths fed. Ongong research shoud be
abe to sove varous probems.
ntroduction
Fnnsh man ndustra energy consumers are paper and forest companes. There are severa ways
to mprove producton processes and decrease energy costs. Frst s energy montorng - compex
procedure to detect a types of possbe osses. Second s proper wastes utzaton - borefnery
nstaaton.
Transportaton needs, deveoped paper ms nfrastructure and avaabe resources are man
factors resutng possbe ntensve bofue producton. In Lappeenranta at Kaukas Pup and Paper
m 2
nd
generaton bodese refnery w be nstaed by 2014 (100 000 tons annuay). Raw matera
s softwood. Technoogy used n process s hydrotreatment of crude ta o. 2020 targets for Fnand
woud cover one fourth of tota bofue need f borefnery n Lappeenranta woud be nstaed.
Energy observaton tests present a energy fows, measure ther amount and ustrate ocaton.
Concusons descrbng detaed energy consumpton stuaton, methods and ways to ncrease en-
ergy effcency are ustratve base for decson-makng on borefnery constructon.
Experimental
Energy audt s Compex system of technca, economca, organzatona and other actvtes fo-
cused on dentfyng opportuntes to optmze the cost-effectve use of energy resources. Meas-
urements and experments are done usng number of equpment, such as therma mage sensors,
gas anaysers, fow/pressure/voume/temperature detectors, pyrometers and others. Engneers and
personne of factory are nvoved nto the process. There are many types of energy audts:
1. Premnary audt
2. Genera audt
3. Infrared thermography audt
4. Investment-grade audt
5. Pouton audt.
Pup and paper ms as we as refneres are ntensve consumers of water, eectrcty and heat.
Hence, energy audt takes qute ong tme and requres experenced audtors. Remarkabe, that

Borefnery and energy savngs

319
energy savng potenta n pup and paper ndustry s st very hgh and for some part requres no
sgnfcant nvestments.
Discussion
Probems reated to research on adopton of borefneres:
Amount and constant composton of raw matera sutabe for certan process
Technoogy deveopment (as ong as borefnery concept s under deveopment technoo-
ges coud be mproved and apped for dfferent ndustres/companes)
Fnanca aspects (cost of technoogy vares due to many factors)
Lack of educated specast wth experence n both-borefneres and pup and paper n-
dustres.
Conclusions
Combned soutons for two or more ndustra ob|ects requre huge amount of work and research. If
those two ndustres are ntensve energy consumers t s needed to fnd out ways to decrease
amount of resources used. Instead of manufacturng more and more power pants t s necessary to
thnk about current energy consumpton.
Energy observaton s perfect opton for both-pup and paper m and chemca refnng. Energy
consumpton report provdes usefu nformaton for constructon and desgn. Fnay by-products (or
even wastes) from paper factory and forestry start nnovaton opportuntes n energy sector and
transportaton.
References
1. UPM press-reease, Prkko Harrea, The Paper Tmes, 1 p. http://news.paperndex.com/New
Pro|ects_MCosures/UPM_to_Bud_the_Wordrsquos_Frst_Borefnery_Producng_
Wood-based_Bodese/.

Towards optma treatment procedure upon fractonaton of Nordc gnoceuoses usng nove
akano amne - superbase onc qud system

320
Towards optimal treatment procedure upon
fracti onation of Nordic lignocell uloses using novel
alkanol amine superbase ionic liquid system
. Anugwom
1
, P. Mki-Arvela
1
, V. Eta
1
, P. Virtanen
1
, J.-P. Mikkola
1, 2

1
Laboratory of ndustrial Chemistry and Reaction Engineering, Process Chemistry Centre,
bo Akademi University, F-20500 bo-Turku, Finland
2
Technical Chemistry, Department of Chemistry, Chemical-Biological Center, Ume University,
SE-901 87 Ume, Sweden
ntroduction
Fractonaton of gnoceuosc matera usng Swtchabe Ionc quds (SILs) as sovents was suc-
cessfuy demonstrated. The recovery and reuse for more than one fractonaton cyce |1, 2|. Fur-
thermore, seectve fractonaton of gnoceuosc matera was ustrated, ncorporaton of dfferent
acd gases upon formaton of the SIL. SILs can easy be syntheszed by passng an acd gas, such
as SO
2
and CO
2
through a mxture of a super-base such as, 1,8-dazabcyco-|5.4.0|-undec-7-ene,
(DBU) and an OH-contanng compound ke gycero (an affordabe bengn moecue aso obtaned
as a by-product of bodese synthess). The carbonate/sufonate form can smpy be swtched back
to ts startng materas by purgng the SIL nert gas (N
2
) |3, 4|.
Experimental
In order to determne the actua dssouton knetcs (.e. the rate of dssouton), a seres of exper-
ments was conducted (4, 8, 12, 16 and 24 hours, respectvey). The parameters affectng the wood
components w be dscussed. Nove DBU-based MEASO
2
SIL was used as fractaton sovent at
100C, Wood to SIL rato was 1:5, wthout any mechanca agtaton. Fresh Wood Chps (Betula
pendula) (3x3x0.2 cm)
SIL treatment of wood resuted n 37% weght reducton n 4 hours, the weght reducton reman the
same unt. The weght of the chps was reduced to 44% of ther nta weght by 24 h wth fresh SIL
under smar condtons as stated earer. The tota wood gnn amount was reduced to 4% from
20% after 24 h treatment. Furthermore, the tota amount of gucose (orgnatng from ceuose hy-
droyss n ne wth the anayss procedure) of the undssoved fracton after SIL treatment n-
creased from 42% (natve wood) to 60% after the 24 h treatment (Fgures 1 and 2). The unds-
soved matera after 24 h was effcenty fbrated as seen n the SEM mage Fgure 3.


321

Figure 1. Gucose content of the undssoved treated brch chp.

Figure 2. Knetc study of SIL treatment of brch usng the foowng Treatment condtons 100C, no
strrng, SIL: Wood (5:1), chps (3 x 3 cm).

Figure 3. SEM mage of 1) natve brch and undssoved fracton after 24 h SIL treatment of natve brch.

322
Acknowledgements
Forest custer Ltd and The Fnnsh Fundng Agency for Technoogy and Innovaton (Tekes) are
gratefuy acknowedged for fnanca support. In Sweden, the Bo4Energy program s acknow-
edged.
References
1. Anugwom, I., Mk-Arvea, P., Vrtanen, P., S|hom, R., Wfr, S., Mkkoa, | .-P. 2005. Carbo-
hydrate Poymers 87, pp. 2005-2011.
2. Anugwom, I., Mk-Arvea, P., Vrtanen, P., Damn, P., Hedenstrm, M., Mkkoa, | .-P.,
Hozforschung. Onne Do: 10.1515/hf-2011-0226.
3. Anugwom, I., Mk-Arvea, P., Vrtanen, P., Damn, P., S|hom, R., Mkkoa, | .-P. 2011. Advances 1,
pp. 452-457.
4. Anugwom, I., Mk-Arvea, P., Vrtanen, P., Mkkoa, | .-P. PCT/FI2011/050959.
Sustanabe Resource Technoogy (SuReTech)

323
Sustainable Resource Technology (SuReTech)
Eva Nordberg Karlsson
1
, Charlotta Turner
2

1
Lund University, Department of Chemistry, Biotechnology,
P.O. Box 124, SE-221 00 Lund, Sweden (www.biotek.lu.se, eva.nordberg_karlsson@biotek.lu.se)
2
Lund University, Department of Chemistry, Centre for Analysis and Synthesis,
P.O. Box 124, SE-221 00 Lund, Sweden (www.kilu.lu.se/cas, charlotta.turner@organic.lu.se)
Abstract
We a need to contrbute to a more sustanabe deveopment - a fact that has become qute cear
observng extreme weathers and dmnshng foss fue sources. In ne wth the 12 Prncpes of
Green Chemstry [1], (recommendng the use of safer sovents, cataysed reactons, energy eff-
cent processes and renewabe feedstocks), research wthn the SuReTech program ams at deve-
opng technooges for the recovery of hgh-vaue compounds from forestry and agrcutura byprod-
ucts. The dea s to create vaue addton, by addng products to aready utzed resources n ne
wth borefnery concepts. Extractons of antoxdzng compounds from byproducts are thus made
by use of carbon doxde and water as sustanabe sovents and combned wth bocataytc conver-
sons for the creaton of compounds wth desred propertes. The byproducts, used as startng ma-
teras, are seected based on annua voumes from the Swedsh agrcutura, food and forestry
ndustry. Substtuents on the compounds are modfed by bocatayss, e.g. usng thermostabe
carbohydrate convertng enzymes seected to ft the condtons n the extracton step. The m-
portance of combnng dfferent scentfc feds to enabe creatvty n sustanabe deveopment s
hghghted.
Value added processing of byproducts from forestry
To mnmze the resources necessary to produce sovents as we as the need of destructon of the
sovents after use, gudenes for seecton wth respect to envronmenta, heath and safety propertes
have been presented |2|. In ne wth the gudenes, pressursed hot water mxed wth ethano was
seected to extract antoxdants from forestry byproducts (bark of spruce |3| and brch |4| (Fgure 1).
Other bark-resources of nterest orgnate from pne, shown to be rch n catechn, but aso contanng
quercetn |5|, whch we n prevous work have extracted from agrcutura (onon) waste n a procedure
nvovng hot pressurzed water foowed by an enzymatc step |6|, used to obtan a unform agycone
product. In ths case, degycosyaton aso ncreases the antoxdzng power. Moreover, addton or
subtracton of substtuents (gycosyaton or acyaton, by gycosdases/gycosytransferases and -
pases, respectvey) affects soubty-aowng use n dfferent sovents (hydrophc or hydrophobc -
and n the onger perspectve a broader use).

Sustanabe Resource Technoogy (SuReTech)

324

Figure 1. Fowchart showng processng of forestry resdues. Vaue added steps are boxed (grey
dashed ne). Extracton and enzymatc converson can be ether on-ne or ndependent steps.
Waste resdues after the added processng are st appcabe for energy producton (dotted box).
The interdisciplinary approach
Borefnery concepts are predcted to gve envronmenta and soco-economc benefts n the ong
term. However, anayses are necessary to fnd bomass feedstocks/appcatons wth the owest
opportunty costs and best envronmenta performance. In our pro|ect we have seen envronmenta
benefts of new processes for added vaue products |7|. Socoeconomc anayss s ongong.
Acknowledgement
We wsh to acknowedge fnanca support from the Swedsh Research Counc Formas for fundng.
References
1. Anastas, P., Warner, | . 1998. Green chemstry: theory and practce, Oxford Unversty Press.
2. Capeo, C., Fscher, U., Hungerbher, K. 2007. What s a green sovent? A comprehensve
framework for the envronmenta assessment of sovents. Green Chem 9, p. 927.
3. Co, M., Fagerund, A., S|oberg, P., Sunnerhem, K., Engman, L., Turner, C. 2012. Extracton of ant-
oxdants from spruce (Pcea abes) bark usng eco-frendy sovents. Phytochem Ana 23, p. 1.
4. Co, M., Koskea, P., Ekund-Akergren, P., Kng, | .W., S|oberg, P., Turner, C. 2009. Pressurzed
qud extracton of betun and antoxdants from brch bark. Green Chem 11, p. 668.
5. Bocaandro, C., Sanhueza, V., Gomez-Caravaca, A.M., Gonzaez-Avarez, | ., Fernandez K,
Roecke, M., Rodrguez-Estrada, M.T. 2012. Comparson of the composton of Pinus ra-
diata bark extracts obtaned at bench- and pot-scaes. Ind Crops Prod 38, p. 21.
6. Turner, C., Turner, P., | acobson, G., Wadeback, M., S|oberg, P., Nordberg Karsson, E.,
Markdes, K. 2006. Subcrtca water extracton and -gucosdase-catayzed hydroyss of
quercetn n onon waste. Green Chem 8, p. 949.
7. Lndah, S., Ekman, A., Khan, S., Wennerberg, C., Br|esson, P., S|berg, P., Nordberg Karsson, E.,
Turner, C. 2010. Exporng the possbtes of usng a thermostabe mutant of -gucosdase for
rapd hydroyss of quercetn gucosdes n hot water. Green Chem. 1, p. 159.
Identfcaton of degradaton products from brch wood n water extracts

325
dentification of degradation products from birch
wood in water extracts
Marc Borrega
1
, Klaus Niemel
2
, Herbert Sixta
1

1
Department of Forest Products Technology, School of Chemical Technology, Aalto University,
2
VTT Technical Research Centre of Finland, Tietotie 2, Espoo, F-02044 VTT, Finland
ntroduction
Hot water treatment of wood pror to pupng operatons s recognzed as a potenta method to
extract the hemceuoses and convert them nto vaue-added products. In addton to ogo- and
monosacchardes orgnatng from the carbohydrates, gnn fractons and organc acds such as
acetc acd can be typcay found n the water extract |1|. Under ntense extracton condtons, con-
sderabe amounts of other degradaton products are aso formed |2|. The goa of ths study was to
dentfy ow-moar mass degradaton products from brch wood n water extracts produced at var-
ous extracton ntenstes.
Experimental
Brch wood chps were extracted wth hot water n a 10 L batch reactor, wth a qud-to-wood rato
of 3:1 g/g. A hgh-pressure pump was used to contnuousy re-crcuate the water through the chp
bed. The temperature n the reactor was rased to the setup temperature (180C, 200C or 220C),
and after an sotherma treatment tme, the water extract was draned through a bottom vave. The
ntensty of any hot water extracton was determned by the we-known P-factor. The water extracts
were anayzed for mono- and ogosacchardes, furfura, 5-hydroxymethyfurfura (HMF) and acetc
acd by HPLC, and for aromatc compounds and poar hydroxy acds by GC-MS. The anaytca
procedures w be descrbed n more deta esewhere.
The water extracts produced at the owest extracton ntenstes (up to a P-factor -1000) were rch
n xyose monomers and xyo-ogosacchardes (Tabe 1). Increasng extracton ntensty ed to
parta degradaton of ceuose n wood, athough ony sma amounts of dssoved gucose mono-
and ogomers were found n the extracts. Increasng amounts of degradaton products from carbo-
hydrates, such as furfura, HMF and aphatc acds were aso formed. In addton to acetc acd, the
GC-MS anayses reveaed numerous poar hydroxy acds (Fgure 1). The most abundant hydroxy
acds ncuded gycoc and 3-deoxypentonc acds, apparenty many derved from xyose.
More than 30-40 aromatc monomers and up to 30 aromatc dmers, orgnatng from the gnn,
were found n the water extracts (Fgure 1). A hgher amount of aromatc compounds derved from
syrngy unts, as compared to those derved from guaacy unts, were detected. The most abun-
dant monomers typcay ncuded syrngadehyde, syrngo, syrngyacetone and 1-hydroxy-3-
syrngyacetone, whereas syrngaresno was the man dmer. A detaed dentfcaton of degrada-
ton products w foow n an extended pubcaton. Such dentfcatons may provde usefu nfor-
maton for assessng the sutabty of water extracts for further appcatons.

Identfcaton of degradaton products from brch wood n water extracts

326
Table 1. Concentraton (g/L) of sugars, furfura, HMF, acetc acd and hydroxy acds n the water
extracts. Sampe name ndcates extracton temperature and sotherma extracton tme. XOS =
xyo-ogosacchardes; COS =ceo-ogosacchardes.
Sampl e P-factor Xylose XOS Glucose COS Furfural HMF Aceti c
aci d
Hydroxy
aci ds
180.10
180.30
200.10
220.2
200.30
220.25
262
766
1057
1322
3600
8166
1.43
11.17
10.50
11.36
2.74
0.18
14.97
16.94
11.59
7.79
0.22
0.03
0.08
0.28
0.33
0.56
2.05
1.94
0.56
0.92
0.81
0.90
0.64
0.44
0.46
3.79
5.00
7.64
18.52
16.11
0.04
0.19
0.22
0.31
1.98
3.51
1.35
5.27
6.23
10.39
20.01
21.20
0.24
0.66
0.98
1.88
2.54
2.84

Figure 1. GC-MS chromatogram of sampe 220.25, wth seected dentfcatons: 1, actc acd; 2,
gycoc acd; 3, syrngo; 4 and 5, 3-deoxy-erythro- and threo-pentonc acds (actones); 6, syrnga-
dehyde; and 7, syrngaresno.
Acknowledgements
Fundng by FIBIC Oy and Tekes wthn the FuBo | ont Research 2 program s gratefuy acknow-
edged.
References
1. Garrote, G., Domnguez, H., Para|, | .C. 1999. Hydrotherma processng of gnoceuosc materas.
Hoz Roh. Werkst. 57, pp. 191-202.
2. Borrega, M., Nemnen, K., Sxta, H. 2011. Degradaton knetcs of the man carbohydrates n
brch wood durng hot water extracton n a batch reactor at eevated temperatures. Boresour.
Techno. 102, pp. 10724-10732.
Akane oxdaton pretreatment of wood materas to produce ethano

327
Alkali ne oxidation pretreatment of wood materials
to produce ethanol
Anne Kallioinen
1
, Matti Siika-aho
1
, Eemeli Hytnen
1
, Maija Hakola
2
, Stella Rovio
1
,
Tarja Tamminen
1
, Timo Repo
2
, Markku Leskel
2
, Niklas von Weymarn
1, 3

1
2
University of Helsinki
3
Presently Mets Fibre Ltd
Abstract
Akane oxdatve fractonaton of woody materas and sugarcane bagasse was deveoped. The
enzymatc hydroyss of akane oxdsed materas worked we even wth ow enzyme dosages and
at hgh dry matter condtons. The resutng ethano yed was on a hgh overa eve. Process con-
cepts were deveoped based on the resuts and the estmates of the feasbty of the process were
cacuated. The resuts ceary showed the promse of the new fractonaton method, but aso nd-
cated the key chaenges n scang up the technoogy to fu ndustra scae.
ntroduction
Pant bomass s the ma|or ready avaabe renewabe source to substtute o as raw matera n
producton e.g. qud fues and chemcas. Feasbe utzaton of the ce wa components by the
sugar route requres effcent methods to fractonate woody raw materas nto utzabe non-
carbohydrate fractons and ready hydroysabe ceuose fracton for hydroyss. Akane oxdaton
s a method, whch fractonates effcenty woody bomass usng smpe chemcas and md process
condtons, gvng carbohydrates wth hgh enzymatc hydroysabty and ow nhbtor content and a
gnn fracton wth nterestng technca propertes.
Earer deveoped cataytc oxdaton method for pretreatng gnoceuosc matera was opt-
mzed and an akane oxdaton pretreatment method was deveoped and optmzed (1, 2). Varous
reacton condtons (qud voume, sod content and partce sze) were studed wth spruce and
sugar cane bagasse.
Akane oxdaton pretreatment, wth or wthout catayst, was shown to be an effcent and hgh
yedng method to separate ceuose from gnn, as compared to steam exposon (Fgure 1). Ox-
daton at hgher sod contents and voumes needs further deveopment and advanced reactor sys-
tems. The akane oxdaton pretreatment aowed shorter hydroyss tmes and ceary ower en-
zyme dosages n enzyme hydroyss, as compared to steam exposon pretreatment. The akane
oxdsed materas worked we n processng at hgh dry matter content and showed no nhbton n
ethano fermentaton, whereas enzymatc hydroyss and fermentaton of steam expoded materas
were sower n hgher dry matter content (Fgure 1). Hgh ethano yeds n short fermentaton were
obtaned wth akane oxdaton athough the apped yeast was not abe to use pentoses present n
the raw materas. A maxmum ethano end concentraton of 49 g/ was obtaned by spruce at 12%
dry matter content.

Akane oxdaton pretreatment of wood materas to produce ethano

328

Figure 1. Fermentaton of akane oxdsed spruce and bagasse and steam expoded spruce and
bagasse at 12% d.w. at 35C wth commerca yeast Red Star. 6 hours prehydroyss wth Cec
Ctec2+Htec enzyme mxture (enzyme rato was 90:10; tota dosage 15mg/g) at 50C, pH 5.
Frst estmates of proftabty of a few dfferent deveoped ethano producton concepts based on
akane oxdaton pretreatment were aso cacuated. Producton costs exceed the assumed ethano
saes prce (0.6 C/L) n most of the studed cases. Key varabe cost tems were feedstock and en-
zymes, as we as eectrcty n the ntegrated sugarcane |uce and bagasse ethano cases. Tota
capta nvestment n the ethano producton processes were estmated to be hgh especay due to
the pre-treatment, sod-qud separaton and requred chemca recovery equpment. Another very
nterestng concept gvng sgnfcant cost savngs woud be the repurposng of cosed ms.
Conclusions
Very good enzymatc hydroysabty and hgh ethano yeds n short fermentaton tme were ob-
taned wth the akane oxdaton pretreatment. Further research s needed for obtanng more rea-
be nformaton for process scae-up and process equpment dmensonng and seecton.
Acknowledgements
Fnanca support from Tekes BoRefne program (pro|ect SugarTech) and from the Academy of
Fnand s acknowedged (pro|ect CaDeWo).
References
1. Hakoa, M., Kaonen, A., Keme, M., Lahtnen, P., Lanknen, E., Leske, M., Repo, T., Rekkoa, T.,
Ska-aho, M., Uustao, | ., Vuorea, S., von Weymarn, N. 2010. Lberaton of ceuose
from the gnn cage: A cataytc pretreatment method for the producton of ceuosc ethano.
ChemSusChem 3, pp. 1142-1145.
2. Rovo, S., Kaonen, A., Tammnen, T., Hakoa, M., Leske, M., Ska-aho, M. 2012. Cataysed
akane oxdaton as a wood fractonaton technque. BoResources 7, pp. 756-776.
Enzymes - toos to upgrade bomass to hgh-vaue products

329
Enzymes tool s to upgrade bi omass to
high-value products
Stina Grnqvist, Jaakko Pere, Matti Siika-aho, Anna Suurnkki, Terhi K. Hakala

The natura resources both on and and n water are sub|ect to steady ncreasng demands on a
goba eve due to the growng word popuaton, cmate change, depeton of foss raw materas
and ncreasng envronmenta oad. The urge to ensure optma, cascaded use of bomass re-
sources has been the drvng force for varous exstng borefnery and boeconomy ntatves. In
borefneres bomass s processed n a sustanabe manner to varous marketabe products and
energy. Boeconomy can be seen as an expanson of the borefnery concept as t ncudes aso the
expotaton of boogca phenomena n processng of non-boogca raw materas or producton of
non-bo products expotng certan boogca prncpes.
Botechnca processng by enzymes offers a possbty to seectvey and effcenty turn bomass
resdues and sde streams nto new materas, chemcas, energy, food and feed n a sustanabe
and affordabe manner (Fgure 1). Due to ther specfy enzymes are powerfu toos to sove the
chaenges reated to the utsaton of bomass n new ways. Compared to tradtona manufacturng
systems, ndustra processes can be performed by enzymes or mcrobes wth sgnfcanty ess
energy, water and wthout the need of aggressve chemcas. Thus, as a resut of ndustra botech-
noogy a more effcent use of natura resources as we as reduced energy and water consumpton
s obtaned.

Figure 1. Enzyme-aded processng of bomass.
A wde varety of potenta enzymes sutabe for processng of forest and agrcutura resdues and
food sde streams are sted n Tabe 1. These enzymes are expected to pay a key roe n future
bomass processng.

Enzymes - toos to upgrade bomass to hgh-vaue products

330
Table 1. Enzymatc toos for bomass upgradng.
Component Enzyme group Tools Expl oitation
Cellulose Ceuases EG Depoymersaton, structure modfcaton
CBH Structure modfcaton
Mx Tota hydroyss
Hemi cellulose Hemceuases Xyanases,
mannanases
Depoymersaton
Accessory enzymes Sde-group ceavng, transfer reactons for
depoymersaton, structure modfcaton,
functonasaton
Mx Tota hydroyss
Lignin Lgnn oxdzng
enzymes
Laccases Radca formaton, functonazaton,
depoymersaton wth medator
LP, MnP Oxdaton, depoymersaton wth medator
Extractives Enzymes actng on
extractves
Lpases, Laccases Degradaton by hydroyss, oxdaton
Pect in Pectnases Pectnases Ceavage, demethyaton
Protei n Proteases Varous proteases Depoymersaton, crossnkng
Others Hydrophobns
Swoenns
Surface hydrophobsaton
Loosenng of ceuose fbre structure

Enzyme technooges for the producton of hgh-vaue poymers and chemcas from forest
resources

331
Enzyme technologies for the producti on of high-value
polymers and chemicals from forest resources
Galina Mai-Gisondi
1
, Filip Mollerup
1
, Maryam Foumani
2
, Thu Vuong
2
, Weijun Wang
2
,
Ossi Turunen
1
, Maija Tenkanen
3
, Emma Master
1, 2

1
Aalto University, Dept of Biotechnology and Chemical Technology, Kemistintie 1, Espoo, Finland
2
University of Toronto, Dept of Chemical Engineering and Applied Chemistry, Ontario, Canada
3
University of Helsinki, Department of Food and Environmental Sciences, Helsinki, Finland
Abstract
Accessory hemceuases and carbohydrate oxdases were produced to taor the branchng struc-
ture of hardwood xyans and for ste-specfc actvaton of seectve hydroxy groups, respectvey.
Whe the accessory hemceuases were chosen to ncrease the unformty of hemceuose recov-
ered from pretreated wood fbre, the carbohydrate oxdases can factate regoseectve chemca
dervatzaton of poysacchardes wth fewer protecton/deprotecton steps. In partcuar, accessory
hemceuases seected for ths study ncude a-arabnofuranosdases from gycosde hydroase
(GH) famy 62, a-gucurondases from GH115, and acetyxyan esterases from carbohydrate esterase
(CE) famy 1. Carbohydrate oxdases ncude ogosaccharde oxdases and gaactose oxdases of
funga orgn. Fttng wth our am to harness enzyme specfcty to synthesze hgh-vaue bopoymers
from wood poysacchardes, n a cases the enzymes were seected and further engneered for en-
hanced actvty on poymerc substrates, ncudng xyans, ceuose, and gaactogucomannan.
ntroduction
The producton of hgh vaue co-products can sgnfcanty mprove the process economcs of gno-
ceuosc borefneres whose man product s boenergy. Ths s partcuary true for forest borefn-
eres ocated n northern countres that rey on sower growng trees that produce hgh-quaty fbre.
The am of our research s to engneer enzymes that can be used to synthesze new, hgh-vaue
poymers and chemcas from renewabe pant materas. Our enzyme approach harnesses 1) the
rego- and stereo-specfcty of enzyme catayzed reactons that have evoved to transform gnoce-
uosc substrates, and 2) our abty to manpuate proten functon usng genetc toos, to enhance
or ater proten functon. Notaby, the cataytc specfcty of enzymes s mportant to reproducby
taor the composton and performance of wood poysacchardes. Moreover, the aqueous and md
reacton requrements of enzyme catayzed reactons can hep retan the degree of poymerzaton
of xyans and gucomannans recovered from pretreatment hydroysates.
Experimental
Each enzyme construct was recombnanty produced n ether E. coli or P. pastoris and purfed to
homogenety usng NNTA affnty resn and on chromatography. Whe protens expressed n P.
pastoris were secreted to the cuture medum, protens expressed n E. coli were recovered from
ce ysates. Inducton of recombnant proten expresson n P. pastoris cutures at 15C and n the
presence of casamno acds and eupeptn ncreased the stabty of chmerc enzymes produced
wth a bactera CBM.
Commerca compounds used to bochemcay characterze purfed hemceuases ncuded pa-
rantropheny acetate, pNP-arabnose, aduronc acds, ceuose acetate, gucuronoxyan, and arab-
noxyan; acetyated xyan was aso produced from gucuronoxyan. In addton to xyan, poysac-
charde oxdases were tested usng gaactomannan, xyogucan, carboxymethy ceuose, and re-
generated amorphous ceuose. Product formaton was montored usng standard chromogenc
detecton or by HPLC. In addton to actvty measurement, affnty ge eectrophoress was used to
characterze the effect of CBM addton on enzyme bndng to varous poysacchardes.

Enzyme technooges for the producton of hgh-vaue poymers and chemcas from forest
resources

332
Result and summary
Gven our am to deveop enzymes for hemceuose and ceuose engneerng rather than conver-
son to sugars, the enzymes were seected based on havng comparatvey hgh actvty on ogo-
merc or poymerc substrates (Tabe 1) |1, 2, 3, 4|. Moreover, to assess the potenta of carbohy-
drate-bndng modues (CBMs) to ncrease enzyme acton on poymerc substrates, bactera CBMs
from fames 3, 6, 11, 22, 29 and 44 were covaenty nked to partcuar enzyme targets (Tabe 1).
Table 1. Enzymes produced and characterzed n the current study.
Catalyti c Domain Predi ct ed Activity Linked CBM fami ly
a

Gaactose oxdase Oxdzes prmary acoho of gaactose 29
Ogosaccharde oxdase Oxdzes the acoho of the anomerc carbon 3, 11, 22, or 44
CE1 Acetyxyan esterase 3 or 6
GH62 arabnofuranosdase None added
GH115 a-gucurondase None added
a.
Bndng affntes are revewed n Boraston et a. |5|

Whe a enzymes targeted were of funga orgn, enzymes seected from GH62 and GH115 were
functonay expressed to hgh yed n E. coli. Moreover, a enzyme actvtes were retaned after
covaent nkage to a bactera CBM. Premnary resuts wth seected oxdases ndcate that the
addton of a CBM does not affect enzyme stabty, but ncreases the specfc actvty of the enzyme
on correspondng poysacchardes. On-gong knetc anayses and affnty ge eectrophoress w
assess the contrbuton of bndng affnty to enzyme effcency on poymerc substrates.
References
1. van den Brnk, | ., de Vres, R.P. 2011. Funga enzyme sets for pant poysaccharde degradaton.
App. Mcrobo. Botechno. 91(6), pp. 1477-1492.
2. Chong, S.L., Battaga, E., Coutnho, P.M., Henrssat, B., Tenkanen, M., de Vres, R.P. 2011. The
-gucurondase Agu1 from Schzophyum commune s a member of a nove gycosde
hydroase famy (GH115). App. Mcrobo. Botechno. 90(4), pp. 1323-1332.
3. Parkka, K., Leppnen, A.S., Ptknen, L., Reunanen, M., Wfr, S., Tenkanen, M. 2010. Oxdaton
of poysacchardes by gaactose oxdase. | . Agrc. Food. Chem. 58(1), pp. 262-271.
4. Lee, M.H., La, W.L., Ln, S.F., Hsu, C.S., Law, S.H., Tsa, Y.C. 2005. Structura characterzaton
of gucoogosaccharde oxdase from Acremonum strctum. App. Envron. Mcrobo.
71(12), pp. 8881-8887.
Boraston, A.B., Boam, D.N., Gbert, H.| ., Daves, G.| . 2004. Carbohydrate-bndng modues: fne-
tunng poysaccharde recognton. Bochem. | . 382, p. 769-781.
Thermostabzng mutatons mproved the stabty of Trchoderma reese GH11 xyanase n hgh
pressure

333
Thermostabilizing mutations improved the stability of
Trichoderma reesei GH11 xylanase in high pressure
H. Li
1
, L. Murtomki
2
, M. Leisola
1
, O. Turunen
1

1
Department of Biotechnology and Chemical Technology, Aalto University, Espoo, Finland
2
Department of Chemistry, Aalto University, Espoo, Finland
Abstract
Hgh pressure can be utzed n botechnoogca appcatons, e.g. n the treatment of food mater-
as and gnoceuose. Hgh pressure s an extreme condton that nactvates the enzymes, at-
hough n a mted range t may aso ncrease enzyme actvty. Ony few earer studes have been
reported to show how mutatons changng the thermostabty affect the pressure stabty. We stud-
ed the pressure stabty of dsuphde brdge mutants of Trichoderma reesei xyanase XYNII at
pressure 500-5 000 bar. The nactvaton of XYNII and ts mutants was strongest above the pressure
of 4 000 bar. We found that the pressure stabty order correated wth the thermostabty order of the
XYNII mutants. In combnaton wth hgh pressure, a md heatng aready nactvated the wd type
enzyme, whereas the thermostabzng mutatons argey counteracted ths effect. Our resuts showed
that thermostabzaton mutatons may ncrease the performance of enzymes at hgh pressure.
ntroduction
Endoxyanases (EC 3.2.1.8) are wdey used and have much potenta n the food, feed, paper and
bofue ndustres. However, hgh temperature and pH mt the utsaton of xyanases n ndustra
appcatons. Therefore, the engneerng of famy GH11 xyanases to toerate extreme condtons
has been a goa n a arge amount of ste-drected and random mutageness studes. Ony a few
enzymatc botechnoogca processes utse hgh pressure, athough there can be unutsed poten-
ta n ths area. Md pressure ncreases enzyme stabty, whch mght be utsed n ndustra pro-
cesses (Krsch et a., 2011). In addton, pressure pretreatment aso enhanced the xyan remova
from Eucayptus Kraft pup by xyanase enzyme (Overa et a., 2012). If hgher pressure and other
condtons together are destructve to enzymes n ndustra appcatons, then deveopng enzymes
to toerate these condtons may have botechnoogca reevance. In ths study, we tested how our
earer mutants of T. reesei XYNII toerated hgh pressure.
Experimental methods
U111 hgh pressure devce (KGT Kramer, Poand) was used to generate pressure for the stabty
experments at pressure range of 500-5 000 bar. T. reesei XYNII wd type and thermostabe mu-
tants DS2, DS5 and DB1 made by ste-drected mutageness were from the earer studes (| ns et
a., 2004; Xong et a., 2004). The enzymes were ncubated for 17 hours n the pressure devce and
the resdua enzyme actvty was measured by DNS (3,5-dntrosasyc acd)-method.
Results
Three thermostabe mutants of T. reesei XYNII were used to test ther behavour at hgh pressure.
The thermostabty propertes of XYNII and the three mutants are summarsed n Tabe 1. The
stabty experments showed that T. reesei XYNII s very stabe at hgh pressure (Fgure 1A); the
nactvaton was fast ony above 4 000 bar. The mutants were ony sghty more stabe at 22C.
When heat was ntroduced nto the system, the pressure and heat together, especay at 40C,
were very destabzng for the wd type XYNII (Fgure 1B). The mutatons, especay the most
stabzng mutant combnaton (DB1), protected aganst the harmfu effect of combned heat and
pressure.

Thermostabzng mutatons mproved the stabty of Trchoderma reese GH11 xyanase n hgh
pressure

334
Table 1. Thermostabty of XYNII and ts mutants (| ns et a., 2004; Xong et a., 2004).

Xylanase T
opt
(C) T
half
at 65
o
C T
m
(C)
XYNII 56-62 <1 mn 63
DS2 52-59 10 mn 65
DS5 56-62 110 mn 68
DB1 63-74 >56 h 82

Figure 1. Inactvaton of XYNII and ts mutants as a functon of pressure. The resuts are shown for
experments at 22C (A) and 40C (B). Symbos: XYNII (), DS2 (), DS5 (), and DB1 (). Fg-
ures are modfed from L et a., 2012.
Conclusions
Thermostabty order of xyanase mutants correated wth pressure stabty order, whch was
XYNII<DS<DS5<DB1. Our resuts ndcated that at ow temperatures (beow 22
o
C) there may be
no essenta dfference n pressure stabty between XYNII and ts mutants. Therma nactvaton
appeared to domnate under hgh pressure at eevated temperatures. In concuson, thermostab-
zaton of enzymes can be mportant for appcatons n hgh pressure.
References
1. | ns, | ., Turunen, O., Lesoa, M., Derrck, P., Rouvnen, | ., Vanotao, P. 2004. Characterzaton of
mutant xyanases usng fourer transform on cycotron resonance mass spectrometry: Stabzng
contrbutons of dsufde brdges and N-termna extensons. Bochemstry 43, pp. 9556-9566.
2. Krsch, C., Zetz, C., Smrnova, I. 2011. Deveopment of an ntegrated therma and enzymatc hy-
droyss for gnoceuosc bomass n fxed-bed reactors. Hozforschung 65, pp. 483-489.
3. L, H., Murtomk, L., Lesoa, M., Turunen, O. 2012. The effect of thermostabsng mutatons on
the pressure stabty of Trichoderma reesei GH11 xyanase. Prot. Eng. Des. Se.,
Do:10.1093/proten/gzs052.
4. Overa, S.C., Fgueredo, A.B., Evtugun, D.V., Sarava, | .A. 2012. Hgh pressure treatment as a too for
engneerng of enzymatc reactons n ceuosc fbres. Boresour. Techno. 107, pp. 530-534.
5. Xong, H., Fene, F., Lesoa, M., Turunen, O. 2004. Engneerng the thermostabty of Trchoderma reese
endo-1,4--xyanase II by combnaton of dsuphde brdges. Extremophes 8, pp. 393-400.
0
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A
Some aspects of the changes n the brch wood morphoogca structure and ts components
composton n the acdc hydroyss process

335
Some aspects of the changes in the birch wood
morphological structure and its components'
composition in the acidic hydrolysis process
Aivars Zhurinsh, Galina Dobele, Janis Rizhikovs, Aigars Paze, Tatiana Dizhbite, Lubova Belkova

Latvian State nstitute of Wood Chemistry, 27 Dzerbenes Str., Riga LV-1006, Latvia
aivarsz@edi.lv
Abstract
Despte the huge scope of research, wood s st nsuffcenty utsed as the source for obtanng
basc substances for chemca and pharmaceutca producton. Pre-treatment of wood s a substanta-
y mportant stage to make ts components more accessbe for converson to vauabe products. Our
goa was to nvestgate the mpact of the md hydroyss pre-treatment of brch wood for mprovng the
ceuosc part accessbe to pyroyss for obtanng sugars and especay anhydrosugars.
Lgnoceuose (LC) was obtaned after separatng hemceuoses from brch wood chps by treatng
wth 3% of suphurc acd from wood o.d.m. and the foowng acd hydroyss wth steam n the tem-
perature range of 100-180
durng 60 mn, wth subsequent aqueous washng of wood resdues

t 4.5. From LC, hooceuose was soated and degree of poymersaton was detected, as we
as -, - and -ceuose content. EPR spectroscopy parameters were determned drecty from the
spectrum, and the amount of paramagnetc centres (PMC) and con|ugaton unts was cacuated.
Results
Important nformaton about the changes n LC was obtaned from electron paramagnetic reso-
nance (EPR), whch showed changes n the organc free radcas amount (Fgure 1). The EPR
spectra of gnoceuoses, obtaned by hydroyss at dfferent temperatures (100-180
), are char-
actersed by the presence of stabe PMC. Takng nto account the hydroyss condtons, the regs-
tered PMC are assgned to the stabe free radcas of poycon|ugated systems (PCS), whch can be
evauated by the amount and szes of con|ugaton unts. Wth ncreasng hydroyss temperature,
the vaue of the g-factor graduay decreases from the vaues, typca for the ocasaton of PMC on
oxygen atoms (for exampe, for the phenoxy radcas of the untreated wood gnn), to the vaues,
typca for PCS. The parameter n of EPR spectra, correspondng to the average number of the
fragments ncuded n the regon of the deocasaton of the non-con|ugated eectron of PMC, char-
acterses the sze of the con|ugaton unts. In the case of ncreasng wood hydroyss temperature,
the n vaue ncreases, begnnng wth the temperature 130
, showng the progress of the process-

es of condensaton and aromatsaton n the gnn (gnoceuose) structure, especay markedy at
160-180
. The amount of con|ugaton unts, takng nto account the compexty of the structure of
the natura poymer wth a system of poycon|ugated PMC, approxmatey corresponds to the con-
tent of stabe PMC of gnoceuoses. The deveoped processes of condensaton n the gnoceu-
ose structure are ndcated by the ncrease n the content of PMC and, correspondngy, con|uga-
ton unts. Wth ncreasng hydroyss temperature above 130
, the formed poycon|ugated sys-

tems of gnoceuoses are eveny dstrbuted throughout the voume of the organc matrx, changng
the nature of the subsequent therma degradaton. Wth smutaneous decreasng (see Tabe 1)
degree of poymersaton (DP) but ncreasng hydroyss temperatures above 150C, pseudognn
arose, and t s reasonabe to beeve that condensaton reactons between gnn and ceuose
occurred; hence, tradtona component detecton methods were not sutabe.

Some aspects of the changes n the brch wood morphoogca structure and ts components
composton n the acdc hydroyss process

336
Table 1. Changes n the free radcas concentraton and DP n LC dependng on pre-treatment
temperature.
Hydrolysis temperature,
o
C g-factor n DP
Brch wood 2,00458 8,653560 553
100 2,00414 9,935548 436
110 2,00427 9,278498 359
120 2,00409 9,935548 342
130 2,00418 10,67404 304
140 2,00395 12,12759 260
150 2,00377 13,93515 170
160 2,00356 15,81822 -
180 2,00337 17,30583 -

Figure 1. Content of -, - and - ceuose n the LC dependng on pre-treatment temperature.
The content of -, - and - ceuose n the LC strongy depends on the pre-treatment temperature
(Fgure 1), and the - ceuose content ncreased up to a temperature of 120C, but after that de-
creased and the content of the -ceuose ncreased, whch testfed the depoymersaton of ceu-
ose macromoecues.
Acknowledgement
The work was supported by the ERAF pro|ect No. 2010/0297/2DP/2.1.1.1.0/10/APIA/VIAA/024
"Deveopment of an nnovatve technoogy of evogucosan producton and utsaton of by-products".
0
20
40
60
80
100
O
r
n
a
r
c
h
1
1
0
1
3
0
1
5
0
Temper atur e, C
C
o
n
t
e
n
t
,

%
-ceuose -ceuose -ceuose
Low temperature sufonaton of gnoceuose for effectve bomass deconstructon and converson

337
Low temperature sulfonation of lignocellulose for
effective biomass deconstruction and conversion
Kai Toven, Karin yaas
Paper and Fibre Research nstitute (PF), Hgskoleringen 6B, NO-7491 Trondheim, Norway
Abstract
Sufte based pretreatment of Norway spruce was studed, comparng a prevousy pubshed sufte
pretreatment process (SPORL) to two modfed sufte pretreatment concepts. To nvestgate the
effects of hemceuose pre-extracton a combned Hot water - SPORL process was tested. Fur-
ther, n a modfed process, here termed "Low temperature sufonaton", the effect of ncreased
gnn remova by seectve sufonaton at md acdc bsufte condtons was nvestgated (cf. the
Borregaard BALI process). Sgnfcanty hgher ceuose converson was found usng ths method,
than usng the SPORL or the Hot water - SPORL process. Enzymatc saccharfcaton yeds n-
creased wth the degree of degnfcaton. Rather extensve dssouton of gnosufonates was ob-
taned whe avodng severe hemceuose degradaton. Hence, ow temperature sufonaton of
spruce gave effcent fbre deconstructon, ceuose converson and gnosufonate formaton.
ntroduction
Few pretreatment technooges have acheved satsfactory enzymatc saccharfcaton yed for
softwoods due to ts strong recactrance. However, recenty sufte processng has shown proms-
ng resuts. In Norway Borregaard has apped for a patent regardng sufte based borefnng n
genera, termed the BALI process |1|, currenty operatng at demo scae. Others have aso demon-
strated hgh enzymatc saccharfcaton and ow nhbtor formaton upon sufte pretreatment of
softwood |2|. Ths atter process, termed SPORL (sufte pretreatment to overcome recactrance of
gnoceuose) gave moderate degnfcaton and good hemceuose remova. In SPORL, hemce-
uose remova was consdered |ust as crtca as gnn sufonaton for ceuose converson. The
ob|ectve of the present study was to compare SPORL to two aternatve sufte based pretreatment
concepts. Frsty, hot water extracton was ntroduced pror to SPORL treatment to nvestgate ef-
fects of hemceuose pre-extracton. Secondy, a modfed bsufte process (Low temperature su-
fonaton) was tested to nvestgate effects of ncreased gnn remova by seectve sufonaton at
md acdc bsufte condtons.
Experimental
Norway spruce wood chps from a Norwegan paper m were used. Hemceuose pre-extracton
was done by hot water treatment (160C, 5 hours). SPORL pretreatments, performed as recom-
mended |2| (3-11% bsufte, 0.5-2.5% sufurc acd, 180C, 30 mn), were foowed by hammer
mng. Low temperature sufonaton was performed at hgh bsufte concentraton (20%), rather ow
temperature (140C), ncreased retenton tme (2-10 hours) and sufurc acd addton for pH con-
tro. Pretreated sampes were anaysed for Kason gnn, carbohydrates and sufonc acd groups.
Enzymatc hydroyss was done usng ceuase (Ceucast 1.5, 10.5 FPU/g od substrate) and
-gucosdase (Novozyme 188, 37.5 CBU/g od substrate) at 50C, pH 4.8 for 48 hours.
In our tras Low temperature sufonaton gave sgnfcanty hgher enzymatc saccharfcaton than
SPORL and Hot water - SPORL pretreatments (Fgure 1). Ceuose converson ncreased wth
ncreasng degnfcaton, ndcatng that enzyme accessbty s crtca. Low temperature sufona-

Low temperature sufonaton of gnoceuose for effectve bomass deconstructon and converson

338
ton gave effcent gnn remova whe avodng severe hemceuose degradaton. After treatment,
35-60% of the hemceuoses were st present. At 75% degnfcaton, more than 70% of the ceu-
ose was converted. For SPORL treatment, approx. 20% converson was obtaned n our tras,
much ower than the reported |2|. The reason behnd ths s currenty unknown.
Low temperature sufonaton removes gnn by dssouton of gnosufonates, cf. the BALI pro-
cess |1|. In sufte pupng gnosufonates become water soube when more than approx. 3 sufonc
acd groups are ntroduced per 10 gnn unts. After SPORL pretreatment the resdua gnn con-
tans 1.2-1.7 sufonc acds groups per 10 gnn unts, suggestng that the SPORL sufonaton s too
ow for dssovng gnn. Hot water pre-extracton of hemceuoses pror to SPORL was not favour-
abe as ths made the gnn ess susceptbe to sufonaton. Thus, the degree of gnn sufonaton
was sgnfcanty ower for hot water extracted wood than for drect SPORL treated wood.

Figure 1. Sufte based pretreatment of Norway spruce. Ceuose converson by enzymatc sac-
charfcaton (eft). Sufonaton and gnn dssouton (rght).
Acknowledgements
for fnanca support, and Mr|ana Fpovc and Ingeb|rg Lerset (PFI) for anaytca work.
References
1. Lersch, M., S|de, A., Frander, A., Rdsrud, G. 2008. Lgnoceuosc bomass converson.
Europe Patent Appcaton WO/2010/078930 Fed December 17, 2008.
2. Zhu, | .Y., Pan, X.| ., Wang, G.S., Gesner, R. 2009. Sufte pretreatment for robust enzymatc
saccharfcaton of spruce and red pne. Boresource Technoogy 100(8), pp. 2411-2418.
0%
20%
40%
60%
80%
100%
60 70 80 90 100
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e
o
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e
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d

b
o
m
a
s
s
,

%
Yed of sods
SPORL pretreatment
Hot vater - SPORL
Lov Temperature Sufonaton
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
110%
120%
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
0,5
0,55
0,6
60 70 80 90 100
D
e
g
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t
o
n

(
)
,

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n

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Yed of sods
Lqud phase acetoxyaton of -pnene

339
Liquid phase acetoxylation of -pinene
M. Golets*
1
, S. Ajaikumar
1
, D. Blomberg
2
, H. Grundberg
3
,

J. Wrn
4
,
T. Salmi
4
, J.-P. Mikkola*
1, 4

1
Technical Chemistry, Department of Chemistry, Chemical-Biological Centre,
Ume University, SE-90187 Ume, Sweden
2
Processum Biorefinery nitiative AB, SE-89186 rnskldsvik, Sweden
3
Aditya Birla Domsj Fabriker AB, SE-89186 rnskldsvik, Sweden
4
Laboratory of ndustrial Chemistry and Reaction Engineering, Process Chemistry Centre,
bo Akademi University, Biskopsgatan 8, F-20500 bo-Turku, Finland
*Corresponding authors Mikhail.Golets@chem.umu.se,
Jyri-Pekka.Mikkola@chem.umu.se
Abstract
Chemca pupng and bo-refnng resuts n many fractons such as. ta o and turpentne that con-
tan substanta amounts of -pnene and other terpenes. Today these fractons are usuay burned
n the recovery boers. However, the northern forest ndustry, prmary utzng the borea forests,
faces serous chaenges from deveopng markets (South Amerca, Asa), because of ower cost of
raw matera resources and abor. At the same tme, there s a growng concern about emssons of
greenhouse gases and securty of suppy connected to the use of foss o for transportaton and as
a feedstock for the chemca ndustry. The mentoned fact renders the substtuton of petrochemca-
reated raw materas an mportant fed of research.
The favor and fragrance ndustry s one of the man users of terpene esters. From those esters,
-terpny and borny acetates are produced from -pnene and commony used for bath products
and perfumes. Due to the mperfecton of conventona two-stage producton method of the men-
toned esters, whch ays n the equpment corroson, envronmenta pouton, arge oad and non-
recycabty of a catayst, the nove one-stage cataytc process s aways of hgh prorty.
The possbty of -pnene qud phase cataytc acetoxyaton s ntroduced n the present study.
The compex product dstrbuton and reacton network anayss, nfuent reacton and cataytc fac-
tors optmzaton, combned wth the reacton knetc modeng were the man ams of research. The
on-exchange resn catayst Amberyst 70 was characterzed as the catayst used n the studed
reacton and compared wth the sovent-catayzed mode. Vauabe combnatons of acetates were
obtaned for both studed modes. A wde range of process factors were studed n the batch (Parr)
reactor used. The mentoned type of reactor s sutabe for the consequent ndustra operatons
scae-up cacuatons.
Apparatus and general reaction procedure
The -pnene acetoxyaton was carred out n a aboratory scae hgh-pressure reactor, equpped
wth a strrer and a heatng |acket. The reacton mxture, contanng 0.1 g of the catayst, 5.5 g -
pnene and 120 m acetc acd was oaded n the reactor. The reacton temperature was ad|usted by
means of the heatng |acket controed by a PC. The strrng speed of 1000 mn
-1
was apped. The
nfuence of varous gas atmospheres, .e. of N
2
, O
2
and H
2,
was studed. GC-GCMS combnaton
apped for the product anayss. The SEM mages were vsuazed wth a Cambrdge Stereoscan
360XP.
For the studed reacton, -terpny, fenchy, verbeny and borny acetates as we as monene,
camphene and -terpnene were a found n the product mxture. The other products were found n
amounts ess than 1 wt% and were consdered neggbe. The formaton of byproducts was not


340
unform n case of a proonged reactons. A temperature range of 25 to 125C and a pressure
range from atmospherc to 20 bar were consdered. The nfuence of the gas
atmosphere, .e. ntrogen, oxygen or hydrogen atmosphere was aso nvestgated. A pressurzng
gas was needed to suppress the evaporaton of the reactants nvoved. Gaca as we as aqueous
acetc acd (2.5 wt% and 5 wt%, respectvey) and aso a bend of acetc acd and touene or ethy
acetate (5 wt%) were tred as co-sovents. The nfuence of each factor was studed n cataytc
(Amberyst 70) and the sovent-catayzed mode. Fgure 1 descrbes the converson of -pnene.

Figure 1. -pnene converson. Symbos: () 100C, 10 bars, N
2
, cat; () 100C, 10 bars, N
2
, no
cat; (+) 75C, 10 bars, N
2
, cat; () 125C, 10 bars, N
2
, cat; () 100C, 20 bars, H
2
, cat; () 100C,
20 bars, O
2
, cat; ()100C, 20 bars, O
2
, no cat; () 100C, 20 bars, O
2
, no cat, 5 wt % ethy ace-
tate/95 wt % acetc acd; ()100C, 20 bars, O
2
, cat, 5 wt % touene/95 wt % acetc acd; (X) 100C,
20 bars, O
2
, cat, 95% aqueous acetc acd.
Accordng to the resuts, the specfc surface area and pore voume were sgnfcanty reduced, thus
ndcatng catayst deactvaton. The average pore sze of the catayst was sghty reduced under
the reacton condtons. The SEM mages scaed at 2.00 m for Amberyst 70, before and after the
reacton, are presented n Fgure 2. It s evdent that the surface has undergone morphoogy
changes. The fresh resn had a sphere dameter of around 350-600 m, whe the spent catayst
contaned spheres of around 400-800 m, thus demonstratng sweng of the resn partces.

341

Figure 2. Amberyst 70 SEM mages - fresh and spent catayst sampes.
Conclusions
The optma reacton condtons aowed reachng yeds of 39.8% of borny acetate and 42.5% of
monene, n cataytc experments. The yeds n the sovent-catayzed process were the foowng:
35.3% of -terpny acetate, 13% of borny acetate, 10.6% of -terpnene, 9% of monene and
14.7% of verbeny acetate, respectvey. Increased temperature or hydrogen atmosphere caused
product ogomerzaton up to 30% n 18 h, whe an oxygen atmosphere counter-effected the o-
gomerzaton.
Acknowledgements
Ume Unversty Busness Graduate Schoo, Processum Borefnery Intatve AB, Adtya Bra
Doms| Fabrker, Homen Energ AB, MoRe Research and Mets Group Husum are gratefuy
acknowedged for the fnanca support. The Bo4Energy program s acknowedged. Rohm and
Haas Nordc representatve s gratefuy acknowedged for provdng the catayst sampes.

Bocompostes based on brch subern

342
Biocomposites based on birch suberin
Dongfang Li
1
, Tommy versen
2, 3
, Monica Ek
1

1
Division of Wood Chemistry and Pulp Technology, Department of Fiber and Polymer Technology,
KTH Royal nstitute of Technology, Teknikringen 56-58, SE 100 44 Stockholm, Sweden
2
nnventia AB, Box 5604, SE 114 86 Stockholm, Sweden
3
Wallenberg Wood Science Center, Teknikringen 56-58, SE 100 44 Stockholm, Sweden
Abstract
The subern monomer, cis-9,10-epoxy-18-hydroxyoctadecanoc acd (epoxy fatty acd or EFA), was
soated from brch (Betula verrucosa) outer bark. The crude EFA was purfed and poymerzed va
pase-catayss. The resutng poyesters were characterzed by MALDI-TOF MS and SEC. Bo-
compostes were prepared through graftng EFA onto ceuose. The products were characterzed
by FTIR.
ntroduction
Increasng the ceuose surface hydrophobcty s an mportant route targeted towards hydrostabty
and mproved barrer propertes. Natura products that are hydrophobc and bodegradabe such as
subern found n brch outer bark coud be sutabe canddates for ths purpose. Subern has a com-
pex structure and many sub-unts. |1| EFA (Fgure 1) s the most abundant sub-unt among the
others, amountng to about 100 g per kg of dred bark. |2, 3| The epoxy functona group of EFA
makes t possbe for ceuose modfcaton.

Figure 1. The structure of cis-9,10-epoxy-18-hydroxyoctadecanoc acd.
In ths study, EFA soated from brch outer bark was used to prepare the poyesters. The character-
zaton was accompshed by
1
H NMR, MALDI-TOF MS, and SEC. Thereafter bocompostes were
prepared through graftng EFA onto ceuose. The products were characterzed by FTIR.
Experimental
Crude EFA was soated by foowng the method of Iversen et a. |1| EFA was poymerzed wth the
pase (Candida Antarctic pase B) as the catayst, and fatty acd-ceuose bocompostes (FACB)
were prepared through the aka-catayzed reacton of ceuose and EFA.
solation of epoxy fatty acid and preparati on of pol yesters
The soaton of crude EFA from brch outer bark was done accordng to the method of Iversen et a.
The obtaned purty was above 95% (examned by
1
H NMR).
The homo-poymerzaton of EFA was successfuy performed through the pase-catayss (ana-
yzed by SEC). MALDI-TOF MS showed the poyesters conssted of near and cycc structures wth
the former domnated the composton.
1
H NMR showed that the epoxy groups were st ntact. The

Bocompostes based on brch subern

343
co-poymers were prepared through the pase-catayzed poymerzaton of EFA and -caproactone,
and smar resuts were obtaned (anayzed by MALDI-TOF MS and SEC).
Exploration and development of fatty acid-cellulose biocomposites
The graftng of EFA onto ceuose coud be theoretcay performed under ether aka or acd cond-
tons, and ceuose reactvty pays an mportant roe n ths reacton. In order to actvate the hy-
droxy groups of ceuose as we as make them stronger nuceophes, ceuose was transformed
to aka-ceuose.
The FTIR spectra of FACB ndcated the presence of onzed carboxyc groups and ong aky
chans wthn the fna structures. None of the spectra showed a sgna of epoxy rng vbraton, nd-
catng the epoxy rng-openng was successfu. These ndcatons support the occurrence of graftng.
Conclusions
The poyesters based on EFA coud be prepared through pase-catayss wthout breakng the
structure of epoxde. The bocompostes shoud be further dentfed and characterzed through
manners such as TGA, HPLC, and CP/MAS
13
C NMR. The successfu preparaton of FACB shows
the possbty of graftng EFA based poyesters onto ceuose.
Acknowledgements
We woud ke to express great thanks to WoodWsdom-Net Research Programme for the fnanca
support to ths pro|ect.
References
1. Iversen, T., Nsson, H., Osson, A. 2010. Patent WO/2010/093320.
2. Nsson, H., Osson, A., Lndstrm, M., Iversen, T. 2008. Bark subern as a renewabe source of
ong-chan w-hydroxyakanoc acds. Macromo. Symp. 272, pp. 104-106.
3. Osson, A., Lndstrm, M., Iversen, T. 2007. Lpase-catayzed synthess of an epoxy-functonazed
poyester from the subern monomer cis-9,10-epoxy-18-hydroxyoctadecanoc acd. Bom-
acromoecues 8, pp. 757-760.

Isoaton of trterpene rch extracts from outer brch bark

344
solation of triterpene rich extracts from
outer birch bark
Janis Zandersons, Janis Rizhikovs, Baiba Spince, Aigars Pazhe, Vilhelmine Jurkjane,
Galina Dobele, Ausma Tardenaka
Latvian State nstitute of Wood Chemistry, 27 Dzerbenes Str., LV-1006 Riga, Latvia
Abstract
Brch wood n the Northern hemsphere s wdey used n the furnture, pup and pywood manufac-
ture. 2% of veneer bocks mass s made up by outer brch bark (BB) (Kstsyn, 1994). It s ready
accessbe and aready concentrated for further processng. In pywood pants of Latva, for exam-
pe, up to 12-14 thousand tons of outer BB can be made ready for the producton of trterpene rch
extractves. Pentacycc upane type trterpenes are promsng startng materas for the synthess of
boogcay actve compounds wth a broad spectrum of medca appcatons (Aakurtt et a., 2006).
Dfferent sovents and ther effect upon the composton of extracts and the contents of the man
trterpenc components n extracts were studed, f the outer BB of the two most wdespread brch
speces n Batc Sea regon states such as sver brch (Betula pendula Roth.) (BB-Pend) and
downy brch (Betula pubescens Ehrh.) (BB-Pub) was used as a feedstock.
Med dry BB sampes were soaked by mxng from tme to tme n deonsed water for 24 h. Outer
BB foated on the top of water was coected and dred up to a mosture content of 2-4 wt.%. Ex-
tracton was carred out n Soxhet apparatuses by the seected sovents for 11 h. Sovents were
evaporated usng a rotatng vacuum evaporator and dred up to an oven dry state.
GC-MS anayss was performed on a 30 m 0.25 m 0.25 m fm HP-5MS capary coumn
(GC-2010 Shmadzu) wth heum as a carrer gas at a constant fow rate of 1 mL/mn throughout
the run. The oven temperature was mantaned at 160C for 1 mn and then programmed at
10C/mn to 300C, whch was mantaned for 15 mn. The components were dentfed by compar-
son of the spectra wth those of the standards and those n the NIST brary of spectra.
Results
Tabe 1 shows that some dfference s detected between the tota yed of extractves f the spec-
mens of outer BB are ocated at dfferent eves of brch stems and aso t decreases wth the crop
age. The betun contents n the extractves of outer BB-Pub are even somewhat hgher than that n
the correspondng extracts of BB-Pend of the same crop age. However, the content of upeo n the
extractves of outer BB-Pub s amost threefod ower. Snce sver brch prevas n Latvan forests, t
was used for further experments.
Dfferent yeds of upeo and betun n varous sovents (6.0% and 8.5% extractves mass n ac-
etone and cycohexane extracts, respectvey) were estabshed (Tabe 2). The tota trterpene yed
s hgher f the cycohexane as a sovent was used.

Isoaton of trterpene rch extracts from outer brch bark

345
Table 1. Varabty n betun and upeo concentratons n ethano extracts of outer BB.
Characteristics of outer BB
sampl es
Solvent Yield of extractives,
% d.b. outer BB
Betul in Lupeol
% d.b. extract mass
BB-Pend, 60 years 95% ethano 36.2 61.7 6.0
BB-Pend, 15 years, 0-60 cm 95% ethano 43.0 59.6 4.4
BB-Pub, 60 years 95% ethano 36.0 63.6 2.1
BB-Pub, 15 years, 0-60 cm 95% ethano 43.1 64.2 1.5

Table 2. Varabty n trterpene concentratons n varous sovent extracts of outer BB-Pend.
Solvent Pre-treat ment Yield of extractives,
% d.b. BB
Betul in Lupeol Total
% d.b. extract mass
Acetone wthout 33.7 73.6 6.0 79.6
Cycohexane wthout 23.1 86.3 8.5 94.8
95% ethano wthout 36.2 61.7 6.0 67.7
95% ethano 3 h H
2
O, 96C 33.0 68.3 8.6 76.9
95% ethano 5 h H
2
O, 96C 33.0 71.5 8.6 80.1

Certan probems n obtanng purfed trterpene preparatons are posed by an admxture of poy-
phenos n outer BB extractves. Pre-treatment of outer BB wth hot water substantay mproves the
extracts quaty (combned betun and upeo yed - 67.7% and 80.1% after 5 hour treatment,
respectvey). The favourabe effect of pre-treatment can be further mproved f eachng wth duted
sodum carbonate souton s reased. It s possbe to mprove the quaty of extracts and the yed
of defnte components by modfyng the extracton technoogy and the approprate choce of sovents.
Acknowledgement
The research has been funded by the European Regona Deveopment Fund, contract No.
2010/0289/2DP/2.1.1.1.0/10/APIA/VIAA/058.
References
1. Kstsyn, A.N. 1994. Outer brch bark extractves: soaton, composton, propertes and appcaton.
Khmya drevesny. Wood Chemstry 3, p. 3.
2. Aakurtt, S., Mke, T., Koskmes, S., Y-Kauhauoma, | . 2006. Pharmacoogca propertes of
the ubqutous natura product betun. Eur. | . Pharm. Sc. 29, pp. 1-13.
Fractonaton and structura charactersaton of softwood kraft gnns

346
0 2 4 6 8 10
0
2000
4000
6000
8000
Lgno-Tech
gnn
M
w

(
g
/
m
o
)
Precptaton pH
Resdua
Buk
Impregnaton
DWL
Fractionation and structural characterisation
of softwood kraft ligni ns
Marina Alekhina
1
, Andreas Ebert
2
, Olga Ershova
1
, Herbert Sixta
1

1
Department of Forest Product Technology,
Aalto University School of Chemical Technology, Espoo, Finland
2
Research Division of Biopolymers, Fraunhofer AP, Potsdam, Germany
Abstract
Lgnn was soated from back quor (BL) by fractona precptaton trggered by step-wse addton
of sufurc acd. The chemca composton and functonaty of the fractonated gnn sampes was
compared wth regard to ther potenta ndustra appcatons.
ntroduction
One of the key requrements for a borefnery concept s the effcent recovery of gnn from process
quors for subsequent utzaton. Unt now, ony about 1.5% of the 70 mon tons per year of gnn
avaabe n the pup and paper ndustry are commercay utzed for other than energy purposes |1|.
Knowedge of gnn man structura characterstcs s requred before ts appcatons can be con-
sdered. In ths work, the effect of degnfcaton ntensty and precptaton pH on gnn structure
was nvestgated.
To expore the gnn propertes aong the dfferent cookng stages, BL sampes derved from pne
kraft cookng were taken durng nta, buk and resdua degnfcaton phases. To fractonate gnn
accordng to the moecuar weght (M
w
), t was precptated by sequenta acdfcaton to pH-eves
of 10.5, 5 and 2.5 usng 6M H
2
SO
4
. Dssoved wood gnn (DWL) was used as a reference, showng
propertes cose to those of natve gnn |2|. The Mw of the fractonated gnn decreased wth de-
creasng the precptaton pH (Fgure 1). In addton, the Mw of gnn ncreased wth ncreasng
pupng ntensty, due to a more condensed structure of the gnn from the resdua degnfcaton
stage.
Figure 1. Precptaton pH vs. M
w
of gnn fractons.


347
However, commercay avaabe gnn (Lngo-Tech) |3| showed sgnfcanty ower M
w
than that of
fractonated gnns. The yeds of gnn obtaned from dfferent fractons and precptated at varous
pH vaues are shown n Tabe 1. Aong wth the reducton n pH of BL, the amount of tota precp-
tated gnn ncreased and the BL coor brghtened. At any pH, the yed of precptated gnn n-
creased from the mpregnaton stage to the resdua degnfcaton stage. The ncrease n precpta-
ton yed can be expaned by the hgher content of co-precptated poysaccharde degradaton
products that are present n the quors obtaned from the ater cookng stages. Nevertheess, the
ma|orty of gnn was precptated at pH 5 for a three BLs, reachng a remova rate of about 70%.
Lowerng the pH vaue to 2.5 resuted n the precptaton of addtona ca. 6% of the tota gnn
dssoved n the souton.
The gnn sampes precptated at pH 10.5 and 5, respectvey, showed hgh purty (ca. 95% of
gnn content). In contrast, purty of commerca avaabe kraft gnn sampes, such as Indun AT
and, especay kraft Lngo-Tech, was consderaby ower. The amounts of ASL, suphur and carbo-
hydrates ncreased wth decreasng pH. Sugars present n the sampes were many attrbuted to
gucose and especay to xyose, derved from the hemceuoses dssoved n the BL. The pres-
ence of mpurtes mght negatvey affect the further processng of the gnn.
Table 1. Yed and chemca composton of dfferent gnn fractons.
Sampl e Yield
Chemical composi tion,
[ % of o.d. sample]
Functional groups
Cooking
stage
Precipit a-
tion pH
[g/L
BL]
[ % on
total
ligni n]
KL
1
ASL
2
Carb.
3
Sulfur
OCH
3
, Phen-OH,
[ % of
o.d. sample
[mmol/g of
o.d. sample]
Impregna-
ton
10.5 8.9 17.2 96.4 1.3 1.1 1.9 14.8 2.9
5 34.0 66.2 90.4 4.6 2.6 5.8 13.3 3.9
2.5 3.1 5.9 79.6 7.7 9.4 12.8 5.1 3.3
Buk
10.5 13.1 20.0 94.4 2.3 2.3 2.2 14.8 3.1
5 44.7 68.3 86.3 4.9 3.4 7.9 14.3 4.4
2.5 4.3 6.5 70.0 10.9 15.1 8.3 6.5 3.6
Resdua
10.5 14.3 19.8 94.0 2.0 2.8 2.4 15.3 2.9
5 51.4 71.2 85.3 5.6 3.9 8.6 14.5 3.9
2.5 4.4 6.1 46.4 9.7 39.3 14.3 17.7 3.3
Indun AT
-
-
- 88.3 - 2.2 - 14.8 3.3
Kraft L-T
4
- - 61.2 4.9 3.3 27.1
5
- -
DWL - - 85.4 6.2 6.0 0.2 19.1 0.9
1
Kason gnn;
2
Acd soube gnn;
3
Carbohydrates;
4
Kraft L-T - Lgno-Tech Iberca (Span), vaues are taken
from |3|;
5
Ash content
As can be seen n Tabe 1, gnns from a cookng stages were modfed to a arge extend when
compare to DWL. Sgnfcant ncrease n phenoc hydroxy group (Ph-OH) content s orgnated
from both demethyaton of methoxy groups and ceavage of ether nkages such as -O-4, -O-4
and 4-O-5 n gnn and therefore, fragmentaton of the gnn. The reactvty of gnns essentay
depends on the number of Ph-OH |3|. Ths s because the unts wth free Ph-OH are abe to form
qunonemethde ntermedates, due to the actvaton of the aromatc rng n the O-poston. The
qunonemethde s then prone to nuceophc reactons at the benzyc carbon atom. Lgnns precp-

348
tated at ower pH had ower methoxy content, whch ndcates that those gnns have more acces-
sbe ortho-postons n ther pheny rngs, and are therefore sutabe for chemca modfcaton.
Conclusions
Lgnn separaton and fractonaton was acheved by seectve precptaton at dfferent pH eves.
Our resuts ndcated that up to 90% of the gnn soubzed n the BL can be recovered n hgh
purty by owerng the pH to 5. Further pH reducton eads to ncreased precptaton of carbohy-
drates, to the formaton of sats and to a decrease n Mw. The gnn sampes obtaned from buk
degnfcaton by precptaton at pH 5 showed hgh amounts of phenoc hydroxy groups and rea-
tvey ow amounts of methoxy groups. These are cear ndcatons of a reactve gnn structure.
Ths fracton aso exhbted hgh purty and reatvey hgh Mw. It can be concuded that there are
cear dfferences among the precptates obtaned at dfferent pH eves wth regard to the compos-
ton and the propertes of gnn.
References
1. Lora, | .H., Gasser, W.G. 2002. | . Poym. Envron. 10, pp. 39-48.
2. Faschng, M., Schrder, P., Wobodt, R.P., Weber, H.K., Sxta, H. 2008. Hozforschung 62(1),
pp. 15-23.
3. Mansour, N.-E.E., Savad, | . 2006. Ind. Crop. Prod 24, pp. 8-16.
Funaoka gnn factatng sustanabe and recycabe bocompostes for transportaton

349
Funaoka lignin facilitating sustainable and recyclable
biocomposites for transportation
Kari Kolppo
1, 3
, Masamitsu Funaoka
2
, Jyrki Vuorinen
3

1
OY Scandinavian Colloids Ltd., Parkanonkatu 4 A 8, F-33720 Tampere, Finland
2
School of Bioresources, Mie University, 1515 Kamihama, Tsu, Mie 514-8507, Japan
3
Plastics and elastomer technology, Tampere University of Technology, F-33101 Tampere, Finland
Abstract
The envronmenta mpact of transportaton s amost entrey caused durng the use of the vehces.
Need to mprove energy effcency and to reduce CO
2
emssons ncrease the mportance of ght
weght composte materas as aternatve materas for vehces n transportaton.
Use of renewabe carbohydrate based oad bearng fbers do offer some advantages even when
compared to gass and carbon fbers: they are ghter n weght, and products produced are aso
softer and smoother to touch. Smoother and softer fbers reduce aso the wear of the producton
equpment. When tradtona pastcs are used as matrx materas, expensve coupng agents are
typcay requred to effectvey transfer the oad to the oad bearng fbers.
Lgnn s natures own bnder and matrx matera for carbohydrate (CH) fber based bocompo-
stes. Funaoka gnn (FL) s soated mantanng gnns natura reactvty, and havng ts structure
smpfed to a controabe and processabe near form. FL combned to technooges common from
pastcs ndustry w factate producton of nove gnn based bocompostes usng naturay renew-
abe CHs as renforcement fbers, and often wthout the use of expensve coupng agents.
The fourth pot scae Funaoka gnn pant |ust started ts producton and w factate producton
of testng materas for matera deveopment. Sampes of commerca nterest coud thus be pro-
duced, whch n turn w attract ndustra nterest n budng the foowng FL pant to Europe.
Foowng presentaton w descrbe reasons and prncpes behnd Funaoka gnn deveopment
and use n materas for vehces n transportaton.

Keywords: Wood ndustry, car ndustry, vehces, envronment, transportaton, bopoymers,
compatbty, sustanabty, recycabty, gnn
Use of renewable raw materials to reduce environmental effects
caused by transportation
Transportaton causes about 20% of CO
2
emssons n Europe. Lfe-cyce-anayss (LCA) and eco-
audt show that most of envronmenta effects n the car fe-cyce (use of raw materas, transport of
the raw materas and parts produced, product manufacture, use of the product, product dsposa)
are created durng the actua use of the car. In addton to potca toos (costs and prces, aws and
restrctons) amed at reducton of the transportaton tsef) the matera reated producton toos
avaabe coud be smpfed to reducton of the consumpton of foss fues. Ths means reducton of
the mass to be transported, and to reducton of the therma and eectrca osses of the vehce and
the engne (Fgure 1).


350

Figure 1. Strategy for matera seecton for transportaton (Granta). |1|
Renewabe raw matera based renforcement fbers coud be functona and useabe n varous
forms n composte producton. Whether stabed, used as such or even n contnuous form the fber
shoud be carefuy seected to sut the needs of the product and ts producton. Propery seected
renewabe carbohydrate based fbers do offer some advantages even compared to gass and car-
bon fbers: they are ghter n weght, and products produced are aso softer and smoother to touch.
Smoother and softer natura fbers reduce aso the wear of the producton equpment.
Lgnn s natures own matrx matera for carbohydrate (CH) fber based bocompostes. Com-
pared to tradtona pastcs gnn mght aow effectve transfer of the oad to the oad bearng fbers
even wthout the use of expensve coupng agents (Fgure 2).

Figure 2. Lgnn coud smpfy producton of compostes. |2|

351
Funaoka gnn (FL) s soated havng ts structure smpfed to a controabe and processabe ne-
ar form and havng ts natura reactvty taored for the chosen CH and desred product. |3| When
combned to sut the chosen CH based renforcement fber, the composte can be taored at moec-
uar eve to desred needs (Fgure 3).
The fourth pot scae Funaoka gnn pant |ust started ts producton n | apan and w factate
producton of testng materas for matera deveopment. |3| Sampes of commerca nterest w be
produced, whch n turn w attract ndustra nterest n budng the foowng FL pant to Europe.

Figure 3. Desgn of propertes at moecuar eve to sut the product requrements. |3|

Figure 4. Producton of functona Funaoka gnn. |3|
Conclusions
Trabant was an East-German composte car produced by VEB Sachsenrng Automobwerke
Zwckau. |4| It was produced from cotton-waste and pheno resn .e. from a fber-renforced ther-
mosettng pastc Duropast. |5| Trabant has often been consdered to be a hstorca amusement,
but t has now been recognzed that t aso ndcated the future for the car. Trabant was but usng
cheap and orgnay ready avaabe raw materas. Now t s aso mportant to produce cars havng
ower gas consumpton and ower envronmenta emssons. Cars produced usng best avaabe
technoogy and modern verson of renewabe and recycabe raw materas are surprsngy smar
to Trabant (Fgure 5).
European wood ndustry that s based on hgh eve know-how and sowy growng forests shoud
no onger compete wth the buk ndustry based on fast growng southern wood. It shoud nstead
combne the speca quates of sowy grown wood to ong term ndustra and scentfc experence
to create nove hgh vaue wood products. Taor made Funaoka gnn combned to appcaton

352
specfc CH matera w mprove compettveness of naturay renewabe resources and European
wood and car ndustry. Car body produced by Toyota from gnn based bocompostes demon-
strates the potenta of Funaoka gnn, and shoud aso functon as an exampe for other appcaton
areas. It s tme to reduce our dependency on o and start takng fu advantage of naturay renew-
abe resources growng n our forests.

Figure 5. Composte cars from hstory and the future.
References
1. Vuornen, | . 2011. Kompostt - uonnonmateraa? Tedett |a tuotteta - muovteknooga t-
nn semnar. Muov-Pastcs 2011, Laht 17.11.2011.
2. Kese, H., Rcher, E. 2003. Lcomont AR 504: Adheson promoter and Compatbzer. Carant
product brochure. 27 p.
3. Funaoka, M. 2012. Rapd refnng of gnoceuoscs to carbohydrates and gnn-based new ma-
teras (gnophenos) and desgn of sustanabe ndustra network connectng forests and
chemca ndustres. The 4th Nordc wood borefnery symposum, Hesnk, Fnand, Octo-
ber 23-25.2012. To be pubshed n Conference proceedngs and n Ceuose Chemstry
and Technoogy.
4. Wkpeda 1.9.2012. Trabant, a composte car produced by VEB Sachsenrngen Automobverke
Zwckau n Sachsen. http://en.wkpeda.org/wk/Trabant.
5. Wkpeda 1.9.2012. Duropast, a fber renforced thermosettng pastc produced from waste
cotton and phenoc resn. http://en.wkpeda.org/wk/Duropast.
Compostes of kraft gnn

353
Composites of kraft lignin
Kalle Nttinen
1
, Lamfeddal Kouisni
2
, Michael Paleologou
2
, Lisa Wikstrm
1
,
Niklas von Weymarn
1
, Tom Browne
2

1
2
FPnnovations, Canada
Abstract
Many materas, man-made and natura, have a composte structure, .e. they comprse two or more
consttuent materas wth dstnct dfferences. Concrete s a common exampe. It conssts of sand
or grave, cement and water. Wood s aso a composte. It has strong, crystane ceuose struc-
tures gued together by hemceuoses and gnn. The unque structure of wood can, however, not
be processed as such usng common ndustra matera processng technques.
For decades, the market for composte materas has wtnessed sma steps towards ncreased
use of bo-based consttuents nstead of the petroeum-based ones and especay, bo-
based/natura fbers nstead of man-made gass fber. A key drver for ths change s the fact that
natura fbers are often cheaper and ghter. Sustanabty ssues aso pay a part n ths change.
In ths research, the man ob|ectve has been to deveop technooges and competences ena-
bng the producton of nove composte materas, n whch wood-derved, ndustra kraft gnn and
ceuose fber are the man consttuents. The gnn woud thus repace the petroeum-based pas-
tcs as matrx consttuent. The more specfc ob|ectves of the research were to determne the met
processabty of kraft gnn, pastcze kraft gnn wth case-sutabe pastczers to ease the pro-
cessng of the matera and produce kraft gnn-based composte test products renforced wth ceu-
ose fber.
Kraft gnn was not processabe wthout pastczaton. Sutabe pastczers were found, the pas-
tczed kraft gnn was met compounded wth ceuose fbers, and test sampes were n|ecton
moded. DSC anayss was conducted and mechanca propertes were measured. The nta tense
test resuts of the pastczed gnn renforced wth ceuose fbers were promsng. Addton of ceu-
ose fbers nto pastczed gnn matrx mproved mechanca propertes of the gnn sgnfcanty.
Composites of thermoplastic lignin
In terature, gnn s typcay used as an adheson promoter between aphatc poymers and natu-
ra fbers or as a component n bends wth an aphatc poymer or modfed starch. In order to m-
prove ts pastcty, gnn s often chemcay modfed by esterfcaton or akyaton. Besdes the
nterna, covaent pastczaton, externa pastcsers such as PVA and PEG (PEO) have been used.
The purpose of pastczaton s to mprove the processabty and performance of the matera by
reducng the strong ntermoecuar bondng and crystanty, and sdng of the poymerc chans n
the matera.
In ths study, the use of PEG-pastcsed softwood kraft gnn as matrx matera n the compo-
stes together wth TMP and beached kraft ceuose fbres was targeted. The gnn used was pro-
duced usng the LgnoForce process deveoped by FPInnovatons. The concept s outned n Fgure 1.


354
Figure 1. Process dagram for thermopastc gnn composte producton.

The degree of pastczaton was evauated by studyng the shft n the Metng and Tg sgnas n
DSC anayss of PEG and gnn, respectvey. Therma decomposton was seen to commence at
above 200C (Fgure 2).

Figure 2. DSC anayss of PEG, gnn and pastczed gnn.

355
Inta batch processng was done to screen the component ratos and the process mts. Based on
these experments, a processng temperature range of 170 to 200C was seected. Mn-scae spec-
mens were mouded to characterse the matera performance. To enabe contnuous, nne pro-
cessng, a method for peetsng the fbres usng an n-house desgned seve compactor was deve-
oped. At ths stage of the pro|ect, the performance of the pastczed gnn compostes, n terms of
tense propertes, was found to be moderatey good n comparson to the reference materas such
as ceuose renforced PP and PLA (Fgure 3). Sgnfcant mprovement s, however, needed n
ductty, envronmenta stabty (mosture, water) and reease of odors.

Figure 3. The performance of the pastcsed gnn compostes n comparson to renforced PP and
PLA reference materas.
Seectve enzymatc degradaton of aka extracted gnn for the producton of hgh-vaue aromatc
components

356
Selective enzymatic degradation of alkali extracted
lignin for the production of high-value aromatic
components
Juho Jrvinen
1
, Ville Sotaniemi
1
, Sanna Taskila
1
, Olli Byman
2
, Kaisu Leppnen
2
, Lauri Hiltunen
3
,
Sampo Mattila
3
, Heikki Ojamo
1
, Hannu lvesniemi
2

1
Bioprocess Engineering Laboratory, University of Oulu, Oulu, Finland
2
Finnish Forest Research nstitute (Metla), Vantaa, Finland
3
Laboratory of Structural Chemistry, University of Oulu, Oulu, Finland
Abstract
In ths study severa funga oxdoreductases were utzed wth the ntenton to break down gnn
seectvey |1|. The am was to acheve controed parta decomposton of gnn and hydroyss of
hemceuose. Aso the use of co-oxdants was studed n terms of boostng the degradaton of
buky gnn |2|. The formaton of monophenoc compounds and the nature of the resdua gnn
were examned. A hemceuose-rch pressurzed hot water extract and gnn rch fracton pooed
from an aka extracton of natve spruce wood was used n the experments.
Funga oxdoreductases were abe to break down aromatc gnn structures and they have a po-
tenta for future utzaton n gnoceuose borefneres. However, the controng of gnn decom-
poston so that t yeds to sma aromatc components has proved to be chaengng. In addton to
sma moecuar weght aromatc compounds, aso the modfed resdua gnn poymer can have
nterestng functona propertes.
ntroduction
Effcent bomass fractonaton s a cruca pretreatment process for most gnoceuose based bore-
fneres. Pressurzed hot water extracton (PHWE) |4| and a succeedng aka extracton are poten-
ta toos to fractonate softwood bomass nto the three man fractons; ceuose, hemceuose and
gnn. Out of these fractons gnn s possby the most dffcut to refne due to ts heterogeneous
and hghy compex poyaromatc structure. However, severa funga oxdoreductases are abe to
seectvey break down gnn, whch coud ead to nove hgh-vaue aromatc products from wood |1|.
Monomerc gnn bocks can be utzed e.g. by the cosmetc ndustry, the pharmaceutca ndustry,
as aroma compounds or precursors for other chemcas.
Experimental
A gnn rch fracton pooed from an aka extracton of natve spruce wood was used n these ex-
perments. Three oxdatve enzymes were tested. These enzymes were manganese peroxdase
(MnP), gnn peroxdase (LP) and accase. The pH of the qud was ad|usted to a sutabe eve for
the enzymes (4.5-5). A treatments ncuded a mxture consstng of 500 M MnSO4, and 50mM
sodum maonate. 0.5% (W/V) Tween 80, 1 mM Gutathone (GSH) and 100 M veratry acoho
(VA) were used as co-oxdants n some experments. A batch-wse method for hydrogen peroxde
addton was created wth the addton of 10-20 mM gucose and 100-200 UL
-1
gucose oxdase.
Sampes were taken at specfed tme ntervas for nucear magnetc resonance spectroscopy
(NMR) and qud chromatography (HPLC) anayss of the produced gnn derved products and the
structure of the resdua gnn poymer.

Seectve enzymatc degradaton of aka extracted gnn for the producton of hgh-vaue aromatc
components

357
Funga enzymes degraded aromatc structures of gnn and apparenty most of the smaer ogo-
and monophenos. Effcent decomposton of the buk gnn was not acheved n ths study. Howev-
er, SEC-anayss (Fgure 1A) showed ncreased amounts of soube gnn n sampes as the treat-
ment progressed, whch coud resut from the break-down or modfcaton of the arger precptated
gnn. In ths respect, the co-oxdants seemed to have a postve effect. 1 D NMR reveaed rapd
reducton n the aromatc regon sgnas n enzyme treated sampes (Fgure 1B).
Decrease n the aromatc sgnas of PHWE sampes was aso observed. The yed of sugars n
enzymatc hydroyss was ncreased n these sampes, possby due to breakdown of gnn and
gnn-carbohydrate compexes (Fgure 1C).

Figure 1. A: SEC-anayss of two separate enzyme treatments. MnP (60 Unts) and accase (20
Unts) wthout added co-oxdants (eft) and MnP (60 unts) aone wth co-oxdants Tween 80 and
GSH (rght). Lnes from ower to upper: 0 h, 21 h and 45 h of treatment. 17.5-24 mn retenton s the
gnn sgna. B: 1D NMR sgna from the aromatc regon of the spectrum n an enzymatc treatment
of aka extract. Lnes: ower (0 h), upper (2 h). C: Yed of PHWE hemceuose sugars n enzymatc
hydroyss was ncreased by a pretreatment wth funga oxdatve enzymes. Lnes: dashed (contro),
sod (pretreated sampes). Anayss was done by HPLC.
References
1. Hatakka, A. 1994. Lgnn-modfyng enzymes from seected whte-rot fung-producton and roe n
gnn degradaton. FEMS Mcroboogy Revews 13(2-3), pp. 125-135.
2. Hamme, K.E., Cuen, D. 2008. Roe of funga peroxdases n boogca gnnoyss. Current
Opnon n Pant Bo. 11, pp. 349-355.
3. Htunen, L., | rvnen, | ., Sotanem, V., Taska, S., Byman, O., Leppnen, K., O|amo, H., I-
vesnem, H., Matta, S. 2012. Anayss of aka gnn degraded by oxdatve funga en-
zymes. XXXI Fnnsh NMR symposum | une 2012. Poster presentaton.
4. Leppnen, K., Spetz, P., Pranovch, A., Hartonen, K., Ktunen, V., Ivesnem, H. 2011. Pressurzed
hot water extracton of Norway spruce hemceuoses usng a fow-through system. Wood
Scence and Technoogy. Wood Sc. Techno. 45, pp. 223-236.
A
B
Tme |h|
0 24 48
Y
d

o
f

S
u
g
a
r
s

|
%
|
0
50
100
C Reducton n the
aromatc regon
From gnns to aromatc synthons by base cataysed degradaton n contnuous reactors - a
tentatve revew

358
From lignins to aromatic synthons by base catalysed
degradation in continuous reactors a tentative review
Detlef Schmiedl
1
, Sarah Endisch
1
, Detlef Rckert
1
,
Rainer Schweppe
1
, Gerd Unkelbach
2

1
Fraunhofer nstitute for Chemical Technology, Pfinztal, Germany
2
Fraunhofer Center for Chemical and Biotechnological Processes, Leuna, Germany
Abstract
Lgnn as a renewabe resource contanng aromatc structures has sustanabe & economca po-
tenta n bo based chemcas, materas & n the energy sector. The ob|ectve of the presented
studes s the generaton of oxy-aromatcs from dfferent gnns (Organosov gnn & Suphur-
contanng gnns). Both the Organosov gnn & the suphur contanng gnn were used for based
cataysed degradaton (BCD) nto oxy-aromatcs (monomer, ogomer). Subsequenty (at p: - 250 bars),
the effect of parameters (catayst, NaOH) & NaOH conc., mneras, dwe tme (t =5-15 mn), tem-
perature (T: 250-350C) was nvestgated. Lqud-qud extracton of reactor water (pH =3) was
performed wth MIBK. Os & tars were characterzed regardng the yed & ther composton. Types
of monomers were summarzed nto groups (guaaco (G), syrngo (S), catecho (C), ogomerc).
Some ogomers n the os were dentfed. To get an overvew about man & sde effects n such a
compex stuaton, the studes on technca gnn were done usng statstca Desgn of Experments
(DoE, Box-Behnken). A detaed evauaton regardng the man & sde effects of process & sub-
strate factors on yed of o & tar, on the Yed of guaaco, syrngo & catecho type monomers n
the o phase and on the carbon baance/ converson degree & on Mw & Mn of tar w be gven.
Methods
The extracts (os) & fter-cakes (tars) were characterzed regardng the yed & ther composton. A
characterzaton of the monomer composton was done usng GC-MSD/FID & eementa anayss
(EA: CHONS-carbon baance). Types of monomers were summarzed nto groups (e.g. guaaco
(G), syrngo (S), catecho (C), ogomerc). Ogomers n the os were dentfed by Infuson & LC
MSD Ion Trap & the composton of the tar by Py-GC-MSD anayss as we as the formed tar by
SEC & EA.
Dependng on the botanca source & the generaton process the used gnns dffer n ther structure
(G-gnn, G/S-gnn, moecuar weght and n mnera & suphur content. The substrate factors ef-
fectng the degradaton process durng the base cataysed ceavage of ary-ary-ether & ary-methy-
ether bonds. On the other hand, process factors (p, T, t, catayst conc. (NaOH) & type of akane &
earth akane catons have a man effect on the ceavage processes, on yed & composton of the
o, on the moecuar characterstc (Mw, Mn) of tar & on the carbon baance.
The foowng fgures ustrate the optons & chaenges of the BCD process on gnns.

tentatve revew

359
Lignin conversion into oil

Figure 1. Effects of dwe tme: 5, 10, 15 mn, T: 300, 320, 340C & NaOH conc. (1%: eft, 3%:
centre, 5%: rght)) on the carbon amount n o orgnatng from suphur contanng gnn (Carbon
(wt.-% of gnn) as degree of converson.

centre, 5%: rght)) on the amount of guaacos & catechos - beow (wt.-% of Lgnn) present n the
o after BCD of suphur contanng gnn.
EstmatedResponseSurface
c NaOH=1,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
4
6
8
10
12
14
16
18
20
C

n

o
C n o
5,0
7,5
10,0
12,5
15,0
17,5
20,0
22,5
25,0
c NaOH=3,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
4
6
8
10
12
14
16
18
20
C

n

o
C n o
5,0
7,5
10,0
12,5
15,0
17,5
20,0
22,5
25,0
EstmatedResponse Surface
c NaOH=5,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
4
6
8
10
12
14
16
18
20
C

n

o
C n o
5,0
7,5
10,0
12,5
15,0
17,5
20,0
22,5
25,0
c NaOH=1,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
1
1,5
2
2,5
3
Y

g
u
a
|
a
c
o
s
Y gua|acos
1,0
1,25
1,5
1,75
2,0
2,25
2,5
2,75
3,0
c NaOH=3,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
1
1,5
2
2,5
3
Y

g
u
a
|
a
c
o
s
Y gua|acos
1,0
1,25
1,5
1,75
2,0
2,25
2,5
2,75
3,0
c NaOH=5,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
1
1,5
2
2,5
3
Y

g
u
a
|
a
c
o
s
Y gua|acos
1,0
1,25
1,5
1,75
2,0
2,25
2,5
2,75
3,0
c NaOH=1,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
0
2
4
6
8
10
Y

c
a
t
e
c
h
o
s
Y catechos
0,0
1,0
2,0
3,0
4,0
5,0
6,0
7,0
8,0
9,0
10,0
c NaOH=3,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdence tme
0
2
4
6
8
10
Y

c
a
t
e
c
h
o
s
Y catechos
0,0
1,0
2,0
3,0
4,0
5,0
6,0
7,0
8,0
9,0
10,0
c NaOH=5,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
0
2
4
6
8
10
Y

c
a
t
e
c
h
o
s
Y catechos
0,0
1,0
2,0
3,0
4,0
5,0
6,0
7,0
8,0
9,0
10,0
tentatve revew

360
Lignin conversion into tar

centre, 5%: rght)) on the carbon amount n tar orgnatng from suphur contanng gnn (carbon
(wt.-% of gnn) upper, as degree of converson & on moecuar number Mn (g/Moes) of tar.
References
1. Mer, | .E., Evans, L.R., Mudd, | .E., Brown, K.A. 2002. Batch Mcroreactor studes of gnn depo-
ymersaton by bases. 2. Aqueous sovents, 2002, SAND2002-1318, Sanda Natona Labo-
ratores, Abuquerque, New Mexco, USA. Pp. 1-51.
2. Mer, | .E., Evans, L.R., Lttewof, A.E., Trude, D.E. 2002. Batch Mcroreactor studes of gnn
depoymerzaton by bases 1. Acoho sovents, 2002, SAND2002-1317, Sanda Natona
Laboratores, Abuquerque, New Mexco, USA. Pp. 1-19.
3. Schmed, D., Unkebach, G., Graf, | ., Schweppe, R. 2009. Studes n catayzed hydrotherma
degradaton processes on Suphur-free Lgnn and extractve separaton of aromatc
SYNTHONs. 60 Poster proceedng: 2
nd
NWBC, 2009, 2-4 Sep, Hesnk, Fnand, 2009.
Pp. 189-197.
4. Pacfc Northwest Natona Laboratores; PNNL-16983: Top Vaue added chemcas from bo-
mass. Voume II - Resuts of screenng for potenta canddates from borefnery gnn,
October 2007. Pp. 1-87.
5. Vgneaut, A., | ohnson, D.K., Chornet, E. 2006. Advance n the therma depoymersaton of gnn
va base-catayss. In: Scence In Therma And Chemca Bomass Converson, 2. A.V.
Brdgwater and D.G.B. Boocock (Eds.). CPL Press, Newbury Berks, UK. Pp. 1401-1419.
c NaOH=1,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
30
40
50
60
70
80
90
C

n

t
a
r
C ntar
30,0
40,0
50,0
60,0
70,0
80,0
90,0
c NaOH=3,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
30
40
50
60
70
80
90
C

n

t
a
r
C ntar
30,0
40,0
50,0
60,0
70,0
80,0
90,0
c NaOH=5,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdence tme
30
40
50
60
70
80
90
C

n

t
a
r
C ntar
30,0
40,0
50,0
60,0
70,0
80,0
90,0
Mn
660,0
675,0
690,0
705,0
720,0
735,0
750,0
765,0
780,0
795,0
810,0
825,0
c NaOH=1,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
600
650
700
750
800
850
M
n
Mn
660,0
675,0
690,0
705,0
720,0
735,0
750,0
765,0
780,0
795,0
810,0
825,0
c NaOH=3,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
600
650
700
750
800
850
M
n
Mn
660,0
675,0
690,0
705,0
720,0
735,0
750,0
765,0
780,0
795,0
810,0
825,0
c NaOH=5,0
300
310
320
330
340
temperature
5
7
9
11
13
15
resdencetme
600
650
700
750
800
850
M
n
Optmzaton of the kraft gnn copoymerzaton wth -caproactone for hgher vaue gnn-
adhesves

361
Optimization of the kraft lignin copolymerization with -
caprolactone for higher value lignin-adhesi ves
Maja Kandula, Stefan Friebel
Fraunhofer WK, nstitute for Wood Research, Bienroder Weg 54 E, Braunschweig, Germany
Abstract
Wthn the pupng process 50 mon tons gnn per year accrue; borefnery concepts add another
20 mon tons to ths amount. There are ony a few ndustra appcatons for gnn such as dsper-
sants or precursors for vann. It s aso used as a repacement for pheno n pheno-formadehyde
resns n pywood. Unt now the ma|orty of the gnn s used to cover the requred energy of the
pupng process. Any excess energy whch s produced s fed nto the natona energy grd. Hence a
concept for the matera use of kraft gnn must mpy a hgher vaue than the proft arsng from
energy recovery.
ntroduction
In order to get a hgher gnn vaorsaton chemca modfcaton and synthess nto poymerc mate-
ras are the best approaches. In a frst step gnn s copoymerzed wth -caproactone to acheve
soubty for poyurethane synthess. In a second step the copoymer s reacted wth 4,4`-
methyene-dphenyene dsocyanate (MDI), 1,6-hexane dsocyanate (HDI) and dmethyene prop-
onc acd (DMPA) to a water dspersbe poyurethane adhesve. In order to synthesze gnn- -
caproactone copoymers on an ndustra scae a defned specfcaton on the gnn purty s neces-
sary. In addton to optmze the reacton and to get a hgh gnn content n the end product ths pre-
treatment s mandatory to assure homogenous reacton condtons.
Experimental
Indun AT was used as softwood gnn obtaned by the kraft pupng process. The esterfcaton reac-
ton wth kraft gnn and -caproactone was syntheszed accordng to de Overa and Gasser |1|. The
kraft gnn pre-treatment was performed wth a bead m wth bead szes about 0,8-4 mm together
wth -caproactone for 10 mn. The reacton was executed wth dfferent amounts of gnn n the
range of 10-40% (w/w). In addton the reacton tme was reduced from 15 to 3-5 hours. Lgnn-
based copoymers were characterzed by dfferenta scannng caormetry (DSC), sze excuson
chromatography (SEC) n THF,
1
H- and
13
C-NMR and the gnn--caproactone-dspersants were
anayzed by aser dffracton measurements.
The apped mng process assures homogenous reacton condtons and a arger reactve surface.
Because of the mechanca pre-treatment wth the bead m the produced copoymers show a faster
reacton knetc and dfferent metng ponts compared to the untreated gnn products. Fgure 1 show
precptated gnn--caproactone copoymer partces n SEM. The untreated gnn copoymers
show a bgger rato of crystane morphoogy resutng n stff and brtte products. Lgnn copoy-
mers whch are pror mechancay treated gettng softer wth hgher gnn content. Durng the es-
terfcaton reacton some SEC sampes were retreved and measured. It s shown that after the
monomer reacton s done the moecuar weght st ncreases and the gnn copoymer reacts fur-
ther. Ths drects to the decreasng of carboxy groups from the gnn whch undergo crossnkng
reactons |2|.

Optmzaton of the kraft gnn copoymerzaton wth -caproactone for hgher vaue gnn-
adhesves

362

Figure 1. SEM pctures of the gnn copoymer eft: untreated rght: pre-treated wth a bead m.
Concl usi on
The condtonng wth a bead m aows the synthess of gnn--caproactone copoymers wth
hgher gnn content compared to non-treated gnn. The surface morphoogy of the copoymer
changed nto a ess crystane one so copoymers wth other characterstcs |ust due to mechanca
pre-treatment are syntheszed. Therefore the thermomechanca behavour aso changed. Summa-
rzng a gnn copoymer wth short reacton tmes and controed crossnkng s produced. A prod-
uct that s exceent quafed for poyurethane reactons to synthesze adhesves was obtaned.
Acknowledgement
Staerke & Nager for provdng Indun AT and to Chrstne Burmester for dong the aser dffracton
measurements.
References
1. De Overa, W., Gasser, W. 1994. Mutphase Materas wth Lgnn. 11. Starke Copoymers
wth Caproactone. Macromoecues 27, pp. 5-11.
2. Matsushta, Y., Inomata, T., Takag, Y., Hasegawa, T., Fukushma, K. 2011. Converson of su-
phurc acd gnn generated durng boethano producton from gnoceuosc materas n-
to poyesters wth -caproactone. | . Wood Sc. 57, pp. 214-218.
Fast cataytc pyroyss of gnn

363
Fast catalytic pyrolysis of lignin
Robertus Dhimas D.P
1, 2
, Dong Jin Suh
1
, Chang Soo Kim
1*

1
Clean Energy Research Center, National Agenda Research Division,
Korea Institute of Science and Technology
39-1 Hawolgok-dong Seongbuk-gu, 136-791, Seoul, Korea
2
Department of Clean Energy and Chemical Engineering,
University of Science and Technology,
113 Gwahangno, Yuseong-gu, Daejeon, 305-333, Korea
*Corresponding author TEL: +82-2-958-6811, mizzou333@kist.re.kr
Abstract
Lgnns from dfferent soaton methods and sources were pyrozed by mcro-pyroyser connected
wth gas chromatograph mass spectrometry. Therma degradaton wth regard to temperature was
nvestgated by anayzng monomerc compounds. The effect of cataysts on therma decomposton
s presented by composton dfference at certan temperature, whch can be nterpreted as en-
hanced degradaton or seectve degradaton. Phenoc compounds and pheno composton have
been changed by appyng catayst at certan temperature. Moreover, ong chan hydrocarbon such
as hexadecanoc acd from empty frut bunches has been detected durng pyroyss, whch may
come from resdua pam o or from recombnaton between broken hydrocarbons from phenoc
compounds.
Introduction
Lgnoceuoscs whch s the most abundant and renewabe matera s the most sutabe resource
to repace foss fue. Severa routes can be apped to gnoceuoscs to obtan approprate fue
form that has hgh energy densty and eco-frendy fue gas. Drect converson from wood to bo-o
through therma converson s beeved to be the shortest and cheapest route. However, hgh oxy-
gen content whch s many from ceuose and hemceuoses coud decrease o stabty due to
the acdty of o |1|. In ths work, gnn whch s resdue of two-step hydroyss of gnoceuoses n
bo-ethano producton was pyrozed. The emnaton of ceuoses and hemceuoses can de-
crease oxygen rato n o product. However, gnn structure orgnay contans oxygen whch s
formng as hydroxy and methoxy group; therefore, cataytc deoxygenaton s necessary.
Experimental
Material and method
Lgnns were prepared by two-step hydroyss of oak wood and empty frut bunch (EFB). Frst step
was conducted wth hgh concentraton of suphurc acd (70 wt%). The second step was conducted
by duted suphurc acd concentraton (30 wt%) and ncreased reacton temperature. Lgnn was
obtaned after fterng the resutants, and been washed and dred before further utzaton.
Pyroyss was conduct wth mcro pyroyzer CDS pyroprobe 5000 US drecty connect to Gas
Chromatography Agent HP 6890 wth HP DB-1701, 30m X 0.32 mm d X 1.00 m fm as a coumn
and compound were detected by Mass Seectve Detector HP 5973. Pyroyss duraton was set n
20 seconds and temperatures were vared from 400-800C. In cataytc pyroyss, rato between
catayst and gnn s set to 2:1.

Fast cataytc pyroyss of gnn

364
Result and di scussion
Pyroyss of EFB and Oak gnn produces varety of compounds whch are many consst of pheno-
c compound. Compounds wth guaacy and syrngy moetes are domnant n Oak gnn pyroyss,
whe n EFB gnn compounds wth hydroxy pheny moetes was aso present n consderabe
rato. Aromatc compound wthout oxygen was found n very sma rato n both of gnn pyroyss
especay n oak gnn. At hgher pyroyss temperature pheno and ts dervatves tend to ncrease
whe guaaco and syrngo and ts dervatves tend to decrease, suggestng that rate of demethoxy-
aton ncreases as temperature ncreases.
Pyroyss under H-ZSM-5 catayst shows mpressve performance n ncreasng aromatcs wth-
out oxygen compound. Fgure 1 shows aromatcs free of oxygen for Oak and EFB gnn wth and
wthout H-ZSM-5. Interestngy, among aromatc compounds free of oxygen 1,3-dmethy benzene
s the hghest rato for Oak gnn, whe 1,4-dmethy benzene s for EFB gnn. Thus, H-ZSM-5
seems to have hgh seectvty n dmethy benzene. Furthermore, severa aromatc compounds wth
doube and trpe rngs were found. It suggested that H-ZSM-5 has a roe n ogomerzaton |2| and
deoxygenaton. Cataytc pyroyss wth varous temperatures shows that H-ZSM-5 s not deactvat-
ed at temperatures above 600C.

Figure 1. Aromatc free oxygen product n Oak and EFB gnn pyroyss wth and wthout H-ZSM-5.
Reference
1. Mohan, D., Pttman, C.U., Steee, P.H. 2006. Pyroyss of Wood/Bomass for Bo-o: A Crtca
Revew. Energy & Fues. 20(3), pp. 848-889.
2. Cheng, Y.T., | ae, | ., Sh, | ., Fan, W., Huber, G.W. 2012. Producton of Renewabe Aromatc
Compounds by Cataytc Fast Pyroyss of Lgnoceuosc Bomass wth Bfunctona
Ga/ZSM-5 Cataysts. Angew. Chem. 124(6), pp. 1416-1419.

Anaytca toos to study the chemstry of hydrotherma gnn depoymersaton

365
Analytical tools to study the chemistry of
hydrothermal li gnin depolymeri sati on
Abdelrahman smail, Margareta Sandahl, Charlotta Turner
Lund University, Department of Chemistry, Centre for Analysis and Synthesis,
P.O. Box 124, SE-221 00 Lund, Sweden
www.kilu.lu.se/cas, abdel_rahman.ismail@organic.lu.se
ntroduction
Lgnn s a natura aromatc poymer, t s consdered to be one of the man factors that mt the
determnaton of the quaty of bomass to be converted to bo-ethano and pup. Hydrotherma de-
poymerzaton of gnn s one of the hot topcs n the quefacton process of bomass. The abty of
gnn degradaton products to re-poymerze and formng char s a fact that hnders the maxmza-
ton of bomass vaorzaton |1|.
Temperature, resdence tme, concentraton, etc are factors affectng the degradaton product
that can affect the whoe process. To enabe the understandng of the chemstry of such compcat-
ed process, robust anaytca toos must be deveoped.
Experimental
Anaytca method based on HPLC-DAD has been deveoped and used to ncrease the understand-
ng of the chemstry of gnn de-poymerzaton process (Fgure 1). The above mentoned factors
are studed to optmze a hydrotherma process of gnn n seaed transparent quartz capares
reactors usng a fudzed sand bath to set the temperature as desred.
Results

Figure 1. Represent 20 standard compounds for gnn degradaton products separated by C18
coumn usng methano and water as mobe phase at 280 nm.
References
1. Lavoe, | . M., W. Bare, Bodeau, M. 2011. Depoymerzaton of steam-treated gnn for the pro-
ducton of green chemcas. Boresour Techno 102(7), pp. 4917-4920.

Pused corona dscharge oxdaton n gnn modfcaton

366
Pulsed corona discharge oxidation in
lignin modification
Alexander Sokolov, Sergei Preis, Marjatta Louhi-Kultanen
LUT Chemistry, Lappeenranta University of Technology
ntroduction
Lgnn s a potenta raw matera for varous products ncudng phenoc substances and aromatc
adehydes (vann, syrngadehyde, vanc acd, syrngc acd) (Rodrgues Pnto et a., 2011), act-
vated carbon, carboxyc acds, and motor fue (Radoykova et a., 2011). Tradtona methods of
gnn modfcaton resutng n phenoc products ncude oxdaton wth ntrobenzene, md wet ar
oxdaton and cataytc oxdaton. Drawbacks of these methods ncude severe toxcty probems
wth ntro compounds, strct safety requrements and thus hgh capta costs, and often posoned
costy cataysts. The study consders the hypothess that modfcaton of gnn wth pused corona
dscharge (PCD) oxdaton at ambent condtons may appear feasbe and benefca method of
gnn modfcaton by ts economc performance and envronmenta safety. The method has hydrox-
y-radca and ozone as the man oxdaton speces effectve n oxdaton of gnn.
Commerca aka gnn supped by Sgma-Adrch was used as an expermenta matera. Fgure 1
shows the outne of the expermenta set-up. Aqueous gnn souton was crcuated from the reser-
vor tank through the reactor by a pump. Souton s spread between eectrodes, where the gnn
aqueous souton s treated wth oxdants. The experments were carred out at akane pH wth
dfferent nta concentratons of gnn and the composton of the gas phase - ar and ntrogen-
enrched ar wth the voumetrc oxygen concentraton of 5 to 7%. The dscharge puse parameters
ncude votage amptude of 20 kV, current of 400 A, and 100 ns duraton gvng the snge puse
energy 0.3 | at puse repetton frequency of 840 puses per second (pps). The concentraton of
gnn was measured photometrcay wth tyrosne
method. Adehyde concentraton was determned
by the coormetrc method deveoped by Evans et
a. (1973).
Lgnn appeared to be easy degradabe by PCD
treatment. On the course of treatment adehydes
accumuaton was observed n a experments.
The expermenta resuts are shown n Tabe 1.
Energy effcency of gnn oxdaton n ar s, as
expected, hgher than n ow oxygen gas, showng
the tendency of growth wth growng gnn concen-
traton. Ths s not true, however, for ow oxygen
oxdaton. One can see no tendency n adehyde
producton yed n ar and the ncreasng adehyde
formaton yed wth ncreasng nta gnn concen-
traton n the ow oxygen atmosphere. It ndcates
the growng seectvty of PCD oxdaton at ow
oxygen concentratons: adehyde formaton pre-
vas over adehyde oxdaton.

Figure 1. Expermenta setup.
Pused corona dscharge oxdaton n gnn modfcaton

367
Lgnn souton was observed to have a bufferng effect: the hgher the gnn concentraton, the
more stabe pH was observed durng the experment.
Table 1. Expermenta resuts.
niti al lignin
concentration,
mg/L
Final l ignin
concentration,
mg/L
Final aldehydes
concentration*,
mg/L
Al dehyde
formed / li gni n
oxi dised, %
Energy efficiency
in li gni n
oxi dati on, g/kWh
Energy efficiency
in aldehydes
formation, g/kWh
Gas composton: 5-7% O
2

74 47,03 2,18 8,08 10,8 0,872
136,82 89,79 5,16 10,97 18,8 2,06
285,05 239,44 6,04 13,24 18,2 2,42
650 604,30 12,44 27,22 18,3 4,98
Gas composton: Ar
78,4 14,25 8,79 13,70 25,6 3,52
141,1 34,2 9,76 9,13 42,8 3,90
276,5 125,42 14,50 9,6 60,4 5,80
558,7 393,36 17,37 10,51 66,1 6,95
*- Adehyde concentraton was recacuated to acetadehyde content

References
1. Radoykova, T., Stanuov, K., Nenkova, S. 2011. Lgnn derved methoxyphenos as ant-oxdant
addtves for gasone. Oxdaton Communcaton 34(2), pp. 463-468.
2. Rodrgues Pnto, P.C., Borges da Sva, E.A., Rodrgues, A.E. 2011. Insghts nto oxdatve
converson of gnn to hgh-added-vaue phenoc adehydes. Eng. Chem. Res 50,
pp. 741-748.
3. Evans, W.H., Denns, A. 1973. Spectrophotometrc determnaton of ow eves of mono-, d- and
trethyene gycos n surface waters. Anayst 98, pp. 782-791.

Synthetc humc materas from gneous waste materas of the South-Afrcan pupng and sugar
ndustres. Synthess and propertes

368
Synthetic humic materials from li gneous waste
materials of the South-African pulping and sugar
industries. Synthesis and properties
L. Tyhoda
1
, T. Rypstra
1
, K. Fischer
2
, T. Rosenau
3
, F. Liebner
2, 3

1
University of Stellenbosch, Department of Forest and Wood Science,
Paul Sauer Building, Bosman Street, Stellenbosch, 7600, South Africa
2
Technical University of Dresden, nstitute of Wood and Plant Chemistry,
Pienner Str. 19, D-01737 Tharandt, Germany
3
University of Natural Resources and Life Sciences, University Research Centre Tulln,
Department of Chemistry, Konrad-Lorenz-Strasse 24, A-3430 Tulln, Austria
Abstract
Over-utsaton, overgrazng and cear-feng of natura forests are current serous envronmenta
ssues. These actvtes ead to so eroson and nevtaby to so degradaton as the ferte top sos,
whch contan most of the accumuated nutrents and humc substances that contro the natura
cyce of organc matter n the bosphere, are ost. Rehabtaton of sos, .e. so mprovement and
re-estabshment of vegetaton, wth ntrogen-rch modfed gnn-based materas that share a num-
ber of smartes wth natura humc substances, appear to provde an effectve souton. Homoge-
neous oxdatve ammonoyss of technca gnns under md condtons usng an mmerson |et set-
up was confrmed to be a sutabe technoogy to smuate the natura humfcaton process. The
formaton of dfferent N-bndng forms and ther mnerasaton n so at dfferent rates render the
ammonoxdsed gnns ong-term N-fertsers. Ammonoxdaton accordng to the proposed proce-
dure was shown to gve an acceptabe ntrogen enrchment of up to 6.25 w% for most of the studed
gneous materas .e. cacum gnosuphonate, pne Kraft gnn (INDULIN AT
TM
), autohydroyss
bagasse gnn (SUCROLIN) and a gnoceuosc resdue from sugar cane bagasse autohydroy-
ss. Pre-oxdaton of the gneous materas, e.g. usng H
2
O
2
, was shown to further ncrease the
ntrogen contents. Performance evauaton of the organo-mnera fertzers on yeow mustard,
Snaps aba, reveaed that ammonoxdsed SUCROLIN and the gnoceuosc resdue, despte
havng dfferent ntrogen contents, resuted n (pant) dry mass yeds that were smary hgh as
when Novhum, a coa-based product, was apped as a reference.
The characterstcs of the products (tabe 1) revea dfferent responses of the raw materas towards
ntrogen ncorporaton, whch are nfuenced by process condtons and ther mnera and gnn
contents as we as the degree of gnn oxdaton. Comparng the two purfed gnns, t was found
that the tota N ncorporated was ceary hgher n the more oxdsed SUCROLIN (6.25%) than the
INDULIN (3.15%). The proporton of NH
4
+
n N-SUCROLIN was about 8% hgher than for N-
INDULIN due to the ts dstncty hgher degree of degradaton of the Sucron as a resut of the
steam exposon process from whch the gnn orgnates. From the pant nutrton perspectve, too
hgh NH
4
+
-N and too ow sob-N contents are not desrabe, due to the rsk of over-fertsng or ntro-
gen eachng and as such, the envsaged ong-term unachevabe. The tota ntrogen and NH
4
+
-N
contents of the N-modfed gnoceuosc resdue are dstncty ower compared to N-SUCROLIN
due to the ower gnn content. The N content n cacum gnosuphonate was n an acceptabe
range. However, the hgh proporton of suphonc groups resuts n a hgh percentage of short-term
pant avaabe NH
4
+
-N (52.7% of tota N) many by catonc exchange. Such hgh NH
4
+
vaues are
usuay not desred for so condtoner, especay when appyng the products on sandy sos snce
the percentage of pant-avaabe ntrogen s too hgh and susceptbe to eachng.


369
The obtaned C/N rato for Sucron and gnosuphonate (9.8 and 12.60 respectvey) were n the
range that s acceptabe for hgh grade humus fractons (9 to 13), whe that of Indun AT and the
gnoceuosc resdue were hgh at 19.8 and 19.50 respectvey. When the gnoceuosc resdue
was pre-treated wth 1% H
2
O
2
pror to oxdatve ammonoyss, a tota ntrogen content of 3.08%,
correspondng to a C/N rato of 15.50 was obtaned.
Table 1. Eementa composton of the products (vaues based on dry matter).
Product Carbon [ %] C/N Rat io
H
2
O
2
Tota N NH
4
+
-N NH
2
-N Sob-N
N-Sucrolin 6.25 38.42 13.00 48.58 61.30 9.80
ndulin AT 3.15 30.5 11.4 58.1 62.5 19.8
N-gnoceuosc resdue 2.64 36.57 14.92 51.59 48.50 19.50
N-gnosuphonate 3.36 52.70 11.90 35.40 42.00 12.60
NOVHUM* 3.5 10.41 14.21 44.73 60.65 ca.11
Natural humus** 1.5 10.25 21...25 ca.50 41.62 ca.17
N-gnoceuosc resdue 1% 3.08 26.95 14.61 58.44 47.80 15.50
Legend: AP =Ambent pressure. HP =Hp pressure (7.5bar). *NOVIHUM =patented reference product. **Vaues obtaned from |2|.
Evaluation on crops
So treatment wth N-modfed SUCROLIN has smar effect on the growth of yeow mustard (Sin-
apis alba) as NOVIHUM, the standard reference product (Fgure 1). Dry mass yeds from N-
Lgnoceuosc resdue (N-LRC) so treatments were consderaby good consderng the ow N
content. However, the ower ntrogen content resuted n reduced yed n the second season. In
contrast, so treatments wth N-modfed cacum gnosuphonate (N-CLS) resuted n very ow
yeds even n combnaton wth urea (NCLS-urea).

Figure 1. Dry mass yeds of yeow mustard treated wth N-modfed products at an appcaton rate
of 1% (w/w).

370
Concl usi ons
The feasbty of utzng the seected raw materas has been demonstrated. There are dfferences
n response towards ntrogen ncorporaton whch are reated to eementa as we as functona
group contents. SUCROLIN yeded a satsfactory dstrbuton of the varous proportons of ntrogen.
The resuts obtaned wth the gnoceuosc resde are qute postve especay when the raw mate-
ra s pre-treated wth H
2
O
2
. The N-modfed product prepared from cacum gnosuphonate had
comparatvey hgh NH
4
+
and ow sob-N contents, ndcatng that stronger oxdatve condtons
shoud be used. Ths woud reduce the water soubty of the products by reducng the content of
suphonc groups on the one hand, whe decreasng the content of NH
4
+
groups on the other hand.
References
1. Fscher, K., Katzur, | ., Chene, R. 1994. Organsche Dngenmtte und Verfarhren zu deren Her-
steung. EP 0689526 B1, 18.3.1994.
2. Fscher, K., Schene, R. 2002. Ntrogenous fertzers from gnns - A revew. In Chemca modf-
caton, propertes, and usage of gnn, ed.; Hu, T.O., Penum Pub. Corp.
3. Lebner, F., Fscher, K., Katzur, | ., Bcker, L. 2006. Novhum
TM
- hgh grade artfca humus and
ong astng fertzer for acceerated rehabtaton of degraded areas. ed.; UNESCO offce:
Be|ng.
4. Wang, P.Y., Boker, H.I., Purves, C.B. 1964. Canad. | . Chem. 42, p. 2434.
5. Schene, R., Pruzna, K.-D., Wenhaus, O., Fscher, K. 1979. ber de Oxdatve von Su-
ftabauge (I). Zestoff und Paper 4, pp. 163-166.
Effect of black liquor type and lignin fractionation on the polymerisation of a Kraft lignin by laccase.
Optimisation of the operation conditions

371
Effect of black li quor type and lignin fractionation on
the polymerisation of a Kraft lignin by laccase.
Optimisati on of the operation conditi ons
S. Gouveia, C. Fernndez-Costas, M.A. Sanromn, D. Moldes
Department of Chemical Engineering, University of Vigo, 36310 Vigo, Spain
Abstract
The capability of the commercial laccase NS51003 from Myceliophtora thermophila, either alone or
in the presence of mediators, to polymerise Kraft lignins isolated from black liquors was evaluated.
A solvent fractionation process was carried out in order to obtain lignin fractions with possible re-
markable polymerisation ability.
To establish the optimum polymerisation conditions, an evaluation on the effects of pH, tempera-
ture, enzyme dosage and treatment time on the molecular weight increase was made.
Polymerisation products were analysed by size exclusion chromatography and Fourier transform
infrared spectroscopy. The results evidence structural oxidation and a major increase in molecular
weight that, in some cases 110-fold its initial molecular weight.
Introduction
A growing awareness of ecological problems by the population and its rulers led to legislation in-
creasingly strict that came to affect conventional manufacturing processes for all industries. The
environmental friendly enzymatic processes already have application in the forest based industry
while many others are being investigated. Laccase is one of the most promising enzymes to be
applied in forest industry particularly in the pulp and paper industry (Widsten & Kandelbauer 2008).
Laccases are phenoloxidases capable of oxidising substrates such as phenolic compounds and
also non-phenolic compounds by means of a laccase mediator system (LMS). Laccases act over
the phenolic structure of lignin where they can both cause delignification (by rupture of lignin bonds)
or, on the contrary, may cause polymerisation (by cross-linking of lignin molecules).
In the pulp and paper industry the undesired lignin is separated from lignocellulosic materials in or-
der to obtain an enriched cellulose pulp. In the Kraft process, dominant in the pulp industry, lignin is
concentrated in so called black liquor that is afterwards incinerated for energy recovery in the process
itself. The Kraft process is in surplus in terms of energy. For this reason a portion of the lignin can be
isolated and removed from the black liquor and used as a raw material in various products, without
any negative effect on the industrial process. Although is well recognized that lignin is a high value,
non-toxic material, lignin has some characteristics such heterogeneous polymer structure, size and
functional groups that hampers its immediate applicability in some specific industrial areas. Lignin
structure modification could be a possible pathway for the resolution of these handicaps.
In the present work laccase capability to oxidise and polymerise Kraft lignins from distinct origins
was evaluated. Furthermore, the influence of lignin fractionation according to their molar mass and
the introduction of some mediators on the enzymatic polymerisation was also studied. The opera-
tional conditions, namely pH, temperature, enzyme dosage and treatment time were optimised in
order to promote polymerisation. Lignins, before and after treatment were characterized by size
exclusion chromatography and Fourier transform infrared spectroscopy.
Black liquors from Kraft cooking of Eucalyptus globulus were kindly provided from the pulp and
paper companies ENCE (Spain) and Portucel-Soporcel (Portugal) and while Europac (Portugal)
supplied black liquor from Kraft cooking of the mixture of Pinus pinaster/Eucalyptus globulus

Effect of back quor type and gnn fractonaton on the poymersaton of a Kraft gnn by accase.
Optmsaton of the operaton condtons

372
(75/25). The correspondng gnns named EK1, EK2 and EK3 respectvey were obtaned by acd
precptaton wth H
2
SO
4
. The back quor from ENCE sub|ected to sovent fractonaton as detaed
n Gouvea et al. (2012) ed to four dstnct gnn fracton: F1, F2, F3 and F4.
The commerca enzyme NS51003 was carfed n a Genera Eectrc Sephadex G-25M coumn before
appcaton. Laccase actvty was determned by the oxdaton of 4-hydroxy-3,5-dmethoxybenzadehyde
azne (SGZ). The effect of pH and temperature on the accase actvty was anaysed by means of
Centra Composte Desgn (CCD) and Response Surface Methodoogy (RSM) ndcatng that the
optmum condtons are 70C of temperature and pH 6. The enzymatc treatment was carred out n
a reacton vesse addng 0.25 to 2 U/mL of NS51003 and 1,5g/L of gnn. The enzymatc reacton
was hed at 60 to 80C for 2 to 24 h and pH vaues from 5.5 to 8.0. A the phenoc compounds
used as medators, namey, syrngadehyde (S), pyrocatecho (P), guaaco (G), vann (V), vourc
acd (AV) and poyphenon 60-Green tea (PH60) were purchased from Sgma-Adrch.
Md-Infrared spectra of the gnn sampes were recorded n a | asco FT/IR - 4100 by ATR tech-
nque. Two Poysec coumns, GPC P4000 and P5000 couped n seres were used to anayse the
gnn sampes by Sze Excuson Chromatography (SEC).
The nta treatments were performed n the condtons determned by the RSM method as the
optmum for accase actvty n SGZ. Based on the enzyme thermostabty n those condtons the
reacton treatment tme was estabshed n 1 h. The presence of medators at the tested concentra-
ton reveaed no detrmenta effect on the enzyme stabty (data not shown). Enzymatc treatment
produced an ncrease n KL1 moecuar weght (Mw) as we as an ncrease n the poydspersty for
a experments. Nevertheess, when comparng the fna vaues wth untreated KL1 vaue, the best
resuts were obtaned n the absence of medators (Contro) where the nta Mw 10-fod.
Knowng that accase actvty may change dramatcay when the substrate s modfed, the opt-
mzaton of operatona condtons was made by evauaton of gnn Mw ncrease. Temperature, pH,
treatment tme and enzyme addton type (snge or contnuous) were ad|ust n order to produce
gnn wth hgher Mw as possbe. The expermenta resuts determned that the best poymersaton
condtons wth accase NS51003 were pH 7.3, T =70C, 2 Um
-1
n a snge addton and 2 h of
treatment tme. A comparson between the dstnct gnns s presented n Fgure 1. F2 fracton was
the best succeeded n mutpyng ts nta weght whe F4 was the one that reached hgher mo-
ecuar weght n absoute terms (data not shown).

Figure 1. Moecuar weght ncrease (average moecuar weght after treatment / nta average
moecuar weght) n gnn sampes after 2 h enzymatc treatment at pH 7.3, 70C and 2 UmL
-1
.
0 5 10 15 20 25
F2
KL1
F3
KL2
F4
F1
KL3
Mw/Mwi
K
r
a
f
t

l
i
g
n
i
n

s
a
m
p
l
e

373
From the SEC chromatogram observaton three peaks can be ceary dstngushed after the enzymatc
treatment. In the case of KL1 (Fgure 2), peak 1 reaches Mw that 110-fod the untreated KL1 Mw.

Figure 2. SEC of untreated KL1 ( ) and KL1 after 2 h enzymatc treatment at pH 7.3, 70C and
2 UmL
-1
( ). Inset: Mw vaues and percentage of area for each peak.
FTIR anayss detected changes n gnn structure after poymersaton. The most reevant dfferences
were observed at the peaks correspondng to C =O stretchng and aso the ntensty for aromatc
rng vbraton pus C =O stretchng ncreased after the treatment wth NS51003 accase. However,
gnn mantaned ts aromatc structure, keepng the typca aromatc trpet. Prevous reports
(Areskogh et al. 2010), usng accase for gnosuphonates poymersaton, obtaned smar resuts.
Conclusions
Structura changes detected by FTIR reveaed that Kraft gnns were successfuy oxdsed by ac-
case NS51003. Ths oxdaton ed to gnn poymersaton wth a factor range that vared accordng
to the type of gnn and operatona condtons.
Lgnn fractons obtaned by sovent fractonaton showed dstnct poymersaton capabty.
Some of the fractons ed to poymers wth hgher average Mw than the unfractonated Kraft gnn.
Aso, accase NS51003 reveaed to be ess effcent poymersng softwood than hardwood Kraft gnn.
The studed medators dd not mprove the degree of poymersaton obtaned by the accase aone.
When operatng under optmum condtons the enzymatc treatment ed to three dstngushabe
poymers wth dfferent moecuar weght dstrbutons. The bggest one of them has ncreased the
nta KL1 Mw by 110.
Acknowledgements
Ths work was funded by Xunta de Gaca (pro|ect 09TMT012E), FEDER Funds and Mnstry of
Scence and Innovaton (pro|ect CTO2009-13651). S. Gouvea s gratefu to Fundao para a Cn-
ca e a Tecnooga - Portuga through grant POP-OREN BD 42684/ 2008 and D. Modes s gratefu
to Xunta de Gaca for an IPP contract. Ence (Span), Portuce-Soporce (Portuga) and Europac
(Portuga) are gratefuy acknowedged for suppyng the back quors. Novozymes (Bagsvaerd,
Denmark) s aso kndy acknowedged for suppyng the accase from M. thermophila.

1
2
3
Peak Mw (Da) Area (%)
KL1 4 567 100.0
Treated KL1 1 504 688 11.3
2 71 836 22.9
3 7 073 65.9

374
References
1. Areskogh, D., L, | ., Geerstedt, G., Henrksson, G. 2010. Structura modfcaton of commerca
gnosuphonates through accase catayss and ozonoyss. Industra Crops and Products
32(3), pp. 458-466.
2. Gouvea, S., Fernndez-Costas, C., Sanromn, M.A., Modes, D. 2012. Enzymatc poymersaton
and effect of fractonaton of dssoved gnn from Eucalyptus globulus Kraft quor. Bore-
source Technoogy 121(10), pp. 131-138.
3. Wdsten, P., Kandebauer, A., 2008. Laccase appcatons n the forest products ndustry: A revew.
Enzyme and Mcroba Technoogy 42(4), pp. 293-307.

Recovery strateges contro the wood hydroysate barrer performance

375
Recovery strategies control the wood hydrolysate
barrier performance
Anas bn Yaich, Ulrica Edlund, Ann-Christine Albertsson
Royal nstitute of Technology (KTH), Fibre and Polymer Technology,
School of Chemical Science and Engineering, Teknikringen 56, SE-100 44 Stockholm, Sweden
ana2@kth.se
ntroduction
Envronmenta concerns together wth the quest of a sustanabe socety have trgged consderabe
efforts n the deveopment of bo-based and envronmentay frendy packagng materas. Wthn
ths context, non-ceuosc poysaccharde materas from pants and wood, such as xyan and
gaactogucomannan, have receved much attenton for potenta use as barrer fms and coatngs
because of ther abundance, the renewabty of ther natura sources, and ther exceent oxygen
barrer property. |1, 2| The ow oxygen permeabty s a resut of the hemceuose hghy packed
structure arsng from the cohesve energy between macromoecuar chans. |3, 4|

However, the use
of hemceuoses n arge scae appcatons s st restrcted by the mutpe step procedure re-
qured for hemceuose extracton and purfcaton, whch reduces the envronmenta and economc
benefts of ther appcaton n packagng. The purpose of ths work s to desgn oxygen barrer fms
and coatngs based on a non-ceuosc poysaccharde-rch wood hydroysate (WH), derved from
hardwood hydrotherma treatment process water. A further am was to mprove the oxygen barrer
propertes n partcuar by controng the recovery routes of WH through dfferent upgradng pre-
treatments.
Experimental
Material s. The hardwood hydroysate, produced from brch mxed wth a sma fracton of aspen
wood chps by hydrotherma treatment n a batch reactor, was kndy provded by Sdra Ce AB,
Sweden. The hydrotherma procedure have been descrbed n more deta prevousy. |5| Hghy
purfed xyan from brch wood and carboxymethy ceuose (CMC) sodum sat was used as re-
ceved from Sgma-Adrch. Commercay used poy(ethyene terephthaate) (PET) fms wth a
thckness of 38 m were kndy supped by Tetra Pak Packagng Soutons AB, Sweden and used
as a coatng substrate.
nstrumentation. Hgh performance anon exchange chromatography (HPAEC-PAD, Donex
ICS-3000) was used for sugar composton anayss. Thermogravmetrc anayss TGA Metter Toe-
do TGA/STDA 851e were used to determne the water and ash content. The contaned hemceu-
oses moecuar structures were studed by proton nucear magnetc resonance (
1
H NMR). Sze
excuson chromatography (SEC) was used to determne moecuar weghts and moecuar weght
dstrbutons, of the dfferent WH fracton wth respect to puuan standards. The WH based fms
and coatngs oxygen barrer and tense performance were characterzed on a Mocon Oxtran 2/20
(Modern Contros, Mnneapos, MN) and an Instron unversa materas testng machne equpped
wth a 50 N oad ce, respectvey.
Upgradi ng pre-treatments The WH was upgraded accordng to one of three aternatve ndus-
tray feasbe routes: 1) utraftraton (resutng n fracton WH1), 2) utraftraton foowed by daf-
traton (WH2), and 3) ethano precptaton (WH3). Pecon cassette fters wth a hydrophc mem-
brane made from regenerated ceuose (PLAC Prepscae, Mpore) wth a nomna cut-off of 1000
Da and a surface of 100 cm
2
, was used durng the utraftraton and daftraton steps. In addton, a
crude WH fracton (WH0) was used where the process water dd not undergo any other treatment
that centrfugaton.
Films and coating preparation WHs based fms and coatngs contanng 40% w/w of CMC and
60% of any of the WH fractons were prepared. The water based CMC/WH mxtures were casted and


376
dred at 23C and 50% RH. For the coatngs, the WH/CMC mxtures were apped onto 12 23 cm
2

PET fms usng pant brush.
The chemca composton, average moecuar weght and structura anayss studes showed that
the upgradng pre-treatments n genera resuted n WH fractons contanng ess amount of gnn
and a arger share of hgher moecuar weght compounds. Furthermore, the hemceuose n the
up-graded fractons had ess branched structures than the one n the crude wood hydroysate
(WH0), whe the degree of acetyaton dd not change durng the up-gradng pretreatments. The
most sgnfcanty changes of the wood hydroysate structure and composton was obtaned by
ethano precptaton.
The oxygen permeabty resuts of the coatngs are represented n Fgure 1. WH-coated PET
fms, regardess of the fracton of WH used, dspay a sgnfcanty ower oxygen permeabty com-
pared to the uncoated fms. The owest OP vaue of 1.3 cm
3
m m
-2
day
-1
kPa
-1
was obtaned for the
coatng made from WH0, whe the hghest OP vaue (6.1 cm
3
m m
-2
day
-1
kPa
-1
) was obtaned for
the ethano precptated WH3. Furthermore, the tense testng showed that fms made from up-
graded WHs dspay hgher Youngs modu and tense strengths compared to those made from
hghy purfed commerca xyan (BrX) and crude WH0.

Figure 1. Oxygen permeabty (OP) of the uncoated and coated PET fms wth coatngs based on
hghy purfed commerca brch xyan (BrX), or on the dfferent wood hydroysate, crude (WH0),
utraftrated (WH1), utraftrated and daftrated (WH2) and ethano precptated (WH3).
Conclusions
Fms and coatngs were successfuy produced from hardwood hydroysates, rch n xyan and
orgnatng from the hydrotherma treatment of brch mxed wth a sma fracton of aspen. The re-
covery routes of the WH had a ma|or mpact on tense and oxygen barrer performance of the re-
spectve fms and coatngs. The crudest WH fracton wthout any upgradng pretreatment produced
coatngs wth the best performance wth respect to oxygen permeabty and was superor to anao-
gous fms based on hghy purfed xyan.

377
Acknowledgements
The authors gratefuy acknowedge VINNOVA (pro|ect number 2009-04311) and Tetra Pak Pack-
agng Soutons AB for fnanca support. Dr. Margareta Sderqvst-Lndbad at Sdra Innovaton AB
s thanked for kndy provdng the wood process water.
References
1. Hartman, | ., Abertsson, A.-C., Lndbad, M.S., S|eberg, | . 2006. | . App. Poym. Sc. 100,
pp. 2985-2991.
2. Edund, U., Ryberg, Y.Z., Abertsson, A.-C. 2010. Bomacromoecues 11, pp. 2532-2538.
3. Ryberg, Y.Z.Z., Edund, U., Abertsson, A.C. 2011. Bomacromoecues 12, pp. 1355-1362.
4. Edund, U., Yu, Y., Zhu Ryberg, Y., Krause-Rehberg, R., Abertsson, A.C. 2012. Ana. Chem. 84,
pp. 3676-3681.
5. Ibn Yach, A., Edund, U., Abertsson, A.-C. 2012. Bomacromoecues 13, pp. 466-473.
Desgn of new boresource packagng from wood hydroysates

378
Desi gn of new bioresource packaging from
wood hydrolysates
Soheil Saadatmand, Ulrica Edlund, Ann-Christine Albertsson
Fiber and Polymer Technology, Royal nstitute of Technology (KTH), SE-100 44 Stockholm, Sweden
Abstract
Two types of hemceuose-based spruce wood hydroysates were upgraded through utraftraton
and daftraton to separate the hgher moecuar weght fracton of the wood hydroysates. Upgrad-
ed wood hydroysates were thereafter used, together wth dfferent co-components to produce fms
wth very good oxygen barrer propertes and acceptabe mechanca propertes.
ntroduction
Softwood hydroysates are quds extracted from hydrotherma treatments of wood. Such process
waters and effuents typcay contan non-ceuosc ogo- and poysacchardes as a man compo-
nent of dry matter, a fracton whch can be recovered and concentrated by dfferent strateges. A
cost-effectve way of addng the vaue of by-products n commerca processes, such as pupng or
fberboard ndustres woud be to utze the wood hydroysates, n a more or ess refned state, n
the manufacturng of poymer products.(Fgure 1) Functonazatons and product formuatons
based on hghy purfed hemceuoses have been reported over the years, but from an economc
perspectve, the hydroysates coud advantageousy be separated from the product streams and
used wthout extensve refnng other than some enrchment n hgh-moecuar weght fractons. The
am was to utze the upgraded wood hydroysates as a barrer matera.

Figure 1. Process fowchart for the deveoped converson of sde-stream of pupng and fberboard
ndustres eadng to fabrcaton of renewabe barrers from wood hydroysate.

Desgn of new boresource packagng from wood hydroysates

379
Experimental
Two types of softwood hydroysate were used; the frst one (SWH) was from hydrothermay treated
wood chps whch were then upgraded through utraftraton and daftraton through membranes
wth dfferent cut-off rato. The second softwood hydroysate (MSW) was a water-based fracton
whch was coected drecty from the fberboard m Masonte AB n Sweden, and upgraded
through utraftraton and daftraton wth 1 kDa cut-off membrane. Both SWH and MSW were
freeze-dred and anaysed usng sze excuson chromatography (SEC), on exchange chromatog-
raphy (IC), nfrared (IR) spectroscopy and nucear magnetc resonance (NMR) spectroscopy. Barr-
er fms were souton casted from SWH together wth carboxymethy ceuose (CMC) or mcrofbr-
ated ceuose (MFC) as co-component and deonzed water. The hemceuose-rch MSW was
chemcay modfed by graftng L-actde branches on the hemceuose backbone, through rng
openng poymerzaton (ROP) of L-actde and the copoymer was used ater as a compatbzer n
poy L-actde (PLLA)/MSW bend fms. Afterwards mechanca and oxygen barrer propertes of the
fms were characterzed.
It was shown that the upgradng condtons and membrane cut-off affects the oxygen permeabty
of the bend fms wth CMC and MFC as co-component. Hgher cut-off rato membranes coud
separate hgher moecuar weght wood hydroysates and the fms made of hgher moecuar weght
wood hydroysates possess better oxygen barrer propertes. On the other hand, addton of chem-
cay modfed MSW enhanced the mscbty of the hydrophc wood hydroysate wthn the hydro-
phobc PLLA matrx whch as a resut mproved the fexbty of the bend fms sgnfcanty.
Concl usi on
Fms wth oxygen permeabty (OP) vaues as ow as 0.35 cm
3
m day
1
m
2
kPa
1
at 50% reatve
humdty, were produced from aqueous soutons from SWH and CMC. Wth ony 1% (w/w) of com-
patbzer the homogenety of the PLLA/MSW fms ncreased substantay that ed to a sgnfcant
ncrease of stran-at-break whch corresponds to a more fexbe fm.
Acknowledgments
Authors are thankfu to FORMAS (pro|ect number 2009-2009), Sdra Innovaton, Sdra Skogs-
garnas stftese fr forsknng, utveckng och utbdnng and Tetra Pak for fnanca support. Inn-
venta AB s aso thanked for the frutfu coaboraton.
References
1. Saadatmand, S., Edund, U., Abertsson, A.-C. 2011. Compatbzers of a purposey desgned
graft copoymer for hydroysate/PLLA bends, Poymer 52, p. 4648.
2. Saadatmand, S., Edund, U., Abertsson, A.-C., Danesson, S., Dahman, O. 2012. Prehydroyss
n Softwood Pupng Produces a Vauabe Borefnery Fracton for Matera Utzaton. En-
vron. Sc. Techno. 46, p. 8389.
Spray appcaton of bopoymers and taored refnng as toos n the producton of formabe paper
matera for nove appcatons

380
Spray application of biopolymers and tailored refining
as tools in the production of formable paper material
for novel appli cati ons
Alexey Vishtal
1
, Elias Retulainen
1
, Timo Rantanen
1
, Sauli Vuoti
2

1
VTT Technical Research Centre of Finland,
Koivurannantie 1, P.O. Box 1603, 40101 Jyvskyl, Finland
2
VTT Technical Research Centre of Finland, Valta-Akseli, P.O. Box 21, 05201 Rajamki, Finland
Abstract
Nove types of fbre-based packagng materas are the promsng drecton n the product portfoo
of modern borefneres. Despte of the advantageous features of fbre-based packagng matera
such as: bodegradabty, recycabty and renewabty, t s ackng the eve of formabty that pastc
packagng materas do have.
The formabty of matera determnes how advanced shapes can be formed for the end product.
In respect to the paper-based packagng, hgh formabty woud aow to produce contaners, trays,
shes etc. wth an advanced desgn, usng deep-drawng or correspondng type of formng process.
The nfuence of hgh-consstency refnng, and combnaton of hgh and ow consstency refnng
as we as the sprayng of dfferent bopoymers on the formabty, strength propertes and dryng
shrnkage of the sampes has been evauated n ths work. By combnng of the above-mentoned
treatments t was possbe to mprove formabty stran of the sampes from 6.5% to 13.5%.
Experimental
The pup used n ths study was market suphate pup from frst thnnng pne (Pnus syvestrs)
produced at UPM Kymmene Petarsaar m. The apped xyogucan (XG) was purfed tamarnd
kerne powder XG; the rest of bopoymers were soated and prepared at VTT Ra|amk.
Hgh-consstency refnng (25% d.s.) was performed at an eevated temperature (110C) usng
wng defbrator devce (Sundstrm et a. 1993). Low consstency refnng (LCR) was performed n
Vaey Beater accordng to SCAN-C 25:76. A4-szed handsheets (grammage 170 g/m
2
), were pre-
pared usng automatc sheet former "| uupe" n VTT | yvsky. Bopoymers as 2% water souton
were sprayed onto wet sheets usng a hgh pressure spray nozze. After sprayng sheets were a-
owed to dry freey. Formabty stran was measured usng 2D-formabty tester deveoped at VTT
| yvsky.
Results
Hgh consstency refnng (HCR) has a postve effect on the eongaton of paper by curng and
axay compressng fbres. LCR straghtens fbres, ncreasng amount of fbre contacts and thus
mproves bondng wthn the sheet (Seth 2005). By varyng the HCR refnng condtons t s possbe
to create deformatons n fbres whch woud exst n fbres after LCR. The mcroscopc mage of the
axa compressons n fbres after combned HCR and LCR treatment s shown n the Fgure 1.
Fgure 2 shows the formabty stran of the paper sprayed wth dfferent bopoymers, the formabty
stran was measured at 72C.

Spray appcaton of bopoymers and taored refnng as toos n the producton of formabe paper
matera for nove appcatons

381

Figure 1. Mcroscopc Images
of the fbres after combned
HCR and LCR treatment.
Figure 2. The nfuence of varous chemca and mechanca treatments
on the formabty stran (72C) of freey dred paper; (HCR-hgh
consstency refnng, LCR-ow consstency refnng, XG-xyogucan,
AG-arabnogaactan, CX-catonc xyan, HXPS-hydroxypropyated starch).
Combned HCR and LCR treatment has mproved eongaton of the paper on the amost 7%-ponts.
Sprayng of the of the carbohydrate poymers has mproved eongaton of the paper on somewhat
0.5-1.5%.
It can be suggested that the addton of carbohydrate bopoymers s mprovng bondng wthn
the sheet by adsorbng on the fbres and creatng ge-ke ayer (Ahrenstedt et al. 2008).
Summary
Inducton of the certan types of fbre deformatons and sprayng of bopoymers s the one strategy
for the mprovement of the strength of fbre |onts and bondng n genera. Strong bondng wthn the
sheet and hgh eongaton potenta of fbres yeds n the paper wth hgh formabty.
Acknowledgements
Future borefnery programme of Forestcuster Ltd. and VTT Graduate Schoo are gratefuy
acknowedged for provdng fnanca support for ths work.
References
1. Seth, R.S. 2005. Understandng sheet extensbty. Pup and Paper Canada 106(2), pp. 33-40.
2. Ahrenstedt, . et a. 2008. Paper dry strength mprovement by xyogucan addton: Wet-end ap-
pcaton, spray coatng and synergsm wth borate. Hozforschung 62(1), pp. 8-14.
Renewabe barrer fms from wood hydroysates

382
Renewable barrier films from wood hydrolysates
Yingzhi Zhu Ryberg, Ulrica Edlund, Ann-Christine Albertsson
Fiber and Polymer Technology, Royal nstitute of Technology (KTH),
SE-100 44 Stockholm, Sweden
Abstract
To study, deveop and enabe ndustray feasbe utzaton of wood hydroysates (WHs), a Han-
sens Soubty Parameter (HSP) mode was deveoped. The mode ams to desgn formuatons
based on WH for effcent oxygen barrer fms and coatngs. Anayses such as Poston Annhaton
Lfetme Spectroscopy (PALS) and oxygen permeabty (OP) tests strongy supported the mode.
ntroduction
WHs are hemceuose-rch bomass derved from qud sde streams of wood processng ndus-
tres. Our HSP mode ams to desgn and predct formuatons of WHs for barrer fms and coatngs
|1-4| for food packagng. The mode cacuated soubty parameters to reate the chemca compo-
ston of WH to oxygen barrer performances.
Experimental
Both softwood and hardwood hydroysates were coected from hydrotherma treatment of wood
chps. Ion exchange chromatography (IC) was used to determne sugar compostons of WH. Fms
and coatngs were produced by castng bends of WHs and other poysacchardes such as carbox-
ymethy ceuose (CMC) or chtosan. Our HSP mode determned the nteractons between compo-
nents n the WH-based fms/coatngs and further predcted OP. PALS and OP tests were conduct-
ed to characterze the fms/coatngs to support the mode (Fgure 1).
Hansen's solubility parameter
The deveoped HSP mode quantfed the correatons between chemca structures and moecuar
nteracton of WH-based fm and coatngs. The resuts showed that there were strong nteractons
between gnn and hemceuose n WH as we as between WH and other co-components such as
CMC and chtosan. Stronger nteractons ead to a densey packed system and may thus ead to a
good barrer performance.
Characteri zation
PALS detected sze and dstrbutons of free voumes n WH-based fms and resuts showed that
the predcted more densey packed fms had accordngy smaer sze for free voumes hoes. OP
tests aso confrmed that fms/coatngs wth a stronger nteracton possessed a ower OP.

Renewabe barrer fms from wood hydroysates

383

Figure 1. HSP mode quantfed nteractons n WH-based fms/coatngs reatng them to oxygen
barrer performance.
Conclusions
We have deveoped a mode based on HSP whch has shown a great potenta to ntroduce WH to
food packagng ndustry. The deveoped mode successfuy quantfed the chemca structure as
we as nteractons n WH-based fms/coatngs. Stronger nteractons resut n a densey packed
matrx and thus tend to have a better oxygen barrer performance. Resuts from PALS and OP
anayses strongy supported the mode.
Acknowledgements
VINNOVA (Pro|ect No. 2009-04311), Sdra Innovaton, Tetra Pak Packagng souton.
References
1. Edund, U., Ryberg, Y.Z., Abertsson, A.-C. 2010. Barrer fms from Renewabe Forestry Waste.
Bomacromoecues 11(9), pp. 2532-2538.
2. Ryberg, Y.Z., Edund, U., Abertsson, A.-C. 2011. Conceptua Approach to Renewabe Barrer
Fm Desgn Based on Wood hydroysate. Bomacromoecues 12(4), pp. 1355-1362.
3. Yu, Z., Edund, U., Ryberg, Y.Z., Krause-Rehberg, R., Abertsson, A.-C. 2012. Poston Lfetme
Reveas the Nano Leve Packng n Compex Poysaccharde-Rch Hydroysate Matrx.
Ana. Chem. 84, pp. 3676-3681.
4. Ryberg, Y.Z., Edund, U., Abertsson, A.-C. 2012. Retrostructura Mode to predct bomass for-
muatons for barrer propertes. Bomacromoecues 13(8), pp. 2570-2577.
hydrophobcty

384
Functionali zing of cellul osic fibres through patented
modi fication reactions to increase hydrophobi ci ty
Kristina Elg Christoffersson
1
, Hans Grundberg
1
, Mrten Hellberg
2
, Ali Naderi
2
, David Blomberg
3
1
Domsj Fabriker AB, SE-89186 rnskldsvik, Sweden
2
OrganoClick AB, Ritarslingan 20, SE-18766 Tby, Sweden
3
Processum Biorefinery nitiative, P.O. Box 70, SE-89122 rnskldsvik, Sweden
Abstract
Ceuose s modfed wth a patented method from OrganoCck to produce a hghy hydrophobc
fbre.
ntroduction
Akoxysanes present hghy reactve speces whch have attaned consderabe nterest by the
scentfc communty and the ndustry, as they aow for ndustra reevant tmes. Today, Organo-
Cck AB s n possesson of a technoogy whch empoys sanes for functonazaton of ceuose-
based materas. Ths process s tested on ceuosc fbres from Doms| Fabrker n order to modfy
the poarty of the fber.
Experimental
Specaty pup wth 100 and 50% dry content were used throughout the pro|ect. The pup was dsn-
tegrated and thereafter strred (soaked) n OC-aquas, (ethano (95% purty) souton contanng
10% actve agents) for 15 mnutes. Excess formuaton was thereafter ftered of and pressed out
and the modfed fbres were dred at 150C for 5 mnutes. The fbres were subsequenty washed (to
remove the catayst) by strrng them n water for 20 mnutes, ftered and paced n the oven unt
they were competey dry.
Results
A hghy hydrophobc fber was syntheszed trough the patented process. The hydrophobcty has
been evauated by a seres of anaytca tests.
Contact ange measurements of sheets produced wth the hydrophobc fbers were performed
wth contact anges of up to 150, see Fgure 1.

hydrophobcty

385

Figure 1. Contact ange measurement.
The fbres preference for varous sovents were tested wth a cear resut that they aways preferred
the most hydrophobc sovent (see Fgure 1 and 2).

Fi gure 2. Non-modfed ceuose n organc sovent/water system.
hydrophobcty

386

Figure 3. Hydrophobzed ceuose n the same system.
Furthermore, anayss of scon content, as we as WRV and Soxhet extracton wth 1-propano
were performed, a ndcatng that the fbre had became more hydrophobc and that the hydropho-
bcty remaned aso after extensve washng.
Conclusion
The possbty of usng the OrganoCck-technoogy to functonaze the specaty ceuose of
Doms| Fabrker AB was nvestgated by usng the OC-aquas product to hydrophobze the f-
bres. It was shown that the mentoned technoogy can be successfuy used to render the fbres
hydrophobc, demonstrated by the arge contact ange (average 139,5 o usng water dropets), by
the scon content, by the WRV and by the fact that the sampes stayed hydrophobc even after a
proonged Soxhet extracton usng 2-propano. It was aso ceary shown that the modfed fbres
prefer organc sovents to water n contrast to untreated fbres.
The potenta future appcatons for the hydrophobc fbres deveoped n ths pro|ect can possbe
be n areas such as bo compostes (e.g. pastc components), and n the constructon ndustry, e.g.
gypsum where a hydrophobc fbre coud be of nterest to make the gypsum core ess sensbe to
mod.
Nanoceuose as a toughenng agent

387
Nanocellulose as a toughening agent
Mindaugas Bulota, Mark Hughes
Department of Forest Products Technology, School of Chemical Technology, Aalto University,
Abstract
Beached brch Kraft pup was oxdzed usng 2,2,6,6-tetramethypperdne-1-oxy radca (TEMPO)
medated oxdaton to obtan TEMPO-oxdzed fbrated ceuose (TOFC). It was acetyated and
added to PLA suspenson n choroform to prepare compostes to weght fractons of 1, 2 and 5%. It
was observed that the mechanca behavour of the composte fms was sgnfcanty atered upon
the addton of TOFC. It was affected by both the weght fracton of TOFC and a DS. Toughness of
PLA ncreased by an order of magntude at a oad of 1 wt% of TOFC wth a DS of 0.6. Athough the
Youngs moduus and tense strength decreased at ow fractons of TOFC an ncrease n both was
acheved at 5 wt% oad of TOFC havng a DS of 0.6.
ntroduction
Bo-compostes have receved a ot of attenton durng the ast coupe decades or so. Many re-
search groups amed to use nanoceuose, due to ts hgh stffness, as renforcng agent of poymer
matrces. Athough many promsng resuts were acheved the deformaton mechansms n ths type
of composte materas have not been expaned yet. Contnuum mechancs, whch s wdey ap-
ped, has ts mtatons due to the assumpton of homogenety. Most of the materas are heteroge-
neous at mcro and nano scaes thus new methods have to be apped. Contradctory reports can
be found n the terature regardng the effects of nanoceuose on poymer matrces thus there s a
need of n depth study of the mcromechancs of nanoceuose renforced compostes.
Heren a study on TEMPO-oxdzed nanoceuose renforced compostes s presented. In par-
tcuar, the toughenng effect of nanoceuose s addressed. The effect of chemca modfcaton of
nanoceuose on the mechanca behavour of compostes s dscussed.
Experimental
Beached brch Kraft pup was oxdzed accordng to the method ntroduced by Sato et a. |1| under
akane condtons. It was mechancay dsntegrated unt a transparent ge was obtaned whch,
hereafter, s termed TEMPO-oxdzed fbrated ceuose (TOFC). TOFC was acetyated n DMF
wth acetc acd at 125 5C for 45 mn. A detaed descrpton of the acetyaton reacton can be
found esewhere |2|.
The degree of substtuton of hydroxy groups was evauated usng a standard Eberstadt method |3|.
Commercay avaabe PLA - poy(actc) acd (NatureWorks 2002D, NatureWorks, Mnnetonka,
MN, USA) was used as the matrx. PLA was dssoved n choroform to obtan a suspenson havng
a concentraton of 2 wt%. Then t was mxed wth the acetyated TOFC dspersed n choroform to
prepare compostes to weght fractons of 1, 2 and 5 wt% by sovent castng.
Toughness ncreased by an order of magntude at a oad of 1wt% TOFC wth a DS of 0.6 and -7 tmes
n the case of TOFC havng a DS of 0.4 (Fgure 1). The Youngs moduus of the compostes wth 1 wt %
oad of TOFC decreased at both DS eves. An ncrease n both the Youngs moduus and tense
strength by 10 and 15% respectvey was observed at 5 wt% oad of TOFC at a DS of 0.6. Addton of 1
wt% of TOFC changes deformaton mechansms at both eves of DS. Stran-to-faure ncreases two-fod

Nanoceuose as a toughenng agent

388
upon the addton of TOFC havng a hgher DS (Fgure 1). Stran-to-faure s -30 and -15 tmes hgher
compared to pure PLA at 1 wt% oad of TOFC havng a DS of 0.6 and 0.4 respectvey (Fgure 1).

Figure 1. Representatve stress-stran curves for fed PLA and pure PLA fm. The nset depcts
the curves up to a stran of 6% |4|.
Conclusions
The addton of TOFC as we as ts chemca modfcaton has a sgnfcant nfuence on the behav-
our of composte fms. The addton of 1 wt% of nanoceuose has resuted n mproved toughness
of the compostes.
References
1. Sato, T., Nshyama, Y., Putaux, | ., Vgnon, M., Isoga, A. 2006. Homogeneous Suspensons of
Indvduazed Mcrofbrs from TEMPO-Catayzed Oxdaton of Natve Ceuose. Bom-
acromoecues 7(6), pp. 1687-1691.
2. Buota, M., Tanpcha, S., Hughes, M., Echhorn, S.| . 2011. Mcromechancs of TEMPO-oxdzed
fbrated ceuose compostes. ACS Apped Materas & Interfaces 4(1), pp. 331-337.
3. Tanghe, L.| ., Genung, L.B., Mench, W.| . 1963. In Methods n Carbohydrate Chemstry, Whster, R.L.,
Green, | .W., BeMer, | .N., Wofrom, M.L. (Eds.). Academc Press Inc., London. P. 201.
4. Buota, M., Hughes, M. 2012. Toughenng mechansms n poy(actc) acd renforced wth TEMPO-
oxdzed ceuose. | . Mater. Sc. 47(14), p. 5517-5523.
Ceuose regeneraton from soutons of eucayptus wood n 1-ay-3-methymdazoum chorde

389
Cel lulose regenerati on from sol utions of eucal yptus
wood in 1-allyl-3-methylimidazolium chloride
A. Casas, M.V. Alonso, M. Oliet, F. Rodriguez
Chemical Engineering Department, Complutense University or Madrid
Avda. Complutense S/N. 28040 Madrid (Spain)
Tel: (+34)913948505, Fax: (+34)913944243
acasasga@quim.ucm.es
Abstract
In ths work, Eucalyptus globulus wood has been dssoved n the 1-ay-3-methymdazoum cho-
rde (AmmC) onc qud empoyng mcrowave radaton as heatng source. The wood dssouton
process was performed n the mcrowave oven at 140C for 20 and 40 mn. Then, ceuose was
regenerated from the wood quors usng methano as antsovent. Fourer transform nfrared spec-
troscopy (FTIR) was empoyed to characterze the recovered product and compare t to the refer-
ence matera, mcrocrystane ceuose (MCC).
ntroduction
Ceuose s the prncpa component of the wood ce wa and the most abundant poymer on Earth.
In the context of the borefnery and the effcent empoyment of gnoceuosc materas, the deveop-
ment of green processes for dssovng wood and separatng ceuose woud be reay nterestng |1|.
Ionc quds are an attractve aternatve n ths regard. Recenty, ILs have been empoyed as wood
and ceuose sovents |2-4|. Thus, the most promsng ILs for bomass dssouton seem to be
those wth acetate and chorde anons, and mdazoum catons |4|. The am of ths work s to re-
generate ceuose from eucayptus wood dssoved n 1-ay-3-methymdazoum chorde, to ana-
yze t by FTIR and compared t to mcrocrystane ceuose.
Experimental
4% sampes of Eucalyptus globulus wood (provded by Torras Pape) were dssoved n the 1-ay-
3-methymdazoum chorde onc qud (AmmC, Iotec) wth a mcrowave oven (Berghof
SpeedWave Four) at 140C and two dfferent dssouton tmes (20 or 40 mn). Ceuose was re-
generated from the wood soutons usng dry methano (Panreac) as antsovent n a 10/1 metha-
no/wood souton rato. Regenerated ceuose was coected by ftraton, dred overnght, and ana-
yzed by FTIR (Mattson Satete 5000); the spectra of regenerated ceuoses were compared to
that of mcrocrystane ceuose (Sgma Adrch), empoyed as reference matera.
The FTIR spectra of MCC and the regenerated ceuoses from soutons of eucayptus wood n
AmmC at 140C and the studed dssouton tmes (20 and 40 mn) are dspayed n Fgure 1. Ac-
cordng to the resuts of the FTIR spectra, regenerated ceuose was very smar to MCC, and
showed the characterstc vbraton bands of the gucose rngs at 1160, 1111 and 897 cm
-1
|4|. In
addton, the characterstc aromatc skeeta vbraton of the gnn rngs, ocated at 1510 cm
-1
, s not
observed n the spectra of regenerated ceuoses, so ceuose s not recovered together wth gnn |3|.
Therefore, ceuose has been successfuy regenerated under the studed condtons.

Ceuose regeneraton from soutons of eucayptus wood n 1-ay-3-methymdazoum chorde

390

Figure 1. FTIR anayss of MCC and regenerated ceuoses (140C; 20 or 40 mn).
Conclusions
The current study shows that ceuose can be regenerated from soutons of Eucalyptus globulus
wood n 1-ay-3-methymdazoum chorde usng methano as antsovent.
Acknowledgment
The authors are gratefu to the "Mnstero de Economa y Compettvdad" and the "Comundad de
Madrd" for the fnanca support of Pro|ects CTO2010-15742 and S2009/PPO-1545, respectvey.
References
1. Xe, H., Kpenen, I., Kng, A., Lesknen, T, | rv, P., Argyropouos, D.S. 2010. Opportuntes
wth wood dssoved n onc quds. ACS Symposum Seres, 1033, p. 343.
2. Fort, D.A., Remsng, R.C., Swatosk, R.P., Moyna, G., Rogers, R.D. 2007. Can onc quds
dssove wood? Processng and anayss of gnoceuosc materas wth 1-n-buty-3-
methymdazoum chorde. Green Chem. 9, p. 63.
3. Casas, A., Aonso, M.V., Oet, M., Ro|o, E., Rodrguez, F. 2012. FTIR anayss of gnn regener-
ated from Pnus radata and Eucayptus gobuus woods dssoved n mdazoum-based
onc quds. | . Chem. Techno. Botechno. 87, p. 472.
4. Casas, A., Paomar, | ., Aonso, M.V., Oet, M., Omar, S., Rodrguez, F. 2012. Comparson of
gnn and ceuose soubtes n onc quds by COSMO-RS anayss and expermenta
vadaton. Ind. Crop. Prod. 37, p. 155.
Producton and separaton of water soube ceo-ogomers by supercrtca water treatment and
membrane ftraton

391
Production and separati on of water sol uble cell o-
oligomers by supercritical water treatment and
membrane filtration
Lasse Tolonen
,
, Annariikka Roselli
, Herbert Sixta
Department of Forest Product Technology, School of Chemical Technology, Aalto University
Authors have equal contribution

Abstract
Mcrocrystane ceuose was dssoved usng rapd supercrtca water treatment. Formed ceo-
ogomers of DP3-9 were separated and concentrated by membrane ftraton (500 Da cut-off).
ntroduction
Supercrtca water treatment dssoves ceuose as a ow moar mass poymer n a very rapd reac-
ton. |1| Ceuose undergoes fragmentaton reactons under supercrtca water condtons resutng
n water soube mono- and ogosacchardes and acds from retroado reactons. Dependng on the
condtons, a certan ceuose fracton s sovated as poymer that regenerates as ceuose II sub-
strate upon coong. |2|
Experimental
A pug-fow reactor was used to treat mcrocrystane ceuose n supercrtca water at 385C for
0.15 s at 25 MPa. After the remova of precptated ceuose, membrane daftraton was performed
by an Afa Lava TestUnt M20 wth a LabStack M20 ftraton modue. Used membrane was a Nadr
NP030 P of 500 Da cut-off. The operated ftraton surface area was 0.144 m
2
. 5 ters of the sou-
ton from the supercrtca water treatment was apped n the ftraton unt. The voume was kept
constant by addng on exchanged water durng the process. In tota 25 ters of permeate was re-
moved. In order to determne the effectveness of the purfcaton, the deveopment of fux, absorb-
ance, and TOC were foowed. Ogomer concentratons were anaysed by HPAEC-PAD wth a PA-
100 coumn.
Supercrtca water treatment at 385C resuted n practcay compete dssouton of mcrocrysta-
ne ceuose. In the foowng 24 hours, 26 wt% of dssoved ceuose precptated at room tem-
perature and was removed by a 5-10 m fter. In subsequent membrane ftraton, ow moar mass
compounds permeated through the membrane and were removed wth permeate whereas the
compounds of hgher moar mass were retaned n the system. HPAEC-chromatograms (Fgure 1)
confrm that a ma|orty of the monosacchardes and degradaton products were removed. A sgnf-
cant amount of the DP3-9 ogomers remaned n the retentate resutng n purfcaton of the ceo-
ogomers. The poymerc ceuose fragments of hgher moar mass were aready argey removed
by precptaton and ftraton pror to the membrane ftraton.

Producton and separaton of water soube ceo-ogomers by supercrtca water treatment and
membrane ftraton

392

Figure 1. Concentratons of gucose and ceo-ogomers n retentate n the begnnng and at the
end of the experment (eft), and n permeate after 3 and 25 ters were removed (rght).
Durng the ftraton, the tota organc carbon content of the souton was reduced from 340 mg/L to
150 mg/L. The deveopment of the absorbance was n accordance wth the TOC-resuts. Durng the
ftraton, the fux decreased from 60 to 32 L / (m
2
h) due to concentraton poarzaton. Fgure 1
shows that athough the 500 Da cut-off membrane s capabe to retan a ma|orty of the ceo-
ogomers n the retentate, a part of the ogomers permeate through the membrane. Therefore, t
seems possbe to enhance the separaton effcency by usng a membrane wth a ower cut-off.
Conclusions
We successfuy demonstrated how ceo-ogomers are purfed by a membrane ftraton wth a 500
Da cut-off membrane. Therefore, t s a feasbe downstream process n the producton of water
soube ogosacchardes from ceuose by supercrtca water treatment. We estmate that the per-
formance of the ftraton can be mproved by optmzng ftraton tme and by seectng a membrane
of ower cut-off.
Acknowledgements
Forest Custer Ltd. through FuBo-programme and Tekes are gratefuy acknowedged for fundng
ths research. Sanna Koutanem and Ma|a Tenkanen are thanked for HPAEC-anayses.
References
1. Sasak, M., Adschr, T., Kuno, A. 2004. Knetcs of Ceuose Converson at 25 MPa n Sub- and
Supercrtca Water. AIChE | . 50, pp. 192-202.
2. Yu, Y., Wu, H. 2009. Characterstcs and Precptaton of Gucose Ogomers n the Fresh Lqud
Products Obtaned from the Hydroyss of Ceuose n Hot-Compressed Water. Ind. Eng.
Chem. Res. 48(23), pp. 10682-10690.
Comparson of oxygen degnfcaton of hgh-kappa pne Kraft pup n throughfow and batch mode

393
Comparison of oxygen delignification of high-kappa
pine Kraft pulp in throughfl ow and batch mode
Vahid Jafari
1
, Herbert Sixta
1
1, 2
1
2
Department of Chemical and Biological Engineering, University of Maine,
5737 Jenness Hall, Orono, ME 04469-5737 USA
*Corresponding author vahid.jafari@aalto.fi
Abstract
A hgh degnfcaton-ceuose degradaton seectvty s needed for oxygen degnfcaton of hgh-
kappa softwood pups n order to produce a beachabe-grade pup of good vscosty. Ths may be
acheved by keepng the NaOH concentraton at a reatvey ow but constant vaue throughout the
degnfcaton process |1|. To evauate ths concept, a 65 kappa pne Kraft pup wth vscosty of
1295 m/g was oxygen degnfed n a throughfow type Berty reactor where the pup s kept n a
basket at medum consstency. A reatvey hgh feed fow rate of the oxygenated caustc souton
resuts n essentay constant NaOH and dssoved oxygen concentratons durng the degnfcaton
process. These experments show that t s possbe to obtan a sgnfcanty hgher degree of deg-
nfcaton n the Berty reactor than n a batch reactor at smar vscostes and gnn-free yeds of
the pups.
ntroduction
A promsng method for ncreasng the effcency of softwood degnfcaton to reach a beachabe
grade pup s cookng to a hgh kappa number pup (60-90) foowed by oxygen degnfcaton to a
gven kappa number |2|. Unt now, the oxygen degnfcaton knetcs of hgh- kappa number pne
Kraft pup has been examned ony n batch reactors. Snce the caustc concentraton decreases n
batch reactors over tme due to acd formaton n the reacton process, the effcency of the process
decreases and requres mutpe stages wth fresh aka ntroducton to reach a beachabe grade
pup. An aternatve approach s to use a through fow reactor wth suffcent suppy of an oxygenat-
ed caustc souton. Ths approach aso may potentay ncrease the pup yed and vscosty of the
fna Kraft pup |3|.
An ndustray produced hgh-yed pne kraft pup (kappa number 65, ntrnsc vscosty of 1295 mg/
and pup yed 51%) was used. Tabe 1 shows the condtons for the batch reactor mutstage oxy-
gen degnfcaton at 10% consstency and 3, 2 and 1% NaOH (o.d pup) correspondng to an nta
aka concentraton of 3.3, 2.2 and 1.1 g/ NaOH. The aka concentratons n three separate fow-
through experments are 1.1, 1.8 and 2.2 g/ NaOH, a at 90 mn, 95C, 7 bar O
2
. The resuts of
these four experments are compared n Fgure 1 and 2.

Comparson of oxygen degnfcaton of hgh-kappa pne Kraft pup n throughfow and batch mode

394
Tabl e 1. Condtons of dfferent oxygen degnfcaton experments
Batch reactor (Airbath digester)

OOO (pulp kappa 65)
3% NaOH 30 mn, 85C, 7 bar O
2

2% NaOH 60 mn, 95C, 7 bar O
2

1% NaOH 60 mn, 95C, 7bar O
2

Berty react or (Continuous stirred t ank reactor)
O (pul p kappa 65) 1.1, 1.8 and 2.2 g/ NaOH 90 mn, 95C, 7 bar O
2

The resuts n Fgure 1 show that the hgh kappa softwood Kraft pup can be degnfed to the same
eve (kappa 20) n both approaches wth a sghty hgher vscosty (30 m/g) n fow-through exper-
ments performed usng 1.8-2.2 g/ NaOH. More mportanty, the mprovement n gnn-free pup yed
obtaned wth the throughfow approach n Fgure 2 s amost 1.5% based on the orgna wood weght.

Figure 1. Effect of aka charge on vscosty and
kappa n fow through and batch reactor.

Figure 2. Comparson of Lgnn-free yed on
wood (%) versus kappa number for pups used
n fow through and batch reactor.

Acknowledgement
The authors ke to acknowedge the Forestcuster LTD for fnanca care.
References
1. van Henngen, A., | , Y. 2012. Southern pne oxygen degnfed pups produced n a Berty
throughfow reactor: How to obtan the hghest degree of degnfcaton whe mantanng
pup yed and quaty. Tapp | ourna 11(3), pp. 9-18.
2. Agarwa, et a. 1999. Knetcs of Oxygen Degnfcaton. | PPS 25(10), pp. 361-366.
3. | , Y., Van Henngen, A. 2007. A new CSTR for oxygen degnfcaton mechansm and knetcs
study. Pup & Paper-Canada 108(5), pp. 38-42.
20 30 40 50 60 70
800
1000
1200
1400
2.2 g/ NaOH
1.8 g/ NaOH
1.1 g/NaOH
OOO
Brown-stock
Ar-bath dgester
Berty reactor
V
s
c
o
s
t
y

(
m
/
g
)
Kappa #
20 30 40 50 60 70
42
44
46

L
g
n
n
-
f
r
e
e

y
d

o
n

w
o
o
d
(
%
)
Brown- stock
Ar-bath dgester
Berty reactor
Kappa #
2.2 g/ NaOH
1.1 g/NaOH
1.8 g/ NaOH
OOO
Hemceuose precptaton n methano-water soutons and ts effect wth soubty parameters

395
Hemicellulose precipitation in methanol-water
solutions and its effect with solubility parameters
Karol Peredo, Andrea Andrade, Miguel Pereira
University of Concepcion, Chile
karolperedo@udec.cl
ntroduction
The nterest n the use of the wood hemceuoses has ncreased n the ast years, specfcay as a
raw matera for materas producton because ther fm formng propertes. Ths research contrb-
utes to the understandng of the phenomenon by studyng the soubty of the hemceuose. Re-
gardng ths, evauaton of Hansen soubty parameters (HSP) w aow a frst step towards the
predcton of hemceuose soubty n dfferent organc sovents. The foowng questons are ex-
pected to be responded regardng precptaton of hemceuoses:
What s the effect of the methano concentraton n precptaton yed?
Whch s the effect of hemceuose structure and purty on ts precptaton?
Are HSP a too to predct precptaton behavor of hemceuose?
Methodology
Background
The HSP concept (Hansen 2000) regards the tota coheson energy for a moecue as a sum of
three ndvdua ntermoecuar nteractons; the nonpoar forces (D), the dpoe dpoe nteractons (P),
and the hydrogen bondng (H) so that the soubty parameter, , may be expressed n accordance
wth eq. (1):
2 2 2 2
d p h
d d d d = + +
(1)
The dfference "R
a
" between the two moecues to be mxed, denoted P and S respectvey, s quan-
tfed by eq. 2 and t represents a measure of the nteracton between two moecues:
2 2 2 2
( ) 4( ) ( ) ( )
a Dp Ds Pp Ps Hp Hs
R d d d d d d = - + - + -
(2)
Experimental
Precptaton wth methano were carred out at concentratons of 4:1, 3:1 2:1 and 1:1 (v/v) from
quors formed wth hemceuoses obtaned from Eucalyptus globulus hooceuose (H
1
) and wood
(H
2
) extractons wth 5% KOH souton at 20C. Precptaton yed was determnate, HPLC anayss
were performed to determne sugar concentraton, whereas moecuar weght where obtaned by
HPLC-SEC. Hansen soubty parameters (HSP) for water and methano were based on terature
(Hansen 1976) whe soubty parameters of hemceuose fragments were estmated from the
group contrbuton method based on the estmaton of moecuar structure. Fms were made by
castng wth de H
1
and H
2
fractons.
Results
For H
1
and H
2
there was an ncreasng trend n precptaton yed wth methano addton for both
hemceuose fractons (Tabe 1) and they are n agreement wth the HSP dfference wth the so-
vent, nevertheess sma dfferences mpes sgnfcant changes n precptaton. From carbohydrate
anayss (data not shown), xyose was the predomnant monomer, ndcatng a ow quantty of ram-


396
fcatons f we consder the mode presented by Evtugun et a. (2003). Consderng ths mode for
H
1
, a xyose near chan was proposed for carry out the cacuatons wth the group contrbuton
mode to obtan the HSP of the H
1
fracton. Lgnn content n H
2
was 12% and ths content was
ncuded n the cacuatons of HSP.
Table 1. Soubty parameters of the dfferent hemceuose fractons.

Figure 1. (A) SEC anayss of hemceuose fracton H
2.
Dotted ne: IR sgna. Sod ne: UV sgna.
(B) hemceuose fms, H
2
(eft) and H
1
(rght).
SEC anayss presented a bmoda behavor (Fgure 1A), showng at east two dfferent popuatons
of precptates at approxmatey 8 kDa (23 mnutes) and 100 kDa (17 mnutes approx.) n hemceu-
ose H
1
, n hemceuose H
2
8kDa and 120kDa. The smutaneous sgna at IR and UV detector
show evdence of gnn assocated to hemceuose, and that s the reason of the dfference be-
tween both fractons. Fms wth the H
1
and H
2
fractons were produced by castng (Fgure 1B), and
the H
2
fms hgher stabty and eastcty, perhaps because the presence of gnn whch can act as
a pastczer, ths topc requres further nvestgaton.
Conclusion
There was an ncreasng trend n precptaton yed wth methano addton for both hemceuose
fractons (H
1
and H
2
). HSP represents the phenomenon of precptaton evauatng the nteractons
between moecues, nevertheess sma dfferences mpes sgnfcant changes n precptaton.
SEC anayss presented a bmoda behavor, showng at east two dfferent popuatons of precp-
tates at approxmatey 8 kDa and 100 KDa (H
1
), and 120 kDa (H
2
). Ths ncrement of 20 kDa coud
be expaned because of the assocated gnn wth the hemceuose. Lgnn present n hemceu-
ose fractons coud act as a pastczer n fms produced.
Acknowledgements
Ths work has been possbe by doctora schoarshp from Conicyt, Che.

397
References
1. Evtugun, D.V., Tomas, | . L. et a. 2003. Characterzaton of an acetyated heteroxyan from Eu-
cayptus gobuus Lab. Carbohydrate Research 338(7), pp. 597-604.
2. Hansen, C.M. 2000. Hansen soubty parameters : a users handbook. Boca Raton, Fa., CRC Press.
Recovery of hgh moar mass hemceuoses from brch saw dust

398
Recovery of high molar mass hemicelluloses
from birch saw dust
Mari Kallioinen
1
, Olli Byman
2
, Tuomas Nevalainen
1
, Sanna Hautala
2
, Veikko Kitunen
2
,
Petri Kilpelinen
2
, Hannu lvesniemi
2
, Mika Mnttri
1

1
Laboratory of Membrane Technology and Technical Polymer Chemistry, Department of Chemical
Technology, Lappeenranta University of Technology,
P.O. Box 20, Lappeenranta, F-53851, Finland
2
Finnish Forest Research nstitute (Metla),
Vantaa Research Unit, P.O. Box 18 (Jokiniemenkuja 1), 01301 Vantaa, Finland
ntroduction
One group of the nterestng raw materas possbe to harvest from borefnery process streams s
the hemceuoses havng a moar mass hgher than 15 kDa. They can be used, for nstance, n
manufacturng of packagng fms. The fracton used n the fm manufacturng shoud contan ony
sma amount of mpurtes such as gnn dervatves. Moreover, the hemceuose content of the
fracton shoud be hgh. Ths study ams to deveopng of a process, n whch the hgh moar mass
hemceuose fracton s produced from brch saw dust.
The hemceuoses were extracted from brch saw dust wth pressurzed hot water n a fow-through
system wth a 300 ter extracton chamber. The extracton temperature was beow 175C and fow-
rate approxmatey 20 L/mn n a the extractons. The wood extract was treated wth the RC70PP
utraftraton (UF) membrane (10 kDa, regenerated ceuose, Afa Lava) to produce the fracton
contanng the hgh moar mass hemceuoses. The fractonatons were performed wth the CR-
fters at 60C at 2 bar. Foung of the membrane was evauated by measurng pure water fux be-
fore and after the fractonaton. Membranes were ceaned wth akane ceanng agent.
Ths study has shown that producng of a hgh moar mass hemceuose rch fracton from brch
saw dust s possbe by combnng pressurzed hot water extracton process wth UF. The best pro-
duced fractons fufed the requrement for moar mass (Tabe 1). However, after the UF the gnn
dervatve content of the fractons was too hgh, about 20% of TDS (Tabe 1). Daftraton after the
UF step was not effcent enough for gnn remova. Ths means that for producng the hgh moar
mass hemceuose fractons, whch contan ony sma amount of gnn, a hybrd process, n whch
gnn dervatves are removed ether before or after the UF step, s needed. The gnn remova step
before the UF mght aso mprove the ftraton capacty, whch decreases sgnfcanty due to the
ncreasng TDS of the feed when the fractonaton was proceedng.
Table 1. Informaton on fractonaton resuts acheved durng ths study.
The birch extr act used as the feed The produced hi gh mol ar mass fracti on
TDS,
%
Hemi celluloses,
%
Average Molar
mass, kDa
Hemi celluloses,
g/L
Lignin from
the TDS, %
4.7 3.3 31 124 18
2.3 1.7 27 93 21

Recovery of hgh moar mass hemceuoses from brch saw dust

399
Ths study proved that the hydrophc RC70PP membrane s a feasbe membrane for concentra-
ton of the hgh moar mass hemceuoses. Athough the foung potenta of the wood extracts s
hgh, the RC70PP membrane s not sgnfcanty foued when wood extracts are treated and ts
ftraton capacty can be fuy restored by akane ceanng (Fgure 1).

Figure 1. Pure water fuxes of the RC70PP membrane measured before and after the fractonaton
of wood extracts wth the CR-350 fter at 50C and at 1 bar. The rotor speed was 9.5 m/s. The
membrane was ceaned wth akane ceanng agent after the experments.
Acknowledgements
The authors are gratefu to the Future Borefnery Research Program FuBo 2 for fnanca support.
0 20 40 60 80
Brch_1, TDS 1.3%
Brch_2 TDS 1.6%
Brch_3 TDS 2.3%
Brch_4 TDS 3.1%
Brch_4.2 TDS 0.3%
Pure water fl ux, kg/m
2
h
Before
After
Scae-up of pressursed hot fow-through extracton system

400
Scale-up of pressurised hot flow-through
extraction system
Petri Kilpelinen
1
, Kaisu Leppnen
1
, Sanna Hautala
1
, Olli Byman
1
, Veikko Kitunen
1
,
Stefan Willfr
2
, Hannu lvesniemi
1

1
Finnish forest research institute (Metla), Jokiniemenkuja 1, F-01301 Vantaa, Finland
2
bo Akademi Process Chemistry Centre, Porthansgatan 3, F-20500 bo, Finland
ntroduction
Ogomerc and poymerc hemceuoses are a renewabe raw matera source, whch s not fuy
utzed n ndustry. Wood hemceuose can be utsed ndustray e.g. for fms and barrers n
packagng. Xyo-ogosacchardes from gnoceuosc bomass have aso been used to produce
food addtves and nutraceutcas |1|. Pressursed hot water extracton (PHWE) usng a fow through
technque has been proven to be an effectve way to extract hemceuoses from wood |2, 3|.
Experimental
Pressursed hot water extracton was performed at two dfferent scaes: aboratory scae (50 mL
extracton vesse) and pot scae (300 L extracton vesse). Laboratory-scae extractons were car-
red out n order to determne the optma extracton condtons (temperature, tme, and fow rate) for
extractng ogomerc and poymerc hemceuose from brch and spruce sawdust. The sma scae
experments are rapd, aowng reatvey quck screenng of the extracton parameters. The best
extracton condtons obtaned n the aboratory scae experments were seected and tested n the
pot scae extracton system (Tabe 1). Extracton vesse was pre-fed wth water usng hgher fow
rate and the actua extracton started when ar was reeased from the extracton vesse and the
sower constant fow through vesse was ad|usted.
Table 1. Extracton parameters.
Spruce Birch Spruce Birch
Voume of the extracton vesse 300 L 50 mL
Sawdust 117 kg 137 kg 19.4 g 22.8 g
Extracton temperature, C 180 165 180 165
Extracton tme, mn 60 60 60 60
Fow, L/mn 20 20 - -
Fow, mL/mn - - 3.3 3.3
Pre-fng stage
5mn
40 L/mn
5mn
40 L/mn
5 mn
6.7 mL/mn
5 mn
6.7 mL/mn

The most of carbohydrates were extracted from spruce sawdust at 20 mnutes (Fgure 1). For brch
sawdust the most of carbohydrates were extracted after 25-30 mnutes.

Scae-up of pressursed hot fow-through extracton system

401

Figure 1. Extracted carbohydrates obtaned wth sma and arge scae extracton vesses.

Yed of the extracted carbohydrates was hgher wth spruce sawdust compared to brch sawdust
due to hgher extracton temperature. Brch sawdust was extracted usng ower temperature to
decrease the formaton of gnn precptates, whch otherwse contamnate the product. Aso arger
300 L extracton vesse gave hgher extracton yed for spruce at the 20 mnutes than 50 mL vesse,
probaby due to technca dfferences between arge scae and sma scae systems, especay the
temperature contro. Xyans from brch sawdust were reeased earer after 20 mnutes wth 50 mL
vesse than wth 300 L vesse.
Conclusions
Based on these resuts, aboratory scae and scaed-up sma pot scae system gave reatvey
smar resuts. Carryng out aboratory scae experments s a rapd way to screen extracton pa-
rameters whch can be apped to arger scae extractons. There are st dfferences between ex-
tracton yed and extracton tme but sma scae extractons gve predctons for further experments
at arge scae.
References
1. Moure, A., Gun, P., Domnquez., Para|, | . 2006. Advances n the manufacture, purfcaton
and appcatons of xyo-ogosacchardes as food addtves and nutraceutcas. Process
Bochem. 41, pp. 1913-1923.
2. Kpenen, P., Leppnen, K., Spetz, P., Ktunen, V., Ivesnem, H., Pranovch, A., Wfr, S.,
Pressursed hot water extracton of acetyated xyan from brch sawdust, Nord. Pup Pap.
Res. | . (Submtted.)
3. Leppnen, K., Spetz, P., Pranovch, A., Hartonen, K., Ktunen, V., Ivesnem., H. 2011. Pressurzed
hot water extracton of Norway spruce hemceuoses usng a fow-through system. Wood.
Sc. Techno. 45, pp. 223-236.
0
5
10
15
20
25
30
0 10 20 30 40 50 60
Tme / mn
Spruce 300 L
Brch 300 L
Spruce 50 mL
Brch 50 mL
g /
Fractonaton of PHW extracts n a pup m borefnery. Part I: a process concept

402
Fractionation of PHW extracts in a pulp mill biorefinery.
Part : a process concept
Tuomo Sainio, Mari Kallioinen, Olli Nakari, Mika Mnttri
Lappeenranta University of Technology, Department of Chemical Technology,
ntroduction
Pup m borefnery schemes have been nvestgated from severa ponts of vew. These ncude
the nfuence of hemceuoses extracton on the quaty of pup and the overa energy baance,
energy effcency of therma separatons, nvestment and operaton costs as we as the roe of
subsdes for process economy. Obvousy, separaton technooges pay a key roe n producton of
bo-based chemcas n forest borefneres. Here we focus on producton of monosacchardes and
other chemcas from hemceuoses extracted from pne wth pressurzed hot water pror to pupng.
The proposed process scheme (Fgure 1) nvoves fractonaton of the hot water extract wth mem-
brane ftraton, hydroyss of hemceuoses wth sufurc acd, and recovery of monosacchardes
and other products by chromatography |1|. Each process step was nvestgated expermentay by
usng an authentc pne extract (P-factor 200).

Figure 1. Scheme for processng pressurzed hot water extracts n a pup m borefnery.
Results
The frst treatment step for hot the water extract s purfcaton and concentraton of the hemceu-
oses by membrane ftraton. Severa membranes were tested (UC030, UFX10, UFX5, GR95PP). It
was found that the extract coud not be concentrated wth UFX5 n a snge step (Fgure 2, eft) but
two ftraton steps are necessary. In the frst step, a 30 kDa UF membrane (UC030) was used to
remove poyphenos. The yed of hemceuoses was reasonaby good snce approxmatey 75% of

Fractonaton of PHW extracts n a pup m borefnery. Part I: a process concept

403
carbohydrates passed the UC030 when VRF was 11. The frst UF stage both purfed the hemce-
uose souton and mproved the ftraton capacty n the second stage where a tghter UF mem-
brane (UFX5, 5 kDa) was used to concentrate the souton (Fgure 2, eft). The tota carbohydrate
concentraton n UFX5 concentrate was 29 g/L. It was not mted by membrane performance but
the amount of avaabe extract. The monosaccharade content of the permeate of the UFX5 mem-
brane was nterestng: t was found to contan mosty arabnose, whch coud thus be recovered as
a separate product fracton.
Hemceuoses recovered and purfed wth utraftraton were hydroyzed to monosacchardes at
80C by usng suphurc acd (5 wt-% to 21 wt-%) as a catayst. The reacton was compete n ess
than two hours at the hghest acd concentraton. Formaton of furans (furfura or hydroxymethy
furfura) from monosacchardes was found to be sow but acetc acd was formed rapdy wthn the
frst 10 mnutes.
Chromatographc separaton wth strong acd on exchange resn (H
+
form) as the statonary
phase was used to fractonate the acdc hydroysate nto a number of fractons. CS16GC (Fnex
Oy, Fnand) was seected out of severa resns tested. Monosacchardes were recovered at hgh
purty (Fgure 2, rght). The acd fracton contaned some monosacchardes, but ths does not ead
to a oss of monosaccharde yed because the acd fracton can be recyced back to the hydroyss
reactor (Fgure 1). The monosaccharde fracton contaned a the dfferent monosacchardes be-
cause they are not separated from each other wth a SAC resn n H+form. The thrd product frac-
ton was neary pure acetc acd. Aso the fermentaton nhbtors were effectvey separated from
other products durng the chromatographc fractonaton.

Figure 2. Left: Utraftraton of PHWE. Rght: chromatographc fractonaton of acd hydroysed
hemceuose concentrate.
These expermenta resuts demonstrate that membrane ftraton and chromatographc separaton
can be combned to produce and recover severa chemcas from pressurzed hot water extracts n
a pup m borefnery.
References
1. Sano, T., Kaonen, M., Nakar, O., Mnttr, M. 2012. Producton and recovery of monosac-
chardes from gnoceuose hot water extracts n a pup m borefnery, Boresource
Technoogy, n press.
Fractonaton of PHW extracts n a pup m borefnery. Part II: enhanced performance of
utraftraton

404
Fractionation of PHW extracts in a pulp mill biorefinery.
Part : enhanced performance of ultrafiltration
Mari Kallioinen
1
, Tuomo Sainio
2
, Mika Mnttri
1
1
2
Laboratory of ndustrial Chemistry,

ntroduction
Utraftraton (UF) n two steps (the 30 kDa UC030 foowed by the 5 kDa UFX5) has been pro-
posed for fractonaton of hemceuoses from pressurzed hot water extract (PHWE) of pne |1|.
Generay, t s expected that hgh temperature mproves the ftraton capacty and ncreases the
energy effcency of the fractonaton process. However, t has been shown that the second frac-
tonaton step s amost mpossbe to perform due to severe ftraton capacty decne and foung f
the frst step s conducted at 70C |2|. The goa of ths study was to fnd out f the proposed frac-
tonaton process coud be enhanced by adsorpton pretreatment.
Experimental
Nononc hydrophobc poymer Amberte XAD-16 (Rohm and Haas) was chosen as the adsorbent.
The pretreatment was done n two ways: by usng the adsorbent n the feed tank durng the ftraton
or by performng the pretreatment as a separate step before the UF fractonaton.
Adsorpton pretreatment decreased the amount of gnn and wood extractves n the extract sgnf-
canty (Tabe 1).
Table 1. Infuence of the adsorbent pretreatment performed as a separate step on the content of
the pne extract.
Ori ginal pine extract Pretreated pine extract
UV-abs. 280 nm 70 24
TOC, mg/L 8 790 5 360
Turbdty, NTU* 3 660 40
Fatty acds, mg/L 16 7
Resn acds, mg/L 18 >5
Lgnans, mg/L 43 >5
*sampe was not preftered

The pretreatment resuted n mproved ftraton capacty at the second fractonaton step (UFX5)
and enabed the operaton of both fractonaton steps at 70C. However, t was aso observed that
the frst fractonaton step wth the 30 kDa membrane s necessary to acheve a stabe ftraton
capacty at the second fractonaton step even n the case of adsorpton pretreatment (Fgure 1).
The best ftraton capacty of the second step (UFX5) was acheved, when the adsorbent pretreat-

Fractonaton of PHW extracts n a pup m borefnery. Part II: enhanced performance of
utraftraton

405
ment was performed n a separate vesse before the frst fractonaton step. Ths opton was thus
adopted for subsequent fractonaton experments performed n sem-pot scae. In the sem-pot
scae the pretreatment enabed a successfu operaton at 70C at the both fractonaton steps. The
ftraton capacty at the second step (UFX5) decreased ony from about 100 ony to 80 kg/(m
2
h bar)
athough the voume reducton factor vaue was as hgh as 28 at the end of the ftraton. The UFX5
membrane was not foued durng the experment.

Figure 1. Ftraton capactes (permeabtes) of the UFX5 membrane at the second fractonaton
step after the dfferent adsorbent pretreatment optons.
Conclusions
Ths study demonstrates that UF fractonaton of wood extracts can be sgnfcanty enhanced wth
the adsorpton pretreatment wth XAD16. Optmsaton of pretreatment condtons and dosng s
needed to mnmse possbe hemceuose osses due to the adsorpton treatment.
References
1. Sano, T., Kaonen, M., Nakar, O., Mnttr, M. 2012. Producton and recovery of monosac-
chardes from gnoceuose hot water extracts n a pup m borefnery, Boresource
Technoogy. (In press.)
2. Kaonen, M., Kovua, E., Puro, L., Mnttr, M. 2011. Infuence of operatng temperature on
fractonaton n utraftraton of wood-based hydroysate, NWBC 2011, Stockhom, March
22-24.
0
10
20
30
40
50
60
0 20 40 60 80
P
e
r
m
e
a
b
i
l
i
t
y
,

k
g
/
(
m
h

b
a
r
)
Fi ltration time, min
Adsorbent n the feed tank,
1st ftraton stage UC030
Adsorbent pretreatment n
the separate vesse, 1st
ftraton stage UC030
Adsorbent pretreatment n
the separate vesse, 1st
ftraton stage UFX5
Extracton of hemceuose and condensed tannn from spruce bark

406
Extracti on of hemicellul ose and condensed tannin
from spruce bark
Katariina Kemppainen, Vidar Grnberg
VTT Technical Research Centre of Finland, P.O. Box 1000, F-02044 VTT
ntroduction
Tannn ndustry s ookng for new ndustra sources for condensed tannns due to the mted ava-
abty of the current raw materas such as Acacia bark and quebracho wood. Spruce bark s a
promsng source of poyphenoc compounds ncudng condensed tannns, whch can be extracted
n an unpressurzed hot water treatment. In addton to phenoc compounds, hot water extracton
dssoves a arge amount of hemceuose and monosacchardes from spruce bark. To be abe to
fractonate these two groups of compounds and to fnd uses for the extractabe bark sugars, t s
mportant to understand the effect of extracton parameters to the extract composton and ts sugar
profe. The research eadng to these resuts has receved fundng from the WoodWsdom-Net
Research Programme whch s a transnatona R&D programme |onty funded by natona fundng
organsatons wthn the framework of the ERA-NET WoodWsdom-Net 2.
Industra shredded spruce bark was coected from FnnForest Loh|a sawm. The bark was ex-
tracted unpressurzed for 120 mn n a 15 L pressure cooker that rotated 2.3 rpm. The amount of
bark durng extracton was 5, 10 or 15% of tota mass and temperature was kept at 60, 75 or 90C.
Two extractons were carred out wth sodum bsuphte and sodum carbonate dosed as 2% and
0.5% of bark dry weght.
Chemca composton of the bark was anaysed ncudng pophc extractves (hexane extrac-
ton), Kason gnn, acd soube gnn, ash and carbohydrates. Neutra carbohydrates were ana-
ysed by HPLC after acd hydroyss and acdc carbohydrates by GC after methanoyss due to ther
degradaton n acd hydroyss. Neutra and acdc monosacchardes n the extracts were anaysed
by HPLC. Tota neutra sugars were anaysed by HPLC after md acd hydroyss. Methanoyss and
GC anayss was performed to anayse soubzed acdc poy- and ogosacchardes n the extract.
Condensed tannn was anaysed wth acd butano method (Gessner and Stener, 2005) usng
commerca sovent purfed quebracho tannn by Svateam, Itay, as standard.
Carbohydrate content of the ndustra saw m spruce bark was 59-63% dependng on the anayss
method (acd hydroyss and HPLC or methanoyss and GC). The most abundant sugars were
ceuosc gucose (22.1% of bark dry matter), non-ceuosc gucose (12.8%) and gaacturonc acd
(8.1%) foowed by sma amounts of arabnose, mannose, xyose, fructose and gaactose (2-4%
each). The bark contaned 31.1% Kason gnn, 2.7% acd soube gnn, 2.9% pophc extractves
and 3.1% ash. However, t must be noted that some phenoc non-gnn compounds n bark such as
hgh moecuar weght tannns precptate n acdc condtons and show up as Kason gnn.
Up to 20.9% of bark dry matter coud be soubzed n the treatment. The extract conssted mosty
of tannn, free monosacchardes and bound sugars. Bound sugars can be hemceuosc or pectc
sugars, gycosdc sugars or sugars bound n some other way and reeased n md acd hydroyss
or methanoyss. Monosacchardes n the extract accounted for up to 4.4% and tota sugars ac-
counted for up to 10.7% of bark dry matter. Maxmum obtaned tannn yed was 9.6% of bark dry
matter whch shows the potenta of spruce bark as a raw matera for ndustra tannn.
Hgher extracton temperature ncreased tota extracton yed and especay the yed of con-
densed tannns but dd not affect the extracton yed of monosacchardes. Increasng sods content

Extracton of hemceuose and condensed tannn from spruce bark

407
durng extracton decreased tota extracton yed sghty. Extracton ads sodum bsuphte and
sodum carbonate mproved the soubsaton of tannn and decreased the extracton of bound
sugars. Out of the ma|or sugars, non-ceuosc gucose and gaactose were extracted most eff-
centy. The monosaccharde and bound sugar profe was smar n a the obtaned extracts. On
average 48% of the extract monosacchardes was fructose and 47% was gucose whereas 67% of
the bound sugars was gucose, 11% gaactose and 9% gaacturonc acd. The hgh amount of sou-
bsed free and bound gucose suggests the soubsaton and parta ceavage of gycosdc com-
pounds durng the extracton.

Figure 1. Tota and component extracton yeds durng extracton of spruce bark at 5-15% bark
content at 60-90C wth or wthout chemcas (2% sodum bsuphte and 0.5% sodum carbonate).
References
1. Gessner, M.O., Stener, D. 2005. Acd butano assay for proanthocyandns (condensed tannns). In:
Methods to study tter decomposton. Graa, M.A.S., Brocher, F., Gessner, M.O. (Eds.).
Sprnger, Netherands, pp. 107-114.
0,0
5,0
10,0
15,0
20,0
60C 75C 90C 60C 75C 90C 60C 75C 90C 60C 75C
5 % 10 % 15 % 10% +
chem
Y
i
e
l
d

(
%

o
f

b
a
r
k

D
M
)
Monosacchardes
Bound sugars
Tota sugars
Tannn
Tota extracton yed
Methods to remove fouants from wood extracts pror to utraftraton

408
Methods to remove foulants from wood extracts
prior to ultrafiltration
Elsi Koivula, Mari Kallioinen, Mika Mnttri

ntroduction
Wood extracts contan hemceuoses, gnn-derved matera, wood extractves and smaer
amounts of other compounds. Hemceuoses can be used n producton of dfferent commodtes f
they can be recovered and purfed from the extract. Utraftraton s a potenta separaton process
for ths purpose. However, gnn and wood extractves cause foung of the membranes |1, 2|,
whch decreases the ftraton capacty.
Adsorpton wth poymerc adsorbents has proven to be effectve n gnn remova, but t has re-
suted n hemceuose osses. Reason for that mght be a nkage between some of the hemceu-
oses and gnn. Thus, pretreatment method shoud break the nkage between hemceuoses and
gnn, and at east party remove gnn but not hemceuoses.
Experimental
In ths study dfferent treatments amng to reduce the amount of gnn n brch extract were tested
and ther effcency was evauated. The effcency of the treatment was ponted out by utraftraton
experments and by chemca anayss of the soutons. Permeate fux and foung were used to
evauate the changes n the ftraton capacty.
Pretreatment
Tested pretreatment methods were enzymatc (accase) degradaton (60C, 180 mn, phase rato
0.01), foccuaton (p-DADMAC, room temperature, phase rato 0.1, mxng tme 30 mn, settng
tme 60 mn), and adsorpton on chtosan (60C, 60 mn, phase rato 0.2).
Filtration
The extract was ftrated wth a ab-scae strred Amcon 8400 fter ce (membrane surface area
0.0040 m
2
, 5.5 bar, 60
o
C, voume reducton factor (VRF) vaue 2) and UFX5 membrane (5 kDa, PSu).
Pure water fuxes (PWF) were measured before and after the ftraton of the extract, and permeate
fux was measured durng the ftraton of the extract.
Analysis
UV absorbance (at 205 nm) and hemceuose content (monomers) were determned from the extract.
UV absorbance refers to the presence of gnn-derved matera, and t was measured wth UV/VIS
spectrophotometer. Hemceuoses after hydroyss were anaysed wth gas chromatograph.
Accordng to PWF measurements (Tabe I), any of tested pretreatments dd not affect the foung of
the membranes, however, when comparng the permeate fuxes, mprovement can be seen wth
enzyme treatment and chtosan adsorpton. Foccuaton decreased the permeate fux. In addton,
enzyme and chtosan treatments decreased the UV absorbance most, whe foccuant seemed to

Methods to remove fouants from wood extracts pror to utraftraton

409
decrease t ess. It was aso notced, that durng enzyme treatment the UV absorbance was frst
decreased more, and after one hour treatment, t started to rse agan towards the orgna vaue,
however wthout reachng t n three hours.
Table 1. Tested pretreatment methods and ther effect on ftraton and UV absorbance of the extract.
Pretreat ment PWF decli ne % Flux (kg/m
2
h) UV (205 nm) - Lignin g/l
None 83 15 479 4.4
Enzyme 83 36 373 3.4
Foccuant 92 12 448 4.1
Chtosan 94 20 259 2.4
Conclusions
Enzyme treatment and adsorpton on chtosan mproved the permeate fux when they were used
pror to utraftraton of brch extract. These two methods aso decreased the UV absorbance of the
extract. Enzyme treatment was most effectve n ncreasng the fux, t was ncreased 140%, and
chtosan adsorpton decreased the UV absorbance most. Foccuaton had negatve effect on per-
meate fux. In future experments, enzyme treatment mght be reasonabe to be stopped wth nhb-
tor at the pont where UV absorbance s owest. In addton, t coud be combned wth adsorpton on
chtosan, or some other adsorbent.
Acknowledgements
The authors wsh to thank Mr Yegor Chechurn for hs vauabe work wth aboratory experments. The
authors are aso gratefu to the Future Borefnery Research Program FuBo for fnanca support.
References
1. Puro, L., Tannnen, | ., Nystrm, M. 2002. Anayses of organc fouants n membranes foued by
pup and paper m effuent usng sod-qud extracton. Desanaton 143, pp. 1-9.
2. Maartens, A., | acobs, E.P., Swart, P. 2002. UF of pup and paper effuent: Membrane foung
preventon and ceanng. | . Membr. Sc. 209, pp. 81-92.
Purfcaton of hardwood-derved autohydroysates

410
Purification of hardwood-derived autohydrolysates
Joni Lehto, Raimo Aln
University of Jyvskyl, Department of Chemistry, Laboratory of Applied Chemistry
P.O. Box 35, F-40014 University of Jyvskyl, Finland
Abstract
Brch (Betula pendula) chps were pre-treated (autohydroysed) at two temperatures (130C and 150C)
and varyng pre-treatment tmes (30-120 mnutes). Produced autohydroysates were purfed wth
respect to non-carbohydrate components, wthout carbohydrate osses, ether by ethy acetate
extracton or XAD-4 resn treatment. Autohydroysates were anayzed n terms of carbohydrates
(mono-, ogo-, and poysacchardes), aphatc carboxyc acds (formc and acetc acds), gnn, and
other organcs (many extractves and furans) before and after purfcaton experments.
ntroduction
Durng the past decades, the converson of bomass nto "green chemcas" has receved a growng
goba attenton |1|. One of the most promsng optons s to ntroduce a pressurzed hot-water
treatment (PHWT) stage nto the exstng kraft pupng process many servng the purpose of re-
coverng soube hemceuoses and other organc components from wood chps pror to degnfca-
ton |2|.
However, autohydroyss s not a seectve extracton process |3|. For ths reason, autohydroy-
sates are chemcay rather compex, contanng a mxture of varous carbohydrates and mnor
amounts of other organcs such as aphatc carboxyc acds, furanoc compounds, and gnn- and
extractves-derved components. As many of these non-carbohydrate compounds can be detr-
menta, especay when consderng the subsequent utzaton of the carbohydrate fracton, the
remova of these nhbtors s necessary.
Experimental
Autohydrolyses
Screened chps were pre-treated n an o-heated batch dgester, at two temperatures (130C and
150C) and wth four treatment tmes (30, 60, 90, and 120 mnutes). Pre-treatments covered the
P-factor range from 10 to 238. Lquor-to-wood rato was 5 L/kg and utra hgh quaty (UHO) water
was used as sovent.
Purificati on of the autohydrolysates
Produced autohydroysates were purfed by ethy acetate extracton and XAD-4 resn treatment.
Analyti cal determinations
The content of soube gnn was determned wth a Beckmann DU 640 UV/Vs-spectrophotometer
at 205 nm. Carbohydrates (monomerc and tota carbohydrates) were anayzed wth a Donex hgh
performance qud chromatography (HPLC) equpped wth a CarboPac PA-1 coumn. Voate acds
(formc and acetc acds) were determned by HPLC (a Donex chromatography system and an
IonPac AS 11-HC anaytca coumn). Furanoc compounds (furfura and 5-(hydroxymethy)furfura)
were determned wth a Waters HPLC system and a Phenomenex Gemn C18 coumn.

Purfcaton of hardwood-derved autohydroysates

411
Results
Ethyl acetate extracti on
Wth ethy acetate extracton, t was notced that n each case, roughy haf of the dssoved gnn
was removed by ths smpe extracton procedure. In addton, the furanoc compounds were effec-
tvey removed, and no detectabe amounts of them were found after extractons. On the other
hand, the resuts ndcated that the ethy acetate extracton had no sgnfcant effect on the concen-
traton of free monosacchardes, or the tota carbohydrate content. In addton, no degradaton of
ogo- or poysacchardes coud be observed, snce, n each case, the monosaccharde-to-
poysaccharde rato remaned rather constant.
Treatment wi th XAD-4 resin
Wth XAD-4 treatment, roughy one-thrd of the dssoved gnn, and neary 90% of the furanoc
compounds coud be removed from the hydroysates. In genera, XAD-4 treatments dd not have
any sgnfcant effect on the concentraton of soube carbohydrates, or on the monosaccharde-to-
poysaccharde rato. Voate acds coud not be removed from the hydroysates wth resn treat-
ments.
Conclusions
Autohydroyss s an effcent and envronmentay frendy method for producng carbohydrate-
contanng hydroysates, whch can be further processed to varous chemcas and bofues. Due to
ther compex chemca nature, addtona purfcaton step s requred.
Sgnfcant amounts of gnn and furanoc compounds were removed from hydroysates contan-
ng carbohydrates (obtaned from the autohydroyss of hardwood chps pror to degnfcaton),
ether by reatvey smpe methods such as sovent extracton (wth ethy acetate) or resn treatment
(wth XAD-4 resn). In addton, purfcaton experments caused no carbohydrate osses or degrada-
ton of ogo- or poysacchardes.
References
1. An, R. 2011. Borefnng of Forest Resources, Vo. 20, An, R. (ed.). Paper Engneers Asso-
caton/Paper |a Puu Oy, Hesnk.
2. Amdon, T.E., Lu, S. 2009. Water-based woody borefnery. Botechn. Adv. 27(5), pp. 542-550.
3. Pamqvst, E., Hahn-Hgerdah, B. 2000. Fermentaton of gnoceuosc hydroysates. I:Inhbton
and detoxfcaton. Bores. Techn. 74(1), pp. 17-24.
Hot water extracton of hemceuose from softwood and sugarcane bagasse usng mcrowave
heatng technoogy

412
Hot water extraction of hemicellulose from softwood
and sugarcane bagasse using microwave heating
technol ogy
Karin yaas
1
, ngvild A. Johnsen
1
, Brd H. Hoff
2
, Mihaela T. Opedal
1
,
Kai Toven
1
, Tore Aa. Gulbrandsen
2

1
Paper and Fibre Research nstitute, NO-7491 Trondheim, Norway
2
Norwegian University of Science and Technology, Dep. of Chemistry, NO-7491 Trondheim, Norway
Abstract
Hemceuose extracton from softwood and sugarcane bagasse was studed usng md extracton
condtons (hot water, mcrowave (MW) heatng) n order to avod extensve hemceuose degrada-
ton. For both raw materas, yeds ncreased up to 10 mnutes extracton tme. At onger tmes, the
carbohydrates began to decompose. The ncrease n yed was most pronounced from 175C to
180-185C. Optmzaton anayses of percentua yed and degree of poymersaton (DP) ndcated
that the best trade-off between the two parameters n the gven temperature-tme regon was 183C
and 12 mnutes extracton for bagasse and 183C and 5 mnutes for softwood. At these condtons,
the optmzaton mode predcted a yed of 62% and a DP of 100 for bagasse and a yed of 50%
and a DP of 31 for softwood.
ntroduction
Pretreatment of gnoceuoses s a cruca step n the producton of fues and chemcas, sgnfcant-
y affectng the composton and structure of ceuose, gnn and hemceuoses. A strategy for
avodng hemceuose degradaton (retan hgh DP) durng pretreatment coud be to extract the
hemceuoses from the raw matera pror to further pretreatment. In ths way the hemceuoses
can be used for other vaue-added products or hydroysed and fermented to acohos. 4-O-
Acetygaactogucomannan (AcGGM) s the predomnant hemceuose n softwoods whereas arab-
nogucuronoxyan s the domnant hemceuose n sugarcane bagasse.
Studes by others |1| on hemceuose extracton from spruce by mcrowave (MW) treatment,
have reported a maxmum yed of 70%wt (referred to mannan) by usng MW-heatng at 200C for 5
mnutes. Ths equas 0.125 g of extracted ogosacchardes per gram dry wood. Decomposton of
the poymers was most prevaent above 200C at 2 mn extracton tme. Further, a study of moar
mass dstrbuton of spruce hemceuoses after SEC-fractonaton |2| found that the ow moecuar
mass fracton contaned many ow weght arabnogucuronoxyan ogosacchardes (DP vaues
from 4 to 20), whe for the fracton euted asty, O-acetygaactogucomannan was domnant, wth a
peak-average DP vaue of 14. The amount of acety sde groups decreased as the DP decreased.
Experimental
Two raw materas were used - softwood sawm shavngs (90% Norway spruce and 10% Scots pne)
and sugarcane bagasse (Braz). A 4x4 factora setup (Temp =175-180-185-190C, tme =2-6-10-20 mn)
was apped. Dsted water was added to gve a sod:qud rato of 1:10. Ths mxture was eft
overnght for soakng pror to extracton. Tras were performed usng a heatng ramp of 1.5 mn.
After extracton, the vesses were cooed (ce bath, 5 mn). The extracton qud was ftered (GF/A,
Whatman, 1.6 m) and stored (-18C) for anayss. The ftrates were anaysed wth respect to car-
bohydrate composton (HPAEC) and sugar moecuar sze dstrbuton (usng SEC-MALS).

Hot water extracton of hemceuose from softwood and sugarcane bagasse usng mcrowave
heatng technoogy

413
Extracton tme and temperature sgnfcanty affected yed, DP and acdty of the hemceuose
extracts. For both sugarcane bagasse and sawm shavngs, yeds ncreased up to 10 mnutes
extracton tme. At onger tmes, the carbohydrates began to decompose. The yed ncrease was
most pronounced from 175C to 180-185C, for both materas. The effect of tme and temperature
on DP dffered markedy for the two raw materas. Whereas the bagasse hemceuoses showed
the hghest DP-vaue around 5 mn extracton tme the softwood hemceuoses started depoymer-
zng aready after a few mnutes. Ths may be reated to deacetyaton of the AcGGM n softwood,
causng a ower apparent DP due to nvsbty of deacetyated compounds n the anayss. Fur-
thermore, the fna pH n the extracton qud was consstenty ower for softwood than for bagasse
at equa yeds. Ths s possby due to a hgher nta acety content n softwood, but coud aso be
an ndcaton of more pronounced deacetyaton n softwood than n bagasse.
Optmzaton anayses of the responses on percentua hemceuose yed and DP ndcated that
the best trade-off between the two parameters n the gven temperature-tme regon s found at
183C and 12 mnutes extracton for bagasse and 183C and 5 mnutes for softwood. At these
condtons, the optmzaton mode predcted a yed of 62% and a DP of 100 for bagasse and a
yed of 50% and a DP of 31 for softwood. Anayses from the cosest correspondng expermenta
condtons (185C, 10 mn and 185C, 6 mn, respectvey) gave hemceuose yed of 60% and
DP =111 (M
w
=38 400 g/mo) for bagasse and 55% yed and DP =23 (M
w
=5 700 g/mo) for softwood.
Acknowledgement
for fnanca support. Prof. | yr-Pekka Mkkoa and Andrey Pranovch (bo Akadem) are acknow-
edged for assstance n SEC-MALLS-anayses. Mr|ana Fpovc and Ingeb|rg Lerset (PFI) are
acknowedged for assstance n HPAEC anayss.
References
1. Pam, M., Zacch, G. 2003. Extracton of hemceuosc ogosacchardes from spruce usng m-
crowave oven or steam treatment. Bomacromoecues 4(3), pp. 617-623.
2. | acobs, A., Lundqvst, | ., Stabrand, H., T|erned, F., Dahman, O. 2002. Characterzaton of
water-soube hemceuoses from spruce and aspen empoyng SEC/MALDI mass spec-
troscopy. Carbohydrate Research 337(8), pp. 711-717.
Modeng of hot water extracton of sawdust

414
Modelling of hot water extraction of sawdust
Susanna Kuitunen, Waqar Ahmad, Ville Alopaeus
Chemical engineering, Department of Biotechnology and Chemical Technology,
School of Chemical Technology, Aalto University
Abstract
In ths paper physco-chemca mode for hot water extracton of sawdust s presented. The mode
takes nto account reevant physco-chemca phenomena: reacton knetcs, acd-base equbrum,
mass transfer, and the on exchange property of wood, .e. the Donnan effect. Furthermore, the
changes n moecuar weght dstrbuton (MWD) of hemceuoses durng the processng are mod-
eed. The mode can be used for a pror predctons on the hot water extracton process behavour
wth dfferent raw materas and processng condtons.
ntroduction
In modeng reacton knetcs of hot water extracton (HWE) of wood, accurate estmaton of hydro-
gen on concentraton s mportant because hydrogen ons catayze many reactons |1|. It has been
shown that Donnan theory can be apped for modeng on exchange, caused by dssocatng acds
and phenos covaenty bound to fbre wa, n water - wood fbre suspenson. Due to the fbres
caton exchange property, hydrogen on concentraton s hgher n qud bound to fbre wa. The
acdc reactons products formed durng HWE aso nfuence on the behavour of the pH and need
to be consdered n the mode especay at ow L:W ratos.
In ths paper, the two recenty conducted modeng works |1, 2| are combned for the compre-
hensve reacton knetc modeng of HWE of wood mea n batch reactor setup.
Simulation model and setup
Speces nfuencng pH n addton to GGM are consdered n the mode. Lgnn, ceuose, and rest
of the wood speces are consdered to be nert matera. GGMs moecuar weght dstrbuton
(MWD) s modeed usng popuaton baance approach |1|.
In the mode foowng phenomena are consdered:
1. H
+
catayzed degradaton of GGM |1|.
2. H
+
catayzed deacetyaton |2|.
3. Dssouton of GGM, acety groups |2|, and methygucuronc acds |2| from fbre wa nto f-
bre wa qud.
4. Mass transfer of a soube speces between fbre wa qud and qud externa to fbre wa |3|.
Degradaton reactons (phenomena 1. and 2.) for GGM and acety groups st attached to fbre,
dssoved nto fbre wa qud, and n externa qud are ncuded nto the mode and assumed to
foow same knetcs.
Expermenta condtons and data ponts used for estmaton of dssouton knetcs of GGM po-
ymers were taken from |3|. Meta on content (havng nfuence on the behavour of pH) |4|, nta
GGM content of wood |4|, and average DP of GGM |5| n wood were taken from the terature.

Modeng of hot water extracton of sawdust

415
Simulation results
Some smuaton resuts together wth the measurement data s shown n Fgure 1. Wth the mode
t s possbe to obtan knowedge on the yed and MWD of the dssoved GGM. Mode aso gves
profes for severa other chemca speces, and pH.

Figure 1. Smuated (nes) and measured vaues (tck marks) at 170C. (a) Concentratons of GGM
poymers w.r.t. tme. (b) Concentratons of Uronc acd and pH w.r.t. tme.
Conclusions
Comprehensve reacton knetc mode for smuaton of batch HWE of wood mea was deveoped.
Smuatons gve pH n both qud phases, concentratons of reacton products (acetc acd, .),
concentratons of matera dssoved from fbre wa (uronc acds, .), and MWD of GGM st at-
tached to wood and dssoved nto qud phases. In the future, mode w be deveoped so that t w
aso predct degradaton of ceuose, xyan, and gnn.
References
1. Vsur, | .A., Song, T., Kutunen, S., Aopaeus, V. 2012. Mode for degradaton of gaactogucomannan
n hot water extracton condtons. Ind. Eng. Chem. Res. 51(31), pp. 10338-10344.
2. Kutunen, S., Aopaeus, V. 2012. The roe of Donnan effect n kraft quor mpregnaton and hot
water extracton, 12
th
European Workshop on Lgnoceuoscs and Pup, Espoo, Fnand.
Proceedngs. Pp. 92-95.
3. Song, T., Pranovch, A., Sumersky, I., Hombom, B. 2008. Extracton of gaactogucomannan
from spruce wood wth pressurzed hot water. Hozforschung 62, pp. 659-666.
4. Koch, G. 2006. Raw matera for Pup n "Handbook of Pup" edted by Sxta, H. Wey-VCH Verag
GmbH. Pp. 21-68.
5. S|strm, E. 1993. Wood Poysacchardes n "Wood Chemstry Fundamentas and Appcatons",
Academc press, 2
nd
edton. Pp. 51-70.
The knetcs of smutaneous aqueous extracton and hydroyss of spruce hemceuoses

416
The kinetics of simultaneous aqueous extraction and
hydrolysis of spruce hemicelluloses
Jussi Rissanen
1
, Henrik Grnman
1
, Chunlin Xu
2
, Jens Krogell
2
, Stefan Willfr
2
,
Dmitry Murzin
1
, Tapio Salmi
1

1
Laboratory of ndustrial Chemistry and Reaction Engineering,
Department of Chemical Engineering, Process Chemistry Centre, bo Akademi University
Biskopsgatan 8, 20500 Turku/bo, Finland
2
Wood and Paper Chemistry, Department of Chemical Engineering,
Process Chemistry Centre, bo Akademi University, Porthansgatan 3, 20500 Turku/bo, Finland
Tel. +35822154555, corresponding author: Henrik.Grenman@abo.fi
Abstract
The aqueous extracton of hemceuoses has ganed an ncreasng nterest wth new emergng
appcatons for hemceuoses n the modern forest-based borefnery concept. The extracton k-
netcs pay a key roe n ther ndustra utsaton. Pressursed hot water extracton of spruce sap
wood was nvestgated n the temperature range 120-170C usng a arge qud-to-sod rato n an
ntensfed cascade reactor system. The resuts show sgnfcant temperature dependence of the
extracton rate, abet ow nfuence of pH. Moreover, a cear dependence of the hydroyss rate on
the temperature and pH was observed. The moecuar mass of the extracted hemceuoses was
nfuenced by the chp sze. A knetc mode was deveoped for descrbng the extracton knetcs.
ntroduction
Acetygaactogucomannan (AcGGM) s the man hemceuose present n softwoods and t can be
utsed for varyng appcatons n ndustry, due to ts boogca and physco-chemca propertes.
Ths, however, requres deep gong quanttatve knowedge of the knetcs and the sod-qud reac-
tons nvoved |1|. The best sovent for extractng unmodfed AcGGM, accordng to current
knowedge s neutra or sghty acdc water. Ouanttatve studes on the pressursed hot water ex-
tracton (PHWE) of hemceuoses found n terature have many focused on hardwoods, due to
ther current use n ndustry and the nformaton reated to softwoods s rather mted |1|. The man
chaenges reated to the effectve ndustra use of AcGGM are the controed extracton and the
abty to contro the hydroyss of the ogomers. Ouanttatve knetc studes of both factors com-
bned wth mathematca modeng are a necessty for ndustra appcatons.
Experimental
The knetc PHWE experments were performed wth a nove cascade reactor system, n the current
study (Fgure 1). The man advantage, compared to tradtona dgesters, s the possbty to contro
the reacton condtons very precsey and rapdy, whch s the bass for reabe knetc experments.
Moreover, the system aows the sampng of both the sod and qud phase durng the reacton.
The system ncudes onne montorng and recordng of the pressure and temperatures nsde each
reactor chamber, whch enabes a detaed nterpretaton of the data as we as reabe modeng.
More than 60 seected sampes of both the sod and qud phases were anaysed for sugar compo-
ston, moar mass, and pH. The anayss of both phases contrbutes to the understandng the over-
a mass baance of the dfferent reactons ncudng the possbe degradaton of the monomers. A
sod-to-qud rato of -180 was used, n order to avod the nterference of thermodynamc mta-
tons. The temperature n the experments was between 120-170C, whch has been shown to be
the most reevant range for PHWE.

The knetcs of smutaneous aqueous extracton and hydroyss of spruce hemceuoses

417
1 2 3 4 5
PI
PI
FI
C
o
e
c
t
o
r

v
e
s
s
e
TIC TIC TIC TIC

TIC
TIC

Figure 1. A smpfed scheme of the reactor setup. The reactors are numbered from 1 to 5.
The new cascade reactor system performed we, enabng an accurate contro of the reacton con-
dtons and sampng. The reacton was ntated and stopped rapdy; the desred reacton tempera-
ture was reached n about 3-4 mn and the quenchng took 1 mn. The overa dssouton rate of the
hemceuoses was hghy temperature dependent wth an actvaton energy of about 120 k| /mo.
However, varatons n the reacton rates of dfferent hemceuos fractons was notced. Ths coud
be utsed n practce for nfuencng the seectvty of extracton by appyng temperature profng.
Aso sgnfcant temperature and pH dependence was shown for the degradaton of the ogomers,
whch can be consdered as a possbty for optmsng ths phenomena dependng on the desred
product. The pH changed throughout the reacton and a systematc correaton wth the converson
was observed. Moreover, the chp sze was observed to nfuence the moar mass of the extracted
hemceuoses. A good ft of the knetc mode to expermenta data was obtaned.
Conclusions
The aqueous extracton of spruce hemceuoses s a compcated ssue as the temperature, pH, as
we as externa and nterna mass transfer phenomena nfuence both the overa rate and the ob-
taned hemceuose propertes. The decoupng and quanttatve assessment of the parameters s
a key ssue for beng abe to mode the phenomena and beng abe to mpement t nto ndustra
producton n order to obtan the desred products for further processng n an effectve way.
Acknowledgements
Ths research was part of the actvtes at the bo Akadem Process Chemstry Centre. Ths study
was fnanced by Forestcuster Ltd. and the Fnnsh Fundng Agency for Technoogy and Innovaton
(Tekes) wthn the framework of the Future Borefnery (FuBo) | ont Research 2 programme.
References
1. Grnman, H., Ernen, K., Kroge, | ., Wfr, S., Sam, T., Murzn, D. Yu. 2011. Knetcs of Aque-
ous Extracton of Hemceuoses from Spruce n an Intensfed Reactor System. Ind. Eng.
Chem. Res. 50, pp. 3818-3828.
Acd functonazed carbon as heterogeneous cataysts for dehydraton of xyose to furfura

418
Acid functionalized carbon as heterogeneous catalysts
for dehydration of xylose to furfural
Emma Sairanen*, Kati Vilonen, Reetta Karinen, Juha Lehtonen
Department of Biotechnology and Chemical Technology
Aalto University School of Chemical Technology, P.O. Box 16100, F-00076 AALTO, Finland
*emma.sairanen@aalto.fi
Abstract
Hemceuosc sugars offer bobased source for the producton of fue and chemca ntermedates
by dehydraton. Dehydraton of xyose was studed usng acd functonazed actve carbon as het-
erogeneous acd catayst. Actve carbon exhbted good actvty and seectvty n the dehydraton
reacton of xyose to furfura, beng aso stabe n the reacton condtons, at 200C n water souton.
ntroduction
Decreasng reserves of foss raw materas and attempts to reduce CO
2
emssons nspre to utze
bo-based aternatves, where non-food bomass, especay gnoceuose, pays the key roe. Sg-
nfcant amount of gnoceuose conssts of dfferent sugars whch can be utzed after hydroyza-
ton. Nowadays the man reacton pathway from sugars to bofues s fermentaton to acohos.
However, the dehydraton of sugars to furfuras s an optona route for the producton of bo-based
transportaton fues and chemcas. |1, 2|.
The dehydraton of sugars s catayzed by acds and currenty the commerca furfura producton
utzes homogeneous acds, typcay suphurc acd. Heterogeneous acd cataysts are more sus-
tanabe by producng ess waste and workng wthout corroson probems. However, heterogene-
ous acd cataysts suffer ow seectvty for dehydraton reacton, cataysng the formaton of sde
products and endng up n ow yeds. Ths s due to dfferent type of actve stes on the surface
(basc, weak acd and strong acd). In addton many heterogeneous acd cataysts have ow stab-
ty n aqueous phase at hgh temperatures (150-350C) used n dehydraton reacton. |3|
Ths study concentrates on the use of new type of heterogeneous acds, acd functonazed ac-
tve carbons, n dehydraton reactons. Acdc surface groups actng as actve stes n xyose dehy-
draton can be created on the carbon surface by qud phase oxdaton, ntrc acd and sufurc acd
beng the most commony used |4|. Oxygen-contanng surface groups are typcay carboxy, phe-
no, and actone groups. Carbons are nterestng materas as catayst n aqueous phase sugar
dehydraton reacton aso because of ther good water toerance. |4|
Experimental
Acd functonazed actvated carbon was prepared by refuxng n bong 3M HNO
3
or 3M H
2
SO
4
or
mxture of them. Functonazaton tme was 2 hours. After refuxng, mxture was cooed down,
washed wth dsted water unt the pH of the washng water was neutra and dred at 80C over-
nght. Dehydraton experments were done n batch reactor at 160-200C and 5 MPa ntrogen
pressure n water souton. Reacton products were anayzed by Agent 1100 qud chromatograph,
wth a refractve ndex detector usng Phenomenex Rezex Monosaccharde RHM H+coumn.
Functonazed actvated carbon cataysts were actve n xyose dehydraton and they aso exhbted
hgher seectvty towards furfura than tradtona sod acd cataysts such as zeotes and TO
2
.
Seectvty to furfura as a functon of converson wth dfferent cataysts s shown n Fgure 1.

Acd functonazed carbon as heterogeneous cataysts for dehydraton of xyose to furfura

419

Figure 1. Furfura seectvty as a functon of xyose converson n dehydraton on dfferent cataysts.
At hgh converson vaues the man sde reacton was the formaton of sods va both poymerza-
ton of furfura and condensaton reacton between sugars and furfura, observed as a formaton of
back precptate after onger reacton tmes. Aso some organc acds were formed va decompos-
ton. In addton to good seectvty, acd functonazed carbon catayst mantaned ts actvty n
consecutve experments, ndcatng that acdc surface stes were nsoube n water used as a
sovent n batch experment at 200C.
The acds used n carbon functonazaton have an effect on the carbon catayst actvty: oxygen-
contanng acd stes formed many n HNO
3
treatment and suphur-contanng surface groups
formed n H
2
SO
4
treatment are both actve n xyose dehydraton. Consequenty, the carbon catayst
treated wth mxture of these acds possessed the hghest furfura seectvty of ths study.
References
1. Ln, Y.-C., Huber, G.W. 2009. The Crtca Roe of Heterogeneous Catayss n Lgnoceuosc
Bomass Converson. Energy Envron. Sc. 2, pp. 68-80.
2. Stcker, M. 2008. Bofues and bomass-to-qud fues n the borefnery: Cataytc converson of
gnoceuosc bomass usng porous materas. Angew. Chem. Int. Ed. 47, pp. 9200-9211.
3. Karnen, R., Vonen, K., Neme, M. 2011. Heterogeneousy Catayzed Reactons of Carbohy-
drates for the Producton of Furfura and Hydroxymethyfurfura. ChemSusChem 4,
pp. 1002-1016.
4. Toebes, M.L., van Heesw|k, | .M.P., Btter, | .H., van Den, A.| ., de | ong, K.P. 2004. The
nuence of oxdaton on the texture and the number of oxygen-contanng surface groups
of carbon nanobers. Carbon 42, pp. 307-315.
Knetc study on the formaton of furfura from pentoses n compex sugar soutons

420
Kinetic study on the formation of furfural from
pentoses in complex sugar solutions
B. Danon
1
, W. de Jong
1
, W. van Well
2

1
Delft University of Technology, the Netherlands
2
DONG Energy, Denmark
Abstract
In ths study the nfuence of compex sugar soutons (e.g. moasses) on the knetcs of the conver-
son of pentoses to the patform chemca furfura s nvestgated. Resuts of two seres of knetc
experments are compared, on the one hand wth moasse (a pentose-rch sde stream of the Inb-
con borefnery) as the feedstock and on the other hand wth pure xyose. Knetc parameters of a
frst-order reacton mechansm for the xyose dehydraton towards furfura are ftted on the obtaned
expermenta resuts. The comparson of these knetc parameters of the two expermenta seres
show that pure xyose both reacts faster towards furfura and resuts n hgher furfura yeds. Presenty,
the mechanstc causes of these dfferences are nvestgated n a more fundamenta study.
ntroduction
One of the (sde) products of the Inbcon borefnery process for convertng gnoceuosc (waste) bo-
mass to boethano s the moasses |1|. These moasses contan many xyan and xyose, but aso arab-
nose, gucose and sma amounts of varous other organc compounds. Prevousy, extensve research
has been performed at Deft Unversty of Technoogy on the knetcs of the formaton of furfura from
pure xyose, va acd-catayzed dehydraton |2|. Currenty, the acqured knowedge s extended for the
dehydraton of pentoses n more compex soutons, such as the prevousy mentoned moasses.

(a) (b)
Fi gure 1. (a) Expermenta setup, (b) frst-order reacton mechansm.
Experimental setup
The experments are performed n a one-ter mechancay strred staness stee autocave reactor,
see aso Fgure 1(a). The reacton temperature (180C and 200C) was reguated by pumpng
heated o through the |acket of the reactor. The operatng pressure n the reactor was the saturaton
pressure of the mxture. Besdes hydrochorc acd (HC), aso sodum chorde (NaC) has been
added as a catayst. The sampes were anayzed usng an HPLC apparatus equpped wth a
Rezex RHM-Monosaccharde coumn, 8% cross nked H
+
, 300 x 7.80 mm, (Phenomenex Inc.,
Torrance, CA, USA). The sacchardes were quantfed by means of an RI detector (Varan Mode 350),
whereas for furfura both an RI and UV detector (Varan Mode 310 Pro Star) were used.


421
In Fgure 2(a) and (b) the resuts of the knetc experments wth xyose and the moasses are
presented, respectvey. It s noted that the squares n (a) represent xyose, whereas n (b) they
denote the tota pentose concentraton. The prnted vaue of the reacton rate constant k
x
s the
sum of k
1
and k
2
, see aso Fgure 1(b).

In the frst pace, the degradaton of the sugars n both seres show an exponenta decay, whch
confrms the assumpton of a frst-order reacton mechansm. Secondy, n both cases the vaues of
k
x
are hgher at hgher temperature, as expected. Fnay, comparng the resuts of the experments
wth
pure xyose and the moasses, two mportant observatons can be made.
Frsty, the degradaton rates of the pentoses (the vaue of k
x
) are ower for the moasses. Ths
s
party due to the fact that there are some poysacchardes (xyans) present n the moasses. The
arge fed squares n Fgure 2(b) ndcate the ast sampe where poysacchardes were observed n
the chromatograms, whch concdes wth the peak of the tota matter, .e. the sum of pentose and
furfura, ndcated by the grey tranges. Another contrbuton to the ower dehydraton rate s the
fact that a part of the pentoses conssts of arabnose. Arabnose s known to be dehydrated sower
than xyose |3|.
Secondy, t s observed that the moar furfura yed s aso ower n the experments wth moas-
se. Whereas n the pure xyose experments the moar yed s around 65%, n the moasses ex-
perments ths yed drops to around 50%. The cause for ths dfference s probaby due to the
rates of the oss reactons of xyose and furfura. Prevousy, an adapted verson of the frst-order
reacton mechansm, where the decomposton reacton of xyose s a second-order reacton wth
both a xyose as a furfura moecue, has been proposed |4|.

(a) (b)
Figure 2. Comparson of knetcs of pure xyose (a) and pentoses from the moasse (b) at two
dfferent temperatures (squares =xyose/pentoses, crces =furfura and tranges =cumuatve).

422
Conclusion and outlook
It s concuded that the dehydraton of pentoses n a compex sugar souton s both sower and yed
ess furfura than n the case of pure xyose. In many studes however the knetc parameters of pure
xyose are used when for exampe the acdc hydroyss of bomass s nvestgated. Therefore, the
nfuence of the presence of other sugars (many the hexoses) on the knetcs of the dehydraton of
xyose w be studed on a systematc bass.
References
1. Larsen, | ., Petersen, M.O., Thrup, L., L, H.W., Iversen, F.K. 2008. The IBUS process - gnoce-
uosc boethano cose to a commerca reaty. Chem. Eng. Techno. 31, pp. 765-772.
2. Marcotuo, G., de | ong, W. 2010. Chorde ons enhance furfura formaton from D-xyose n dute
aqueous acdc soutons. Green Chemstry 12, pp. 1739-1746.
3. Kootstra, A.M.| ., Moser, N.S., Scott, E.L., Beeftnk, H.H., Sanders, | .P.M. 2009. Dfferenta
effects of mnera and organc acds on the knetcs of arabnose degradaton under gnoce-
uose pretreatment condtons. Bochemca Engneerng | ourna 43, pp. 92-97.
4. Wengarten, R., Cho, | ., Curts Conner, Wm. | r., Huber, G.W. 2010. Knetcs of furfura producton
by dehydraton of xyose n a bphasc reactor wth mcrowave heatng. Green Chemstry
12(8), pp. 1423-1429. Resuts and dscusson.
D-Xyonate and xyto as borefnery products from hemceuose

423
D-Xylonate and xylitol as biorefinery products
from hemicellulose
Mervi Toivari, Yvonne Nygrd, Maija-Leena Vehkomki, Laura Ruohonen,
Merja Penttil, Marilyn Wiebe
VTT, Technical Research Centre of Finland
Tietotie 2, Espoo, P.O. Box 1000, F-02044 VTT, Finland
Abstract
The European pro|ect BIO-COmmodty REfnng - BIOCORE s deveopng and anaysng the n-
dustra feasbty of a borefnery for converson of a varety of non-food bomass, ncudng cerea
by-products (straws etc.), forestry resdues and short rotaton woody crops, nto 2
nd
generaton
bofue, chemcas and poymers.
The key technoogy n BIOCORE s the organosov pretreatment wth acetc and formc acds,
deveoped by CIMV, whch aows extracton of the three ma|or components of bomass; ceuose,
hemceuoses and gnns. In the BIOCORE pro|ect, D-xyose n the hemceuose fracton s con-
verted to xyto or D-xyonate botechncay. The producton s evauated through the whoe vaue
chan from straw harvestng to the fna product.
The need for robust, effcent and safe bocataysts was addressed by engneerng an ndustra
Saccharomyces cerevisiae stran, soated from spent sufte quor and a smary robust Candida
speces for xyto and/or D-xyonate producton.
D-Xylonate production at low pH
Low pH producton of organc acd s consdered advantageous for down stream purfcaton. A non-
conventona yeast of Candida sp. expressng a D-xyose dehydrogenase encodng gene produced
up to 171 g
-1
D-xyonate from 171 g
-1
D-xyose at a rate of 1.4 g
-1
h
-1
and yed of 1.0 g |g sub-
strate consumed|
-1
. Remarkaby, the productvty was amost unaffected when the pH was reduced
to 3.0 (Fgure 1a). Hgh eves of D-xyonate producton at ow pH has not prevousy been reported
(Fgure 1 b). From the CIMV hemceuose hydroysate, 40 g xyonate
-1
was produced from 48 g
xyose
-1
n fed-batch cuture.

Figure 1. a) Producton of xyonate at pH 5.5 and at pH 3.0 wth Candida sp. b) Producton of
D-xyonate at hgh pH (>5.5) (grey) and ow (pH <4.0) (back) usng modfed yeast or E. coli.

D-Xyonate and xyto as borefnery products from hemceuose

424
Xylitol production with Saccharomyces cerevisiae and Candida sp.
from pure substrate or from D-xylose in hemicellulose fractions
On pure substrate the engneered Candida sp. stran had hgher producton rate than the eng-
neered ndustra S. cerevisiae stran, but the yed was ower. Xyto tters up to 160 g
-1
and yeds
of 70-90% (g product/ g xyose used) were obtaned on pure substrate.
The CIMV hemceuose fracton s rch n formc and acetc acds and contans varous phenoc
compounds. In addton to the CIMV hemceuose fracton aso other pretreated bomass hydroy-
sates, orgnatng from wood and wheat straw and contanng ess formate, were tested for xyto
producton. The engneered strans performed we producng up to 88 g
-1
xyto (dependng on the
hydroysate, stran and condtons). Contnung metaboc engneerng efforts on mprovng the to-
erance of the engneered yeast towards formc acd together wth process technca deveopments
are key to ncrease the xyto productvty even further. The resuts are hghy encouragng for
future pot scae tras.
Acknowledgements
Fnanca support by the Academy of Fnand through the Centre of Exceence n Whte Botechnoogy
- Green Chemstry (grant 118573), from the VTT Graduate Schoo (Yvonne Nygrd), and the Eu-
ropean Commsson through the Seventh Framework Programme (FP7/2007-2013) under grant
agreement N FP7-241566 BIOCORE are gratefuy acknowedged.
References
1. Lu, H., Vadehuesa, K.N., Nsoa, G.M., Ramos, K.R., Chung, W.| . 2012. Hgh yed producton
of D-xyonc acd from D-xyose usng engneered Eschercha co, Boresour. Techno.
115, pp. 244-248.
2. Nygrd, Y., Tovar, M.H., Pentt, M., Ruohonen, L., Webe, M.G. 2011. Boconverson of D-
xyose to D-xyonate wth Kuyveromyces acts. Metab. Eng. 13, pp. 383-391.
3. Tovar, M.H., Ruohonen, L., Rchard, P., Pentt, M., Webe, M.G. 2010. Saccharomyces cere-
vsae engneered to produce D-xyonate. App. Mcrobo. Botechno. 88, pp. 751-760.
4. Tovar, M., Nygrd, Y., Kumpua, E.P., Vehkomk, M.L., Bencna, M., Vakonen, M., Maahemo, H.,
Andberg, M., Kovua, A., Ruohonen, L., Pentt, M., Webe, M.G. 2012. Metaboc eng-
neerng of Saccharomyces cerevsae for boconverson of D-xyose to D-xyonate. Metab.
Eng. 14, pp. 427-436.

Seectve oxdaton of uronc acds nto adarc acds over god cataysts

425
Selective oxidation of uronic acids into aldaric acids
over gold catalysts
Sari Rautiainen
1
, Jingjing Chen
1
, Klaus Niemel
2
, Markku Leskel
1
, Timo Repo
1

1
Laboratory of norganic Chemistry, Department of Chemistry, A.. Virtasen Aukio 1,
P.O. Box 55, 00014 University of Helsinki, Finland
2
VTT Technical Research Centre of Finland, P.O. Box 1000, 02044 VTT, Finland
Abstract
Adarc acds were produced by seectve aerobc oxdaton of uronc acds usng god nanopartce
cataysts. Neary quanttatve conversons and seectvtes were acheved n akane aqueous me-
dum n md condtons. Adarc acds represent nterestng budng bock chemcas for poymer,
food and pharmaceutca ndustres and wth the new oxdaton method they can be produced from
uronc acds found n hemceuoses.
ntroduction
Adarc acds, or dacds of sugars, have potentay numerous appcatons n poymer, food and
pharmaceutca ndustres. |1| However, current methods for ther producton by oxdaton of mono-
sacchardes suffer from ow seectvtes or the use of strong oxdzng agents such as ntrc acd or
beach. |2| The potenta of dacds as budng bock chemcas can ony fuy be utzed f they can
be effcenty produced from carbohydrates.
Supported god nanopartces have shown superor seectvty and stabty n the aerobc oxda-
ton of acohos and carbohydrates under md condtons. |3| In case of monosacchardes the ade-
hyde group s seectvey oxdzed and the correspondng adonc acd s produced. Oxdzng the
prmary hydroxy group to obtan the adarc acd, e.g. gucarc acd, requres more severe cond-
tons and resuts n oss of seectvty. |4|
In case of uronc acds the oxdaton of the prmary hydroxy s performed aready by nature.
Uronc acds are found n hemceuoses n both hardwood and softwood and can amount up to 2%
of wood dry weght. |5| At the moment, hemceuoses are the argest poysaccharde fracton wast-
ed n borefneres. Here, we present an effcent new method for convertng uronc acds nto adarc
acds under md condtons usng a god-paadum catayst (Fgure 1).

Figure 1. Cataytc oxdaton of gucuronc acd to gucarc acd.
Experimental
The god-paadum catayst was prepared by mpregnaton on A
2
O
3
. |6| The oxdaton of uronc
acds were carred out n aqueous meda under controed pH. As acd s produced n the reacton,
the addton of sodum hydroxde was needed to neutraze the acd and mantan constant pH.
Doxygen was bubbed at 100 m/mn through the reacton mxture. The products were dentfed by
1
H-NMR and GC-MS after trmethysyaton.

Seectve oxdaton of uronc acds nto adarc acds over god cataysts

426
The god-paadum catayst seectvey oxdzed the adehyde group of the substrate resutng n
neary quanttatve converson to e.g. gucarate n 60 mn at 60C and pH 9. The reacton of gaac-
turonc acd proceeds sghty sower. At ower pH, the actvty of the catayst dropped and the reac-
ton ddnt reach fu converson. No sde products were detected and no reacton occurred wthout
the catayst.
Conclusions
In summary, we have demonstrated that gucuronc and gaacturonc acds can be seectvey ox-
dzed nto the correspondng adarc acds over god-paadum catayst. Amost quanttatve conver-
sons nto gucarate and gaactarate were acheved n md condtons wth oxygen bubbng.
References
1. Werpy, T.A., Petersen, G. 2004. Top vaue added chemcas from bomass. Voume I, U.S. De-
partment of Energy (DOE), Goden, CO, DOE/GO-102004-1992.
2. Ibert, M., Marsas, F., Merbouh, N., Brckner, C. 2002. Determnaton of the sde-products
formed durng the ntroxde-medated beach oxdaton of gucose to gucarc acd. Carbo-
hydr. Res. 337(11), pp. 1059-1063.
3. Mrescu, A., Pre, U. 2007. A new envronmenta frendy method for the preparaton of sugar
acds va cataytc oxdaton on god cataysts. App. Cata., B 70, pp. 644-652.
4. Drkx, | .M., van der Baan, H.S., van der Broek, | .M. 1977. The preparaton of D-gucarc acd by the
oxdaton of D-guconc acd cataysed by patnum on carbon. Carbohydr. Res. 59, p. 63.
5. Gro, F.M., Fonseca, C., Carvahero, F., Duarte, L.C., Marques, S., Boge-ukask, R. 2010.
Hemceuoses for fue ethano: A revew. Bores. Techno. 101, p. 4775.
6. Herzng, A.A., Carey, A.F., Edwards, | .K., Hutchngs, G.| ., Key, C.| . 2008. Mcrostructura
Deveopment and Cataytc Performance of Au-Pd Nanopartces on A
2
O
3
Supports: The Ef-
fect of Heat Treatment Temperature and Atmosphere. Chem. Mater. 20(4), pp. 1492-1501.
In stu poymerzaton of poyanne n wood veneers

427
n situ polymerization of polyaniline in wood veneers
Stacy Trey
1, 2
, Shadi Jafarzadeh
3
, Mats Johansson
2, 4

1
SP Trtek, SP Technical Research nstitute of Sweden,
P.O. Box 5609, Drottning Kristinas vg 67, SE-114 86, Stockholm, Sweden
2
Wallenberg Wood Science Centre (WWSC), KTH Royal nstitute of Technology,
Teknikringen 56-58, SE-100 44 Stockholm, Sweden
3
Division of Surface and Corrosion Science, Chemistry Department,
KTH Royal nstitute of Technology, Drottning Kristinas vg 51, SE-10044 Stockholm, Sweden
4
Fibre and Polymer Technology, KTH Royal nstitute of Technology, SE-10044 Stockholm, Sweden
Abstract
The present study descrbes the possbty to poymerze anne wthn wood veneers to obtan a
sem-conductng matera wth sod wood actng as the base tempate. It was determned that t s
possbe to synthesze the ntrnscay conductve poymer (ICP) poyanne n stu wthn the wood
structure of Southern yeow pne veneers, combnng the strength of the natura wood structure
wth the conductvty of the mpregnated poymer. It was found that poyanne s unformy ds-
persed wthn the wood structure by ght mcroscopy and FT-IR magng. A weght percent gan n
the range of 312 wt % was obtaned wth a preferenta formaton n the wood structure and ce
wa, rather than n the umen. The modfed wood was found to be ess hydrophc wth the addton
of phosphate doped poyanne as observed by equbrum water sweng studes. Whe wood
tsef s nsuatng, the modfed veneers had conductvtes of 1 10
4
to 1 10
9
S cm
1
, demon-
stratng the abty to tune the conductvty and aowng for materas wth a wde range of appca-
tons, from ant-statc to charge-dspersng materas. Furthermore, the modfed veneers had ower
tota and peak heat reeases, as determned by cone caormetry, because of the char propertes of
the ICP. Ths s of nterest f these materas are to be used n budng and furnture appcatons
where fame retardance s of mportance.
ntroduction
Interest n ntrnscay conductng materas has been profc n the past few decades wth the most
recognton of the area beng the 2000 Nobe Prze n chemstry for the deveopment of conductve
poymers awarded to Heeger, MacDarmd, and Shrakawa. Tradtona metas are nferor n terms
of ther mechanca propertes and conductvty, whe requred hgh oadng eads to heaver and
nfexbe systems.
Prevous research, nvovng the coatng of wood sawdust wth poyanne, has demonstrated
that poyanne coatngs on wood and ceuose fbers can ead to ncreased fre retardancy. How-
ever, mpregnatng an anne monomer souton nto wood and syntheszng poyanne n-stu, n
order to take advantage of the compex and robust structure of wood tsef, has receved ess attenton.
The am of ths pro|ect s to use the compex structure of wood as a renewabe matera that s by
nature a ght yet strong matera and modfy wth ntrnscay conductve poymers n order to obtan
a nove functona matera. The proposed advantage s not ony to obtan a conductng matera but
aso to address other mportant restrctons for wood such as the effect of modfcaton on the d-
mensona stabty, strength, fre resstance, and morphoogy of the conductve poymer wthn the
archtecture of the wood structure.
Experimental
The crown cut/fat cut Southern Yeow Pne (Carona pne) veneer was receved from Specased
Veneers Ltd., Ayesburg, Unted Kngdom. After condtonng at 65% RH, the veneers had approx-
matey 11 wt % mosture content and a densty of 530 kg/m
3
. The anne (99.5% purty), phos-

In stu poymerzaton of poyanne n wood veneers

428
phorc acd (85 wt % n H20, 99.9% trace meta bass), suphurc acd (95-98%), dodecybenzene-
sufonc acd sodum sat, and ammonum peroxydsufate (APS) (98%) were a used as receved
from Sgma Adrch. The mpregnated veneers resuted n 10 wt% dry poyanne n wood.
The modfed veneers were found to be sem-conductve and the ma|orty of poyanne was deter-
mned to be ocated n the mdde amea. (Fgure 1) The modfed veneers aso had better dmen-
sona stabty and were more hydrophobc than untreated wood.

Figure 1. FT-IR magng (each mage 150 150 m) of the cross-secton of the unmodfed veneer
(top row) and 0.2 PANI-PA modfed veneer (bottom row) wth the vsbe mage to the far eft, the
average absorbance second to the eft, the band rato mage (1480:1080 cm1) second from the
rght, and the band rato ustrated n the seected spectra to the far rght.
References
1. Trey, S., | afarzadeh, S., | ohansson, M. 2012. In stu Poymerzaton of Poyanne n Wood Ve-
neers ACS App. Mater. Interfaces 4(3), pp. 17601769.
Pre- and post-processng of sod bofues and bo-ash nto new constructon materas

429
Pre- and post-processing of solid biofuels and bio-ash
into new construction materials
Valter Wigren, Bob Talling
Ekolite nc., Tykistkatu 4D, 20520 Turku, Finland
valter.wigren@ekolite.fi
Abstract
Ash derved from bomass combuston s composed of a compex heterogeneous mx of norganc
compounds. Many nterestng propertes such as eechng of eements and settng behavor wth
water strongy correate wth composton and structure. Ekote has studed ashes wth specfc
nterest to sef-hardenng. The compostons and structures of ashes have been studed wth XRF,
XRD and SEM/EDS - methods. In addton the hydraton behavor of ashes has been tested n a
aboratory. Ekote has aso tested and verfed a specfc mechanca actvaton treatment for ashes
n order to enhance ther hydraton behavor. Actvaton s based on hgh speed mpacts of partces
n the mng chamber. Cosons cause chemca and physca changes on matera. Actvaton
treatment s performed n a dsntegrator m. Ash quaty s heavy dependng on combusted bo-
mass type and combuston condtons. Currenty aboratory tests are beng performed on enhancng
ash quaty and combuston propertes wth optmum bomass mxes and sutabe addtves.
Ashes produced by fudzed bed combuston of woody bomass mxed wth dfferent quanttes of
peat have been anaysed. The ma|or ash formng eements are S, Ca, A, Fe, Na, K and P. At tem-
peratures beow 900C the ash does not competey met nto gass, but s aso consttuted by var-
ous mnera scates aong wth suphate and carbonate speces, whch woud break done at hgher
temperatures nto oxdes. When the mcrostructure s observed by a SEM t s seen that scates
tend to form arger aggomerates. Carbonates and oxdes form reguar shaped smaer crystas or
aternatvey fakes adsorbed on the surfaces of the arger scate aggomerates.
Sgnfcant dfferences were observed n the hydraton behavour of anaysed ashes. Ths s be-
eved to be the resut of ashes contanng dfferent sod phases havng dfferent soubtes. The
water to ash rato upon hardenng vared between 0,15 and 0,65. Ths water to ash rato coud be
sgnfcanty reduced for a ashes by mechanca treatment of ashes n dsntegrator - m.
ntroduction
Ekote s presentng the deas and some premnary resuts, whch are reated to the Sustainable
util ization of ash, slag and pyrol ysi s residuals TUUL Proj ect, a part of Tekes Green Growth
Program. In the Tuu pro|ect more than 10 ndustra partners and research departments of Unver-
stes and Research Insttutes are partcpatng unt | une 2015.
Experimental
Ten dfferent ash sampes were coected from woody bomass utzng Fnnsh heatpants. Ana-
ysed ashes were produced by pants usng modern fudzed bed technoogy n whch the operatng
temperatures are between 750 and 850C. One sampe was coected from a sma scae heatpant
usng conventona movng - grate technoogy for reference. The bomass bend used for producng
the ashes on a of the pants does not sgnfcanty change between pants. Woody bomass
makes >80% of a used fue whe the rest s mosty peat.
The eementa and mneraogca composton of the coected ashes were measured usng a
Phps PW 1050 - XRD - apparatus. The mcrostructure of the ash sampes was observed usng a
scannng eectron mcroscope (SEM) couped wth a tp capabe of eectron dspersve scannng
(EDS) for eementa anayss.

Pre- and post-processng of sod bofues and bo-ash nto new constructon materas

430
The hydraton behavour of the ashes was montored n the aboratory by mxng the sampes
wth water to obtan a dsperson of standard vscosty for a sampes.
El emental composition
The eementa compostons of studed ashes vary. The most abundant eements found n the ash-
es are S (30 w% to 60 w%), A (10-20 w%) and Ca (10-40w%). The most scon-rch ash sampe
s coected from a grate - boer. A grate boer aso tends to have the hghest content of unburnt
carbon as ndcated by a hgh LOI vaue. Gasfcaton resdues have aso hgher LOI vaues than
fudzed bed combustors.
Mi neralogical composi tion
The ma|or crysta phases n the anaysed ashes are fedspar - mneras and scon doxde as
quartz or crstaobte. It s nterestng to note that both cacte and caca were found n the sampes.
Ths ndcates that at east some of the cacum present n the woody bomass s reactve durng
combuston of these materas.
Mi crostructure
The mcrostructure s ceary very heterogeneous consstng of arger uneveny shaped partces or
aggomerates and unformy shaped spheres or rectanguar crystas. Usng EDS - technque t was
found out that the arger uneveny shaped aggomerate partces consst many of scate - type
structures (fedspar mneras) and the unform rectanguar shaped crystas are cacum oxde or
carbonate crystas. The even spheres that are sometmes seen are key scates n gassy form.
Hydration behaviour
Settng and hardenng wth water mxes dfferentated greaty between sampes. Wthn the ten
coected sampes ten dfferent water-to-ash ratos were defned. Vaues range from 0,15 to 0,65.
By mechanca treatment wth dsntegrator m water to ash ratos were found to decrease on aver-
age by 30%.
Conclusions
Ten bomass ashes were anaysed for eementa composton, mneraogca structure, mcrostruc-
ture and hydroogca behavour. Ashes composng many of S, A and Ca have a mcrostructure of
sma crystas of cacum carbonate or oxde and arger aggomerates of sceous structures. Mxng
wth water creates hardened structures.

Carbon footprnt of wood borefnery products - case Forchem ta o dervatve products

431
Carbon footprint of wood biorefinery products
case Forchem tall oil derivative products
Anna Kumpulainen
1
, Tiina Pursula
1
, Jatta Aho
1
, Janne Lukkarinen
2
,
Anu Valtonen
2
, Minna Lhdekorpi
2
1
Gaia Consulting Oy, Bulevardi 6A, F-00120 Helsinki, Finland
www.gaia.fi, firstname.lastname@gaia.fi
2
Forchem Oy, P.O. Box 16, F-26101 Rauma, Finland
www.forchem.com, firstname.lastname@forchem.com
Abstract
Ta o products are natura raw materas for many ndustra processes whch serve consumers n
a varety of ways. They are used, for exampe, n pants and coatngs, pup and paper chemcas,
prntng nks and bo fues, ony to menton few. Ta o s a resdue of the chemca pup ndustry.
Pne, used as the raw matera for ta o, s a renewabe natura resource whch grows n northern
forests.
Carbon footprnt s one mportant eement of sustanabty of wood borefnery products. Lfe-
cyce assessment s the best currenty avaabe methodoogy for carbon footprnt cacuatons of
products. Gaas experts cacuated the carbon footprnt of Forchems products, ncudng bo-fue
Fortop600, Ta O Fatty Acd, Ta O Rosn and Dsted Ta O. Accordng to Gaas cacuatons,
the products have a mnma carbon footprnt. Producton of aternatve products for same end-
usage woud cause 12-35 fod emssons compared to those of Forchems products.
Methods
Carbon footprnt cacuatons were conducted foowng the best avaabe methodooges, .e. fe
cyce assessment standards (ISO 14040 and ISO 14044). Emssons are cacuated for year 2010.
The presented resuts ncude emssons from raw matera producton, transportaton and opera-
tons n Rauma refnery (crade-to-gate).
Prmary data was coected and used for a processes under the contro of Forchem. Secondary
data was coected from avaabe databases (mosty Econvent v. 2.1) and used to estmate the
emssons of raw matera producton and transportaton. When more accurate data was avaabe n
terature, the database data was further modfed e.g. wth natona nformaton for transportaton
emssons. Emssons of crude ta o producton (CTO) were assumed to be 3.5% of the emssons
of sufate pup producton. Ths s based on the average amount of CTO produced as sde-product
n sufate pup processes n Fnand (mass bass). The drect emssons (e.g. eectrcty and fue
use) were aocated to dfferent products based on actua utty consumpton for each product.
Transportaton emssons and raw matera emssons, ncudng process water, were aocated to
dfferent products on mass bass (producton amounts). Emsson factor for average Nordc pup m
s utzed here, as 90% of the CTO orgnates from Nordc pup ms. The cacuaton was conduct-
ed for busness-to-busness purposes.
Results
Forchem TOFA Ta O Fatty Acd has ower carbon footprnt compared to aternatve materas
such as soybean o n e.g. pants and coatngs. The carbon footprnt of Forchem TOFA s ony
78 gCO
2
eq./kg, whereas soybean o fatty acd has sgnfcanty hgher carbon footprnt wth
1457 gCO
2
eq./kg. Ths makes greenhouse emssons of vegetabe o aternatves as hgh as
12-fod compared to emssons of Forchem TOFA.

Carbon footprnt of wood borefnery products - case Forchem ta o dervatve products

432
Forchem DTO Dsted Ta O has ower carbon footprnt compared to aternatve materas such as
soybean o n e.g. pants and coatngs. The carbon footprnt of Forchem DTO s ony 76 gCO
2
eq./kg,
whereas soybean o has sgnfcanty hgher carbon footprnt wth 920 gCO
2
eq./kg. Ths makes
greenhouse emssons of vegetabe o aternatves as hgh as 12-fod compared to emssons of
Forchem DTO.
Forchem TOR Ta O Resn has a ower carbon footprnt compared to producton of gum rosn.
Its carbon footprnt s ony 71 gCO
2
eq./kg, whereas gum rosn has a sgnfcanty hgher footprnt
wth 980 gCO
2
eq./kg. Ths makes greenhouse emssons of gum rosn as hgh as 14-fod compared
to emssons of Forchem TOR.
Fortop600 s a qud bofue, whch repaces heavy fue o (HFO) n customer appcatons. Car-
bon footprnt for Fortop600 s 71 gCO
2
eq./kg, sgnfcanty ower compared to carbon footprnt of
HFO, 430 gCO
2
eq/kg. When effectve heat vaues are taken nto account, carbon footprnt for pro-
ducton of Fortop600 s 1,9 gCO
2
eq./M| , whereas producton of HFO causes sx tmes hgher ems-
sons. Combuston of bofues s cassfed to be carbon-free n the EU emssons tradng scheme.
Takng ths nto account the greenhouse gas emssons of HFO are as hgh as 35-fod compared to
emssons of Forchem Fortop600.
The man resuts of carbon footprnt cacuatons are summarzed n a fgure beow.

Figure 1. Carbon Footprnt of Forchem CTO dervatve products and ther substtutes.
Conclusions
Accordng to Gaas cacuatons, Forchems ta o derved products have a mnma carbon foot-
prnt. Producton of aternatve products for same end-usage woud cause 12-35 fod emssons
compared to those of Forchems products.

Seres tte and number
VTT Technology 53
Tte NWBC 2012
The 4th Nordic Wood Bi orefinery Conference
Author(s) Kaus Neme (Ed.)
Abstract Ths proceedngs book s based on a tota of more than 120 ora and poster presen-
tatons n the 4
th
Nordc Wood Borefnery Conference, hed n Hesnk 23-25 October
2012. As a whoe, the contrbutons ceary demonstrate the ncreasngy mportant
roe of the wood-based ndustry as a source of dfferent renewabe materas,
chemcas and energy products (n addton to the more tradtona products).
ISBN, ISSN ISBN 978-951-38-7880-1 (soft back ed.)
ISBN 978-951-38-7881-8 (URL: http://www.vtt.f/pubcatons/ndex.|sp)
ISSN 2242-122X (URL: http://www.vtt.f/pubcatons/ndex.|sp)
Date October 2012
Language Engsh
Pages 432 p.
Name of the pro|ect 4
th
Nordc Wood Borefnery Conference
Keywords Borefnery, nnovaton, wood, forest, bomass, pup, bochemcas, bomateras,
bofues, ceuose, gnn, hemceuose
Pubsher VTT Technca Research Centre of Fnand
P.O. Box 1000, FI-02044 VTT, Fnand, Te. 020 722 111
V
T
T

T
E
C
H
N
O
L
O
G
Y

5
3

N
W
B
C

2
0
1
2

ISBN 978-951-38-7880-1 (soft back ed.)
ISBN 978-951-38-7881-8 (URL: http://www.vtt.f/publications/index.jsp)
ISSN 2242-122X (URL: http://www.vtt.f/publications/index.jsp)
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Sponsors:

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by standard near regresson technques to yed the optma vaues of

CTec2, from Novozymes, usng

Utzaton of byproduct streams treated by wet oxdaton

durng 60 mn, wth subsequent aqueous washng of wood resdues

, showng the progress of the process-

, the formed poycon|ugated sys-

Figure 1. Process dagram for thermopastc gnn composte producton.

Recovery strateges contro the wood hydroysate barrer performance

Authors have equal contribution

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