) -71.

- - H.

12. Hidrocarburi sintetice

din carbune, din ~isturi
~i nisipuri bituminoase

78.

MAXIMILIANA PATRA$CU

82- SG.

12.1. lntroducere
1976. p. 27 1- 274.

- --~

1ntre solutiile m ajore cu perspecti\a de aplicare in viitorul apropiat,

adoptate pentru depa~irea crizei encrgetice este utilizarea resurselor fosile
,neconventionale": carbune, ~isturi ~i nisipuri bituminoase. Pc llnga folosirea lor ca atarc. drept combustibil, ele constituic materii prime din care
sc pot obtine hidrocarburi (nnmite hidrocarburi sintcticc [ I, 2]) ~i numeroase
prod use chimicc valoroas ~-~ca.:1ol , amoniac, sulf, fenoli, crezoli, ra~ini
etc.) [2, 3, 4]. Procedecle ~'3.uce rc d.: l1iP-ocarburi sintetice (benzina)
din cabune sint cunoscut c ~i au fost aplicat.e la scara industriala in Germania inca de acum 50 ani [5, 6, 1!8~ . Cercetarile d in ultimii 20 ani a u pus in
evidenta t chnologii noi de obtinere a hidrocarburilor sinteticc ~i a unor produse chimicc din carbunc, ~ is turi ~i nisipuri bituminoase [7 - 10]. Exist a
astazi in studiu in faza pilot sau de demonstratie 56 procese de prelucrare
a carbunelui, dintre care 31 pentru producerea gazului de sinteza [11]. Multe
dintre accstca sint avansate ~i aproape de s tadiul industrial [12- 17, 119].
Singuru1 procedeu de fa bricare a combustibililor lichizi din carbune, aplicat
la scara industria1a, este procedeul SASOL , bazat pe sintcza F ischer-Tropsch,
care este In functiune in Africa de Sud din 1955 ~6, 13, 18-20].

12.2. Carbunele
Transformarea carbunclui in hidrocarburi sc poatc cfcctua pnn mat
multc cai, prezentatc schematic in fig. 12. 1.
Procesele de hidrogenare (catalitica) ~i de rafinarc cu solventi din care
rez.ulta direct fractiuni lichidc, sint numite proccsc de lichefiere directa a
dirbunelui. Gazeificarea conduce la produsc lichide prin intermediul gazu1ui
d e sint ez~t, de aceea cste considera t procedeu de lichefiere indirecta .

303

Piroliza

CO +3H2
Gazeificare

C0+2H2

,,Gaze.

~ombusj

f1b!le

~.
Metano!

n(co;fH2)-

Sinteza de
metanol
Sinteza
Fischer- Tropsdl

Si{!teza
Bergius- Piei
Procedeu

Exxon

12. I. Schema de prelucrare a dlrbunelui.

Prin lichefiere directa se urmareste reducerea masei moleculei de carbune

~i cre~terea raport~H./C in aceasta, de la aproximativ 0,8 p1na}a valc:rf~ ..

siniilare cu acelea""itie~st:i'bil.if~:"'tle circa 2,0 [21-23, 120]. In acela~~
timp, prin reactiile de hidrogenare sint 1ndepartati sulful, azotul ~i oxigenul.
Puterea calorica ridicata ~i structura predominant aromatica a moleculelor
rezultate constituie avantajele proceselor de lichefiere directa [22]. Acesta
prezinta insa ~i dezavantaje, ca: temperaturi ~i presiuni ridicate de lucru,
ceea ce impune un echipament costisitor; consum mare de hidrogen al carui
cost este ridicat; dezactivarea catalizatorului datorita reactiilor de cocsare
~i a depunerilor de substante anorganice; rafinarea produseior lichide brute
rezultate din catbune este mai costisitoare dedt a acelora provenite din
petrol; riscurile potenjiale (toxicitatea ~i natura cancerigena a unor comporiente) la manipularea cocsului ~i a produselor lichide [22].
. --Procesele de gazeificare a carbunelui prezinta o setie de- avantaje ~i
. CJ,l1Ume: purificarea gazului de sinteza ~i faptul di: procesele de conversie
au loc la temperaturi ~i presiuni moderate,prin urmare, nu se pune problema
unor materiale ~i a unui echipament costisitor; procesele de conversie catalitica in faza gazoasa sint mai u~or de realizat dedt cele in tripla faza din
. pmcedeul de lichefiere direct a, prin hidrogenarea catalitica; otravirea catalizatorului se poate preveni mai lesne prin purificarea gaiului, iar reactiile
de cocsare sint considerabil recluse, intrucit se lucreaza la temperaturi mai
CDborite; riscul manipularii produselor lichide ~i a cocsului sint reduse [22].
12.2.1. Piroliza
Piroliza sau descompunerea tennica a cihbunelui se efectueaza prin
indilzirea dirbunelui la temperaturi de 450qC sau mai rriari, in absenta aerului. Din descompunere rezulta gaze, gudroane (fractiunea lichida) ~i un
304

Sinteza de
metana/

J ~~~::~~

Tropsch

Si[lteza
Bergius- Pier
Procedeu
Exxon

lleculei de carbune
018 pina la valori
3, 120]. In acelasi
azotul ~i oxigenui.
cica a moleculelor
recta [22]. Acesta
ridicate de lucru,
' hidrogen al carui
cdiilor de cocsare
;elor lichide brute
na provenite din
:1a a unor compoe de avantaje_ ~i
sele de conversie
se pune problema
:e conversie cata:..
:n tripla faza din
, ; otravirea cataului, iar reactiile
temperaturi -inai
sint recluse [22].

efectueaza prin
i, in absenta aea lichida) ~i un

reziduu solid (carbunele rezidual). Se tinde spre manrea produc}iei de fractii lichide, din care ulterior prin hidrotratare sa se ob}ina petrol sintetic
sau combustibil lichid cu continut reclus de 'SUlf. Distribu}ia produselor depinde de temperatura de piroliza, obtinerea de lichide fiind favorizata de
temperaturi mai coborite [24].
Reac}iile de descompunere termica a carbunelui fiind puternis: endoterme (circa 1,16 MJfkg [24]) este necesar un mare aport de caldura. In cazul
in care se urmare9te o productie ridicata de frac}ii lichide, aportul de caldura
trebuie sa fie ~i rapid, pentru ca timpul de !?edere al carbunelui in zona de
reactie sa fie extrem de scurt, evitindu-se astfel cracarea produselor volatile
din carbune. Prin excluderea oxigenului din zona de reactie se obtin cantitati maxime de fractii lichide. Aceasta se rcalizeaza cu ~iteze de' incalzire
ridicate, in strat mobil, purtatorul de caldura fiind chiar carbunele rezidual,
incalzit separat la 650-870C, prin combustia lui partiala. La viteze mari
de incalzire toate reac}iile sulfului din carbune (organic sau anorganic) decurg
simultan, o mare parte din sulf trecind in fractiunile licbide ~i in carbunele
rezidual ~i mai putin in gaze [25].

1ntr-un~alt ptocedeu [26, 120] piroliza carbunelui se efectueaza in trepte,

la temperaturi din ce in ce mai mari, in reactoare in strat fluidizat. Numarul
treptelor 9i temperaturile variaza in functie de tendinta de aglomerare a
carbunelui. Caldura de reactie este furnizata prin arderea unei parti din
~~arbunele rezidual in ultima treapta ~i transportaiJ;~ gazele arse, care
~ala in...-COI~urent cu carbunele.
,,~.;,~
-~-~~
S-au publicat corelari [117] asupra unor proprietati fizice (masa moleculara, parametrii critici 9i tensiunea de vapori) a produselor lichide din
sintetice.
gudroane si
' din titeiuri
, ,
">

12.2.2. Gazeificarea

Procesul de gazeificare a carbunelui se efectueaza prin introducerea

simultana deabur 9ioxigen (sau aer) in stratul de carbuneincandescent [f.:JJ.
Caldura dezvoltata din reac}iile exoterme de combustie este consumata de
_reac}iile endoterme ~intre carbune ~i.-vaporii de apa) [ 18]. -Cu -cit temperatura
stratului esj_~ m,ai _ridicata (datorita unei proportiimai wa_ri d~ oxigen),.0u
atit cre~te randamentu1. 0 temperatura prea ridicata conduce la fonnare
.de clincher:, .c.eeaccecauzeaza canalizari in- strat ~i prin unnar~, reducefea
randamenfului. Pe de alta parte, la folosirea unei proportii prea mici de (>xigen.seAormea:za particule fine de cenu~a, care cauzeaza aease-menea.cana:-Jizari in stra-t 9i conduce la obtinerea unui gaz cu putere calorica mica, Con- trolul proportiei abur-oxigen se efectueaza simplu. prin masurarea ,,tempt::c
raturii desaturaJie a fluxului insuflat" (temperatura amestecului abur-oxigen
inainte de introducert:Ja lui in reactor) [10]. -Etapele prindpale in procesele de gazeificare a carbunelui J:n vederea
obtine:rii de gaze s!nt schematizate in fig. 1L2; Gazeificarea cu aer conduce
la obfinerea de gaze cu confimit ridicat de azot (circa 50% voL) 9i cu putere
calorica mica de circa 5-6 .M]jm3 (LBG) [28].
.
Prin folosirea de oxigen in locul aerului se obtin _gaze cu putere caloriFa
medie (MBG), variind intre 11 ~i 19 MJjm3 , in functie de contiriutul de mefan

-=c

305

-1
I

Carbune
Abur

Gaze cu
..---------.putere
L-_c_om_,_Pr_e_s,_e_~ca/~i~
medie

(NBGJ

Aer

Abur

Aer

Gaze
naturale
,----------,smtetice
cuputere
~-----.-----c--'arorica more
. . - - - - ' - - - - - . ( SNG)

12.2. Procese de gazeificare a carbunelui pentru obtinere de gaze combustibile.

[28]. Procesul este mai costisitor fiind necesara o instalatie de producere a

oxigenului.

,. .,
In cazul in care dupa gaz~-~J,l,:Q~~rvine un proces de metanare se obtin gaze cu putere calorica mare (33-38 MJ/m3), numite gaze
naturale sintetice (SNG) [28].
Aceste gaze se utilizeaza in cea mai mare parte drept combustibil. Gazele cu putere calorica mica se utilizeaza in industrie la diverse cuptoare
~i cazane, de regula la locul de producere a lor sau foarte aproape de acesta,
transportul lor la distanta mai mare fiind neeconomic [28, 29]. Arderea lor
in cuptoarele ~i cazanele existente pentru combustibili gazo~i conduce la
reducerea capacitatii acestora. Se impun deci, fie modificari importante ale
cuptoarelor in functiune (temperatura flacarii este mai coborlta, volum mai
mare de gaze arse pe tona de combustibil etc.)~ fie cuptoare de constructie
nona. Pe de alta parte, d~g;:lj<ti~<!. in atmQsf~ra a gazelor arse pune probleme
poluare [28, 29]. . _ ___ _ _ _ _ _
_ ._ _
Gazele naturale siritetice pot fi transportatela distante mari prin cond11ctele existente de gaze naturale ~i pot fi utiljzate in cuptoarele care ard
combustibili: gazo~i; dar"sint costisitoare"eo:in.parativ cu gazele cu putere
calorica medie.
-~- ----_ Dupa unii, [28Jol;)tiRetea_de gaze_cu~_puterec'alorica medie poate fi lila.i
avantajoasa, deoarece ritilizarea lordreptcombustibil necesita putine modificari la cuptoarele actuale; saupot servi camaterie prima pentru fabricarea
de amoniac ~i metanol. ___- __-_._- _--_ _ _ _

Se presupune {30} folo.s;itea dtept combustibil a unui amestec de 85% vol.

gaze cu putere caloridi mic;'t ~i 15% vol. gazenattirale. Amestecul are o putere calorica inferioara de 11 MJ/m3 .
Tipurile clasice degazeificatoare ale carbunelui, prezentate schematic
in fig. 12.3, sint [18, 3.1}: Lurgi ta presiune ridicata, Koppers-Totzek la presiune atmosferica 9i Winkler in strat jluidizat.

ae

306

~s

Ji:t're caloriaa m!riJ, .

'=JG)

Gaze cu

===---tpulPr;;>
~
medie
(MBG)

-~--""-

Gaze
naturale

_:J_r_es-ie----.fsinlPtice

caloricii more
(5NG)

C>ranare

I. .

gaze combustibile.

b
atie de producere a
ne un proces de me1
IJ/m3), numih~ gaze:;~J.
-

_:-'~--:~~

pt combustibiL Gala diverse cuptoare

e aproape de acesta,
28, 29]; Arderea lor
: gazo~i conduce la
icari importarite ale
:.:oborita, volum mai
toare de constructie
arse pune proble~e

ante-mari-p:r:in Goncuptoarele J:are _ard

u gazele cu putere
c

medie poate fi mai

:cesita cpu tine :ffiodi13. pentru fabiicarea
<mestec de 85% vol.
Amestecul_ are o purezentate schematic
j;pers-Totzek la pre-

i
l'
-l

\I

12.3. Tipuri de gazeificatoare clasice:

a- Lurgi; b- Koppers-Totzek; c- Winkler; 1 -distribuitor; 2 - gd\.tar; 3 - manta de :dicire; 4 - racitor
de gCl._z~_;_ 5 - carbune; 6 - oxigen (sau aer); 7 - abw;
8- abur din mantava de racire; 9 ...:cen,u~a; 10~-gaz
brutpmdus; 11- zgura; 12- zgui:agranulafa;.c13flux de iii eire; I - zan a de usc are; II - zona d.,<levolatilizare; III - zona de reducere; IV --: zona de com:bustie; V - wna de cenu~a; VI ..:.. strat fluidiza-t:

1n ultimile decenii auaparui:~~~anumitele gazeificatoate din ,genetatia

doua" [32], ~i anume-: Lurgi British Gas f.n masa de zgura (fig. 12.4) [31,)3];
Shell-Koppers in masa de zgurii, la p_resiuni ridicate [27, 34, 35]; Britis~'Gas
Combinat cu o etapa in masa de zgura ~i_aUa in flux antrenat [27, 31,_ 36J;Jexaco cu suspensie de carbune in apa [27, 37, 38]; Combustion Engineeriit,g" in
j lux antrent, lapresiune atmosjericii [39]; Tri-Gas in strat j luidizat [40J.::J->ri:n~
cipalele caracteristici ale acestor gazeificatoare sint prezentate in tabelur12.1
~i compozitia gazului de sihtezarezulfat in tabelul 12.2.

Tabe! 11 l 12.1. Caracteristici ale reactoarelor de

ga1:~ificare

Lurgi - British
Lurgi
'
Gas
[6,27, 121]
[27.31, 121]

Caracteristica

Uimensiunile ciirbunelui
la alim~ntare
'Tehnica de lucru

Temperatura, oc
Presiune, bar
Necesarul de:
-oxigen
- abur
Raport molar abur/
oxigen (abur/aer)
:Eficienta termica neta, %
(energia produselorfenerc
gia carbunelui introdus)

<'~

a carbunelui

II

British Gas
Combinat
[27,36, 121]

I
>

[Koppers- Totzek
[27. 34]. 121]

II

50% gr. sub

6 mm.
strat
..strat d:scendentl et. 1: masii de
zgur~;
descendent. . zgura
et. 2: strat

6 mm

6- 50 mm

.,~

550-900
20-30
scazut
ridicat

490-500
23-40

mobil

I
I

90% gr. sub

9Q fLID
strat mobil;
masa de zgura

sub 28

scazut
scazut

1500-1600
atrnosferica
ridicat
red us

<2
64

72

58

Spre d~osebire d~ gazeificator~gi original, la gazeificatorul Lurgi-BriGas, in masa d~:: zgura, nu e~~ :ijrtft pll'~ne-re*ictii asupra calit&tii
:sorturilor de carbune care pot fi utilizate ~i acestea se refera la punctul ridi-cat de topire al cenu~n [33].

-"'>.,._tish

12. 4. Gazeificatorul Lurgi-British Gas !n niasii de zgura:

1 - distribuitor; 2 - carbune; 3 -:- abuq;i oxigen; 4 - gaz
brut prod us; 5 - lichid de ricire; 6 ~ a pi:.:' de 'racire; 7 -

308

cenu~a.

ui

Gas
inat
121]

. sub
m

csa de

/Koppers- Totzek
[27,31], 121]

I 90%90
I

Shell - Koppers
[27, 35, 121J...

gr. sub

90% gr. sub

90 fill
strat mobil

l.l.ID

stra t ~obil;
masa de zgura

at

Texaco
[27, 37, 121]

<6 mm
strat mobil
descendent

Co1nbustion
Engineering
[39, 121]

< 20

mesh

strat mobil
in doua etape

\Yinkler
[27, 121]

100 fill
('Tal. medie)
strat fluidizat

1 500- 1600
atmosferica

1450-1500
18-30

ridicat
red us

ridicat
red us

1300
21,5-82,5
ridicat
zero

1070
atmosferica

Tri-Gas
[40]

925-1020
1,5-2,0

strat fluidizat in 3 etape

1 100
17

moderat
moderat

(0,85-':; 1,35)
58

75

ifica torul Lurgi-Brictii asupra calitatii

.era la punctul ridi-

j --- .

as in masa de zgur:ii:
bur l;li oxigen; 4.- gaz
- apa de racire; 7-

57

Procedeul Shell-Koppers poate fi aplicat pe 0 mare Yarietate de carbuni,_

car bunele brun cu pu tere calorica inferioara de 2500 kcal/kg ( 10,45 MJ/kg), .
''(:~~ni,?_ybbitumt~i ~i ligniti, avind 4000 kcal/kg (16,~~J[kg), pina la
'CarbffiiT bituiiilno~ cu putere caloridi inferioara de peste 4Gti'O kcalfkg: -~
pot gazeifica chiar ~i rezidii grele ca acela rezultat din distilarea in vid a produsului de la lichefierea directa a carbunelui, care are un procent ridicat de
cenu~a ~i contine particule de carbune neconvertit [35]. Cu toata varietatea
materiilor prime, compozitia gazului de sinteza prcdus nu variaza sensibiL
Se apreciaza [35) c3. investitia pentru o instalatie de gCJ.zeificare ShellKoppers situata in SUA (1979), care ar produce 36 mil. Nm3 /zi gaz de sinteza brut (fara uscare ~i purificare de solide ~i H 2S) din carbune cu 10%,,
cenu~a ~i 10% umiditate este de 793 mil. S. In aceasta investitie sinJ incluse
toate instalatiile de manipulare, depozitate ~i pregatire a dirbunelui, de
fabricar.e_a_oxigenuluL~i detra:tare a apei. Variatia .. costtiJl,li.prCd!l~.:tlmLJ!l
functie de pretul carbundui este ilustral:a in fig. _12.5,_alllb~lesostuti f~ind .
expiimate in $/mil. BTU. Costul gazului de sinteza rezultat din carbune
cu pret scazut, ca acela obtinut dintr-o mina de suprafata,este de circa 2,84,: .
S/GJ,in timp ce gazul provenitdintr:-un carbune mai ~cuwp; ca.c:elprov~nit
dinmirlg.~de=adinciine, caracteristice Europei, ar !mtea fi de~4,7.4 $/GJ,:~cGQs._.
.. turile benzinei ce ar fi. prcdma din cele 2 tip uri ar fi de 4, 74~i_re~pectiv: 8;5Y
S/GJ [35];
.
.

.
In procedeul Combustion Engineering gazeificarta ~e ieallztaza {1J:Htr ,.
Jn doua etape. Inprima etapa ..:_ccmbustia - 1/3 din totalulde c~.rbune
se arde cu. aer piria aproape de combustia ccmpleta. peritr1J. a prctluce un
ga zavind circa 1750C. :tn a doua etapa -zona de reducere gazulfier,
7
binte Vine Ill contact CU carbunele proa~pat ~i C'U un mare deficit de aer !:e
formeaza gazul de sinteza brut.
. .
Din tabelul .12.2 se observa ca spre deosebire de gazeificatoareleLtngr
original sa.u modifica( in procedeele Koppers-Totzek, She11-Kopper.sJi }'ede.l~

68-72

I~
I

~~.

I'.
:

w
'"""

,;:

/ ' ,' '

\J
Tabelttl 12.2. CompoziJia. tipicii. a gmitllui de sintezii. uscat, rezultat din deversele tipuri de gazeificatoare

Lnrgi - British Gas in mas{t

de zgurit

Lurgi
[6)

KoppersTolzek
[6)

[31]

ShellKoppers
[27]

Combustion
Engi nccri ng
[.19]

'r'!~xaco

[37]

Winlder
[6]

,",'i~"

brnn

cim

en
10%

cu

4-8%

cu

dur

21%

CellU!j{l.

cer1u~rt

C<~ll n~(l.

dil(:rst:
tip uri

en

cu!O';I,
ceu u~rt

10';{,

brnrr

ceu u~i"l.

c
20

23

56,5

56,6

.'iri,3

57,5

(ill

4:l,.'i

7,5- JO,O

38

.?7 .

39

2.9,0

30,7

2'J, I

30,5

.10

34,6

5,0-9,5

40

ho

27 :

3, 1

2.,0

5,3

10,5

18,6

12,5-3,0

l2.

10

6,9

7,3

7 2 i.'.
I

\,

--

-3,4

4,~

12,7

12,8

4,5

11, 1

10,8

12,8

{~~

,,~

~./

0,2

0,4

1,5

0,8

2,9

0,0-1,0

9,2

9,2

1,5-5,4

0,0-0,3

20
.I

1,5

74,0-58,0

0,5

8,8

12.5. Varia\ia costului produsului in procedeul

Shell- Koppers (baza carbune bituminos de Illinois;
$ 1979);
1 - sinteza indirecta a benzinei; 2- metanol;
3 - sinteza directa a benzinei; 4 - gaze cu putere calorica medie.

J[
1 BTU=7,053 k)
L-~o~ft~j:-77,o~~J.~s~~~~o~2~.5~J~,'o~

Cestui. carbune!ui {!i /mil. BTU}

xaco se obtin cantitati foarte mici de metan, ceea ce constituie un avantaj

pentru obtinerea gazului de sinteza in vederea fabricarii de hidrogen sau
de amoniac [18].
Gazeificarea in strat fiuidizat (tip Winkler) prezinta o seri~ de avantaje,
ca: pregatire minima a carbuhelui bn.'i, tomum specific mic de oxigen, gaz
de sinteza cu un continut redus de componente inerte, cu efecte reduse dt
poluare, constructie simpla [5].

Unul dintre fenomenele care produc dificultati in exploatarea gazeificatoarelor in strat fluidizat este aglomerarea particulelor. Pentru evitarea
acestui inconvenient, in procedeul Tri-Gas, aflat in stadiu de instalatie pilot
[40], se efectueaza inainte de gazeificare 0 devolatilizare a carbunelui, la
temperaturi de pina la 650C, cu ajutorul caldurii gazelor produse in ultima
parte a procesului de gazeificare .. Astfel se elimina din dirbune gudroanele,
care ii confera acestuia proprietati plastifiante Ia temperaturi ridicate, ca
acelea din timpul gazeificarii .
. rn general,
~onsideri
procesulde d~volatilizare se deda~oarain
doui'l, sfadii. In primul tree ill. faza gazoasa nidrocarbutile grele, cu rapoarte
atomice HfC mici, care condenseaza atunci d11dgaz;111esteracit. In al doilea
sta9-'i11, ca_re are lot Ia fempetatwi mai .ridicate, c1evo1atilizarea include 'TRc
p~:r:t:.a.leg~ turilor atomice in. hidrocarburi. Substan{ele~ volatile produse .au
fa.J::loarte H/C mari 9i ramin in f9-za gazoasa atunti dndprodusul este racit
la temperatura ambianta. Catbunele devolatilizat are o structura mai gra.c
fitica ~i Hjf; ma,i scaiut. Determi11arile .efectuate [40] aupermis stabilirea
in functie deraport11l H/C al carbrinf!lUi brut; a conditiilor deoperare 11,ece.c
safe p.eii tru .a realiza o dev9la ti~izare core~p}lnzatoare i:l'rainte de gazeificare.
Dintre acestea cea ma.i importanta este temperatura din reactor.
.
Din procesul de gazeificare a carbunelui rezulta 111 majoritatea proccdeelor 9i o fractiune lichida, Cu a:rii in urma; separarea produselor continute
in aceasfa nu era economica. Astazi, daforita cre~terii continue a pretului
petrolului, se efectueaza cetcetaripentru stabilirea unor procedee de sepa:-o
rare a produselor secundare din fractiunea lichida ~i a economicitatii Jor.

se

--

ca

----------

---------

Un studiu recent se ocupa de caile de separare a produselor secundare ohtinute prin gazeificarea lignitului in strat fluidizat [41]. Din fractiunea lichida
bruta rezultata din proces, se separa printr-o succesiune de operatii produse
secundare, ca: acizi crezilid (utilizati la fabricarea de pesticide, ra~ini, fenolice, solventi, dezinfectanti, produse de parfumerie etc.), piridina, hidrocarburi olefinice si smoala.
Pentru a fi u'tilizat ca materie prima in procesele de fabricare a hidrocarburilor sau produselor chimice gazul de sinteza rezultat prin gazeificarea
carbunelui necesita modificarea ratiei CO/H 2 , astfel incit sa se obtina proportiile indicate in fig. 12.1. Atit procesele de imbogatire in H 2 , cit ~i cele
de sinteza a hidrocarburilor sail altor produ~i chimici, se realizeaza catalitic.
Obtinerea unuia sau altui "prodtis ~i randamentul procesului depind de catalizatorul utilizat. Cel mai u~or de obtinut sint produ~ii alifatici oxigenati, ca
alcooli ~i aldehide [12].
DJua produse de baza pt:;_ntru fabricarea multor altor produse chimice
sint metanolul ~i amoniacul. In prezent, gazul de sinteza din care se obtin
aces tea pro vine in cea mai mare parte din reformarea gazelor naturale. Cu
cre~terea pretului hidrocarburilor se indica 0 orientare treptata spre carbune,
ca sursa a gazului de sinteza [31J.

F abricarea m?-tanolului. Comersia gazului de sinteza in metanol se efectueaza pe doua cai, ambele catalitice [6, 22]: la presiune inalta (300 bar)
~i tempera,turi de 320-380C, utilizata exclusiv pina in 1960 [27], ~i la presiune jie-2,_~- (19_Q bar) ~i temperatura de circa 250 C, care a inloe'!ilii pe scara
larga procesnfla presiu~icata C27J.
"" -;:r:~
Dupa separarea impuritatilor, gazul de sinteza este supus unui proces
de conversie in vederea modificarii ratiei H 2/CO la circa 2/1 [18], apoi urmeaza indepartarea C0 2 ~i a compu~ilor cu sulf (H 2 S ~i COS). Astfel pregatit,
gazul d:: sinteza este introdus in reactorul de sinteza a metanolului. Cataliza
metanolului este foarte selectiva, dar cu conversie redusa, de aceea sint necesare recirculari mari [23].
Interesul pentru fabricarea metanolului a crescut datorita posibilitatii
de a-l transformain benzina (p_r()cedeul :cy!obil, descris mai jos), sau de a-J
utiliza drept combustibil in motoarele auto, fie ca atare, fie in amestec cu
benzina [6, 18, _2Z]. ____----, ~---Se prevede ca in urmato.rii ani ~a fie pl!se l.rr functi:une mai multe instalatii dedabricare a metanoluiui din >carbune, de diverse capacitati; in SUA
_!?i Europa [14, _U, jL,, :45], {Jneleproiept~j~i, prop11nfabricarea de metanol
~i producere toncomitepta~aeknetgie- electridi ptin folosirea gazului de sinteza in tr ~o instalaiie"-eneFget-iea~u,(;iduc combiJ}a t. [46l
Fabricarea dmon~at'ul1-t-t.-P~f1trri;pregatireaamestecului de gaze cu care
se alimenteaza insta.laJi<t de $i:nteza a amoniacului, gazul brut de la gazeifi~ator estepurificatdeH2S s,i COS, apoi CQ este convertit in C0 2 in prezenta
. de abur. Dupa 1ndepartat;<)<LC02, gazele sint spalate en azot lichid; astfel
indtsa ajunga la co~poziti.a YoluJI1ic3. _75% H 2 ~1 25% N 2 , apoicomprimate
la 220 bar ~i introduse in I'eactorulde- sinteza a amoniacului [18]. 0 mare
instalatie de fabricare a amoniacului ~i a metanolului din catbune, cu 0 productie de 1ooo. tjii(amoniac+ metanol), bazata pe 6 gazeificatoare KoppersTotzek, situat~i la Modderfontein, inAfrica~de Sud, este exploatatade peste
cinci ani [47]. Sc apteciaza dl in ''iii:orul apropiat vor fi puse in fnnctiune,

312

luselor secn.1dare obDin fractiunea lichida

e de: ?perarii produse
peshc1de, r;'C"ini fenoc:c.), piridini, hidro-

in diverse par-ti ale lumii ~i alte instalatii de fabricare a amoniacului pornind

de la dirbune [48-51].
Un studiu din 1979 [50] evalueaza costurile comparative de investitie,
de exploatare ~i de producere a amoniacului din gaze naturale, benzina,
combustibil greu (procedeul de oxidare partiala Texaco) ~i carbune (procedeul Koppers-Totzek). Luind ca baza de referinta in toate cazurile o instalatie de capacitate anuala de 340 000 t amoniac datele relative privind fa~.
bricarea amoniacului se prezinta in tabelul 12.3. Se obser\'<'1. ca fabricarea
amoniacului din carbune este justificata numai in cazul in care costul dJ.r..:
bunelui este redus, astfel inclt sa compenseze cheltuielile mult niai rria.ri
de investitie ~i ale ccmsumurilor energetice.

de fabricarF: a hidrotlta t prin g~eificarea

dt sa se obpna pro~ire in H 2 , cit si cele
'e realizeaz;;. catalitic.
oului depinc de catalidifa tici oxi~-c:na ti, ca

Tabelul 12.3. Date relative asupra fabricarii amoniacului

ltor produo.-: chimice

"za din car-: se obtin
gazelor na~crrale. Cu
;eptata spr": f3.rbune,

19~0 [27_; ~i la pre-

~e

a mlocm: pe scara

Gaze B
. bCom-j _
ct J enZli ustl- Carna u- I b"l I b
t rale I na I
l
I
une
'
I
I greu

i in metanr.I se efeciune inalt~ i300 bar)

1

Fabric~t din:

Costuri: - investitie
- energi~
- materie
/~"~
prima
-.~~r
'i:t>-tal f:le-.~o~
produqie
Energie in materia
prima
>

:e supus ur..:.:i proces

,ca 2/1 [18~: apoi ur.OS). Astft. pregatit,
metanoluhi_ Cataliza
sa, de ace!%. sint ne-

Sinteza hidrocarburilor. Din gazul de sinteza se pot obtine hidrocarburi

pe doua cai_: sinteza Fischer-Tropsch ~i procedeul Mobil (prin inter'medlul metanolulm).
..~

Procedeul SASOL, aplicat la scara industriala in Africa de Sud, bazat

pe sintez<l; Fischer-:-Tropsch, constituie o forma imbunatatita a proc~$_ulp,i
aplicat in Gennania in perioada 1930....:.1945.Instalatia SASOL l, 1n"f'nP"c:...
tiune D.in 1955-[19,--~2{)~52~ -rr8; 120;' 122],. produce 300 000 tjan~pifi!_g\rse~
prirna:re [6]; utilizirrd gazeificatoare Lurgi; care au fost considerate mai;:<i,-V;-an.:.
ta:joase penfr1l caT1JJJ.I1efe sud..:africal1, cataderizat printr-un contim.it#~~tC
de cenu~ajcirca 350/o gr: cenu~a; 10/7. gL U.miditate, 22,3% gr. suJ:)~an}~.
volatile; l9;94~1J{~fputere caloridi)'[6,l8].~ Pentru sinteza Fischer-Tr.o;R~ctti~.
se fo16se~te uli grlip ~de readoani calalitice ill stra t fix (Arge) ~i un .gt);fp~:ctetc~C . c
reacfoare in stratfluidizat (Syntho1) [6, 18, 19, 22; 118].
,
in cadrul __ complexului >de la Sen.1nda. (Africa de Sud) in 1980 _a,i~1riit
in functiune o a. douajpstala}ie tip SASOl -_SASOL II -_.care ~in_;.,..1~&2,
dnd va func~iopa la capacitate~vno-cmala; va~.produce din 14 miL tf~fi{.qat,~
bune gazeificate 111 J6 gazeificatoare Lurg1, cirbt 2;5 mil. tfan prod;u~fl~~~,;
19, 52-56, 118, f2l]. OX:igenill micesar pentru gazeificare (9500 fi~'W<~i c ~
peritru reformarea metanului rezultat tJ.in proces (3700 t/zi) este produs~~ri_
6 unitati tip Lincle, fiecare cu o capacitate de 2500 t/zi oxigen.
,:;/ ;
Gazulbn.rt proi:l11s in ~azeific~toare are compozitia volumica. [19j~,""~!o/e
(CO+ H 2), 9,4% CH4;32o/6 C0 2 ,0,7% H 2 S, 6,3% N 2 , 0,15% hidrocato~~i~r
lichi?~

da tori ta pr.>5ibili ta tii

mai jos), ::::.u de ~-1
e, fie in arriestec cu
une mai mnire instacapacitati, i.n S"CA
abricarea de.metanol
sirea gazubi de sin?

~lui de ga.z.;: cu care

:ul brut de k. gazei. it in CO 2 ir>orezen ta
u azot licl:&.i,.a,sH~l
\J 2 , a poi CCP"'"prirna t e
iacului [18~. 0 mare
n carbune, Dl o pro:eifica toare Koppers. exploatat;;. de peste
fi puse in f?.mc}iune,

::-:F._

Il

.. I

~.

__ ,-,_~ _,,-, <.,, J','

~-----~~---~
I

'

:Qupa purificarea ,rectisol'' se obtin 28 mil. m 3/zi gaz,de sinteza, care con tine
84% vol. (CO+ H 2 ), 13,5% vol. CH 4 , 1,5 %vol. C0 2 , restul fiind mai ales
N 2 Continut11l de sulf se red1;1ce la 0,07 ppm [19].
Pentr11 sinteza Fischer-Tropsch s-au prevazut 7 reactoare in strat fluidizat(Sy)lthol) cu un nou catalizator, tip ~sASOL, pe baza de Fe, a carui
experimentare prealabila in vederea operarii satisfacatoare a reactorului,
a durat 5 ani {19]. Acestea lucreaza la 320C ~i 23 bar.
La Secunda se afla. in constructie instalatia SASOL III, de aceea~i capacitate ca ~i SASOL II [52, 54-57], care va functiona la capacitatea de
proiect in 1984[19, 52]. Aceasta instalatie areparametri analogi cu SASOL II,
dar cu o productie mariti de motorina obtinuta in contul benzinei.
Capacitatea fiecarei instalatii SASOL din complexul deJa Secunda este
echivalenta cu o rafinarie de aproximativ2,5 mit tfan petrol. Pe llnga hidrocarburi gazoase ~i lichide se obtin ~i compu~i chimici, in total 20 produse
finite. Productia anuala a acestui complex, la capacitatea normala de functionare este prezentata in tabelul 12.4.
Tabelul 12.1. Prcductia complexului
SASOL-Secunda
:Mii
t/an

%
gr .

.,..,~
~<#~i<'~

'co"rri'B~ibi!i Iichizi

(benzina
petrol
reactor + combustibil Diesel)
Etilena
Gudroane

Amoniac
Sulf
Alte chimicale

1850 171,0
180
7,1
i
180
7,1
110
4,4
100
4,0
85
3;4

[
I

~----

Total

[ 2 505 100,0

- . Eficient~:te;mica a instalatiilor SASOL II ~iiil este 6.0%, iar>Cheltuie----lile-_de i11vesti}ie sint ~ T 10~ $. groductia Ia ca:pacitatea de proiect--;t acestui
wm.pJex~va-permite.Africii.-aeS:ud sa- devina independenia-~de importul- de
p.etw!J52, 54].JnJ985 instaJ~ti;ile .SASOL II ~i Uf:vor fi competitive cu ~o
m:finaiie~(de: egaJa. capadtateJ$cun pre} al petrolri1ui?de JQ~~ft. ~ .~v ~ . .

~ . Siciri SUA. se afla in con1:nictie o ins talatie de fabricate a cowbustibi~

-lilor,~fa-u_tO:~pri:ii -prbcedeul de 'licheflefe indirec'ta ~ ~ ~ 8.AS0I:;~~ca-re ~ va~produce
iri 1985 [20, 58}. ~ .
~ ~~..
.~ .
. . .
--. Inprocedeul Mobil(vezica;p. I:l)benzina se ohtineprin convetsia cata;Iitis~,~a)n.(.:tanolului~ln eto-qa~t;ry.pte: Jn prima, cinet;in01u1 SE; fl"an,s,forma in
dimetH(Oter:; In a doua, di~et~eJeruLest~ convertit in ~ hidrocitrburi~;&lefinice,
~~ca~e apoise trabsformain ~rhate ~iizoparafine [22,.2'7, 121}: P.~'tataHza
tonilspecific, cu proprietati z;eolitice, din seria ZSM-5 [22, 27, 58J;seformeaza. 0 ca.ntitate mare de hiO.rocarburi eli masa moleculara relittiv mica
~i .pulin cq~s. Cea Jll.ai grea bidroc;arbura care rez1,1lt8, est~ qureilplj tetrame til benien simetric) [22]. f>i:ocesul se poate (iesfa~ura in' rea~t6iiccu strat
fix; sau cu shat fluidizat. Utilizarca stratului fluidizat prezinta fata de va.,314

1teza, care contine

"'tul fiind mai ales
:oare in strat fluiza de Fe, a carui
)are a reactorului,
II, de aceeasi cala capacitat;a de
logi cu SASOL II,
l benzinei.
'e la Secunda este
0l. Pe linga hidrototal 20 produse
normala de func-

'-"~
.....

~,--~,~

rianta cu strat fix avantajul unei selectivitati mai ridicate la benzina si a

rinui schimb de caldura mai bun !22, 271. 0 i~stalatie industriala cu rea~tor
in strat fix va intra in functiune
1986" in ~oua Z~elanda [59, 121], in timp
ce . varianta in strat fluidizat este in stadiul de instalatie
de demonstratie
'
'
(in SUA ~i RFG), premergator proiectarii unei instalatii industriale [22, 59].
Benzina finita obtinuta prin procedeul J.Iobil are calita}i superioare
(cifra octanica f:'ira adaus, COR 93; nu con tine sulf ~i azot) [27].
Mobil ~i Lurgi au efectuat itnpreuna un studiu comparativ, tehnico-economic, privind producerea de benzina prin procedeele SASOL ~i Mobil [22].
1n tabelul 12.5 se prezinta bilanturile materiale ale celor doua procedee,
stabilite peritru ptoiectele a doua instalatii cu gazeificatoare Lurgi, cu o
productie de 8 106 m 3/zi. Din comparatia efectuata [22] rezulta ca procedeul Mobil (carbune - metanol- benzina) ar prezenta. fata de procedeul
SASOL (Fischer-Tropsch) urmatoarele avantaje: selectivitate mai mare, ceea
ce conduce la ran dam en te mai mari de benzina ; cifra octanica a benzinei
mairidicata (93 fata de 91); continut mai redus de olefine in benzina (11%
gr. fata de 20% gr.); eficienta termica (calculata~ca raport intre energia
tbtala ie~ita ~i energia totali intrata) mai ridicata (62% fata de 58%); numar
mai mic de Hape in procesul de prelucrare pina la obtinerea benzinei finite
(ambele procedee au cite 9 etape pentru producerea prin gazeificare a gazului de sinteza purificat; apoi pi:nii la benzina finita :1Iobil are 9 etape, in timp
ce la SASOL sint 18 etape).
Din studiu a reie~it ca amh....lt: proced::e necesita cheltuieli de investitie
ridicate. Pretul estimat al benzrn":it-x:-te tu irca iii.~ mai mare la procedeul
Fischer-Tropsch.
Cercetarile prezente ale lui :Jlobil sl:nt orientate ~i spre obtinerea directa
din gazul de sinteza a benzinei cu cifr?, octanica ridicata, fara a mai trece

in

Tabelul 12.5. Comparatie intre procedeele :\Iebil 9i SASOL

1
1

Procedeul
Mobil

Procedeul
SA SOL

60%, iar cheltuieproiect a acestui

~a de imporhtL<l~
competitive cu o
0 $/t.
are a combustibicare va produce
in conversia catase transfornaa in
ocarburi olefinice,
121]. Pe ca taliza2, 27, 58], se forJara rela tiv mica
t durenu1 (tetra1 reactor cu: strat
zinta fata de va-

Intrari
--carbune;- tfzl. Apa. m 3 /h.
Produse
Benzina,
m 3 /zi
C3 lichefiat,
m 3 /zi
Butam;
m 3 fzi
- Combustitli1 Diesel,
m 3 /zi
COmbi.lstibil.
m 3 /zi
Gaz naturalsintetic, (SNG), mii m 3 /zi
Alcool, t/ zi
C.orntmstibil echivalent 1 , m 3 fzi
Alte pr:oduse
Putt~re (e1ectrica), k\V
Carbunepulbere, t/zi
Amoniac, tfzi
Sulf, tfzi
Eficienta (fata de puterea calorica superioara),
1

25210
62 964

2 L59

116
--+z3'

7 242

366
99
4 904'
231
7 147

1088
93

93

4 202

55

55

62

5!\

Toate produsele conrertite in combustibil echin}ent la 39,71 G J/m3 .

315

prin faza metanol [22].

zent, procedeul prezinta
tele unei uzuri rapide a
lui ~i a producereii unei
dicate de gaze u~oare.

GAZ .BRUT SPRE

~PUR!FICARE

Sl

METANARE '
I

SUSPENSiE

DE-----

CARBUNE

Pina in preinconveniencatalizatoruproportii ri-

1N.

ULEI

12.2.3. Hidrogazeificarea

12.6.

Realizarea catalitica a gazeificarii

carbunelui la temperaturi mai caborite dedt cele din ins tala tiile actuale
(950- 1700C) permite obtinerea de
cantitati mai mari de metan, cu randamente termice mai ridicate si costuri
mai scazute pentru etapa de' metanaHimo
re 160].
'GAZEiFiCA.RE
-In procedeul Hygas, [33, 120] gaA2- 0 ETAPA
zul brut se obtine intr-un reactor preGAZEiFiCA.RE
vazut cu cinci zone separate (fig. 12.6),
CU !JBU.R
in care se men tin straturi fluidizate
?I OXIGEN
de carbune. Gaz~l pentni hidrogaiei~~
ficare (bogat in hidrogen) se produce
....,.APIWENfRu""'in .,_fulfa de gazeificare. Reactorul IuOP.RiRfit.
. . creaza la 80 bar cu un regim de lucru
.R~ACT!EI pentru fiecare zona aratat in tabeC.4RBUNE 1u 1 12. 6. L a 1e~1rea
. .
d'm reactor, gazu1
~w::ziDUAt
- brut are compozitia: 26,4% CH4 ;
Reactorul Hygas.
22,5% H 2 ; 32,9% H 20; 7,4% CO;

7,1% C0 2 ; 1% C2H 6 ~i 1,5% H 2 S.

Pe baza descoperirii actiunii substanVJor akaline [150, 6Ij, care la un
adaus de 15% mol. KOH la carbune maresc viteza de gazeificare de 10
ori, la Exxon s-a elaoorat un proces tehnologic de gazeificare mai simplu,
care nu ar necesita-instalatiile de fabricare a oxigenului, de conversie a CO
~i de metanare [60].
Tabelul 12.6. Regimul de lucru
Zona
(strat fluidizat)
Uscare suspensie

!Tempera.tura,ll
[
C
I
.
'

315

Presiu.mC
bar

67~

100

Prod use

Reactanti

Carbune ;;;i ulei

\
Vapori de ulei care
[ a fest folosit pentru
I suspensie
Carbune ;;;i gaze din I
20% din carbune
hidrogazcificare etapa j transformat in metan
u~or

Hidrogazeificare
etapa 1

705-815

67-100

Hidrogazeificare
etapa 2
Gazeificare cu
abur ~i oxigen

925-980

67-100

980-1040

67- 100

316

CaFbune {li gaz bo-1.

25% din carbune
gat in hidrogen
transfonnat in met;in
Carbune -reziduaL
j
abur ~i oxigen
Hidrogen

l~

.~

i
l

:wl [22].
prezinta
rapide a
reii unei

Pina in preinconveniencatalizatoruproportii ri-

12.2.4. Lichefierea directa

Se cunosc trei cai de lichefiere directa a carbunelui [21, 62], ale caror
scheme de principiu sint prezentate in fig. 12.7. Schema din fig. 12.7, brepre:iinta procesul necatalitic de rafinare cu solvent a carbunelui. Procesul
de lichefiere din fig. 12.7, c, de hidrogenare a carbunelui prin intcrmediul
unui solvent donor de hidrogen, prezinta fata de eel de hidrogenare cata-

u~oare.

eificarea
:a tali tica _a- gazeificarii
mperaturi mai coboJin ins tala tiile actuale
)ermite obtinerea de
ni de metan, cu ranmai ridicate si costuri
c:ru etapa de' metana-

Oz
C02 (pierderi)

l Hygas, [33, 120] ga-

ne intr-un reactor prene separate (fig. 12.6),

;:in straturi fluidizate
ul pentni hidrogazeihidrogen) se produce
ificare. Reactorul lucu un regim de lucru
cona aratat in taberea din reactor, gazul
)ozitia: 26,4% CH4 ;
J% H 20; 7,4% CO;
C2H 6 ~i 1,5% H 2 S.
[60,-61],-care-la un
~le gazeificare de 10
zeificare mai simplu,
1i, de conversie -a-cO

Gaze
Distil ate

:::arbJne

Gaze

i,.,..---;p:-

f
C02 (pierderi)

Gaze
Distilate

Soiv-ent
boga:in H2:o.-J_---~

Reziduu

Solvent
sarac -in H2

Produse

Il

;t

Vapori de ulei care

a fost folosit pentru
suspensie
20% din carbune
transformat in metan
25% din cii,rbune
transforma t in me tan

Hidrogen

CO { ierderi J

c
12.7. S:h3me-de p:in~ipiu pentru lichefiere~ directa a carbunelui:

a - lichefieni catalii:ica \hidtogenare catalitica); b - lichefiere nccatalitka; c - lichefiere cu ,solvent donor de hidrogen".

litica (fig. 12.7, a) avantajul protejarii catalizatorului de influienta nociv~

a contactului cu carbuncle. Sohentul se recupereaza din produsele de reactie, se hidrogeneaza !?i se reintoarce la reactorui de hidrogenare a carbunelui.
Lichefierea directa a carbunelui este in faza instalatiilor pilot sau de
demonstratie in multe tari cu bogate rezerve de carbune (SUA, Australia,
Anglia,. Canada, RFG, Sardinia etc.) [36, 45, 63, 64].
Hidrogenarea catalitica. Hidrogenarea carbunelui in wderea fabridirii de
combustibili lichizi prin procedeul Bergius-Pier (fig. 12.7, a) a fost aplicata
industrial in Germania cu peste 40 ani in urma [6, 13]. Lucrind la presiuni
de 200-700 bar !?i temperaturi de 400-500(, in prezenta de catalizatori
oxizi de fer, sau clorura de staniu, carbuncle in suspensie in ulei recirculat
se convertete intr-o gama larga de hidrocarburi, din domeniul gazelor li,_
chefiate, benzinei si motorinei !6l.
Variante ale ~cestui proces- ~are urmaresc marirea randamentului termic, realizarea procesului in conditii mai putin severe ~i diversificarea produselor, sint in prezent in curs de experimentare in Sl;A, RFG, Anglia,
Japonia !?i Polonia [6, 121].
Unul dintre acestea este procedeul Dow [65], in care hidrogenarea suspensiei de carbune se efectueaza intr-o emulsie apa-ulei in care este fin dispersat catalizatorul (de ordinul micronilor). Suspensia de carbune in ulei
recirculat (40% carbune in suspensie) se am~steca cu o solutie apoasa dintr-o
}_a;e, sau mai mul.te saruri ale metale~{)f;~~<;tjvne,.~cat~!J.i.a (Va, Fe, C?,
~o, \V), contmutul de metal achv adaugat la suspens1e puhd \ana
intre 80 i 1300 ppm. 1n solutia apoasa raportul metal/apa variaza intre
1/5 i 1/30. Se lucreaza la 140 bar ~i 460 oc i o alimentare de 560 kg/h carbune
pe m 3 de reactor. Distributia componentilor in produsul net obtinut este
prezentata in tabelul 12.7.
A

Tabelul 12.7. Distributia componentilor

in produsul net rezultat
din procesul de lichefiere
Dow

Baza: kg produs/100 kg dirbune liber

de apa

~i cenu~a.

C1
~-~

c 5 ~zoooc

200-100C
400--'500C
500C -0

co

C02

H 2S
Solupe apoasa
Consum de hidrogen,
%; gr.

7,3
~8

13.2
28,6
4,9
2,6
0,8
0,6
2,6
10,7
5,2

Rezultatele experientclor efectuate pe o instalatie pilot (capacitate lO()

kgfzi carbune) au arafat ca procede11l Dow ofera avantaje tehnice in ceea
ce priveti~ cataliza, separarea uleiului 4ezasfaltat 9i sirnplitatea reactorului.
Pe baza lor s-a elaborat proiectul unei iristalatii industriale de lichefiere a

318

carbunelui cu capacitate de 10 000 t/zi ~i cu o eficienfa calculata de 76%

[66]. Se va produce combustibil gazos cu putere caloridi de 7350 kcal/Nm3 ,
gaze lichefiate, benzina-petrol cu final sub 250C ~i combustibil lichid cu
punct de fierbereriditat. Costul estimat al produselor [66] de circa 124 Sjtep,
se poate considera ca foarte optimist.
In toate procesele de hidrogenare a carbunelui, aplicate la scara industriala, reactiile a.u loc in faza lichida (suspensie de carbune in ulei greu).
Timpulnecesar desfa~urarii reactiilor variaza intre 20 s ~i 2 ore. Unele date
[23] de laborator ar arata ca hidrogenarea carbunelui in faza solida, maruntit la 200 mesh, s-ar putea realiza in timp mai scurt, cu catalizator continind
15% clorura stanoasa.
..
In .faza de cercetare se afla un proces nou de hidrogenare a carbunelui,
necatalitica, intr-o singura etapa, numita ,hidropiroliza rapida" [67, 68].
Produsele reactante, lignit ~i H 2 J.ncalzite in prealabil, sint contactate in
echicurent intr-un reactor in care semen tin presiuni de 140~ 170 bar ~i terhperaturi de 800-900C respectiv.

influienta nonva
produsel~ de reac~
nare a dirbunelui.
tiilor pilot sau de
: (SUA, Australia,
ederea fabricarii de
a) a fost aplicata
1crind la presiuni
1 ta de catalizatori
'in ulei recircula t
meniul gazelor li:mdamentului terdiversificarea pro_:A, RFG, Anglia,
hidrogenarea suscare este fin dis:: carbune in ulei
:tie apoasa din tr-o . ,
;tica (Va Fe C~~~
:nsie putid ~-ari~c-,.---~/
apa variaza intre
~ 560 kg/h carbune
net obtinut este

12.2.5. Lichefierea prin rafinarea carbunelui cu solvent- procesul SRC

1~

I-l~~

I
~T

-l
\

I
t (capacitate 100

tehnice in ceea
tatea reactorului.
le de lichefiere a

t
l

,(

Carbunele pulverizat (astfelincit 80% gr. sa treaca prin sita de 200mesh)

intr-un spafiu cu gaz inert incalzit se ame~Ga cu un solvent aromatic greu
(ulei.-B.e antracen sau tetralina). Suspensl:a"Ffe :drbune .ln,.;;;c.JY-ent (40% gr.
carbune, 60% gr. solvent) se preincalze~te in prezenta de H 2 , la o presiune
de 105 bar, pina la 400-41YC, apoi se mentine sub agitare intr-un vas un
timp suficient pentru ca sa se dizolve carbimele in solvent. Reactia fiind
exoterma, temperatura in vas se ridica pina la circa 455C. Dupa r3.cire, la
315--.:345 oc ~i reducerea presiunii la 14 bar, din produs se separa gazele,
care serecircula in suspensia de carbune. Substanfele anorganice ~i carbtmele
nedizolvat se separa prin filtrare; namolul obtinut se gazeifica pentru a
produce hidrogenul necesar procesului [69].
.
.. Filtrahil este supus d1stilarii in vid pentru recuperarea produselor ~i
a solventului, care se recircula in proces. La baza coloanei de fracJionare
_se_ separ_a un produs cu consistenta unei smoale.
_ ~In~t_alaJja E_ilot inifi3. (SRC I) cu capacitatea de .50 tfzi ci!rb:tJile <J,up~
o functionare de, 4 ani a fost modifica ta - SRC II - [69] . produsriL final
'(catbunerafinaFcu solvent) obtiriindu-se sub forma lichida: [70; ElJ;; ~In SUA este incurs de proiectare o instalatie de derilonstratie c_;{ico ca"' .
. pacitaJe;=df.~69.()fLtfzi-carbune ~i -se intrevede .posibilitateac consti:uifcidc:Jmei
in:sta:la}iidndustriale, cu o prelucrare(l990) de 30 000-t/zi d.-rbune di:::.Po'Nhatan, din care sevor produce aproximativ 14 300 m 3 /zi, sau 4 miL:tepfan~
Prin hidrotratare~ ~i reforniarea, fractiunilor lichide se pot obtinebfnzina
auto, ct1 cifra o_ctanka ridicat~, combustibil reactor, Diesel ~iarpmai~'fBTX).
Separarea tenu~ii ~i a dirbunelui neconvertit din solutia: solvinJ:Ce.)c;tract
estecea mai critica etapa a procesului din cauza dimensiunii ~i t<>rJit~L pal;'~
ticulelor (ace foarte fine), dt ~i _a temperaturii ridicate c4re in~I'~"Uileaz;a
precipitarea asfaltenelor cu masa moleculara ridicata. Pentru simpJ.ificarea
operatiei de filtrare, utilizata in procesul SRC, al carei cost repn)zil;J,ta circ::a
. 10% din costul total a:.J. procesului [71], Combustion Engi_neering ~tuinmus
a elaborat un procedeu de separare a cenu~ii ~i carbunelui necqpyeitit din
l19

solutia solvent-extract [72] prin introducer~a unui lichid cu caracter pronuntat parafinic, considerat antisolvent. ;
A fostde asemenea experimentat [73] pe o instalatie integrata in instalatia pilot SRC un procedeu de separare a cenu~ii ~i a carbunelui neconvertit dupa indepartarea solventului utilizat in procesul SRC, constind in adaugarea unui ,solvent critic" ~i mentinerea unor conditii de temperatura ~i
presiune care sa realizeze dizolvarea selectiva a compu~ilor organici. Cele
doua faze nemiscibile care se formeaza prin adaugatea solven tului. se decanteaza
Un alt proces de lichefiere a carbunelui p:rin extractie cu solvent, aplicabil mai ales carbunilor cu continut ridicat de substante volatile si cu
tendinta redusa de aglomerare a' fost experimenta.t in SUA ~i Angli~ [71,
74]. Acest proces, numit ,extracj1:e sttpercritica", se bazeaza pe capacitatea
vaporilor de solnnt aflati cu putin peste punctul critic, de a extrage produsele
lichide cu punct ridicat de fierbere din carbune, dnd acesta se indllze~te
la 350-450( [71, 74]. In prezenta gazului comprimat (vaporii de solvent)
volatilitatea produselor cu masa moleculara mare din carbune cre~tf considerabil [74], permitind e\aporarea lor la temperaturi mult mai coborite
decit punctul de fierbere.
Dintre solventi s-a selectionat pentru procesul industrial toluenul (Tcr =
= 319C; Per= 40,6 bar).
Extractul (dupa indepartarea solventului) este un produs solid de cu,_J9are bruna, cu masa moleculara 3~~linct de topire coborit (50C inel ~i
bila), continut redus de sulf ~i azot, IfPsit'cl'Fmateriale aruocganice, care poate
fi supus hidrotratarii pentru obtinerea de hidrocarburi lichide ~i produse
chimice.
S-a elaborat proiectul unei instalatii industriale cu o capacitate de 9072 t/zi
carbune subbituminos, din care sa se obtina 1116 tfzi extract [74]. Instalatia este prevazuta en 8 extractoare (diametru 3,8 m; inaltime 6,1 m)
care opereaza in paralel, en strat mobil descendent de carbune pulverizat
(sub 1,6 mm) in contracurent cu vaporii de toluen. Costul investitiei s-a estimat la 279 mil. $, iar pretnl de cost la produsului 1a 250 $/tep, comparabil
estimativ en costurile produselor obti1mte din alte procese de conversie a
. ~arbunelui -['74].
12.2.6. J;.H;hefierea dirbuJ!elui prin tratarea cu solvent donor de hidrogen
. '~ Solventul dono:r de hidrogen, are dubla ar;1}Jip.e:.c<l ~olvent, ~i contribuielareactia derupere alegaturii c~c prin.:yt:direa deradicali de hidrogen. In atest fel, se formeaza produse cu masa moleculara mica. Cel mai
c:u.I1oscut solvent donot .c1e hidrogeiJ.. este tetralina [25].
Procesul~ numit ,Exxmt Donor Solveni, .este aplicat in fazi pilot in
SUA (Cresap, West Virginia) ~i consta dintr:.o etapa de lichefiere directa a
carbunelui bituminos cu solvent donor, la presiune joa~a. Extractul este
apoi supus hidrogenarii catalitice in strat expandat, dupa care intrco instalatie de fractionare se separa in benzina', solvent ~i combustibil greu [75].
Din: proces se produc cca: 0;43 m 3 produse Echide pe tona de carbune. Rezidiile constau din lichide depunctde fierbereridicat, dirbune neconvertit
~i materiale anorganice din carbunele brut {76].

320

>

>

lichid cu caracter proalatie integrata in instai a dirbunelui neconverl SRC, constind in adau1ditii de temperatura si
ompu~ilor organici. Ceie
'olventului. se decanteaza
\:tractie cu solvent, apli'-lbstante volatile si cu
in SUA ~i Angli~ [71,
bazeaza pe capacitatea
c, de a extrage produsele
ind acesta se incalzeste
nat (vaporii de solve~t)
in carbune cn:ste consituri mult mai' coborlte
:dustrial toluenul (Tcr

un produs solid de cuire coborit (50C inel si

:: anorganice, care poa te
>buri lichide ~i produse
o capacitate de 9072 t/zi
t/zi extract [74]. In3,8 m; inaltime 6,1 m)
c de carbune pulverizat
ostul investitiei s-a estii 250 $/tep, 'comparabil
procese de conversie a

vent donor'de hidrogen

: ca sol\'en t, si contriea de radicali de hidroJlecuiara mica. Cel mai
'5].
tplicat ]n faza pilot in
t de lichefiere directa a
joasa. Extractul este
dupa care intr-o insta: combustibil greu [75].
r; tona de carbune. Reat, dirbune neconvertit

in 1980 Exxon a pus in functiune la rafinaria Baytown, Texas, o instala tie pilot de lichefiere dire eta a 250 t(zi carbune bituminos de Illinois (nr. 6).
Se a~teapta ca datele fumizate de exploatarea instalatiei sa permita extrapolarea procedeului la scara industriala, la finele anului 1982 [76, 121].
In >vederea valorificarii rezidiilor din procesul ,Exxon. Donor Sohent"
se cerceteaza alimentarea lor intr-o instalatie de cocsare Flexicoking. Cheltuielile pen tru cercetarea, proiectarea, constructia ~i exploa tarea unei ins tala tii
prototip Flexicoking de 70 tfzi reziduu se apreciaza la 45,6 mil. S [76].
>

12.2. 7. Gazeificarea dirbunelui ,;in situ"

!ncercari de gazeificare a carbunelui ,in situ" (in subteran) sint in curs
de efectuare in zonele in care extragerea carbunelui este considerata neeconomica prin me to dele mini ere cur en te [48, 77-79, 121]. Cea mai veche dateaza de peste patru decenii ~i a fost aplicata in URSS, ling~ .i\loscova [79].
Prin gazeificarea subterana carbunele este oxidat partial cu oxigen (sau
aer) ~i abur obtinindu-se gaze cuputere calorica medie (sau mica). Injectia
reactantilor in stratul de carbune ~i colectarea gazului combustibil se face
prin sonde prevazute de la suprafata pamintului pina in stratul de carbunc.
Sondele de injectie trebuie sa patrunda pina la baza stratului de carbune.
"'-"" <,- .:.J~T<?fesul ofera avantajul obtinerii unui gaz cQ.t!ll_Justibil cu calitati similare
gazelor obtlnute din alte procese de gazeificare, i1eosturi mult"'-~ recluse
[79]. Orientativ, se prezinta compozitia volumica a gazului rezultat din
gazeificarea subterana a unui lignit din Texas (efectuata in conditii de laborator): 14,9% H 2 ; 21,5% CO; 11,1% C0 2 ; 49,4% ).' 2 (Ar); 2,9% CH 1 ;
0,2% C2H 6 [80].
0 problema dificila a gazeificarii ,in situ" o constituie poluarea apelor
din subteran cu produsele rezultate din proces. Cei mai nocivi sint produ~ii
fenolici. Analizele efectuate pe durata a peste doi ani, in vederea: stabilirii
gradului de poluare in subteran, au aratat in cazul cercetat ca produsele
contaminante sint adsorbite chiar de carbuncle nears in imediata vecinatate
a zonei de _gazeificare.
12.2.8. Consideratii speciale

~i

economice

_ Sulful este un element nedorit in prelucrarea carbunelui, deo?Iec~.;pro::

duce dificultati prin otravirea cata:lizatorilot, efecte de coroziun~,-~L-~epcr
luare. El este prezent in carbune-iri compu~i organici (mercaptani ~t s11lfuri)
~i anorganici (sulfuri ~i sulfati). Continutul de sulf in carbune variazalntre
0,2 ~i 11% gr., majoritatea dirbunilor avind 1-3% sulf: Cea ma:iJ11_a.iyparte
a sulfului este sub forma de FeS2 _ (pirita ~i marcasita). Sulful Mga:t9tganic _
(tiofeni, dibenzotiofen ~i sulfur!a:lifa:tice) reprezinta 1/3-1/2 din suHU::itot~l
continut. Sulfatii nu depa~esc0,1% gr. ~i pot fi neglijati [25]..____
_,
in procesele de gazeificare, sulful se converte~te in H 2 S, care trece lil
gaze. Tratarea acestora in vederea purificarii lor depinde de -pt(}pJ.:ietiJJle
gazuhii ~i de procesulde gazeifitare utilizat [25].
.___ -- - , .; >
in procesele de lichefiere dire eta in prezen ta de hidrogen; toi s11lflil
din pirite ~i numai o parte din cellegat organic se transforma in H:is.-s1llf111

tiofenic nu se reduce cu u~urinta ~i se va gasi in fractiuuile lichide obtinute.

De exemplu, un combustibil lichid rezultat din lichefierea unui carbune cu
1,1% gr. sulf tiofenic poate con tine circa 0,7 gr. sulf [25]. Prin urmare, contJ.nutul de sulf ~i formele sub care seprezinta in carbune constituie un factor
important in stabilirea posibilitatii de aplicare a procesului de lichefiere a
dirbunelui. Aplicarea unor procese de desulfurare a dirbunelui sint in faza
de cercetare [81].
0 privire generala asupra literaturii 1977- 1981 privind conversia carbunilor arata ca toate procesele de conversie a carbunelui in hidrocarburi
sint in prezent in stadiu de pilot sau instalatie de demonstratie. Exceptie
face procedeul SASOL, discutat mai inainte, care se gase~te in exploatare
la scara industriala. Este probabil ca abia in 1990 unele din aceste procese
sa fie aplicate la scara industriala [63] ~i in deceniul 1990-2000 o parte mai
importanta a materiilor prime utilizate in combinatele petrochimice sa provina din carbune [3].
S~au efectuat numeroase evaluari economice comparative ale proceselor
de gazeificare ~i de lichefiere directa a carbunelui [4,7, 10, 13, 123], bazate
pe o mare varietate de ipoteze ~i procedee financiare, ceea ce le limiteaza
valabilitatea la cazurile pentru care au fost intocmite [60]. Ca date orientative se pot mentiona: invsetitia pentru a produce 1 GJ/zi (producere de
metan) este de 5000 $, cu o eficienta termica medie de 67%; la un pret de
. _ .:.z-_' 1 $/GJ dirbune, de 19 $/GJ produs cheltuieli d~ ~erare, costul productiei
"'"___ c.revineJa 3~2cJ,.. $JGJ produs; admitind un benefici~<1e-JQ.%,pr,~tY.J.ie_ yinzare
revine la 226 $/1000 m 3 gaz ~i 284 $Jt produs lichid [60}. De asemenea, orientative pot fi considerate ~i costurile din tabelul12.8. prezentate de dr. Kraaijwld la al 10-lea Congres Mondial al Petrolului [63].
Tabelul 12.8.

Costurile combustibililor obtinuti din

ciirhune prin diverse metode'
'

Gaze combustibile cu putere

caloridi medie
Produs din procesul SRC
Metanol
Petrol sintetic din procesul de
lichefier_e cu solvent .cl_o11or de
hXcirogen
Btmzina din mdanol
Benzina din procesul cu sohent
aonor de hidl-ogen

12.3.

~isturi

3 S/MJ
$/MJ
S/MJ

4-5
5

- 6 $/MJ
6_c7

$/MJ

8-9

$/MJ

bituminoase

Utilizarea: ~isturilorbituminoase [82] pentru generarea de enetgie a fost

aplicata pe. plan local din primul sfert al sec. XX, la inceput in proportie
redusa, apoi treptat amplificata. 1rt prezent, in RSS Estonia circa90% din
energia teimica ~i electrica este obtinuta din ~isturile bituminoase(kuken;ita),
partial prin arderea lor in stare de solid pulverizat ~i mai ale_s folqsind combustibil gazos cu putere caloric3. ridicata ( 10-12 Mcal/m3 ) rezulta't <;lin prelutrarea termid a. kukersitei [13; 83, 84].

322

--1

ctiunile lichide obtinute.

lefierea unui carbune cu
f [25]. Prin unnare, conmne constituie un factor
rocesului de lichefiere a
carbunelui sint in faza
privind conversia carbunelui in hidrocarburi
demonstratie. Exceptie
e gase~te in exploa tare
mele din aceste procese
I 990-2000 o parte mai
le petrochimice sa pro-

1parative ale proceselor

',7, 10, 13, 123], bazate

e, ceea ce le limiteaza
ite [60]. Ca date orien1 GJ/zi (producere de
de 67% ; la un pret de
;rare, costul productiei
1O% pretul de vinzare
0]. De asemenea, orienJrezentate~e dr. Kraaij-

nuti din

S/MJ
S/MJ
S/MJ
$/MJ
S/MJ
3/MJ

area de energie a fost

ia inceput in proportie
Estonia circa 90% din
ituminoase (kukersita),
mai ales folosind coml/m3) rezulta t din pre-

Datorita rezervelor, importante de ~isturi a unor tari (vezi cap. 1) ~i

extragerii relativ u~oare a compu~ilor organici din ~isturi, prin transformarea
kerogenului (material organic cu masa moleculara mare) in ulei, a crescut
in ultimul timp interesul pentru utilizarea lor ca sursa de obtinere de hidrocarburi, care sa inlocuiasca petrolul ~i gazele naturale, ~i pentru fabricarea
unor produ~i chimii organici (circa 40) [3, 82, 83]. Tari cu resurse apreciabile de ~isturi bituminoase, ca: SUA, URSS, Brazilia, Australia, Maroc etc,
au cercetat diverse procedee supraterane [63, 85-89, 121, 124] si subterane
[10~ 63, 85, 89-94, 121] de prelucrare a ~isturilor ~i au trecut la' proiectarea
~i construirea unor instalatii de demonstra tie sau industriale, care vor fi
puse in functiune in acest domeniu [17, 63, 85, 95-104].
Hotaritor in prelucrarea ~isturilor in vederea fabricarii de hidrocarburi
sintetice este continutul de substante organice in ~isturi. Din acest punct
de vedere, ~isturile bituminoase se pot clasifica in urmatoarele grupe [83]:
a) !?isturi cu putere caloric5. mare (cu minimum 15-20% ulei prin metoda Fischer);
b) ~isturi cu putcre caloridi mica (care au un continut de ulei de 10-15%
prin metoda Fischer)~
c) ~isturi care contin compu~i organici cu punct ridicat de congelare.
Exista in studiu procese tehnologice (Tosco, Paraho, Union Oil, Superior
Oil, Lurgi) [63, 95], care au functionat cu capacitati de pina la 1500 tjzi,
cu preiecte pentru a fi extrapolate la 10 000 tjzi [63].
_j.t'),_._
PrOc-to:sulLurgi/Ruhr-gas de prelucrare a carbunelui s-a a:pll;:af ~i 'la.-ta.-~,
bricarea hidrocarburilor lichide ~i gazoase dintr-o varietate larga de !?isturi
)>i nisipuri bituminoase [86]. Temperaturile de operare cu ~isturi (300C)
sint mai coborite dedt la prelucrarea carbunelui, iar produsele produc mai
putine eroziuni decit nisipurile ~i carbunele rezidual. Datele experimentale
cu )>isturi de Colorado, care au putere calorica mica [63] ~i un continut ridicat
de azot organic legat (circa 2% gr.) [88], au permis proiectarea unei instalatii care prelucreaza 8000 t/zi ~isturi, cu un continut de ulei de aproximativ
0,114 m 3 /t, ceea ce revine la circa 10% gr. fata de ~isturile brute. Cheltuielile
de investitie (echipament ~i montaj) s-au est1mat la 125 miL $ (1976). Productia relativa ~i proprietatile produselor lichide sint prezentate in tabelul 12.9.

-- __Sisfurile din URSS fac parte din categoria ~isturil~or cl1 p~f~;~ c:~l~~ic_a
mare-)>i-a.u un continut redus de sulf (circa 1% gr.) [63]. In URSS se utilizeaza
in prezent doua tipuri de retorte pentru prelucrarea kukersitei- Kiviter
!?i Galoter - ale caror principale date tehnologice sint prezentate in tabelul
12.10. [83]. - ... . - ...
.
l.JleiUI de ~ist brut, obtinut prin diverse procedee, se caracterizeaza priR:
continut destul de mare de hidrogen (,...._,11%), continut ridicat de azot (......... 2%)
~i sulf in proportie moderata (sub l %) [9]. Pentru obtinerea de combustibili
finiti (gaze lichefiate, benzina auto, petrol reactor ~i motorina'~iesel) este
necesara rafinarea uleiului de ~ist brut prin tehnologiile utilizate la prelucrarea petrolului, ca: hidrotratare, hidrocracare, cracare catalitica in strat
fluidizat, cocsare 1ntirziata etc.
Un studiu recent [87] a analizat, pe baza datelor de laborator ~ide scara
pilot, diverse_ alternative_ de prelucrare a ~isturilor in SUA, utilizind cea
mai moderna tehnologie verificata, la o capacitate de prelucrare a 1-2 module de de 2,9 106 m 3 /an combustibili san petrol sintetic. Ca:facteristicile

323

~isturi bituminoase- Prodnc\ia relativii

ale produselor lichide

Tabelul 12.9. Prelucrare

~i

proprietiiti

Tabelul 12.11 Caracteristicile produselor finite ob\inute din ulei de

Paraho

Ulei greu
(faxa pulbere)
Produqia relativa
Densitate, kg/dm3
V!scozitate, eSt
lnflamare, C
Congelare, C
Cocs Conradson, % greut.
Putere calorica, superioaril.,
kcal/kg
Analiza elementara:
C,
~,~ gr.
H,
01~ gr.
s,
~10 gr.
N,
~~ gr.
0,
% gr. (prin dife.
reuta)

1,7
0,956f50C
115,8f50C
153
23,7
8,1
9 892

Ulei mediu

4,8
0,816/20C
1,53/20C
< + 20
<- 40
0,43

0,8

Tabelul 12.10. Principalele date tehnice ale retortelor Kiviter

~i

Benzina auto:
- presiune de vapori
Reid, bar
- sulf, % gr.
- COR (neetilata)
COM (neetilata)
- distilare, C- 50%
-finaL
(max.)
Petrol reactor:
- densitate relativa
- inflamare, C
- punct de solidificare, C
- punct de fumegare, mm
- sulf, % gr.
Combustibil Diesel:
- densitate relativa
- punct de congelare, C
- sulf, % gr.
- distilare, C- 50%
- indice cetanic
Cocs:
- sulf, % gr.
- azot, % gr.
-volatile, % gr.
Petrolul sintetic dupa operatia
cle hidrotra tare:
- densi tate rela ti va
- pu.nct de anilina, C
- punct de congelare, C
- viscozitate, eSt Ia 50C
-carbon Ramsbottoms, %
- sulf, ppm
- azot, ppm
- oxigen, ppm
- distila tie, C
initial
10%
30%
50%
70%
90%
final

10 990

1.,2

Dimensiunea particulelor de ~isturi, mm

Continut uleios (metoda Fischer), %
Debit de alimentare, ~isturi, t/zi
Continut de ulei, %
- fata de ~isturile alimentare
- prin metoda Fischer
Putere ca1oridl superioara a uleiu1ui de ~ist, kcalfkg
Randament chimic, %
Consumuri specifice pe tona de ~isturi:
- energie electrica, kWh
- abur de 5-8 bar
- apa, m 3
Exploatare anuala, %

'
1
0,699/20C

10 441
88,5
12,5
0,7
0,5

fabricat prin procedeul

Benzina
Hidrotratare Hidrocracare

85,6
10,7
1,0
1,5

~ist

(analize ASTM)

84,2
13,2
2,6

Galoter
Retorta
Kiviter

Retorta
Galoter

25-125
22- 24
1000

0-25
22-24
3 000

16- 16,5
75-80
9 400
72-74

16-17
75-85
9 500
76,4

14- 18
50-60
0,2-0,5
90-92

20
10

4-8
80-85

produselor finite obtinute din ulei de 9ist Paraho in diversele cazuri considerate sint prezentate in tab. 12.11 [87].
Alternativele cele mai eficiente sint hidrotratarea-hidrocracarea 9i hidrotratarea-cracarea catalitica. Pentru a produce aceea9i cantitate de produse
distilate varianta cocsare intirziata-hidrotratare necesita cu 17-22% mai
mult ulei de 9ist brut.
Constructia unei noi rafin5xii cu capacitate de 2, 9 10 6 m 3 (an combustibili produse finite in apropierea minei de 9isturi se apreciaza la 500 mil. $
(1979). Costul total de prelucrare al uleiului de 9ist brut variaza intre 63
9i 76 $(m3 , mai coborft pentru alternativa hidrotratare-cracare catalitica.
Prin dublarea capacitatii 9i amplasarea rafinariei linga un mare centru
urban costul total de prelucrare scade la 50-63 $(m3 , dar cresc investitiile
la 8-900 mil. $.

0,703
0,03
93,0 (min)
85,0
107

<

216

HidrotratareICocsare intirziataCracare ca tali tica

Hiidrotra tare

0,703
0,03
95,0
84,0 (min.)
97

<

216

<

~~3

~03

9~5

~5

116
2~

0,7923
41 (min.)
-51
30
< 0,01

>

0,8324
-18 (max.)
< 0,01
260

46

0,8324
-18 (max.)
< 0,01
260
46

0,8251
-18 (max.)
< 0,01
260
45
0,65
4,1
10

0,8458
79
38
10
0,10
75
1000
170
149
204
260
316
399
482

566

Hidrotratarea uleiului de 9ist brut pentru a produce 5,8 106 m 3/an petrol sintetic ar necesita o investitie de 600 mil. $ :;;i un cost de prelucrare
de circa 41 $(m3 [87].
.
Estimari 1979 arata ca pretul petrolului sintetic variaza intre 41 $(m3
(in cazul utilizarii etapei de denitrificare, etapa prioritara privind indepartarea azotului organic continut in mare cantitate) :;;i 61 $(m3 (cind se adauga
9i alte etape de hidrotratare) [88].

324

.,
~

a25

Cercetarile privind piroliza cu abur a uleiului de ~ist pentru fabricarea

de etilena au aratat ca, in general, din uleiul de :;;ist nehidrogenat se pot
obtine 20-25% etilena :;;i 40-45% total olefine, valori comparabile cu
cele stabilite pentru materii prime petroliere, in timp ce din uleiul de :;;ist
hidrogenat rezulta 30-34% etilena :;;i peste 50% total olefine [8.8].
Dificultatile care apar la prelucrarea supraterana a :;;isturilor bituminoase o constituie mai ales aspectele ecologice legate de depozitarea :;;isturilor
epuizate 9i revegetarea terenurilor de pe a caror suprafata s-au exploatat
9isturile.
In ceea ce prive:;;te depozitarea de:;;eurilor, (:;;isturi epuizate) cercetarile
efectuate in URSS [83] au dovedit d\. este posibila revegetarea terenurilor
pe care se depun straturi de 9isturi epuizate de grosime redusa, daca acestease acopera ulterior cu un strat subtire (circa 1 em) de pamint fertil 9i se in
.saminteaza cu iarba.
E~te posibila, :;;i este de preferat, valorificarea :;;isturilor epuizate prin
extragerea de substante anorganice (in Suedia se obtine uraniu), sau fabricare de ciment (URSS), sau de alte produse (in SUA din Nachcolite :;;i Dawsonite se obtin cenu9a sodica 9i alumina) [63, 105].
Extragerea substantelor organice din :;;isturi in subteran (,in-situ") se
face in funqie dro continutul de ulei al acestora. Pentru cele mai bogate,
care contin 63-125 dm3/t 9ist [90, 91], se utilizeaza injectie de abur supraincalzit la presiune de cca. 100 bar :;;i 540C [91]. La cele cu continut reclus
de ulei (12-38 dm3 /t :;;ist [90]) p6:1 injectia de abur ~;;i aer incalzit are loc
in strat combustia partiaHi a substantelor organice :;;i totodata antrenarea
substantelor volatile. Combustia arc loc la temperaturi ale stratului de 7609800C [89]. Se precizeaza ca se poate realiza indepartarea a circa 90% din
uleiul continut in :;;isturi; restul de 10% ramine in carbuncle rezidual care
se arde [92].
Pentru realizarea procesului in subteran se foreaza sonde, cele pentru
injectia aburului :;;i aerului pina la partea superioara a stratului, in timp ce
.acelea pentru captarea uleiului :;;i a gazelor pina la baza stratului.
Avantajele prelucrarii ,in-situ" sint: eliminarea exploatarii miniere, revegetarea terenurilor dupa exploatare :;;i dificultatile de depozitare a :;;isturilor
epuizate; se reduce consumul de apa.
ln prezent, se studiaza in SUA la nivel de faza pilot, premergator unei
dezvoltari industriale extinsa pe 30 ani, un proces modificat de combustie
,in-situ", care consta din combinarea combustiei subterane cu prelucrarea
in retorte supraterane prin procedeul Tosco. Aproximativ 20% din stratul
de 9isturi este exploatat prin metode miniere :;;i prelucrat in retortele Tosco,
apoi 9isturile epuizate sint reintroduse in subteran, sub forma de suspensie
in apa, in zonele in care combustia s-a terminat. Avantajul acestui proces
consta in reducerea costurilor de exploatare miniera :;;i de prelucrare la suprafata, inclusiv reducerea consumului de apa la jumatate [78].
Un alt procedeu de prelucrare ,in-situ" a 9isturilor 9i a nisipurilor bituminoase elaborat de Badger-Texaco Inc. 9i in curs de testare [94], utilizeaza
pentru fncalzirea straturilor de 9isturi unde din domeniul frecventelor radio,
produse de conductori introdu9i in sondele forate in strat. Undele emise de
dectrozi incalzesc :;;isturile pina dnd materialul organic se transforma intr-un
. lichid, care se deplaseaza, este captat prin conducte 9i adus la suprafata
[94, 98]. Fata de prelucrarea ,in-situ", acest procedeu ar prezenta avantajul
, ~2G

ca nu necesita fisurarea straturilor pentru o mai buna circulatie a fluidelor

9i prin urmare, o mai unifonna distributie a caldurii [98].
Se apreciaza di. fabricarea de combustibili din 9isturi bituminoase acolo unde exista depozite convenabile - este mai avantajoasa dedt producerea de combustibili sintetici din carbne [11, 60], intrucit tehnologia de
fabrica.re a acestora din 9isturi este cunoscuta, mai simpla 9i mai apropiata
de aceea a prelucrarii petrolului.

12.4. Nisipuri bituminoase

Canada (161 109 t bitum) 9i Venezuela sint [106-108] unele dintre
putinele tari cu rezerve importante de nisipuri bituminoase cu un continut
mediu de bitum de 12% gr. (pentru randamente de extractie vezi cap. 1~.
Din depozitul de la Athabasca (Canada), estimat la 102 109 t bitum, numai
5% se gase~te in straturi situate la adincimi de pina la 50 m, care pot fi exploatate la suprafata [106, 107], ceea ce revine la 6,1 109 t bitum, sau pentru
o conversie de hidrocarburi sintetice de 69%, corespunde la 4,21 10 9 m~
(3,7 10 9 tep) [106]. Celelalte depozite pot fi exploatate prin procedee miniere
de subteran sau prin prelucrari ,in-situ" [106].
Canada a J:nceput productia de petrol sintetic din nisipurile bituminoase
J:n 1967, dar abia fn 1978 (GCOS- Great Canadian Oil Sands) s-a produs
la capacitatea de proiect (2,2 mil. t(an petrol sintetic) [106-109]. Din 1978
a intrat in functiune a doua instalatie de fabricare a hidrocarburilor sintetice
din nisipuri (SC - Syncrude Canada) cu o capacitate de 6,5 mil. t/an petrol
sintetic [106, 121], care in 1980 a functio11at la capacitatea de proiect [110]..
0 a treia. instalatie (Alsands), cu o capacitate similara cu Syncrude Canada
va fi pusa in functiune J:n 1986 [111, 121]. Canada va produce J:n 1990 J:ntre
23 9i 27,5 mil. tfan petrol sintetic [109, 112], din care J:n 1984 o parte va fi
prelucrata fntr-o rafinarie proiectata sa prelucreze in exclusivitate petrolul
sintetic provenit din nisipurile bituminoase [45, 111].
Schema generala de prelucrare a nisipurilor bitu.minoase este aratata
in fig. 12.8. Spre deosebire de aceasta, prima instalatie (GCOS) utilizeaza
cocsarea intlrziata a bitumului obtinl:nd cocs, gaze ~i distilat lichid cu final
510C. Din distilat se obtin trei fractiuni (benzina, petrol :;;i motorina), care
dupa hidrotratare dau prin amestecare petrol sintetic [106].
Randamentul In petrol sintetic al instalatiei SC este mai mare dedt
la instalatia GCOS, iar petrolul are densitatea mai ridicata (0,865-0,875
fata de 0,845-0,855). Ambele au finalul de distilare sub 524C ~i un continut redus de sulf [106].
Pretul petrolului sintetic obtinut din nisipurile bituminoase In Canada
variaza intre 148 ~i 180 S/t [109].
De9i fabricarea de hidrocarburi sintetice din nisipuri bituminoase necesita perioade lungi pina la punerea In functiune a instalatiilor, investitii
foarte mari, costuri ridicate de operare :;;i riscuri tehnice :;;i alte tari cu resurse de nisipuri bituminoase, ca: Venezuela, SUA, Madagascar 9i Turcia,
fac cercetari in vederea exploatarii depozitelor lor [113-115]. Au aratat

327

SOLVENT
EXPLOATPRM. EXTRACTiE
ISTURI
cu '
. .
,
fv'INIERA
/JPA CALDA

finit petrol sintetic. Cocsul se gazeifica pentru a produce combustibil gazos,

lipsit de sulf. Capacitatea prevazuta a instalatiei este d<O 22 200 m 3/zi petrol
sintetic. Costul ei se estimeaza la 4-4,5 miliarde $ (1980), dar datorita inflatiei ar putea c).epa~i 7 miliarde $ [108].

RECUPERARE

12.5. ProprieHi.ti comparative

GAZE
CONBUST/B!L
(OEPOZIT)

12.8. Schema generala de prelucrare a nisipurilor bituminoase.

de asemenea interes pentru acest domeniu India, Mexic, Franta. Indonezia

~i Albania [113].
De peste 15 ani se cerceteaza diverse procedee de prelucrare a nisipurilor
bituminoase ,.in-situ" [94, 108, 113, 116], atlt in Canada dt ;;i 1n SUA. Se
pot aplica acelea~i metode ca ;;i cele amintite pentru ~isturile bituminoase
(injectie de abur, combustie, 1mcalzirc cu unde clectromagnetice sau acustice),
precum 9i explozii subterane nucleare sau de produse conventionale [107, 108].
In Canad'3. se va construi la Cold Lake, 1ntre 1981-1987 o instalatie
industriala de prelucrarc ,.in-situ" a nisipurilor bituminoase, prin injectie
de abur. Bitumul obtinut se supune cocsarii (procesul Flexicoking). Distilatele rezultate s!nt hidrotratate ~i apoi amestecate pentru a obtine ca produs
377 1

71

I :.P'

:V

376

-78L-~~~---k---L--~--~--L-~--~--~

70

75

20

25

30

35

40

45

50

'/, Oisttlat
12.9. Curoelc clc distilare ale petrolurilor sintetice de diverse
provenicnte ~i a unui petrol (titei) natural:
1 - petrol natural; 2 - petrol sintetic din procedeul de lichefiere H-Coa.l; 3 - ulei de ~ist din procedeul f'araho; 4 - petrol din nisipuri bituminoase.

3~8

1n fig. 12.9 se prezinta curbele de distilatie ale petrolurilor sintetice

obtinute din carbune prin hidrogmare catalitica (procedeul H-Coal), din
~isturi (procedeul Paraho) ;;i din nisipuri, in comparatie cu un petrol natural
(titei) din SUA [9]. Se observa ca petrolurile sintetice contin fntre 65 ;;i 80%
hidrocarburi care distila peste 316C. Proportia de hidrocarburi grele cre~te
in ordinea petrol provenit din ~isturi ;;i petrol obtinut din nisipuri bituminoase

BIBLIOGRAFIE
1. * * * O.G.J., 1980, 10mart.,p.54-55.
2. Wall, J.D., Hydr. Proc., 1981, iun., p. 119-123.
3. Johnson, Axel, R., et al., Hydr. Proc., 1979, sept., p. 109- 113.
4. Lin, C. T. et al., Hydr. Proc., 1980, mai, p. 229-233.
5. Camps, J. A. ~i Turnbull, D. M., O.G.J., 1979, 8 oct., p. 68-70.
6. Peters, W. et al., WPC 10, RTD2.
7. * * WPC 10, Bucure~ti, 1979, sept., RTD2.
8. * O.G.J., 1979, 17 sept., p. 92-97.
9. Gallangher, J.P. et al., CEP, 1979, iun., p. 56-62.
10. Fisher, Sidney, T., O.G.J., 1981, 23 febr., *. 82-91.
11. * * * Hydr. Proc., 1980 ,mart., p. 15-17.
12. Me Kelvey, K. N., CEP, 1979, mart., p. 45-48.
13. Suciu, G. C., Proc. Econ. International, vol. 1, nr. 3, spring 1980, p. 18-22.
14. * * * O.G.J., 1981, 26 iun., p. 115-116.

15. * O.G.J., 1981, 26 ian., p. 122.

16. * * * 0. G.J., 1981, 16 feb., p. 81.
17. * * O.G.J., 1981, 12 ian., p. 28-29.
18. Clark, D., Hydr. Proc., 1979, ian., p. 56C-56J.
19. * * Chern. Eng. News, 1979, 17 sept., p. 13- 16.
20. * * Hydr. Proc., 1980, mart., p. 9.
21. Wojciechowski, B. W., Hydr. Proc., 1980, mai, p. 237-241.
22. Harney, Brian, M. ~i Mills, Alex, G., Hydr. Proc., 1980, feb., p. 67-7 L
23. Schroeder, W. P., Hydr. Proc., 1976, ian. p. 131- 133.
24. Sass, A., CEP, 1974, ian., p. 72-73.
25. Attar, A., Hydr. Proc., 1979, iun., p. 175- 179.
26. Scotti, L.]. et al., CEP, 1975, apr., p. 61-62.
27. LeBlanc, J. R. et al., Hydr. Proc., 1981, iun., p. 133-137.
28. Sensing, T. A. et al., CEP. 1980, ian., p. 64-67.
29. Hossain, S.M. et al., Hydr. Proc., 1980, oct., p. 79-86.
30. Sinor, J. E., Hydr-Proc., 1979, iul., p. 159- 162.
31. Gray, J. A., CEP, 1980, mut., p. 73-80.
32. Leonard, J.P. ~i Fr<tnk, M. E., CEP, 1979, inn., p. 68-72.
33. Starr, F., The lil>titution of G1'l E:1gm~;rs, 45th Autamn M;;ting, Co.n.nlnic. 110 ,
6
London, 1979, nov.

329

Cel specific,precu

LICHEFIEREA DIRECTA A CARBUNILOR

Carbunele poate fi lichefiat direct (DCL) Ia 450-500C si 15-30 MPa pe un solvent si cu
un catalizator potrivit. In multe procese solventul ales are rol in transferul de caldura si masa
in reactia chimica si functioneaza ca donor de hidrogen prin transferul hidrogenului din faza
gazoasa spre carbune. Catalizatorii au rolul de a creste viteza reactiilor dorite cum ar fi cele
de cracare, hidrogenare si inlaturare a 0, S,N. Procesul de lichefierea directa a carbunelui a
fost dezvoltat din punct de vedere comercial in Germania pe baza studiilor lui Friederich
Bergius din 1910. Concomitent cu procedeul Bergius ((proces de hidrogenare ce are loc
catalitic Ia presiune inalta) s-au dezvoltat alte tipuri de procese reprezentate de tipul PottBioche de dizolvare intr-un solvant a carbunelui,care au fost dezvoltate tot inaintea razboiului
II mondial. Comparativ cu procesul ICL (indirect liquefaction of coal) procesele DLC (direct
liquefaction of coal)produc o mai mare varietate de produse(in primul rand nafta) cu o inalta
eficienta energetica, de altfel procesul prezentand dezavantajul ca aceste produse prezinta
dificultati in exploatare datorate abrazivitatii suspensiei de praf de carbune, a necesarului
unui solvent donor de hidrogen costisitor (precum tetralina) si dificultatilor de separare a
particulelor de carbune din produsii lichizi. Procesele DLC devin optiune viabila pentru
producerea combustibililor sintetici cand pretul titeiului este in jur de 70-80 $ /baril si devin
mult mai atractive pentru tari fara acces Ia titei, precum China, Coreea, Japonia, etc.Bazate
pe cele doua procese prezentate mai inainte (procedeul de hidrogenare Bergius si procesul
cu solvent donor de hidrogen Pott-Bioche) au fost dezvoltate dupa anii, 70 ai secolului XX, o
mare varietate de procese DLC cum ar fi SRC-1 si SRC-2 (Solvent Refined Coal), procese
dezvoltate in numeroase tari prezentate in tabelul nr.l.
Tabel nr.1 Procese DLC majore dezvoltate in lume
Tara

Proces
SRC-1
SRC-2

USA

Capacitate (t/zi)

Timp

1974

50-25

1974-1981

Dizolvarea coal

"
Strat mobil

Ni/Mo

250

1979-1983

H-Coal

Strat fluidizat

Co-Mo/alumina

600

1979-1982

1985-1992

1990

HTI

Japonia

Catalizator

EDS

CTSL

Germania

Reactor

"
Strat suspensie

IGOR

. Strat fix

PYROSOL

Strat fluidizat

Ni/Mo
Gel Cat

Ni-Mo/alumina 200

BCL

Strat fix

Fe

50

BCL

Strat fix

Ni-Mo/alumina 50

Nedol

Strat fluidizat

pi rita

150

1981-1987
1977-1988
1986-1990
1996-1998
1996-1998

Cel specific,precu

UK

LSE

RCAP

2,5

1983-1995

LSE

Strat fluidizat

2,5

1983-1995

1986-1990

Fe

2002-2004

Fe

3000

2002-2004

USSR

CT-5

China

Shenhua-1
Shenhua II

Mo
Strat suspendat
II

Se va discuta aici realizarile privind influenta unor factori (temperatura,solvent, presiune,

atmosfere,etc.) asupra reactiilor de Ia DCL precum si efectul pre-tratarii carbunilor
(umflare,tratament termic,tratament hidrotermal,etc.), ca si dezvoltarea reactoarelor in cazul
proceselor DCL in mai multe trepte,catalizatori avansati si co-lichefierea sistemelor carbunibiomasa.
Temperatura
Mecanismul DCL este foarte complex si pana acum incomplet cunoscut.ln general, procesul
DCL are loc in doua etape:ruptura structurilor macromoleculare ale carbunelui in fragmente
radicalice Ia temperaturi ridicate sistabilizarea si hidrogenarea acestor pentru a produce
molecule cu masa moleculara mai joasa.La temperatura inalta moleculele din carbune pot
craca prin rupere termica a legaturilor carbon-carbon. Temperatura este astfel unul din cei
mai importanti factori care influenteza formarea radicalilor liberi si desfasurarea in
continuare a reactiilor radicalice. Astfel de reactii nu pot decurge Ia temperaturi joase, in
timp ce Ia temperaturi foarte inalte pot fi determinante reactiile nedorite de formare a
cocsului. Astfel pentru a avea loc reactiile dorite Ia DCL trebuie lucrat Ia o temperatura
optima. Aceste conditii optime a fost recomandata in literatura de specialitate Ia un nivel
375-450(. Astfel Ia 375C se realizeaza o conversie de 45% si ea creste Ia un nivel de 91% Ia
450C, dar Ia aceasta temperatura se formeaza si ponderi apreciabile de cocs.
In procesul DCL foldepinde nu numai de temperatura dar si de viteza de ichide tii petroliere
rmarea de fracincalzire. Astfel, lichefierea Ia temperatura programata (TPL) pare a fi
superioara si mult mai efectiva in conditiile unei rapide incalziri ale carbunelui. Procesul TPL
decurge astfel: imbibarea carbunilor Ia temperatura de 200C pentru 15min si lenta incalzire
pana Ia temperatura finala cu rC/min, urmata de o imbibare timp de 30 min Ia temperatura
finala 300-425C.Prin controlul vitezei de incalzire carbunele lichefiaza eficient Ia o viteza a
clivajului pirolitic a legaturilor mai slabe odata cu minimizarea intreruperii lantului radicalic.
Lichefierea carbunelui in conditiileTPL realizeaza conversii de 77-81% Ia 400C, in timp ce Ia
o rapida incalzire pentru procesul DCL duce Ia conversii de 71-72%.
Solventul
In multe din procesele DCL rolul solventului este de a stabiliza radicalii liberi prin donare de
hidrogen, promoveaza cracarea macromoleculele de carbune si previne condensarea si
cocsarea radicalilor prin diluarea intermediarilor. Mai mult, solventul faciliteaza transferul de
masa si caldura in procesul de lichefiere,lasificare bazata

de asemenea faciliteaza ca

transportator de hidrogen de Ia faza gaz spre carbune. Solventii utilizati in DCL pot fi

Cel specific,precu

clasificati in patru categorii, categorii ba za.te pe efectul lor specific asupra carbunilor:
specific, ne-specific,degradant si reactiv. Cel specific, precum piridina si NMP (N-metilpirolidona) poate dizolva 20-40% din carbune Ia 200C. Solventul nespecific precum
alcoolul,benzenul,eterul si acetona, etc poate dizolva numai urme de carbune lalOOOC. Acesti
solventi sunt donori de electroni si dizolvarea carbunilor in ei este un proces fizic si are loc Ia
temperaturi coborate (lli200C). Procesele de extractie chimica au loc ce folosesc alte doua
categorii de solventi sunt conduse Ia temperaturi mai inalte. Solventii degradanti precum
fenantridina si uleiul antracenic etc poate extrage mai mult de 90% din carbune Ia 400oC.
Dupa extractie solventul poate fi aproape complet recuperat din solvent. Polimerizarea
fragmentelor de carbune decurge in lichefiere acestuia cu degradarea solventului, ce poate
fi incetinita prin contributia hidrogenului Ia inalta presiune cu stabilizarea fragmentelor de
carbune facilitata de rolul solventul de a transfera si a deplasa hidrogenul (de Ia faza gaz Ia
carbune). Solventii reactivi sunt solventi care pot reactiona cu carbunele in lichefiere, asa
cum este fenolui.Solventii DCL, tetrahidrofluorantrenul (4HFL), dihidroantracenul (2HAn), etc
si solventii nedonori sunt decalina, pirenui(PY), fluoranten (FL) si antracenul (An),etc.
Presiunea si atmosfere
In procesele DCL presiunea ridicata este benefica si are rolul de a mentine solventul si
produsii de reactie in faza lichida, previne depunerea de cocs pe peretii reactorului si
suprafata catalizatorului prin inhibarea reactiilor reactiilor nedorite, promoveaza
hidrogenarea prin mentinerea presiunii partiale a hidrogenului. Cu toate acestea,
considerente economice dicteaza folosirea unei presiuni coborate a hidrogenului in procesul
de lichefiere a carbunelui. Odata cu progresele inregistrate recent in tehnologia DCL , in
particular, in dezvoltarea unor catalizatori si solventi mai performanti, sitatea folosirii unei
presiuni ridicate poate fi mai relaxata Ia cca 20MPa. S-a a demonstrat ca daca se foloseste un
solvent cu punct de fierbere suficient de ridicat carbunele poate fi lichefiat chiar Ia presiune
atmosferica, desi multe din produse sunt fractiuni grele si randamentul in ulei a fest de
numai 10%. In prezenta de solvent cu proprietate donoare de hidrogen foarte buna procesul
de lichefiere poate decurge Ia presiuni relative mai joase, desi conversia lichefierii carbunelui
poate fi marita in mod apreciabil prin ridicarea presiunii de operare.
Desi s-a stabilit ca atunci cand se foloseste un donor bun donor de hidrogen in lichefierea
carbunelui se atinge o conversie inalta in prezenta de atmosfera de azot, cele mai multe
instalatii DCL opereaza sub atmosfera de inalta presiune de hidrogen. Asistata de
transportarea hidrogenului de catre solvent, faza gazoasa de hidrogen poate fi transferat
catre cocs. Hidrogenul molecular insusi este un agent hidrogenant slab datorita stabilitatii
puternice a legaturii H-H,dar molecula de hidrogen poate fi disociata in atomi reactivi de H in
conditii severe de operare si in prezenta unui catalizator potrivit.
Este de mare interes studierea in lichefierea carbunilor folosirea unor gaze alternative
convenabile ca sursa, precum CO, amestec co+H 2, CO+H20, H2+H20, singaZ+H20, N2 si CH4,
etc. Astfel s-a stabilit ca un carbune inferior poate fi convertit in produsi utili in conditiile
unor randamente ridicate pri desfasurarea reactiei de lichefiere in atmosfera de CO+H2 in
prezenta unui catalizator alcalin. Recent s-a stabilit efectul controversat al prezentei
atmosferei de abur. Un efect nedorit este actiunea deterioranta a apei asupra catalizatorului,

-------"

-~----------------

Cel specific,precu

prin scaderea activitatii acestuia si promovarea formarii C0 2 .1n contrast apa ca solvent in DCL
creste unele efecte pozitive in particular in atmosfera de CO. Astfel, apa in calitate de solvent,
in atmosfera de CO duce Ia randamente ridicate a formarii de ulei+gaz in converia de
lichefierea carbunilor, decat in atmosfera de H2 si N2, ele, randamentele, raman and mai mici
decat in cazul folosirii solventului tetralina si atmosferei de H2

Reactor DCL

Cat&b'~t

wltttdrawaj--?-

Cel specific,precJ

H-Coal process

RECYCLE HYDFIOOEN

COAL

RECYCLE SlURRY OIL

Exxon hydrogen donor solvent plant

RECYCLE HYDROGEN

FUEL GAS
~r---~~-L~T~

COAL
HEAVY OIL

RECYCLE SLURRY OIL

7
Processes for the Conversion of Biomass
7.1

Introduction

Biomass is the oldest source of energy and currently provides roughly 10% of total energy demand. Traditionally, biomass in the form of fuel wood used for heating and cooking is the main source of bioenergy, but
liquid biofuel production has shown rapid growth during the last decade. Similar to crude oil, biomass can be
and is processed in several ways. Figure 7.1 gives an overview showing different approaches and processes
for biomass conversion [1].
Biomass can be gasified at high temperature in the presence of a substoichiometric amount of oxygen and
the produced synthesis gas (Chapter 5) can be further processed to obtain the "normal" product spectrum,
including, for example, methanol and Fischer-Tropsch liquids [2] (Chapter 6). During pyrolysis, a simple
process similar to coking in the oil refinery, which takes place at intermediate temperature in the absence of
oxygen, biomass is converted into a liquid phase, referred to as bio-oil [3]. This process is robust and can be
used with a large variety of feedstocks but the bio-oil produced is a low-quality fuel with low stability and
the yield is modest.
Not all biomass conversion processes are analogous to oil-related processes. Completely different
approaches also suggest themselves. The underlying reason is the completely different structure of biomass
compared to crude oil. Figures 2.22-2.24 in Chapter 2 show that biomass has a highly functionalized structure
and contains a large amount of oxygen, in sharp contrast with crude oil. The highly functionalized structure
has resulted in an extensive biotechnological industry, the most important process being the production of
ethanol by fermentation of sugars obtained from sugar cane and com. Another category of potential processes
involves dissolution and depolymerization (by hydrolysis) of lignocellulosic biomass into the corresponding monomers. Such processes are hot topics in R&D. Obvious monomers are sugars, the most important
being glucose from cellulose and xylose from hemicellulose. The sugars may subsequently be fermented or
converted to useful chemicals by (bio )catalytic means.
Thus, biomass conversion processes range from high-temperature thermochemical processes, such as
combustion, gasification, and pyrolysis, to more subtle (bio)chemical processes in the liquid phase, such as
hydrolysis and fermentation. The former category is very robust because the detailed structure of the biomass
only plays a minor role and the complete organic part of the biomass is converted into a large pool of chemical
compounds of various nature. The latter e::ategory is different due to the possibility of selective conversion

Chemical Process Technology, Second Edition. Jacob A. Moulijn, Michie! Makkee, and Annelies E. van Diepen.
2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd.

222

Processes for the Conversion of Biomass

Heat
Methanol
Liquid fuels

Liquid fuels

Ethanol
Butanol
Lactic acid
Hydrogen
Methane

Terpenes

etc.

etc.

Ethanolamine
Butanediol
Styrene
etc.

Figure 7.1

Sorbitol
Xylitol
lsosorbide
Hydroxymethylfurfural (HMF)
etc.

Routes and products in biomass conversion processes._

routes under milder conditions. For this class, the biomass structure offers the potential of efficient processes
with high yields of target products.
QUESTIONS:
Referring to Figure 7.1, discuss the main process aspects. In which processes does catalysis
play a role? Is the separation of the product(s) an issue? What are the reaction conditions
(temperature, pressure)?
It might be wondered whether it would not be advisable to process biomass in the existing industrial
infrastructure, such as in oil refineries. The simplest way would be to defunctionalize the biomass, so that
the stoichiometry of the products approaches that of crude oil, and subsequently utilize these products as
feedstocks for the refinery. It has been proposed to do this by hydrodeoxygenation (HDO), similar to other
hydrotreating processes such as hydrodesulfurization (HDS) described in Section 3.4.5. However, it can easily
be shown that for the major sources of biomass the economics of such a process are questionable.

QUESTIONS:
Estimate the economic feasibility of the production of hydrocarbons by HDO based on
lignocellulosic biomass. (Hints: Assume a simple composition for the biomass and the
product. Do not take into account the processing costs, but limit yourself to the prices of
reactants and products. Follow an optimistic scenario and assume 100% yields and no
waste.)
Compare the temperature profiles in the reactors for a typical HDS process and HDO of
lignocellulosic biomass.

Production of Biofue/s

223

Apart from the cost factor, there is the question what the optimal products of biomass conversion are. A priori
there is no need to copy the hydrocarbon industry. In principle, for several reasons it is most attractive to
produce oxygen-containing products. Firstly, less oxygen atoms need to be removed, saving process steps and
hydrogen (typically used for removing oxygen). Secondly, the product quality might be better with oxygen
atoms present. For instance, in the case of diesel fuel, oxygen-containing molecules often result in smokeless
combustion and, as a result, less pollution 1 . Thirdly, when less oxygen is removed less mass is lost.
A fundamental point is the following: Intuitively, it is clear that it would be attractive for the products to
have a structure similar to that of the feedstock monomers. The consequence of making such products would
be that only a minimal number of bond breaking and forming steps would be required. Usually this leads to
an efficient process as far as the chemistry is concerned. Therefore, in deciding upon the desired products,
it makes sense to take into account the structure of the feedstock. One of the great challenges in biomass
applications is to identify attractive molecular structures.
QUESTIONS:
In analogy with crude oil applications, a possible product spectrum from biomass consists
offuels and chemicals. Would this be the optimum product spectrum or is there a priori a
preference for either fuels or chemicals? Take into consideration the market volumes and
prices.
Oxygen-containing molecules in diesel fuel often result in less pollution, as suggested by
the smokeless combustion. However, under some conditions health effects still could be
significant. Explain.

7.2

Production of Biofuels

Biofuels are growing tremendously in volume; Figure 7.2 shows the global trend. The major biofuels are
bioethanol and biodiesel. Bioethanol has the greater global importance, but biodiesel is the most common
biofuel in the European Union (EU) (Figure 7.3).
Bioethanol was first used as an oxygen-containing additive for gasoline and later also as a primary
transportation fuel, mainly in Brazil, the United States, Canada, and some European countries. Bioethanol
can also be used as a feedstock for the production of ethyl tert-butyl ether (ETBE), which blends more
easily with gasoline and has a high octane number (118). Currently, the use of biodiesel is limited to low
concentration mixtures with oil-derived diesel.
QUESTIONS:
What fractions of gasoline and diesel are based on biomass in the world and in the EU (see
also Chapter 2)?
The contribution of bioethanol to the Greenhouse Effect is said to be lower than that of
oil-based gasoline. Is this statement always correct?
Table 7.1 shows the status of various technologies used for the production of biofuels. Current commercial
technologies for producing bioethanol and piodiesel are based on food crops that can be easily converted. A

1 Smokeless

combustion not necessarily means cleaner combustion. Although the total weight of particulate matter in the exhaust gas is
lower, the number of particles may be the same or even higher (but of smaller size).

224

Processes for the Conversion of Biomass

2500
biodiesel
Q)

::;

2000 r------1 bioethanol

"iti'
Q;

.e, 1500
c
0

ti;:;)
"0
0

1000

a.

(j)
;:;)

15

500

03

I I
-"'~ -"'" -"''1- r:>~ -"''>- -"'~ -"'li::l ~
'1-\J' '1--v- '1-\J' '1-(J "'-v- '1-\J' '1--v- '1-(J
Figure 7.2

fSr::>co '1-(Jr::><b ')..~....~

Global biofuel production [4].

major disadvantage is the direct competition with food supplies. Biogas, a gas mainly consisting of methane,
is also produced on a commercial scale by anaerobic digestion (Section 13.4.2).
Technologies for the production of more advanced liquid biofuels, based on lignocellulosic biomass, are
currently at the large-scale demonstration stage. The lignocellulosic-biomass derived biofuels produced by
thermochemical methods, such as pyrolysis and gasification, are much more similar in composition and
fuel value to oil-derived fuels than conventional biofuels. They may offer a really sustainable alternative as
transportation fuels; they have lower requirements for land and fertilizer, and often there is no competition
with usage as food.

7.2.1

Bioethanol and Biobutanol

At present, virtually all bioethanol is produced from food crops, with about 75% being produced from sugar
crops, including sugarcane, sugar beet, and molasses; the remainder is mainly produced from corn. Bioethanol

Figure 7.3

Breakdown of EU biofuel consumption for transportation by type (total: 73.9 million metric tons oil
equivalent) [5].

Production of Biofuels

225

Status of the technology used for the production of biofue/s [6].

Feedstock

Process

Development stage

Sugar and starch crops

Lignocellulosic biomass

Hydrolysis and fermentation

Pretreatment, hydrolysis and
fermentation
Transesterification
Transesterification
Hydrotreati ng
Gasification + FTb
Gasification + methanol
synthesis
Methanol dehydration
Hydrolysis and fermentation
Pretreatment, hydrolysis and
fermentation
Pyrolysis
(pretreatment,) hydrolysis
and chemical conversion
Anaerobic digestion
Steam reforming
Gasification
Various

Commercial
Demonstration

Vegetable oils, animal fats

Microalgae
Vegetable oils
Lignocellulosic biomass
Lignocellulosic biomass
Biomethanol
Sugar and starch crops
Lignocellulosic biomass
Various
l~uranics

13 iogas/B iomethane
Hydrogen

Lignocellulosic biomass
Sugar and starch crops
Biomass
Organic waste
Biogas
Lignocellulosic biomass
Various novel routes

Commercial
Basic and applied R&D
Early commercial
Demonstration
Early commercial
Demonstration
Early commercial
Demonstration
Basic and applied R&D
Basic and applied R&D
Commercial
Demonstration
Demonstration
Basic and applied R&D

"Biomass-to-liquids.
I' fischer-Tropsch synthesis.
cDimethyl ether.

is produced by fermentation of sugars using microorganisms such as yeasts. This process can be applied to
a variety of feedstocks, provided the structure is made accessible to fermentation. For starchy crops this
is done by enzymatic hydrolysis to produce mainly glucose. For the more difficult lignocellosic biomass,
the technology is more complex (Figure 7.4). Processing of lignocellulosic biomass is currently the topic
of a large research effort. The most important challenges being addressed are the current need for a costly
pretreatment of the biomass to free the cellulose and hemicellulose and the fact that hemicellulose consists
of pentose sugars that are not easily fermentable. However, in recent years much progress has been made in
the development of microorganisms suitable for the fermentation of these pentose sugars.
During pretreatment, the feedstock is subjected to conditions that disrupt the fibrous matrix structure of
the lignocellulose, resulting in the separation of the hemicelluloses from the polymerous cellulose chains
and the interwoven lignin that binds them together (Section 2.3.4). Numerous pretreatment strategies have
been developed to enhance the reactivity of cellulose and to increase the yield of fermentable sugars [7, 8].
Hydrolysis releases the individual sugar monomers (glucose) from cellulose. The cellulose and hemicellulose
sugars can be fermented to ethanol (see also Section 13.4.1) by yeasts that have been modified to ferment
both hexose and pentose sugars and have been adapted to deal with the inhibitory materials that are produced
during pretreatment of the biomass [7 ,8]. Distillation and dehydration of the aqueous ethanol solution produces
anhydrous ethanol of 99.9 wt% purity, acceptable for mixing with gasoline [7]. Currently, a discussion is
taking place about the suitability of 96 wt% etlianol (the azeotrope of ethanol and water) for blending with
gasoline. A range of coproducts, such as various chemicals, lignin, and heat or electricity may also be
produced.

226

Processes for the Conversion of Biomass

Lignocellulosic
biomass

cellulose&
lignin

or

Ethanol

Chemicals
Figure 7.4

Lignin

Heat or electricity

Biochemical production of ethanol from lignocellulosic biomass.

QUESTIONS:
Estimate the maximum yield of bioethanol that can be produced.
What are the largest contributors to the cost of producing bioethanol from lignocellulosic
biomass? How could these be reduced?
There is an increasing interest in the use of biobutanol as a transportation fuel. Butanol better tolerates water
contamination, is less corrosive than ethanol, has a higher energy content, and is more suitable for distribution
through existing pipelines for gasoline. In blends with diesel or gasoline, butanol behaves more favorably
with respect to the formation of stable mixtures than ethanol in case of contamination of the fuel with water.
Blends of 85% butanol with gasoline can be used in unmodified gasoline engines.
Butanol production differs from ethanol production primarily in the fermentation process (different microorganism) and there are minor changes in the downstream distillation section (Section 13.4.1).
The number of announcements for commercial biobutanol plants is increasing rapidly. Currently, several
bioethanol plants are being converted to biobutanol plants.

QUESTIONS:
Why does biobutanol tolerate water contamination better than bioethanol? What are disadvantages ofbiobutanol as a fuel?

7.2.2
7.2.2.1

Diesel-Type Biofuels
Transesterification

So-called biodiesel is a mixture of methyl or ethyl esters of fatty acids (FAMEs and FAEEs). The ester
group increases the oxygen content of diesel-biodiesel blends, improving the combustion efficiency of the
conventional fossil-fuel-based diesel. Biodiesel is produced by catalytic transesterification of vegetable oils
with low molecular weight alcohols like methanol or ethanol [9-13]. The most employed vegetable oils in

Production of Biofuels
0
II
H3C-o--c-R1

0
II
H2C-O-C-R1

~
I ~
I

HC-O-C-R2
e-

catalyst

+ 3 CH30H

H2C-o--C-R3
vegetable oil
(triglycerides)

Scheme 7.1

methanol

H2~-0H

0
II
H3C-o--C-R2

+ HC-OH

0
II
H3C-Q--C-R3

H2C-OH

FAME

227

glycerol

Transesterification of vegetable oil with methanol. FAME= fatty acid methyl esters. R1, R2 , and R3
are long-chain hydrocarbons.

Europe are rapeseed, soya bean, and sunflower oils. On the other hand, palm oil is considered an excellent
feedstock for biodiesel production in tropical countries such as Malaysia and Thailand.
The preferred (homogeneous) catalysts are sodium hydroxide (NaOH) and sodium methoxide (NaOCH3 ).
The reaction can also be catalyzed by acids, but these are much less active. Scheme 7.1 shows the transesterification reaction of a vegetable oil with methanol. The reaction is reversible and excess methanol is used to
shift the equilibrium towards the formation of (methyl) esters.
It is common for oils and fats to contain small amounts of water and free fatty acids (FFAs)- fatty acids that
are not attached to the glycerol backbone - which give rise to side reactions. The free fatty acids (RCOOH)
react with the alkaline catalyst and form soap (Scheme 7 .2), as a result of which part of the catalyst is
neutralized and is no longer available for transesterification. Furthermore, the presence of soap may interfere
with subsequent processing steps. Therefore, the FFA content should be smaller than 0.5 wt%. If water is
present, it can hydrolyze the triglycerides and form a free fatty acid (Scheme 7.3), thereby increasing the
tendency towards soap formation. The water content should be less than 0.2 wt%.
Figure 7.5 shows a simplified block diagram for the production of biodiesel using an alkaline catalyst. The
triglycerides are first pretreated by "degumming" for removal of phospholipids, drying, and, if necessary,
removal of free fatty acids. Phospholipids are triglycerides with two fatty acid chains and one side chain
formed by a phosphate ester [14]. If the triglycerides contain too much free fatty acids, these are converted
to the corresponding methyl esters in the presence of an acid catalyst. Alternatively, the free fatty acids are
separated from the feed for disposal or separate treatment in an acid esterification unit.
After pretreatment, the tryglicerides are subjected to transesterification with methanol in the presence of
an alkaline catalyst. The methyl esters are subsequently separated from the heavier glycerol phase by phase
separation. The catalyst is then neutralized by adding an acid, for example, hydrochloric acid, after which
washing to remove minor amounts of by-products and drying yields a biodiesel ready for use.
Excess methanol is recycled. The resulting crude glycerol (circa 80--85 vol.%) can be used as such
or be purified further by chemical treatment, evaporation, distillation, and bleaching to yield glycerol of
pharmaceutical quality (>99.5 vol.% ). Today, the crude glycerol that is not purified is largely burned, which
must be considered as a tragic waste of a potentially very useful organic raw material [15], as shown in
Section 7.3.2.

0
II
HO-C-R1 + NaOH
Scheme 7.2

Soap formation in the presence of a NaOH catalyst.

228

Processes for the Conversion of Biomass

H3C-OH

catalyst

triglyceride

I ~
H C-O-C-R2
I ~
H3C-O-C-R3
3

diglyceride

Scheme 7.3

0
II
HO-C-R1

fatty acid

Hydrolysis of a triglyceride.

QUESTIONS:
What is the reason for carrying out the transesterification process instead of using the oils
and fats directly as fuels?
The concentration of water has to be kept low. Why?
Calculate the atom economy and E-factor (see Section 12.2) of the transesterification
process. How is the phase separation done? What would be the impurities in the crude
glycerol?
Why and how would glycerol be bleached?
Obviously, glycerol is produced as a by-product. Are the amounts produced large (compare
with the world market for glycerol)?
What would be markets for crude glycerol and refined glycerol?
Suggest conversion routes for the production of marketable products from glycerol.
Although chemical transesterification using a process involving an alkaline catalyst results in high conversions
of triglycerides to their corresponding methyl esters in short reaction times, the reaction has several drawbacks.
The process is energy intensive, recovery of the glycerol by-product is difficult, and neutralization of the
catalyst produces a large amount of waste salts.
Oils& Fats

Methanol
Catalyst

---+

Methanol

Crude glycerol

Figure 7.5

Simplified block diagram for the production of biodiesel using an alkaline catalyst.

Refined
glycerol

Production of Biofuels
Table 7.2

229

Comparison of alkali- and enzyme-catalyzed transesterification processes [13].

Reaction temperature (K)

Yield of FAME
FFA in feedstock
Water in feedstock
Recovery of glycerol
Purification of FAME
Production cost of catalyst
Catalyst separation

Alkaline catalyst

Lipase catalyst

320-350
Normal
Saponified
Interference with reaction
Difficult
Repeated washing
Low
Difficult

305-315
Higher
Converted to FAME
No influence
Easy
None
High
Difficult

QUESTIONS:
Explain why the chemical transesterijication process is energy intensive.
New processes have been proposed, such as a catalyst-free process based on supercritical methanol [ 16] and an
enzyme-based process [10, 13, 17]. Enzymes like lipases are able to effectively catalyze the transesterification
oftriglycerides in both aqueous and non-aqueous systems [13] (Table 7.2). Enzyme processes outperform the
classical process in several aspects. In particular, glycerol can be easily removed and free fatty acids can be
completely converted to the alkyl esters, which .makes the process also suitable for processing cheap waste
oils and fats. On the other hand, the production cost of a lipase catalyst is significantly greater than that of an
alkaline one. In addition, the need for a difficult catalyst separation step remains.

QUESTIONS:
Draw a process scheme for transesterification based on a lipase catalyst. Why can a
neutralization step be avoided?
As mentioned above, it is not possible to perform an alkali-catalyzed transesterification process for oils with
a high FFA content. For such oils the use of solid acid catalysts is recommended, because these catalysts
can simultaneously catalyze the transesterification of triglycerides and the esterification of free fatty acids
to methyl esters. Solid acid catalysts have a strong potential to replace homogeneous catalysts, eliminating
separation, corrosion, and environmental problems [10, 18]. Figure 7.6 shows a simplified block diagram for
a solid-acid-catalyzed transesterification process.
Oils& Fats

Methanol

Biodiesel

Refined
glycerol

Figure 7.6

Simplified block diagram for the production of biodiesel using a solid acid catalyst.

230

Processes for the Conversion of Biomass

R1-H
C02
catalyst

+ H2

""

....

R2-H

C3Ha

R3-H
Vegetable oil
(triglycerides)

Scheme 7.4

H20

Green diesel

Hydrodeoxygenation of vegetable oil to produce green diesel.

QUESTIONS:
Figure 7.6 includes a purification step for the biodiesel product stream. What would be the
major impurity? How would you perform the purification?

arc
rrac

7.2.2.2

n~c)

Hydrodeoxygenation

An alternative to transesterification is the catalytic hydrodeoxygenation (HDO) of vegetable oils [19-24]

(Scheme 7.4). The primary product is a diesel fraction consisting of branched alkanes, referred to as green
diesel or renewable diesel. The molecular structure of green diesel molecules is indistinguishable from that
of conventional oil-derived diesel molecules. Coproducts include propane and naphtha, while carbon oxides
and water are formed as by-products.

QU

Figure 7.7 shows a simplified flow scheme for a HDO process developed by UOP/Eni. Vegetable oil
is combined with fresh and recycle hydrogen and fed to the catalytic reactor, where it is converted into
a branched-alkane-rich diesel fuel. The water and carbon dioxide formed by the deoxygenation reactions
Tab
fror

c
Vegetable oil

fee<
The
Propane&
light ends

Naphtha

Green diesel
Reactor

Figure 7.7

Separator

Fractionator

Simplified flow scheme of the UOP!Eni Ecofining process for the production of green diesel.

7.3
Jusl
deri
of I
exp
sucl
and
The
che

QU

Production of Bio-based Chemicals

Table 7.3

23 7

Comparison of diesel fuel properties [2 7, 23].

Oxygen (wt%)
Sulfur (ppm)
Heating value (M)/kg)
Distillation range (K)
Cetane number
Stability
C0 2 emissions (kg/MJ)

Oil-based
ultra-low-sulfur
diesel

Biodiesel

Green diesel

0
<10
43
470-620
40

11
<1
38
610-625
50-65

0
<1
44
535-590
70-90

Good

Poor

Good

0.08

0.06

0.04

are separated from the fully deoxygenated hydrocarbon product. The deoxygenated liquid product is then
fractionated to remove the small amount of light fuel coproducts. The excess hydrogen is recovered and
recycled back to the reactor.
QUESTIONS:

What reactions occur in the UOP/Eni process? What would be the process conditions
(temperature, pressure)?
Compare the HDO process with the transesterification process. List advantages and disadvantages.
Why can the economics of HDO of triglycerines be favorable while those of HDO of
lignocellulosic biomass generally are not?
Table 7.3 compares the properties of green diesel with those ofbiodiesel and ultra-low-sulfur diesel produced
from crude oil.
One of the most important advantages of the HDO route from an economic viewpoint is that the bio-based
feedstocks can be processed at refineries using existing equipment, thereby minimizing capital costs [22].
The produced fuels are good examples of "drop-in" fuels.

7.3

Production of Bio-based Chemicals

Just as the petrochemical industry is based on a relatively small number (circa 20) of so-called base chemicals
derived from oil components (Chapter 2), a bio-based industry could be envisioned based on a small number
of building blocks, so-called platform molecules, derived from biomass components. A priori it is to be
expected that biomass-based platform molecules are quite different form oil-based base chemicals. Several
such molecules have been identified (Figure 7 .8) [25, 26]. These molecules have multiple functional groups
and possess the potential to be transformed into numerous commercially relevant value-added chemicals.
The chemicals produced from these platform molecules may be the same as those produced from oil-derived
chemicals or different but with the same function, or they may even be completely new.
QUESTIONS:

When considering the group of platform molecules proposed, do you feel that this list is
complete and that all molecules proposed are good choices? Suggest additional platform

=-

:--

=~

232

Processes for the Conversion of Biomass

OH

~OH

HO~OH

HOTYOH

OH
ethanol

OH

OH

/'--_
HOr

HO~OH

OH

sorbitol

y0loH

HO~OH
0

0
levulinic acid

hydroxypropanoic acid

/OH

OH

OH

lactic acid

y ~y ~'-/

xylitol

glycerol

OH

succinic acid

HO\JO
furfural

hydroxymethylfurtural (HMF)

Figure 7.8

furandicarboxylic acid (FDCA)

isoprene

Bio-based platform molecules [26].

molecules. (Hint: start from the composition of biomass and minimize the number of
reactions needed.)
What is the main general difference of the platform molecules as compared to oil-based
base chemicals?

7.3.1

Ethanol

Ethanol has an enormous potential as a feedstock for the production of bulk chemicals (Figure 7 .9). Steam
reforming of ethanol [27] using a metal-based catalyst can serve as a renewable source of hydrogen. This
route has been widely investigated in recent years. The process is similar to steam reforming of methane
(Chapter 5). The reforming reaction (7.1) is highly endothermic and requires temperatures of 870 to 1200 K.
These high temperatures may result in the formation of by-products such as carbon monoxide and methane.
In addition, deactivation of the catalyst by the formation of coke deposits often has to be coped with.
(7.1)
The production of ethene by the catalytic dehydration ofbioethanol has been discussed in Section 4.5.4. High
crude oil prices and the rapjd development of fermentation technologies have increased the attractiveness of
the bioethene route in comparison with the classical steam cracking process. Ethene is an important starting
material for the production of polymers (Chapter 11).

-_

Production of Bio-based Chemicals

CO+ H2

233

steam reforming

syngas
butadiene

~0
acetaldehyde

~OH

)l -

H20

OH

acetic acid

Figure 7.9

~0~
ethyl acetate

Ethanol as a platform molecule for the production of chemicals.

QUESTIONS:

In steam reforming of ethanol, which reactions cause the formation of carbon monoxide
and methane? What are other possible by-products?
How does processing scale influence the choice of process for ethene production?

7.3.2

Glycerol

The growing production of biodiesel by transesterification of vegetable oils with methanol or ethanol has
led to the surplus production of glycerol. This observation has stimulated an immense research effort into
possible (new) uses. Glycerol is an intermediate in the synthesis of a large number of compounds used in
industry. Figure 7.10 shows some of the most important and novel routes for the conversion of glycerol into
useful chemicals.
Like ethanol, glycerol can be converted to synthesis gas by reforming. Because the process operates at
relatively low temperature, reaction 7.2 is the most important reaction.
Llr H298 = 129 kJ jmol

(7.2)

This reaction takes place in the liquid phase and is termed "aqueous phase reforming". This process offers
a number of advantages as compared to steam reforming of ethanol. Firstly, the higher reactivity of glycerol
allows the reforming process to be carried out at milder temperatures (typically 470-550 K). Unwanted
reactions are kinetically restrained under these conditions. Secondly, the process is more versatile and
reaction conditions and catalysts can be selected to transform concentrated aqueous solutions of glycerol
(as those produced in biodiesel production) into either syngas or hydrogen-enriched streams by coupling the
reforming process with water-gas shift processes [28].
Currently, one of the most promising routes for upgrading glycerol is the production of C3 diols by
dehydration and subsequent hydrogenation of the formed intermediate. Propene glycol (1,2-propanediol), the
main product obtained by this route, is used in the production of polyester resins, antifreeze, pharmaceuticals,
and paints [28].
Glyceraldehyde and dihydroxyacetone can be readily formed by mild oxidation of aqueous glycerol in air.
These intermediates can be transformed into lactic acid by isomerization reactions using zeolites, leading to

234

Processes for the Conversion of Biomass

isomerization/

OH
lactic acid

O~OH
OH
glyceraldehyde

-H2~02
CO+ H2
syngas

steam reforming

~isomerization

HO~OH
0
dihydroxyacetone

02 ~H2 0
H2
-CH 3 0H

1,2-ethanediol
ethene glycol

/-H20
ijoH

HO~OH

-H20
O~OH -----+

0
1-hydroxy-2-propanone

H2

foH
OH
1,2-propanediol
(propane glycol}

Figure 7.10

~
0
acrolein

3-hydroxypropionaldehyde

H2

HO~OH
1,3-propanediol

Main routes for the aqueous phase transformation of glycerol into chemicals.

a mixture ofL- and D-lactic acid. This route offers a simple, clean, and non-enzymatic alternative to classical
fermentation for the large-scale production of lactic acid, which is an important chemical that is used for
production of biodegradable polymers and solvents [28, 29]. It should be noted that the enzymatic route leads
to either L- or D-lactic acid.
QUESTION:
For which applications would the selective production of either
interesting?

7.3.3

L-

or D-lactic acid be

Succinic Acid

At present, succinic acid is produced by the hydrogenation of petrochemically-derived maleic anhydride

(Section 10.5), from which a wide range of chemicals is produced. Several bacteria can produce succinic
acid as a major fermentation product; biomass-derived succinic acid could serve as an attractive replacement

Production of Bio-based Chemicals

H,N~NH,

235

I
(NVo

H2N~NH2 N~N

\__j

0
succinoamide

1,4-diaminobutane

succinonitrile

2-pyrrolidone

reductive
ami nation

HO,
/'-....
/'-....
'-./
'-./
'OH
1,4-butanediol
hydrogenation

fumaric acid
dehydrogenation

tetrahydrofuran

(yo

cyclization

j.m.,;,.uon

q:

0H

hydrolysis

OH

y-butyrolactone

maleic anhydride

Figure 7.11

0
maleic acid

Succinic acid as a platform molecule for the production of chemicals.

for maleic anhydride. In addition, succinic acid could be used as a monomer for the production of polymers
that are currently derived from butane. The use of succinic acid as a platform molecule is summarized in
Figure 7 .11. Promising derivatives from succinic acid are tetrahydrofuran, y -butyrolacetone, and butanediol,
as well as various pyrrolidones [30].
Major issues for the practical use of succinic acid are its high recovery and purification costs. The separation
of by-products, such as acetic acid, formic acid, and lactic acid, has a crucial effect on process costs. Several
methods for purification of succinic acid, including electrodialysis, precipitation, and extraction, have been
reported [31]. A lot of attention is given to genetic manipulations and process improvements aiming at
suppressing the formation of by-products. For the use of succinic acid as a starting material for further
conversion, an elegant technology would be one that eliminates the need for the recovery of succinic acid by
performing the conversions in situ in the fermentation mixture [30].

QUESTIONS:
What is electrodiaiysis? Why is it applicable, in principle, in the purification of bio-based
succinic acid?

236

Processes for the Conversion of Biomass

Do you have ideas for the in situ conversion of succinic acid inside the fermenter? (Hint:
Why would it be difficult to recover succinic acid from the fermentation medium? Think in
terms of hydrophilicity and hydrophobicity.)

7.3.4

Hydroxymethylfurfural (HMF)

Biomass-derived hexose sugars, obtained from cellulose, hemicellulose, or starches, can be dehydrated to
form furan compounds such as hydroxymethylfurfural (HMF). The process is typically carried out in aqueous
mineral acids such as hydrochloric or sulfuric acid. The use of these acids has a number of disadvantages, such
as difficult recovery of the acid, the necessity to employ expensive reactor materials resistant to corrosion, and
the formation of a large number of by-products, because of the instability of HMF under acidic conditions.
Current research is focused on the use of solid acids, which (i) can easily be separated and recycled, (ii) allow
higher reaction temperatures, thereby shortening reaction time and decreasing the amount of decomposition
by-products, and (iii) have properties that can be tuned to improve the HMF selectivity [28].
HMF has an enormous potential in the production of substitutes for oil-based monomers in the synthesis of
large-scale polymers including polyesters, polyarnides, and polyurethane (Figure 7.12). A notable example
is furan dicarboxylic acid (FDCA), which has a chemical structure and properties similar to terephthalic acid
(TPA) (Section 9.5).
Polycondensation ofFDCA with ethene glycol (which can be produced from glycerol (Figure 7 .10) or from
ethanol via ethene and ethene oxide) yields poly-ethene furanoate (PEF) in the same way as polycondensation
of TPA with ethene glycol yields poly(ethene terephthalate) (PET).
The conversion of HMF to FDCA is a favorable reaction which can even be carried out at ambient
temperature [32]. The success of this technology depends on the design of efficient routes for HMF production.
Avantium [33] has developed a different approach. This approach avoids the aforementioned problems of
HMF instability by dehydration of the sugars to form a stable HMF ether derivative, which then undergoes
catalytic oxidation to form FDCA (and its derivatives).

7.4
7.4.1

The Biorefinery
Biorefinery Design Criteria and Products

Biomass is a feedstock that can be used in many different applications. In general, multiple products will
be produced and in recent years the concept of biorefineries, analogous to oil refineries, has emerged. The
term biorefinery refers to a facility (or group of facilities) that combines the production of transportation
fuels and chemicals with energy production. By producing several products, a biorefinery takes advantage of
the various components in biomass and their intermediates, thereby maximizing the value derived from the
biomass feedstock.
Figure 7.13 gives a schematic listing of the main criteria for the design of a biorefinery and a possible
product spectrum to be expected. For economic reasons, in general biomass processing will be performed in
large-scale processes. It has not been attempted to give a full list of potential products here; this can be found
in the literature, for example [34].
The demand for renewable biofuels, which can only be produced from biomass, is growing rapidly. As
a consequence, the main challenge for biorefinery development seems to be the efficient and cost-effective
production of transportation biofuels, while from the coproduced biochemicals additional economic and
environmental benefits can be gained [19].

The Biorefinery

polymers

dimethylfuran (DMF)
hyd,ogenolyl

OH

OH

o~o

HO~OH
dihydroxymethylfurfural (DHMF)

furan dicaboxylic acid (FDCA)

hydrogenation

oxidation

C-C coupling,
aldol condensation

aldol adduct

aldol adduct

hydrogenotlon

hydrogenUon

OH

OH

OH

RVR2R3\J
~ ~ ~
/R
1--....._

saturated adduct
hydrogenation
dehydration

/0"-.

/0"-.

saturated adduct

alkane

alkane

Figure 7.12

hydrogenation
dehydration

HMF as a platform molecule for the production of chemicals and biofuels.

237

238

Processes for the Conversion of Biomass

----I~ Food, feed
----1~

Biomass

Paper, pulp, viscose, construction materials, sugar, etc.

,----I~ Chemicals

c.----1,.. High-performance transportation fuels

----I~ Electricity
----1~ Low-performance fuels

Figure 7.13

Criteria for the design of a biorefinery with its products [7 }.

The objective of a biorefinery is to replace conventional fossil fuels (crude oil, coal, and natural gas) and
fossil-fuel products (mainly gasoline, diesel, and syngas) with biofuels produced by biomass upgrading. The
most important energy products that can be produced in biorefineries are:

gaseous biofuels (biogas, syngas, hydrogen, biomethane),

liquid biofuels for transportation (bioethanol, biodiesel, Fischer-Tropsch fuels, bio-oil), and
solid biofuels (pellets, lignin, charcoal).

With respect to chemicals, the same chemicals may be produced from biomass instead of from fossil fuels,
or molecules having a different structure but an equivalent function may be produced.

7.4.2

Biorefinery Concepts

In view of the list of criteria and the product spectrum it is not surprising that a large variety of designs
are conceivable for a biorefinery. Apart from the technological processes to be used, the type of biomass
to be processed has to be decided upon. However, there is now wide acceptance that future biorefinery
feedstocks should be really sustainable. Such feedstocks could be dedicated energy crops (e.g., starch crops
or short-rotation forestry) supplemented with residues from agriculture, forestry, industry, and so on.
Several ideas have been put forward for processing such feedstocks. Two main types of biorefinery can be
distinguished: a fermentation-based refinery (or sugar platform) and a thermochemical refinery, which could
have a syngas platform or a pyrolysis platform as the basis. A combination is also possible.
Figure 7.14 shows an example of a conceptual biorefinery scheme. A sugar platform breaks down lignocellulosic biomass into different types of sugars for fermentation or other (bio )chemical processing into

Figure 7.14

Concept of a biorefinery [35}.

The Biorefinery

239

various fuels and chemicals. In a syngas platform, biomass is transformed into synthesis gas by gasification. The synthesis gas can then be converted into a range of fuels and chemicals by catalytic chemical
processes.
A biorefinery should preferably produce [19, 35]:

at least one high-value chemical or material, in addition to low-value, high-volume products (like animal
feed and fertilizers);
at least one energy product besides heat and electricity; the production of at least one biofuel (liquid,
solid, or gaseous) is then required.

7.4.3

7.4.3.1

Core Technologies of a Thermochemical Biorefinery

Pyrolysis

Pyrolysis is the thermal decomposition of organic material in the absence of (molecular) oxygen. A number
of pyrolysis processes have been described in previous chapters (Chapters 3-5). Pyrolysis can also be an
important conversion technology within a biorefinery [3, 36]. It can be applied as a primary unit to convert
biomass into bio-oil as feedstock for downstream processes. In biorefineries that first fractionate the biomass
into hemicellulose, cellulose, and lignin, pyrolysis can play a role as processing unit for one or more of these
fractions. Finally, pyrolysis can be used as a more peripheral unit, for example, to treat side streams that
originate from other processes within the biorefinery.
Figure 7.15 shows a simple representation of a biomass pyrolysis process.
QUESTIONS:
Pyrolysis is the key technology in many large-scale processes. List the most important ones
and evaluate them with respect to optimal conditions.
Why does Figure 7.15 include the term "hydrophilic organics" instead ofjust "organics"?

Table 7.4 summarizes the main pyrolysis technologies and their products. Slow pyrolysis is designed to
maximize the yield of solid char, while fast pyrolysis (also referred to as flash pyrolysis) maximizes the yield
of liquid bio-oil. In general, the goal of pyrolysis in biorefineries is to maximize the yield of bio-oil.

Biomass

~
~

Figure 7.15

Gas:

C02 , CO, CH4 , H2 , C2 gases

Bio-oil:

Hydrophilic organics, water, tars

Char:

Fixed carbon, volatile material, ash

Simple representation of a biomass pyrolysis process.

~"""'-~-o;---~-

--

240

Processes for the Conversion of Biomass

Table 7.4

Modes of pyrolysis and major products.

Heating rate

Conditions

Fast

Reactor temperature 770-820 K,

very high heating rates, >1000 K!s,
hot vapor residence time 1-2 s
solids residence time <5 s
Reactor temperature 720-770 K,
heating rate range 1-1000 Kls,
hot vapor residence time 10-30 s
solids residence time hours-days
Reactor temperature <720 K,
heating rate up to 1 K!s,
hot vapor residence time hours
solids residence time hours-days
Reactor temperature ~560 K,
solids residence 10-60 min

Intermediate

Carbonization
(slow)

Torrefactiona
(slow)

Typical product
composition
(wt%)
Char: 12
Bio~oil: 75
Gas: 13
Char: 25
Bio~oil:

50

Gas: 25
Char: 35
Bio~oil:

30

Gas: 35
Solid: 80
Bio-oil: 0
Gas: 20

aTorrefaction is a mild pyrolyis process that converts biomass into a denser, more brittle, solid form.

QUESTIONS:

The properties (and therefore the performance) of the bio-oil produced depend on the
reaction conditions. Would a low or a high heating rate result in bio-oil with the best
performance? Do you expect upgrading reactions to be required? (Hint: evaluate the
properties of pyrolysis gasoline.)
The technology, and in particular reactor design, will depend on the reaction conditions.
Suggest suitable reactor configurations for the four cases listed in Table 7 .4.
Fast pyrolysis using fluidized bed reactor technology is the preferred method, because this technology is well
understood and can therefore be scaled up relatively easily. Figure 7.16 shows a typical configuration.
During fast pyrolysis, the usually finely ground and dry biomass (typically 10 wt% moisture) is rapidly
heated to temperatures around 800 K. This causes the release of a wide variety of vapor phase thermal
degradation products that are quenched within a few seconds to produce bio-oil, a mixture of condensed
organic compounds and water. In addition, char and non-condensable gases are formed.
A simple method for the rapid heating of biomass particles is to mix them with moving sand particles in
a high-temperature fluidized bed. High heat transfer rates can be achieved due to the small size of the sand
particles (about 250 J.llil). The heat required is generated by combustion of the pyrolysis gases, and/or char,
and is transferred to the fluidized bed by heating coils.
Char acts as a cracking catalyst, so rapid and effective separation from the pyrolysis product vapors is
essential. To this end, cyclones are usually used. This also avoids large quantities of char and sand ending up
in the bio-oil.
After leaving the cyclone unit, the cleaned gases must be cooled rapidly to prevent secondary reactions
from taking place and to form the bio-oil and non-condensable, recyclable product gases. Quenching in
product bio-oil or in an immiscible hydrocarbon solvent is widely practiced.

The Biorefinery

Fluidized bed
reactor

Figure 7.16

Cyclones

Quench
cooler

24 7

Electrostatic
precipitator

Pyrolysis of lignocellulosic biomass in a fluidized bed reactor.

Subsequently, electrostatic precipitators are used for coalescence and collection of what are referred to as
aerosols. These are incompletely depolymerized lignin fragments which appear to exist as a liquid with a
substantial molecular weight [3].

QUESTIONS:
How would you classify the pyrolysis processes discussed in previous chapters. What is the
size of the biomass particles used in a fluidized bed pyrolysis reactor?
Name possible reactions that would take place if no quenching were peiformed.
How does an electrostatic precipitator work?
Careful handling and storage of the char is required. Why?

Bio-oil is composed of a complex mixture of oxygenated hydrocarbons containing an appreciable amount

of water from the original feedstock and formed during pyrolyis. It cannot be used as such but has to be
upgraded before it can be used as a transportation fuel or for the production of chemicals.
One option to upgrade the bio-oil is to gasify it (Section 7.4.3.2) and convert the produced syngas to, for
example, Fischer-Tropsch liquids.
Catalytic upgrading of bio-oil for the production of transportation fuels or oil refinery feedstocks involves
full or partial deoxygenation. The oxygen is either rejected as water, for instance by hydrotreating (HDO), or
as carbon dioxide by catalytic cracking on zeolites (Section 3.4.2) [3, 36].
In an industrial process, the char and gas by-products (both 10-20 wt%) would be used primarily as a
fuel for the generation of the required process heat (including feedstock drying). However, active carbon or
carbon black could be produced from the char left. The char has also been proposed as a soil improver.
Although the bio-oil produced during fast pyrolysis can be upgraded to transportation fuels and chemicals,
its high oxygen content makes it corrosive and unstable. It also contains metals and nitrogen that cause
deposits on refinery catalysts, and the upgrading process requires large amounts of expensive hydrogen due
to the extremely aromatic nature of the; bio-oil.
A catalytic approach to pyrolysis could produce an improved bio-oil. By using multifunctional catalysts
to remove the oxygen and contaminants, a bio-oil could be produced that is highly carbon efficient, requires
less hydrogen to upgrade, and can be easily integrated into existing refineries [36, 37].

242

Processes for the Conversion of Biomass

Table 7.5

Comparison of coal and biomass gasification.

Coal gasification
Plant size (MWela
Reactor temperature (K)
Pressure
Gasification agent (typical)
Sulfur content of gas

>100
1250-2200
10--40 bar
Oxygen
High

Biomass
gasification

<80
1070-1120
Atmospheric
Air

Low

'MWe refers to electric power.

7.4.3.2

Gasification

Gasification technology aims to convert the feedstock to a maximum amount of gas, mainly consisting of
carbon monoxide, carbon dioxide, hydrogen, and nitrogen. In Chapter 5, the gasification of coal has been
discussed. Table 7.5 compares the characteristics of the gasification of coal and biomass. Coal gasification
plants are generally large, while the output of biomass gasification plants is restricted. Biomass is typically
gasified at lower temperatures than coal; also unlike coal, bio-gasification typically occurs at atmospheric
pressure [38] and with air rather than with pure oxygen [39]. The relatively low content of sulfur and other
contaminants requires less investment in gas cleaning.

QUESTIONS:
Explain the differences between biomass and coal gasification.
One of the major problems in biomass gasification is how to deal with tar formed during the process. Biomass
is much more prone to producing tars than coal. Tar is a complex mixture of condensable hydrocarbons, which
includes single ring to five ring aromatic compounds along with other oxygen-containing hydrocarbons and
complex polycyclic aromatic hydrocarbons [40]. Tar can be damaging to the gasifier, as it tends to stick to the
walls and clog the entrance and exit ports [38]. Furthermore, tar is undesirable because of various problems
associated with condensation, formation of tar aerosols, and polymerization to form more complex structures
that cause problems in engines and turbines using the produced gas [41].
Control technologies for tar reduction can broadly be divided into two approaches [40]: (i) prevent tar
build up by manipulating the gasifier conditions (primary methods) and (ii) hot gas cleaning after the gasifier
(secondary methods, Figure 7 .17).
Secondary methods may be chemical or physical treatment [40]. The former consists of thermal or
catalytic tar cracking, the latter uses mechanical methods, such as cyclones, filters, rotating particle separators,

Biomass

Clean syngas
Figure 7.17

Concept of tar reduction by secondary methods.

The Biorefinery

243

electrostatic precipitators, and scrubbers. Although secondary methods have proved to be effective, treatment
Inside the gasifier is gaining increasing attention due to economic benefits.
In primary methods, operating parameters, such as temperature, gasifying agent, residence time, and
catalytic additives, play an important role in the formation and decomposition of tar.
QUESTIONS:
Do you expect more are less tar formation in biomass gasification than in partial oxidation
of crude oil or gasification of coal?
Transport and handling of biomass is a challenge. Continuous feeding of biomass calls for special technology,
in particular because it contains a large amount of water and has a highly fibrous structure. After pretreatment
by fast pyrolysis or torrefaction, handling of the biomass is much simpler [38].
Pretreatment by fast pyrolysis is the first stage in the overall gasification process (Section 5.3 ). The produced
bio-oil can easily be poured into the gasifier bed of most types of gasifier.
Torrefaction (for definition see Table 7.4) destroys the fibrous nature of biomass. The product of torrefaction
is a conglomeration of pellet-like chips called torrefied biomass, also sometimes called "bio-coal." In fact,
torrefied biomass closely resembles coal in appearance, and greatly approaches its properties, as well.
Torrefaction can be used for most types of biomass. Its most suitable usage is in pretreatment for use in
entrained-flow gasifiers. Torrefied biomass is extremely brittle and can easily be crushed into particles of the
small size ( <0.1 mm) required for processing in these gasifiers [38].
At present, a few small industrial scale and pilot plant biomass gasification plants are in operation. In
addition, some power plants cogasify coal and biomass. Advantages of cogasification over stand-alone
biomass gasification are that the economies of scale inherent in coal conversion can be exploited and that
biomass utilization can be greatly improved due to a synergistic effect [38,42]. Currently, also, the cofeeding
of (pyrolysis) bio-oil is under investigation.
QUESTIONS:
Does the density of biomass differ from that of conventional fossil fuels? If so, are there
any consequences regarding processing of the biomass?
Compare cofeeding of pyrolysis bio-oil with cofeeding of biomass as such. Which option
do you prefer and why?

7.4.4

Existing and Projected Biorefineries

Table 7.6 shows examples of biorefineries at different stages of development. It illustrates the large R&D
efforts required in realizing processes for the utilization of lignocellulosic feedstocks.
QUESTIONS:
Compare the various feedstocks in the examples. When you would want to build a new
plant as soon as possible, what feedstock would you select? In your discussion, include the
product(s) you would want to produce.

7 .4.5

Possibility of Integrating a Biorefinery with Existing Plants

A logical question is whether a biarefinery can be integrated with existing plants such as oil refineries or
coal gasification plants. It is instructive to evaluate the processes in Figure 7.1 with respect to the potential
of merging them with oil refinery processes. For example, biomass can be used directly in an oil refinery for
combustion purposes.

244

Processes for the Conversion of Biomass

Table 7.6

Examples of biorefineries [43].

Platform

Feedstocks

Products

Si.ll11.

Crop Energies AG
(Germany)

c6 sugars

Bioethanol, animal feed,

electricity

CoiJllri

Permolex (Canada)

c6 sugars

Avantium Furanics
(Netherlands)

C6/C 5 sugars and

lignin

Sugar and starch

crops (sugar,
cereals)
Starch crops
(wheat, barley,
corn)
Starch crops,
lignocellulosic
crops or residues

Sofiproteol (France)

Ensyn (Canada)

Transesterification
and other
chemical
processing
C6/Cs sugars and
lignin
C6/C 5 sugars and
lignin
Pyrolysis

European Bio-Hub
Rotterdam
(Netherlands)

Syngas
C6/C 5 sugars, lignin
and protein

Green Biorefinery
(Austria)

Biogas and organic

solution

M-Real Hallein AG
(Austria)

C6 sugars

Lignocellulosic
crops or residues

Neste Oil (Finland)

Hydrodeoxygenation

Zellstoff Stendal
GmbH (Germany)

Lignin

Vegetable oils,
animal fats
Lignocellulosic
crops or residues

Lenzing AG (Austria)

Cs sugars and lignin

Lignocellulosic
crops or residues

High mark
Renewables
(Canada)
WUR Micro-algae
Biorefinery
(Netherlands)
Raquette Freres
(France)
Virdia (USA)

c6 sugars and biogas

Starch crops and

organic residues
(manure)
Micro-algae

lnbicon !BUS
(Denmark)
Lignol (Canada)

Oil and organic

solution

Oil crops (rape,

and sunflower
seeds)
Straw
Lignocellulosic
crops or residues
Lignocellulosic
residues
Lignocellulosic
biomass
Biofuel process
residues
Grasses

Bioethanol, food (bakery,

flower, gluten), animal
feed
Synthetic biofuels,
chemicals and
polymers, electricity
and heat
Biodiesel, glycerol,
chemicals and
polymers, animal feed
Bioethanol, animal feed,
electricity and heat
Bioethanol, chemicals,
biomaterials
Synthetic biofuels,
flavorings, polymers,
fuels, heat
Synthetic biofuels,
chemical
Feed, chemicals, fuels
Organic acids,
biomaterials, ferti Iizers,
biomethane or
electricity and heat
Bioethanol, biomaterials
(paper products),
electricity and heat
Green diesel

( )/)l/11' ' '

I 'Ji"l

( {)/Jlf

I Jf i ' . f

1'11<>1

l'il()l
( ( J/ I rJ I P ,

!)c'llli'll

1, ,

l)('!Jlfli

!,

(OJ II (I.!;.,!

( )/j

!1 J H I<

Biomaterials (paper
products), electricity
and heat
Biomaterials, chemicals,
food, electricity and
heat
Bioethanol, animal feed,
fertilizer, electricity and
heat
Chemicals, biodiesel,
electricity and heat

c(l/llllir. ' , [

Starch, chemicals, animal

feeds
Refined C6/C5 sugars and
clean lignin

CorJ"''' ,,

C<llllflr ,, ~.i:

C<liJIIII' ,, ',,

Fur1d.Jr r ,, 11:

Starch crops

C6/Cs sugars and

lignin

Lignocellulosic
biomass

<--~~

'1'1''" -i
/1'',1',,"

C6 suga~s

:1

Piled

I.

t"''

'-!

The Biorefinery

245

The pyrolysis process also nicely fits within an oil refinery: a bio-oil is formed that can be separated from

the hydrophilic biomass and can be used as a feedstock for further upgrading in an existing refinery [3].

It' used in this manner, such a feedstock is referred to as a "drop-in fuel"; the use of drop-in fuels allows
maximum integration with the existing refinery infrastructure without major changes.
Gasification of biomass is another example of a process that can be implemented relatively easily. In fact,
l!llme coal gasification plants already cogasify a large amount of biomass. In addition, if the syngas produced
Ill upgraded to liquid fuels, these can be used in the blending section of an oil refinery.
A recent concept that has attracted much interest is the decentralized production ofbio-oil for transportation
to a central process plant for gasification and synthesis of hydrocarbon transportation fuels or alcohols [3].
The implementation of depolymerization (by hydrolysis) and fermentation processes in an oil refinery is
hardly realistic, except for some final products such as bioethanol derivatives that can be blended with existing
refinery products. In addition, during biomass conversion specific molecules can be produced and blending
them with streams in the oil refinery results in downgrading of the bio-based product stream. Thus, in most
llases a dedicated plant is needed for efficient biomass conversion by these routes.
1.4.6 Biorefinery versus Oil Refinery
The biorefinery differs profoundly from the oil refinery in terms of feedstock properties, process technology,
product spectrum, investments, and environmental impact. Table 7.7 compares a number of characteristics.
The oil refinery is associated with a high feedstock price and low-cost processing, whereas for the biorefinery
the opposite is the case: a low-cost feedstock combined with high processing costs. The latter is due to several
reasons, such as a low energy density, high water content, and high separation costs.
The variety in composition of biomass feedstocks is both an advantage and a disadvantage. An advantage
is that biorefineries can make more classes of products than can oil refineries, and they can rely on a wider
l'ange of feedstocks. A disadvantage is that a relatively large range of processing technologies is needed, and
most of these technologies are still at a pre-commercial stage [34].
For the production of biofuels, the high oxygen content of biomass is a disadvantage, because it reduces the
heat content of molecules and usually gives them high polarity, which hinders blending with conventional fuels
144]. Therefore, expensive deoxygenation is required. In contrast, for the production of bio-based chemicals
the presence of oxygen may be regarded as an advantage, because oxygen provides valuable physical and
chemical properties, and oxidation reactions, which are often difficult and environmentally harmful, may be
avoided. Instead, there could be a shift towards "greener" reduction reactions.

Table 7.7

Comparison of a biorefinery and an oil refinery.

Feedstock

Process technology
Conversion steps
Product spectrum
Investments
Environment

Biorefinery

Oil refinery

Highly varying composition

High 0 content, low S content
Low density (high volumes)
Lignocellulosics low cost, oils expensive
Large range of processes
Bio and cl)emical
Complex
High
Footprint can be low

Rather constant composition

Hydrocarbons, some S
High density
High cost
Relatively simple
Mainly chemical
Relatively simple
Low
Large footprint

246

Processes for the Conversion of Biomass

7.5

Conclusions

Biomass has a high potential both as an energy carrier and as a feedstock for the chemical industry. Lignoccl
lulosics are abundantly available and are the preferred biomass feedstocks for the production of chemicals.
Instead of just substituting present-day fossil-fuel-derived fuel components and chemicals by bio-based ana
logues, it is better to judge the potential product spectrum of biomass conversion taking into account the very
different structure of biomass compared to fossil fuel feedstocks.
In view of the non-homogeneous composition of biomass, a biorefinery that integrates several technologic1l
processes is often the best option. Because biomass is highly functionalized, subtle technology in the liquid
phase that is adapted to the specific feedstock is most appealing. When dealing with a well-defined feedstock
a dedicated plant could be justified. In practice, several technologies will be used in parallel. For instance, in
all plants waste streams that must be cleaned are present. For this, robust, non-specific technology is required.
Thus, conventional technologies such as combustion, gasification, and anaerobic fermentation will be applied.
Economic evaluation is a crucial phase in R&D programs for biomass conversion processes. In general,
compared with fossil fuels, biomass is characterized by a combination of a relatively cheap feedstock requirinp
comparatively complex processing, resulting in high investment and operation costs.

QUESTIONS:
Make a table with prices of the various feedstocks. Compare these data with the market
prices of the products. What are your conclusions?

References
[1] Sanders, J.P.M., Clark, J.H., Harmsen, G.J., Heeres, H.J., Heijnen, J.J., Kersten, S.R.A., van Swaaij, W.P.M., and
Moulijn, J.A. (2012) Process intensification in the future production of base chemicals from biomass. Chemical
Engineering and Processing, 51, 117-136.
[2] Puig-Arnavat, M., Bruno, J.C., and Coronas, A. (2010) Review and analysis of biomass gasification models.
Renewable Sustainable Energy Reviews, 14, 2841-2851.
(3] Bridgwater, A.V. (2012) Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy, 38, 68-94.
[4] Lamers, P., Hamelinck, C., Junginger, M., and Faaij, A. (2011) International bioenergy trade: a review of past
developments in the liquid biofuel market. Renewable Sustainable Energy Reviews, 15, 2655-2676.
{5] Eurobserv, E.R. (2011) Biofuels barometer. Systemes Solaires- Le Journal des energies Renouvelables, 204,68-93.
[6] lEA (2011) Technology Roadmap Biofuels for Transport. International Energy Agency, pp. 52. www.iea.org (last
accessed 13 December 2012).
[7] Stephen, J.D., Mabee, W.E., and Saddler, J.N. (2012) Will second-generation ethanol be able to compete with
first-generation ethanol? Opportunities for cost reduction. Biofuels, Bioproducts and Biorefining 6, 159-176.
[8] Brodeur, G., Yau, E., Badal, K., Collier, J., Ramachandran, K.B., and Ramakrishan, S. (2011) Chemical and
physicochemical pretreatment of lignocellulosic biomass: a review. Enzyme Research, 2011, Article ID 787 532, 17.
(9] Ma, F. and Hanna, M.A. (1999) Biodiesel production: a review. Bioresource Technology, 70, 1-15.
[10] Helwani, Z., Othman, M.R., Aziz, N., Kim, J., and Fernando, W.J.N. (2009) Solid heterogeneous catalysts for
transesterification oftriglycerides with methanol: A review. Applied Catalysis A, 363, 1-10.
(11] Murzin, D.Y., Miiki-Arvela, P., and Simakova, I.L. (2012) Triglycerides and oils for biofuels, in Kirk-Othmer
Encyclopedia of Chemical Technology, John Wiley & Sons, Inc.
[12] Meher, L.C., Vidya Sagar, D., andNaik, S.N. (2006) Technical aspects ofbiodiesel production by transesterification:
a review. Renewable Sustainable Energy Review, 10, 248-268.
(13] Fukuda, H., Kondo, A., and Noda, H. (2001) Biodiesel fuel production by transesterification of oils. Journal of
Bioscience And Bioengineering, 92, 405-416.

pulverized coal (pc) combustion. Pc-systems have been the standard combustion
system in large-scale coal combustion tbr many years because of their high
etliciency and ability to burn fines. The advantage of these systems is operation at
h'w excess air with high boiler efficiency by using accurate combustion temperature
control systems gained from coal combustion. The disadvantage is the requirement
for fuel pre-trealment especially the panicle grind size comparable with pcc.)mbustion. Suspension fired combustion can be seen in Figure L5.

Puhcrit.c<i fud and

primary ar ll(m b~ll mill

Figure 4. 5

lit1iue. fl1mncc
,.ide ~ails

Suspension tired combustion

In fluidi;;,ed-bed systems the combustion bed consists of sand hich is kept

suspended by the high underfire air velocities. The bed material and the fuel are
milwd in a highly turbulent suspension. Roth bubbling fluidized bed (BFB) and
circulating fluidized bed (CFB) types are. suitable for combustion of biomass fuels.
The sand particle size is about l mm and the height of the bed is approximately 1
m The temperature in the bed can vary from SSO"C to 900"C Primary air is
blown through small nozzles in an air distributor plate and the fluidizing velocity
varies from l m/s to 2.5m/s. The BFB system. as can be seen in Figure 4.6, is a
multi-fuel combustion system suitable for reactive fuels like wood. bark and other
bio-{i.lc!s. This system is quite flexible regarding fuel size and moisture content
Less reactive fuels can also be combusted w ~ome extent rmct co-fired with reactive

Figure 4.!0 Biomass gasification with reburning [14)

Also as reburning fuel, biomass is superior to hard coal with regard to both

emissions and burnout. Experiments performed by TPS in lhe APAS programme

[14] demonstrated that co-combustion of gasifier gas (from biomass and waste)
with coal gave. an NO reduction in the order of7(l% at SOOppm initial NO emission
level. All HC-containing fuels gave significant NO reduction while HC-free fuels
did not give the same reduction. Figure 4. J0 shows a schematic layout of a process
for biomass gasification and rebuming m a coal tired boiler.
Large scale tests at Vestkraft performed in the APAS programme [12) where two
wal burners were retrofitted with straw injectic.n up to 25% confirmed the positive
effects of biomass addition on NO, emis5ions.

As for fluidized bed cocombustion, positive effects on the SOz emissions were
achieved in suspension-tired systems also Problems in suspension-fired systems
are related to the chlorine and potassium content in the fuel. giving some increased
emissions ofHC! and limited increase in corrosion"
Recent research [ l 51 on chlorine related corrosion in bmlers show that there is a
threshold where chlorine deposit is observed at the superheater surfaces. The
combination of chlorine with alkali will form alkali chloride condensation.
Condensation of these alkali vapors causes both deposits of ch!onne and alkali on
the surfaces. The chlorides react to form sulfates and release chlorine-containing
gases like HCl (under moist oxidizing conditions). However, for this scenario to
happen, there has to be enough sulphur and experimental indication of this

4S

Biomass Feedstock Characteristics

In order to improve or develop energy conversion processes for biomass, it is important
to understand its composition. Most land biomass is composed primarily of cellulose,
hemicellulose, lignin and proteins [9]. Celluloses are composed oflong chains of
saccharides. Proteins are found in most biomass, but are particularly abundant in
herbaceous species. Lignins are phenolic polymers that contribute to structural rigidity of
plant tissues. Table B provides the compositions of representative types ofbiomass fuel
and the carbon content and higher heating value (HHV) of the components. The moisture
content of biomass varies widely. Due to the ability to dry biomass naturally without
energy input, the dry-basis energy content is the most appropriate metric.
Bermuda Grass
(herbaceous)
[%mass]

Poplar
(woody)
[%mass]

Pine
(woody)
[%mass)

Refuse Fuel
(waste)
[%mass)

Carbon
Content
[%mass)

HHV
[MJ/kg]

Cellulose

32

41

40

66

40-44

17

Hemicellulose

40

33

25

25

40-44

17

Lignin

26

35

63

25

Protein

12

53

24

Ash

17

Biomass
Component

Table B: Biomass composition and chemical properties J

0 )

Several types of biomass are used as energy conversion feedstocks, including wood,
agricultural and forest product residues, municipal solid waste, and industrial waste.
Except for the production of com-derived ethanol as a transportation fuel, there few large
scale efforts to grow crops intensively for conversion to energy carriers. It has been
proposed that fast growing species such as switchgrass or sugar cane would be an
economical option for energy-dedicated crops [11]. High quality woody feedstocks such
as hybrid poplar and pine have also been considered [12]. These feedstocks could be
combusted, gasified, or biologically digested, depending on the composition of the fuel
and the desired energy carrier product. Many plant species are potentially viable energy
feedstocks and can be selected based on cost, net greenhouse gas emissions, and
appropriateness to the intended energy conversion process and growing environment.
Biomass has some advantageous chemical properties for use in current energy conversion
systems. Compared to other carbon-based fuels, it has low ash content and high
reactivity. However, high moisture, a tendency to form tars, and an ash chemistry that
leads to the formation of low melting point solids when heated presents challenges to
some conversion methods [13]. Some biomass feedstocks may be high in nitrogen and
chlorine. The combination of both alkalis and chlorine can corrode metals that form the
structure of conversion devices. Under some conversion conditions, higher N content
may lead to the formation of nitrogen oxides. Sulfur concentrations are much lower than
in many coals, decreasing the potential for sulfur oxide creation during conversion.

GCEP Biomass Assessment- Spring 2005

362

CHAP'l Ell

CHEMICAL EQUILIBRIA

More specifically, for a generalized version of reaction E, with phases not specified:

a A + b B ==" c C + d D

f\

(2b)''

(acf(an)J
(aA)"(as)h

Because activities are unitless, so too is K.

A note 011 good practice: In some cases you will see an equilibrium constant denoted
Kp to remind you that it is expressed in terms of partial pressures. However, the subscript P is unnecessary.
Chemical equilibria with reactants and products that are all in the same phase
are called homogeneous equilibria. Equilibria C, D, and E are homogeneous. Equilibria in systems having more than one phase are called heterogeneous equilibria.
Equilibrium F is heterogeneous; so too is the equilibrium between water vapor and
liquid water in a closed system:
(G)

In this reaction, there is a gas phase and a liquid phase. Likewise, the equilibrium
between a solid and its saturated solution is heterogeneous:
(H)

The equilibrium constants for heterogeneous reactions are also given by the general expression in Eq. 2: all we have to remember is that the activity of a pure solid
or liquid is 1. For instance, for the calcium hydroxide equilibrium (reaction H),
2

K = aca2 ' (amrl = [Cal+][OH-]2

aCaiOll),
'--..----'

1 for a pure snlid

because the calcium hydroxide is a pure solid. Remember that each [JJ represents
the molar concentration of J with the units struck out. Similarly, in the equilibrium
between solid nickel, gaseous carbon monoxide, and gaseous nickel carbonyl used
.in the purification of nickel,
Ni(s)

+ 4 CO(g) ==" Ni(C0} 4 (g)

The pure solid nickel must he present for the equilibrium to exist, hut it does not
appear in the expression for the equilibrium constant.
Some reactions in solution involve the solvent as a reactant or product. When
the solution is very dilute, the change in solvent concentration due to the reaction
is insignificant. In such cases, the solvent is treated as a pure substance and ignored
when writing K. In other words,
for a nearly pure solvent: a 5,,1vent = 1
A final point to bear in mind is that, when a reaction involves fully dissociated
ionic compounds in solution, then the equilibrium constant should be written for
the net ionic equation, by using the activity for each type of ion.
SELF-TEST 9.2A

Write the equilibrium constant for the reaction of silver nitrate with
sodium hydroxide: 2 AgN0 3(aq) + 2 NaOH(aq) ""Ag2 0(s) + 2 NaN0 3(aq) +
H 2 0(l). Remember to use the net ionic equation.
[Answer: K ~~ li[Ag~f[OH fl
SELF-TEST

9.2B Write the equilibrium constant K for P4 (s) + 5 0 2 (g)

:=

P4 0

111 (s).

Each reaction has its own characteristic equilibrium constant, with a value
that can be changed only by varying the temperature ('rable 9.2). The extraordinary empirical result, which we justify in the next section, is that, regardless o{ the
initial composition of a reac:tion mixture, the composition tends to adjust until the

"U THE THFJ\i'v!ODYNAMIC ORlCl.N Of FQUil JHRll'M CONSTAf"TS

363

TABU 9.2 Equilibrium Constants for Various Reactions

Reaction

T(K)*

Kt
c

+ Cl 2(g)

2 HCl(g)

4.0 X 10
4.0 X 10 1'
5.1 >._ 1o~

4.0 X 10 31
4.0 X 10 18
5.1 X 10 8

H 2 (g) + Br2 (g)

300
500
1000

2 HBr(g)

.300
500
1000

1.9 X 10 17
1..3 X 10 1'!
3.8 X l(f

1.9
1.3
3.8

H2(g)

+ !2 (g)

H 2 (g)

2 Hl(g)

2 BrCI(g) ==" Br 2 (g) + Cl 2 (g)

2 HD(g)

F2 (g)

==" H 2 (g) + D2(g)

2 F(g)

31

298
500
700

794
160
54

794
160
54

300
500
1000

377
32
5

377
32
5

X
X
X

10 17
101li
104

100
500
1000

0.52
0.28
0.26

0.52
0.28
0.26

500
1000
1200

3.0X10" 11
1.0 X 10- 2
0.27

7.3 X 10- 1'

1.2 X 10- 4
2.7 x 10-'

Cl 2(g)

2 Cl(g)

1000
1200

1.0 X 10-5
1.7 X 10-3

1.2 X 10- 7
l.7X 10--s

Br 2 (g)

2 Br(g)

1000
1200

3.4 x
1.7 x

4.1 X 10!
1.7 x w-'

800
1000
1200

2.1 x
0.26
6.8

w-s
w- 3
w- 3

!2(g)

2 !(g)

3.1 X 10 5
3.1 x 10-'
6.8 X 10- 2

2 NH 3 (g)

298
400
500

6.8 X 105
41
3.6 x w- 2

4.2 X 10 8
4.5 X 10 4
62

2 S0 2 (g) + 0 2 (g)-:---- 2 S0 3(g)

298
500
700

4.0 X 1024
2.5 X 10 10
3.0 X 104

N/}1(g) ==" 2 N0 2(g)

298
400
500

9.9 X 1025
1.0 v 1012
1.7 X 10 6
6.1 X 10-3
1.44
41

N 2 (g) + 3 H 2 (gl

0.15
47.9
1.7 y 103

significant figures
1

K, is the equilibrium constant in terms of molar concentrations of gases (Section 9.6).

actiuities giue rise to the characteristic ualue of K for the reaction and temperature
(Fig. 9.3).
The equilibrium composition of a reaction mixture is described by the
equilibrium constant, which is equal to the activities of the products (raised to
powers equal to their stoichiometric coefficients in the balanced chemical
equation for the reaction) divided by the activities of the reactants (raised to
powers equal to their stoichiometric coef(icie11ts).

9.3 The Thermodynamic Origi~ of Equilibrium Constants

Guldberg and Waage's description of equilibrium was entirely empirical. Now,
though, chemists know that the law of mass action is a consequence of thermodynamics and that the apparently mysterious form of K arises from thermodynamic
considerations. \Ve begin our exploration of the thermodynamic basis for equilibrium by analyzing how changes in Gibbs free energy determine the tendency of a
reaction to go in the forward or the reverse directions. We then explore how the

Products
FIGURE 9.l Whether we start with purt>
reactants or with pure products, a
reaction mixture will always tend toward
a mixture of reactants and products that
has a composition in accord with the
equilibrium constant for thl: rcddirm at
I he temperature of the experiment.

".6 THE EQUILIBRIUM U.ll"\STANT lN Tl::Ri\\S OF MOLAR COi'iCENTRATlOl"\5 OF CASES

9.6 The Equilibrium Constant in Terms of Molar Concentrations

of Gases
The equilibrium constant in Eq. 2 is defined in terms of activities, and the activities
are interpreted in terms of the partial pressures or concentrations. Gases always
appear in K as the numerical values of their partial pressures and solutes always
appear as the numerical values of their molarities. Often, however, we want to discuss
gas-phase equilibria in terms of molar concentrations (the amount of gas molecules in
moles divided by the volume of the container, LJJ = n/\l), not partial pressures. 'T<> do
so, we introduce the equilibrium constant Kc, which for reaction E is defined as

. _ [c]'[D]'1
K, -

C,\F[V~

(10)

with each molar concentration raised to a power equal to the stoichiometric coefficient of the species in the chemical equation. As usual, we have replaced [J]/co by
IJI itself, which represents the numerical value of the molar concentration of the
gas J. for example, for the ammonia synthesis equilibrium, reaction C,
K

=.

[NH3f
-[

(11)

lN2j HJ'

We are free to choose either K or K, to report the equilibrium constant of a

reaction. However, it is important to remember that calculations of an equilibrium
constant from thermodynamic tables of data (standard Gibbs free energies of formation, for instance) and Eq. 8 give K, not Kc- In some cases, we need to know K,
after we have calculated K from thermodynamic data, and so we need to be able to
convert between these tvvo constants.
HOW DO WE DO THAT?

The overall strategy for finding the relation between K and K, is to replace the partial
pressures that appear in K by the molar concentrations and thereby generate K,. For
this calculation, we write activities as PlPo and U]/c and track the units by keeping po
and C0 in our expressions.
Our starting point is Eq. lb in its complete form:
0

K .... l~d_~~_)_'}PD/Pot- (Po)a b(PcnPD)J - (po a+b-ic+di(Pc)'(PD)J

-

(P A /Po)''(P B.;pa)b(Po)c-rd(p
)a(p )b-.
.
.
. A . B

The molar concentration of a gas J is

write the ideal gas law P1V = n 1RT as
P1 =

n 1RT

'v

('P A .
}"(P
l.b
. B

IJJ = n;fV. \'V'e assume ideal gas behavior and

. 1
= RTLJJ

11 1

= RT-V

When this expression is substituted for each gas in the expression forK, we obtain
'P )'"P ld
(RT[C' 1)'(.RT1D 1)d
rc]crDld
\_L_L~ =.
<
l l = RT'"'J-(a+b!L~--!,

(RT[A])''(RT[Bj)b

(I'A)a(Pll)"

[Af[Bj"

At Lhis point we recognize that KC' Eq. 10, in its complete form can be written as follows:

K ([Ch-onfDlicoid
' j .
L

c-

([A}!c )"([B}/c
0

'

)b

(_ala
-h[Cf'
fold
L
L ~
l J - (

(c )c+J[A}'[BJI' :-0

0 )''

,C

I, ''

di[C:]' [D_;d
[A]"[B]b

and therefore

[C]'[D}1

f,=\fTsr

When we substitute this expression into the equation for the ratio of partial pressures
we ohtain

371

372

CHAPTER q

CHEMICAL EQUILIBRIA

We conclude that

A useful way of remembering the general form of the expression that we have
derived is to write it as

' - (.coRT)iliz
po
Kc

(12a)''

K-

where !1n is the change in the number of gas molecules between reactants and
products in the chemical equation, calculated as !1n = 1/pndncts - nrean.uJt< (so
!':in= 2- (1 + 3) = -2 for reaction C). If no gases take part in the reaction or
if tJ.n = 0, then K = Kc The same relation holds between Q and Q"' the reaction
quotient in terms of concentrations. Equation 12a is commonly written more
succinctly as

(12b)

(RT)"n Kc

but the full version clarifies the units and should be used in calculations. Some values of K, are listed in Table 9.2.
EXAMPlE 9.6

Converting between K and K,

At 400.C, the equilibrium constant K for 2 S0 2 (g)

What is the value of Kc at this temperature?

+-

0 2 (g)

:==

2 S0 3(g) is 3.1

10 4

STRATEGY Because po = 1 bar and C0 = 1 mol L- 1, it is sensible to use R expressed in

bars and liters, R = 8.3145 X 10-2 LbarK- 1 mol- 1, and to note that

po

Reo
Then, Eq. 12a can be written as
K

T
\t>.u
(.12.03 K ) Kc

To use this equation, identify the value of !J.n for the reaction, convert the temperature
to the Kelvin scale, and rearrange it to solve for Kc
SOLUTION From the chemical equation !J.n
' 273.15 K = 673 K.

l From K =

(T/12.03 K)..,"K,
in the form K, = (T/12.03 K)-.l 11 K,

c=

2 - (2

1) = -1 and T 400.

( 673 K )
2

..

l\., = \l .0J K,t X (3.1 X 10 ) ~ 1.7 X lO

,;

: SELF-TEST 9.7 A The equilibrium constant for the ammonia synthesis (reaction C) is
K = 41 at 12rc. \Vhat is the value of K,. at that temperature?
[Answer: !J.n = -2; so Kc = 4.5 X 104 ]
SELF-TEST 9.7B At 12fCC, the equilibrium constant for N 2 0 4 (g) o= 2 N0 2 (g) is
K = 47.9. \Vhat is the value of K, at that temperature?

For thermodynamic calculations, gas-phase equilibria are expressed in terms

of K but, for practical calculations, they may be expressed in terms of mohu
concentrations by using Eq. 12.

9.7 Alternative Forms of the Equilibrium Constant

The powers to which the activities are raised in the expression for an equilibrium
constant must match the stoichiometric coefficients in the chemical equation, which
is normally written with the smallest whole numbers for coefficients. rherefore, if
we change the stoichiometric coefficients in a chemical equation (for instance, by

640

Free Energy and Equilibrium

Any amounts of PC1 5 , PC1 3 , and Cl 2 that satisfy the equilibrium-constant
expression will lead to an equilibrium situation. For ideal systems, the
activity of each substance is the unitless ratio of its actual concentration
to the concentration in its standard state. For nonideal systems, the activity
is at least related to concentration, and can be thought of as an "effective
concentration."
7. The equilibrium constant for a chemical reaction can be calculated
from the standard free energy change of reaction, D..G 0 :
D..G 0 = -RTln Keq
or
Keq = e-<t:.GD!RT)
(17-4)
Since, in the standard free energy change for reaction, I:::.G 0 , we assume
that the partial pressures of all components are 1 atm, the standard free
energy change is not a function of pressure. Any pressure variations in
reactants or products are expressed by the logarithmic term in the general
free energy equation

D..G = 1:1G 0 + RTln Q

(17-5)
0
Because jj,G is independent of pressure, the equilibrium constant, Keq,
also is independent of pressure. No matter how much we compress a mixture of PC15 , PC1 3 , and Cl2 gases, the ratio of their activities at equilibrium (equation 17-3) will not change. When the gases are compressed,
the equilibrium conditions will shift so that the equilibrium constant is the
same after the shift as before.
The standard free energy change does vary with temperature. In all
of our free energy calculations, we have assumed that the temperature
is 298 K, often omitting the subscript 298 from the term D..G~ 98 . But the
free energy of a gas reaction with all gases at 1 atm partial pressure, for
example, generally will not be the same at 1000 K as at 298 K. Hence,
the equilibrium constant, Keq> also will vary with temperature. In what
follows we shall see some examples of this behavior.

Stoichiometry and the Equilibrium Constant

The expression for the equilibrium constant depends on how the equation
for the reaction is written. For example, the reaction for the production of
ammonia can be written in terms of producing 1 mole of ammonia:
~
a
(1) iN2(g) + ~H2(g) <=Z NHs(g)
Kl = li~H;I2
aN2 aH2

or of using 1 mole of nitrogen or 1 mole of hydrogen:

a2

K 2-~
3
aN2aH2

(3)

tN 2 (g) +

a21J

H 2 (g) <=Z fNH 3 (g)

K3 =

aM:saH2

In each case the exponent of the activity, a, in the equilibrium-constant

expression is the coefficient of that substance in the chemical equation.

641

17-1 The Properties of Equilibrium

Reaction 2 is twice reaction 1 and three times reaction 3; thus equilibrium

constant K 2 is the square of K 1 and the cube of Kg. In general, multiplication of the reaction equation by any number, n, raises the corresponding
equilibrium constant to the nth power.
The reverse of reaction 2 is

Thus the equilibrium constant for the reverse reaction is the inverse of the
equilibrium constant for the forward reaction.
If we add two reactions to give a third reaction, the equilibrium constant of the third reaction is the product of the equilibrium constants of the
first two:

Kr -

aco2
acao2

Kz

aH 2 oaco
aH 2aco 2
aH oaco

2
Kg=--=---aH2acao2

K3

= KrKz

If (1) + (2)
(3), then K 1K 2
K 3 This multiplicative property of
equilibrium constants corresponds to the principle of additivity of free
energies, introduced in Chapter 2 for enthalpies as Hess' law.

Standard States and Activities

We can extend the concept of activity, and therefore of free energy changes
and equilibrium constants, to solids, liquids, and components of solutions,
if we define the activity of any substance as the ratio of the concentration of
that substance to its concentration in a chosen standard state. When calculating equilibrium constants, this standard state obviously must be the same
as the standard state for which the thermodynamic data are tabulated if we
are to calculate Keq from such data. The standard states used for calculating
the free energy values in Appendix 3 are listed in Table 17-1.
For gas reactions the activities of reactants and products are unitless
quantities that are numerically equal to the partial pressures in atmospheres. It is ~ammon to use equilibrium constants calculated from the
partial pressures of the reactants and products. For example,
K _

p-

PPCI 3 PCI 2
PPCis

We shall use this terminology occasionally since it is so common. However,

643

17-2 Reactions Involving Gases

17-2

REACTIONS INVOLVING GASES

Let's apply the previous conclusions to reactions in which all reactants and
products are gases. We shall do this in a series of examples, each of which
will illustrate a new idea.

Experimental Measurement of Equilibrium Constants

Example 1

Ammonia, nitrogen, and hydrogen are at equilibrium in a steel tank at

298 K. An analysis of the contents of the tank shows the following partial
pressures of the three gases:
PN 2 = 0.080 atm
PH 2 = 0.050 atm
PNH 3 = 2.60 atm
What is the equilibrium constant, Keq' for the reaction

N 2 (g)

Solution

+ 3H2 (g)

(1 7-6)

2NH 3 (g)

The equilibrium constant is calculated to be

2

Keq

a
=~
=
aN 2 a!i 2

(2 60) 2

(0.080)(0.050)3

= 6.8

X 105

Example 2

The preparation of sulfur trioxide from sulfur dioxide is an important step

in making sulfuric acid. A mixture of S0 2 and 0 2 gases is passed slowly
through a tube containing a platinum catalyst heated to 1000 K. The
outflow gases are analyzed and the following partial pressures are found:

Pso 2 = 0.559 atm

Po2 = 0.101 atm
Pso3 = 0.331 atm
What is the equilibrium constant, Keq' for the reaction

2SOz(g)

Solution

The answer is

+ 0 2 (g)

2S0 3 (g)

( 17 -7)

647

17-2 Reactions Involving Gases

Dissociation of Ammonia at 298 K

Total

2n

2n

2n(1 -a)

na

3na

2n(1 +a)

3a

Start:
Equilibrium:

(1 -a)

Mole fraction:

Partial pressure:

aA
K _aN
_2_2
eq-

2(1 +a) 2(1 +a)

1+a

a~H

(1- a)P

aP

3aP

1 +a

2(1 +a)

2(1 +a)

aP
2(1 +a)

27a 3 P 3
8(1 + a) 3

(1

+ a) 2 = ____
27
a P _

(1 - a)2P2

16 (1 - a 2) 2

= (0.0) + 3(0.0)- 2(-16 63) == +33 27 kJ

Keq = 10-(33.27/5.831l = 10-5.832 = 1.5 X 10-s
K = 3}_ a4P2
1.5 X 10-

D.GO

eq

16 (1 - a 2)2

~2 = 0.94
1 - a

X 10-3

fraction, a, of the ammonia has dissociated. Then, of the original 2n moles

of ammonia, 2na moles will have reacted and 2n(l - a) moles will be left.
For every 2 moles of ammonia that decompose, 1 mole of nitrogen
and 3 moles of hydrogen are formed. At equilibrium, the 2na moles of
dissociating ammonia produce na moles of nitrogen and 3na moles of hydrogen, as shown on the line of Table 17-2 marked "Equilibrium." The total
number of moles of the three types of molecules has increased as a result of
the dissociation. There now are 2n(l - a) + na + 3na = 2n(l + a) moles
of gas, whereas prior to dissociation there were only 2n moles. The total
number of moles is recorded at the righ(of the table.
The mole fraction of each component in the reaction mixture is found
by dividing the number of moles of each component by the total number
of moles. At this stage, the advantage of using fractional dissociation, a, is
obvious, because the number of moles, n, drops out of the problem. In the
third line of the table, headed "Mole fraction," the mole fraction of each
component at equilibrium is given in terms of the degree of dissociation of
ammonia.
In the next line of the table, each mole fraction is multiplied by the
total pressure to yield the partial pressure of that component. These partial
pressures are then substituted into the equilibrium-constant expression, assuming the activities of the three gases to be numerically equal to their

 particular attentions for atom economy reactions, energy saving and to obtain high
selective

processes

(100/'o

selectivity)

as

well

as

for

chemic-,

regie-

or

enantioselectivity.
significative integration of chiral catalysis in industrial processes for the production
of pure enantiomers and to take benefit of natural chiral substrates for the direct
production of the desired molecules where enzymatic catalysis will play a major role.
More important use of renewable raw materials
use of physico-chemical technologies such as supercritical media, microwave" ionic
liquids, phase transfer, ...

Selected examples of fine chemical transformations catalyzed

by

heterogeneous catalysts
Catalysis developed in organic transformations involve, metal supported, solid
acid or basic, oxides, sulfides, fluorides, mulitifunctional materials, with a controlled
porosity, hybrid materials which are able to induce an enantioselectivity, and then
biocatalysts. First, simple reactions were studied and then the development of works
related to the materia! preparations, chemistry of surfaces, organometallic chemistry
and multistep reactions are now successfully investigated.
Based on the Berzelius and Sabatier works on the hydrogenation, heterogeneous
catalysis was mainly investigated in gas phase as in petrochemistry processes. However,
as mentioned above, this experience was applicable to other reactions and we
deliberately present here few significant examples chosen according to their history,
their originality and their scientific breakthrough.

2.1 - Industrial synthesis of mercaptans and their derivatives

Exploitation in 1958 of the gas reserve of Lacq rich of H 2 S rapidly leads SNPA
to develop the sector of th!ochemistry and an important panel of chemicals such as
mercaptans, sulfides, disulfides, po!ysulfides, sulfoxides, thioacids, thiophene, ... (9).
New chemical routes based on the sulfa-hydrolysis of alcohols or aldehydes (9b,c),
selective addition of H 2S to olefins (9a) in the presence of supported sulfides or resins
were discovered. These resulting compounds find various applications in the field of

agrochemistry, animal food; pharmaceuticals, lubricants, petrochemistry, cosmetics and

odorous gas. In this field, heterogeneous catalysis contributed to the development of
the Lacq reserve.

2. 2 - Direct synthesis of amines starting from acids or esters

<~.~-l.i

--' r..__c. . _
---

Aliphatic amines called "fatty amines" gather all primary amines (R1NHz),
secondary (R 1RzNH 2 ), and tertiary amines (R 1RzR 3NHz) where R1, Rz or R3 exhibits: a
hydrocarbon chain composed of 8 to 22 atoms of carbon. Fatty amines are mainly used
as intermediates for the preparation of quaternary ammonium salts (R3N+X-), well known
surfactants. Among these fatty amines, methyialkylamines are of great importance and
they are obtained in two steps from fatty acids: a) formation of nitrile and b) alkylation
and methylation in the presence of hydrogen (scheme 1). These multistep reactions are
performed in the presence of bifunctional catalysts (hydro-deshydrogenating sites and
acido-basic sites) stable in the presence of water and ammonia. Catalysts for
hydrogenation involving copper or nickel were specifically design for the methylation
step with methanol or by HMTA (hexamethylenetetramine) (10).

a)

b)

N -----;

Scheme 1 :Reductive amination of acids or esters (DMAA : dimethylalkylamine,

DAMA : dialkylmethylamine, DAA : dialkylamine, TAA : trialkylamine)

2. 3 - Catalytic fluorination
The Arkemc. fluorous derivatives come from the fabrication of fluorhydric acid
at the beginning of the XX century followed by the production of chlorofluorocarbons
(CFC) in the years 1940-50 (lla).Fol!owing the Montreal act in 1987, these compounds
were replaced by HCFC (hydrochlorofluorocarbon), these latter exhibiting a lower
impact on the ozone layer. Thanks to their physical properties and their low toxicity,
HCFC are now used as cooling fluids, expansion agents and solvents for house cleaning.
Various techniques and fluorous agents allow the introduction of fluor to organic
substrates among them the fluorination by HF in liquid phase or gas phase (llb,c).
Fluorinations in liquid phase are generally performed in the presence of homogeneous
catalysts such as HF-SbCI5.
In gas phase, a CI/F exchange can occur or addition of HF on an olefin in the
presence of a catalyst involving chromium oxides. For example, fluorination of CF3CHzCI
with HF in gas phase was successfully performed at 380C in the presence of a
chromium-alumina oxides first fluorinated (12). Active sites would be constituted here
of chromium atoms reversibly oxidable on the catalyst surface where it is necessary to
control the Lewis acidity (promoter addition) to allow the fluorination reaction to take
place instead of secondary Deacon or deshydrofluorination reactions (12).
Transposition of this fluorination route to the preparation of fluorinated organic
building blocks such as fluoroaromatics from chloroaromatics is now on the way (13) and
will open a new access to the fluor chemistry for many applications.

2. 4 - Selective hydrogenation over supported metal catalysts.

Selective hydrogenation of carbonylated compounds to unsaturated alcohols was
performed in the presence of chromite type (copper) catalysts. The reaction mechanism
including the nature of the active centres was described in various publications and
involves a hydride transfer (14, 15). The reaction conditions are quite severe since
temperature ranging from 200 to 300C and high pressure sometimes higher than 100
bar are required.

Precious metals offer great advantages compared to non precious metals thanks
to their higher activity allowing to perform the reaction at lower temperature and
pressure. These reaction conditions are milder and generally lead to higher selectivity
and consequently to a lower production of wastes.
Chemically modified Raney metals were also effective under mild conditions (low
temperature and pressure) with carbonylated derivatives (14,17) and in the case of the
hydrogenation of nitriles.

3 - Hydrogenation of a,J) unsaturated carbonyl compounds

Hydrogenation of citral to geraniol and nerol (Scheme 2) is one of the most

illustrating examples. Over Rh-Si0 2 catalyst (dispersion 80'/'o, 80 bar, 340K), the
reaction is not selective and leads to citronella! and then citronellol. However, if the
catalyst is modified with SnBu 4 in order to obtain a (Rh) 2 SnBu 2 catalyst, the selectivity
is increased to 95'/'o to geraniol and nerol (3,7-dimethyl-2,6-octadienol) without loss of
activity (18). In this particular case, the selectivity results from a perfect control of
the catalyst surface with the aim of obtaining quasi exclusively the desired catalytic
sites "single-site heterogeneous catalysts" which would result from a combination
between rhodium and tin (4).

~
X~
...

.CHO.

C itr.onellal

Citronellol

Scheme 2: selective hydrogenation of citra!

(+OM)
CH 3 (CH 2 hCH=CH(CH 2 )yCH 2 0H --~ CH 3(CH 2hCH=CH(CH 2) 7C0 2(CH 2) 8CH=CH(CH 2hCH 3
oleic alcohol

oleyl oleate

CH 3(CH 2hCH=CH(CH2)jCH20H

Scheme 3: Hydrogenolysis andt transesterification of unsaturated fatty esters.

4 - Hydrogenolysis of unsaturated fatty esters

Selective hydrogenolysis of unsaturated fatty methyl esters to unsaturated

alcohols requires, as mentioned above, a perfect control of the chemioselectivity. In the
case of fatty esters, such as methyl oleate (methyloctadec-9-enoate), it has been
shown that the selectivity to unsaturated alcohol (octadec-9-enol) was obtained in the
presence of supported bimetallic Ru/Co or Ru/Sn catalysts (yield

> 80'/'o).

However, this

result closely depends on the transesterification reaction between methyl oleate with
oleic alcohol which avoids the formation of the saturated ester (scheme 3) (19, 20).
The control of these reactions results from an appropriated distribution of
hydrogenating and basic sites on the solid surface. Different RuSnx centres would be
responsible of the selective hydrogenation whereas

SnOx would

favour

the

transesterification reactions or/and the cis/trans isomerization of the double

bond (20).

5 - Hydrogenolysis/hydrogenation of polyo!s

Main alcohols obtained from sugars hydrogenation are sorbitol produced from
glucose, mannitol from fructose or xylitol from xylose (21). The conversion of glucose is
total with a selectivity to sorbitol higher than 99% over Ru/C (22). The reaction of
glucitol in the presence of bimetallic catalysts involving copper clearly evidences the
selective formation of isosorbide with a bimetallic catalyst copper/ruthenium (22a, 23).
Under similar conditions, glycerol can be selectively hydrogenolysed to ethylene glycol
or 1,2-propandiol in the presence of Raney copper (24).
Catalytic hydrogenation of three aldonolactones (C6, C5 and C4), from industrial
origin, to the corresponding po!yo!s (sorbitol, arabitol, erythritol) was also carried out
over ruthenium catalysts (25).

6- Hydrogenation of dinitriles to diamines

Aliphatic primary diamines are important intermediates in the polymer industry.

For example, the tetramethylenediamine is a monomer for the production of polyamide
4,4

whereas

methy!pentamethylene

diamine

is

used

for

the

production

of

thermoplastics. Similarly, hexamethylene diamine is involved in two well known important

industrial productions: nylon 6,6 by copolymerization with adipic acid and isocyanates by
reaction with phosgene. Isocyanates are also important intermediates in the paint
industry.
The main route to obtain diamines is the hydrogenation of the corresponding
dinitriles, generally over Raney nickel catalysts (26a, b) or Ziegler (26b, c). However,

numerous secondary products can be formed, especially after the cyclisation step. From
the Rhone Poulenc work, it clearly appears that at a laboratory or industrial scale, Raney
cobalt or nickel catalysts are the most appropriated. Catalyst modifications by doping
with metals, addition of ammonia or mineral bases increase the activity and the
selectivity to primary amines allowing to reach the industrial norms (26c). Moreover,
these works allow to define the rules for the choice of catalysts, solvent, experimental
conditions, ...
By comparison with first works in this field, new families of catalysts highly
selective and constituted of metallic or bimetallic supported sites, Raney metals, were
discovered. Obviously, these catalysts find other applications in other selective
hydrogenations (27).

6.1 - Basic Catalysis: Selective esterification or/and etherification of alcohols

Basic catalysis found these last years numerous and important applications for
the selective transformation of renewables such as alcohols, sugars, saccharides, ...
Indeed it was evidenced that over such catalysts secondary reactions and by-products
were lowered. Moreover the more recent works done in the preparation of minerals or
hybrids mesoporous and basic catalysts opened a new field of investigation as
illustrated with the examples below:

6. 2 - Selective reactions from glycerol

In France as well as in Europe, North and south America, the increasing
production of biofuels (specially biodiesels) leads to a huge extra production of glycerol
which could reach 3 MT in the next years (28). It follows that the glycerol or glycerine
price recently drops which as a counterpart leads to an increase of biofuels price. For
that reasons it seems important to develop the glycerol chemistry and to improve the
known processes or/and to find new reactions and applications.
One of them is the setective transformation of glycerol to monoglycerides after
reaction with fatty acids or esters. Nevertheless, as glycerol has 3 hydroxyl groups
with similar pKa (- 14), new and highly selective routes must be found in order to avoid
usual protection and deprotection steps. Over mesoporous and basic catalysts it was
recently discovered that monoglycerides could be directly obtained from glycerol (29-

31) or glycidol (32) which represent one of the first examples of shape selectivity in
fine chemistry.
Other reactions are the direct and selective synthesis of polyglycerols or
polyglycerol esters. Indeed over similar catalysts a "diglycerol and triglycerol" mixture
was obtained from pure glycerol with 90% yield (29, 33). Moreover starting from a
mixture of glycerol and fatty methyl esters (C 12 to C18 ) diglycerol esters were
selectively formed (33).
In both cases stable and basic catalysts were obtained from the incorporation of
basic sites in the framework of mesoporous materials or by grafting of strong organic
bases over the surfaces of similar solids (34, 35).

7 - Selective synthesis of saccharose ethers

Over a catalyst such as PS-NOH which exhibits a lipophilic part (Polystyren/PS)

and hydrophilic/basic sites (ammonium hydroxide) sucrose is deprotonated so that in
the presence of epoxides sucroethers are selectively obtained (36, 37). The reaction
was also successfully used with other disaccharides such as trehalose and isomalt
(scheme 4).

6 OH
HO+f;o
2
HO 3
OH
0

OH

~/
oOH
OH

HO
sucrose
OH

OH

H~
::~

... ..
. OH . .
.... mixture of

..

OH

Scheme 4: selective etherification of saccharides

7 1 - Selective Oxidations

.c'

From controlled oxidation reactions, various fine chemical products can be

obtained. But, as for the above reactions, some new catalytic materials have to be found
from previous works done for gas phase hydrocarbons oxidation or from the liquid
phase oxidation of various compounds involving homogeneous catalysts. Some of the
recent or promising reactions are presented below:

7. 2 - Polyols oxidation
The selective oxidation of glycerol which exhibits primary and secondary alcohol
functions is a quite interesting example. From results obtained during the last decade it
appears that it is possible to selectively activate one of the alcohol functions when the
reaction is performed with air in water at a controlled pH over a supported metal (Pt,
Pd) and promoted (Bi) catalyst (38). The oxidation of the primary hydroxyl group into
glyceric acid is favoured over Pt or Pd at a basic pH while the secondary function is
rather oxidized into dihydroxyacetone over the same metals when promoted with
bismuth and in an acidic medium.
The glucose oxidation into gluconic acid or glucaric acid can be performed with
air in water in the presence of supported bimetallic (Pd-Bi) catalysts which lead to an
important reaction rate and selectivity (39, 40).
The oxidation of pentoses and hexoses into furfural or furan derivatives is also
an important reaction. One of these compounds (5- hydroxymethylfurfural) obtained
from the fructose dehydration (41) can be selectively oxidized into 2,5 furan dicarboxy
aldehyde over a Vz0 5 /Ti02 catalyst (42). Such compounds are of interest for the
preparation of diamines, Schiff bases and fungicides.

8 - Oxidation of aromatic compounds over immobilized phtalocyanines

For such reactions, hybrid catalysts were selected. Indeed organometallic

complexes grafted over well chosen supports are promising catalysts especially for
selective oxidations since it is often difficult to avoid consecutive oxidation of primary
products over more conventional catalysts. Less studied than porphyrins, complexes
known to mimic the active sites of enzymes (Cytochrome P450, peroxidases, ... ),
Metallophtalocyanines (MPc) were selected for selective oxidation while using a clean

oxidizing agent (hydrogen peroxide or oxygen). Heterogeneous catalysts were obtained

from a covalent grafting of some of the above complexes over silica (43). According to
the procedure it was possible to get monomers or dimers of these complexes on the
silica surface (Scheme 5) with different catalytic properties.

Scheme 5 : general representation of supported iron complexes {43)

As

an

example

the

selective oxidation

of

2,3,6-trimethylphenol

or

2-

methylnaphtalene into quinones is directly correlated to the structural organisation of

the catalytic sites (43b). 2-methylnaphtaquinone (vitamin K3) and trimethylquinone
(precursor of vitamin E) are obtained respectively with a selectivity of 45'Yo and 87'Yo
(43c).
This oxidation process is also useful for other aromatic compounds especially
substituted or polyfunctionalized phenols such as the bis-terbutylphenol or the
acetamidophenol with quinones yields reaching 93'Yo.

9 - Epoxidation of esters or terpenes

Sunflower or soya oils are epoxidized (scheme 6) with yields over 85'Yo in the
presence

of

phosphotunsgtic

species

alone

or

immobilized

i)over

silica

via

phosphoramides ligands or ii) over hydroxyapathite via phosphates species or included in

the interlamellar space of hydrotalcites (44b ,c and 45).

Scheme 6: epoxidation of polyunsaturated triesters.

Terpenes such as pinene or limonene (scheme 7) are selectively epoxidized with

hydrogen peroxide over catalysts containing methyltrioxorhenium (MTO/MeRe0 3 ). One
of the main products, campholenic aldehyde, is an important intermediate in the
manufacture of perfumes (46 ).

Scheme 7: epoxidation of terpenes

In order to get heterogeneous catalysts some "MTO-polyaminesNoxides" complexes

were prepared from polypyridine or polystyrenamine polymers.

9. 1 - Acid catalysis reactions

Zeolites were successfully used in petrochemistry and refining processes on
account of specific acidity and porosity and these properties can be also useful for fine
chemicals as reported hereafter.
The preparation of aromatic ketones which are important precursors in the
synthesis of perfumes, UV absorbents, anti-inflammatory such as paracetamol,
ibuprofen or naproxen (scheme 8) is often performed with acid chlorides as acylating
agents and A!Cb as acidic catalyst.
The replacement of AICI3 by an acidic, non corrosive and reusable solid catalyst
but also the replacement of anhydrides or acetic acid was also investigated. The
interest of zeolites for the industrial manufacture of aromatic ketones was clearly

pointed out in the works of Rhone-Poulenc (47). Two processes were proposed the first
one for the selective acetylation of

CH COCI- HCI
3
AlClj

OCH3

OCH3

(c)(c)(
~

r6lo(

-------

CHCOOH
I

COCH3

CH3

Naproxene

Scheme 8: Acylation of aromatic ketones.

anisole into paramethoxyacetophenone over a HBEA zeolite and the second one for the
conversion of veratrole to dimethoxy-3,4acetophenone over a HFAU zeolite.
Acylation of other aromatics (48) or heterocycles such as benzofuran (49) were also
investigated over different types of zeolites.
Nevertheless the applications of zeolites in fine chemistry are not so numerous
due to the narrow size of the pores (<1 nm) of that materials compared to the size of
many of the organic reagents or products. However, since the beginning of the nineties
the growing investigations in the preparation of mesoporous materials opened a new
field of investigation for getting new multifunctional catalysts with a pore size between
2 and 10 nm.

9. 2 - Enantioselective catalysis
Enantioselective catalysis are well known reactions since the natural chirality
plays a determining role in the human life. The numerous works performed in that area
opened a large field of investigation and some of the authors of that more important
works got the Nobel prize. Indeed the use of asymmetric catalysts for the synthesis of
optically active compounds 'is a very promising route even if using homogeneous
complexes with which it was easier to induce steric and electronic effects by
modification of the ligands of the complex. Such works opened new and huge markets
for pharmaceuticals and agrochemicais (50, 51). Moreover several reports of
asymmetric heterogeneous catalysis also appeared in the literature. In France, F.

Agbossou-Niedercorn (52) for homogeneous catalysis and M. Lemaire et al (53)

presented in recent reviews some of the main trends of the researches done in
asymmetric catalysis.
"One of the main drawbacks to the industrial development of asymmetric
catalysis could come from both the price and the toxicity of the organometallic
complexes used as catalysts or ligands (very high e-factor). Moreover if the
experiments about the heterogeneous catalysis were done very early as soon as the
discovery of asymmetric catalysis over transition metal complexes (Knowles and Kagan
(54)), the problems resulting of the complex solubility as well as that of the reduced
activity of the heterogeneous systems relative to the homogeneous ones was opened
and is still alive". That sentence from an article of M. Lemaire (53) is rather accurate to
describe the main breakthrough. Different strategies were suggested in order to get
enantioselective catalysts (55a); i) modification of metal particles with a chiral
compound, ii) grafting of a chiral complexe over the support, iii) preparation of a chiral
support, iv) modification of the reagent with a chiral ligand, ...
Besides the works of Bayston (51 p.210) and Noyori (64), M. Lemaire et all have
studied the asymmetric reduction of different compounds. From modified 6,6'-diamBINAP ligands alone or/and grafted over silica , the asymmetric hydrogenation of
ketones, ketoesters

was performed with a high turn over number (TON) and

significant enantiomeric excess (ee). They also reported the heterogeneization of a

bis(oxazoline) ligand by grafting over silica and its successful use in the Diels-Aider
reaction.
M. Besson et al also done an important piece of works about hydrogenation and
hydride transfer (55). Catalysts are obtained from the association of metal particles
for the hydrogen dissociation and complexes (bisoxazolines, diphosphines, ... ) acting as
chiral modifiers for the hydrogenation of acetophenone pJ3 unsaturated ketones or
others.
D. Brunei et al have investigated the anchorage enantiomeric-ephedrine on MCM41 type MTS materials which were tested in the reaction of benzaldehyde with

diethylzinc but a rather low (ee) was obtained even after surface modifications of the
mesoporous support (51, p.275).
Enzymes grafted over organic or inorganic supports was also recently studied for
getting new heterogeneous and enantioselective materials (51,p.97).

9. 3 - E/ectrocatalysis
The principles of electrocatalysis largely used for fuel cells can also have
interest in electrosynthesis. The significant improvement of the selectivity should come
from the finding of new catalytic electrodes and the choice of experimental conditions.
Some selected results presented below clearly illustrate those suggestions.

10 - Electrocatalytic reduction of carbonyl compounds

Pyruvic acid obtained from glucose fermentation was selectively transformed

into lactic acid or pinacol ( 2,3 dimethyltartaric acid) with a yield respectively of 80/'o
or 60/'o ( 56,57). The first reaction was done at a pH of 10 over Pb or Cu electrodes
while the second one occurred in acidic media mainly over a Pb electrode.

11 - Reactions in the presence of electrodes modified with a redox mediator

From the electrochemical activation of chemical mediators such as TEMPO

immobilized at the surface of a non catalytic material, it is possible to control the
chemic- and/or the region-selectivity of the carbohydrates oxidation (58). The
dehydrogenative activity of oxoammonium cations (active form of amminoxyle radicals)
leads to the selective oxidation of secondary hydroxyls groups in the presence of
primary ones. When immobilized at the surface of carbon electrodes these cations were
used for the activation of cyclodextrins. In fact the use of cyclodextrins for
vectorization is limited by their !ow solubility in water.
Nevertheless cyclodextrins have amphiphilic properties and a cavity in which
hydrophobic molecules can be included so that it is possible to get some "host-guest
complexes" soluble in water. In order to obtain the solubilization effect, cyclodextrins
must

be

chemically

modified

while

keeping

coordinative

properties.

Their

transformation into "percaboxylated" compounds with an improvement of their solvating