Biodiesel Fuels fromVegetable Oils: Transesterification

of Cynara carduncul us L. Oils with Ethanol

J. M. Enci nar,* J. F. Gonzal ez, J. J. Rodr guez, and A. Tejedor
Departamento deI ngeniera Qumica y Energetica, Universidad deExtremadura, Avda. de
Elvas s/ n, 06071 Badajoz, Spain
Received J uly 17, 2001. Revised Manuscript Received November 9, 2001
A study was made of the transesteri fi cati on reacti on of Cynara carduncul us L. oi l by means of
ethanol , usi ng sodi um hydroxi de and potassi um hydroxi de as catal ysts. The objecti ve of the work
was to characteri ze the ethyl esters for use as bi odi esel s i n compressi on i gni ti on motors. The
operati on vari abl es empl oyed were temperature (25-75 C), catal yst type (sodi um hydroxi de and
potassi um hydroxi de), catal yst concentrati on (0.25-1.5 wt %), and ethanol /oi l mol ar rati o (3:1-
15:1). Oi l mass (200 g), reacti on ti me (120 mi n), and al cohol type (ethanol ) were fi xed as common
parameters i n al l the experi ments. The evol uti on of the process was fol l owed by gas chromatog-
raphy, determi ni ng the concentrati on of the ethyl esters at di fferent reacti on ti mes. The bi odi esel
was characteri zed by determi ni ng i ts densi ty, vi scosi ty, hi gh heati ng val ue, cetane i ndex, cl oud
and pour poi nts, characteri sti cs of di sti l l ati on, and fl ash and combusti on poi nts accordi ng to I SO
norms. The bi odi esel wi th the best properti es was obtai ned usi ng an ethanol /oi l mol ar rati o of
12:1, sodi um hydroxi de as catal yst (1%) and 75 C temperature. Thi s bi odi esel has very si mi l ar
properti es to those of no. 2 di esel fuel .
Introduction
Di esel fuel s have an essenti al functi on i n the i ndus-
tri al economy of a country. They are used i n ci ty buses,
l ocomoti ves, el ectri c generators, etc. The di esel fuel
consumpti on of devel oped countri es has been i ncreasi ng
steadi l y over the l ast few decades and l ooks set to
conti nue i nto the future. An al ternati ve di esel fuel must
be techni cal l y feasi bl e, economi cal l y competi ti ve, envi -
ronmental l y acceptabl e, and readi l y avai l abl e.
1
Gi ven
these requi rements, tri gl yceri des (vegetabl e oi l s/ani mal
fats) and thei r deri vati ves may be consi dered as vi abl e
al ternati ves for di esel fuel .
2-5
Vegetabl e oi l s are wi del y
avai l abl e from a vari ety of sources, and they are
renewabl e. Al so, these fuel s are easi l y bi odegradabl e,
they have a practi cal l y nul l sul fur content, and thei r
transport and storage offer no probl ems. Moreover,
vegetabl e oi l s sequester more carbon di oxi de from the
atmosphere duri ng thei r producti on than they add to i t
when they are burned. Therefore, they hel p to al l evi ate
the i ncreasi ng carbon di oxi de content of the atmosphere.
Thei r mai n drawback i s pri ce, whi ch i s hi gher than
petrol eum-deri ved di esel s. I n consequence, thei r use
must be accompani ed by a pol i cy ori ented toward thei r
total tax exempti on.
The heati ng val ue of vegetabl e oi l s i s si mi l ar to that
of fossi l di esel , but thei r use i n di rect i njecti on di esel
engi nes i s l i mi ted by some of thei r physi cal properti es,
especi al l y thei r vi scosi ty. Vegetabl e oi l vi scosi ty i s 10
ti mes greater than that of di esel oi l , wi th consequent
poor fuel atomi zati on, i ncompl ete combusti on, carbon
deposi ti on on the i njectors, and fuel bui l d-up i n the
l ubri cant oi l s. Therefore the resul t can be seri ous engi ne
deteri orati on so that i t i s absol utel y necessary to subject
the vegetabl e oi l s to treatments that di mi ni sh thei r
vi scosi ty. There are four possi bl e treatments: di l uti on,
mi croemul si fi cati on, pyrol ysi s, and transesteri fi cati on,
1,3
among whi ch the l ast has doubtl ess been the most
commonl y empl oyed.
The transesteri fi cati on reacti on,
6
al so cal l ed al cohol y-
si s, i s the di spl acement of al cohol from an ester by
another al cohol i n a process si mi l ar to hydrol ysi s, except
than an al cohol i s used i nstead of water. The resul t i s
that tri gl yceri de mol ecul es (90-98% of the oi l ), whi ch
are l ong and branched, are transformed i nto smal l er
esters whose si ze and properti es are si mi l ar to those of
di esel oi l s.
7
The process al so forms gl yceri n as byprod-
uct. The overal l transesteri fi cati on reacti on can be
represented by
Transesteri fi cati on consi sts of a sequence of three
consecuti ve reversi bl e reacti ons. The fi rst step i s the
* To whom correspondence shoul d be addressed. Phone: 34 924
289672. Fax: 34 924 271304. E-mai l : jenci nar@unex.es.
(1) Sri vastava, A.; Prasad, R. RenewableSustainableEnergy Rev.
2000, 4, 111-133.
(2) Shay, E. G. Biomass Bioenergy 1993, 4, 227-242.
(3) Schwab, A. W.; Bagby, M. O.; Fri edman, B. Fuel 1987, 66, 1372-
1378.
(4) Freedman, B.; Butterfi el d, R. O.; Pryde, E. H. J . Am. Oil. Chem.
Soc. 1986, 63, 1375-1380.
(5) Freedman, B.; Pryde, E. H.; Mounts, T. L. J . Am. Oil. Chem.
Soc. 1984, 61, 1638-1643.
(6) Otera, J. Chem. Rev. 1993, 93, 1449-1470.
(7) Qui ck, G. R.; Woodmore, P. J.; Wi l son, B. T. Engi ne Eval uati ons
of Li nseed Oi l and Deri vati ves. I n VegetableOils Diesel Fuel: Seminar
I I I , ARM-NC-28; Bagby, M. O., Pryde, E. H., Eds.; U.S. Department
of Agri cul ture: Peori a, I L, 1983; p 138.
tri gl yceri de (TG) + 3ROH 98
catal yst
3RCO
2
R + gl yceri n (1)
443 Energy & Fuels 2002, 16, 443-450
10.1021/ef010174h CCC: $22.00 2002 Ameri can Chemi cal Soci ety
Publ i shed on Web 01/23/2002
conversi on of tri gl yceri des to di gl yceri des, fol l owed by
the conversi on of di gl yceri des to monogl yceri des, and
fi nal l y monogl yceri des i nto gl yceri n, yi el di ng one ester
mol ecul e from each gl yceri de at each step. Stoi chi omet-
ri cal l y, three mol es of al cohol are requi red per mol e of
tri gl yceri de, but i n practi ce a hi gher rati o i s empl oyed
i n order to di spl ace the equi l i bri um to greater ester
producti on. Al though the esters are the desi red products
of the reacti ons, gl yceri n recovery al so i s i mportant due
to i ts numerous appl i cati ons i n di fferent i ndustri al
processes. Vegetabl e oi l s al so contai n free fatty aci ds
(general l y 1-5%), phosphol i pi ds, phosphati des, car-
otenes, tocopherol s, sul fur compounds and traces of
water.
8
Consequentl y some of these components al so can
be present i n the fi nal products.
The al cohol s most frequentl y empl oyed are short-
chai n al cohol s, such as methanol , ethanol , propanol , and
butanol . These al cohol s present few di fferences wi th
respect to the ki neti cs and fi nal yi el d of esters. Freed-
man et al .,
5
usi ng methanol , ethanol , and butanol i n a
process of transesteri fi cati on of soybean oi l , obtai ned
yi el ds from 96 to 98%after an hour of reacti on. The use
of other types of oi l s modi fi ed the fi nal yi el d: they
obtai ned 93% of methyl ester usi ng cottonseed oi l and
98% usi ng soybean oi l . These yi el ds were i ndependent
of the type of al cohol . Therefore, the eventual sel ecti on
of one of these three al cohol s wi l l be based on cost and
performance consi derati ons. I n general , both methanol
and ethanol can be easi l y obtai ned from pl ant materi al s.
Because methanol i s al so cheaper, i t i s the most com-
monl y empl oyed al cohol . Neverthel ess, si nce ethanol , as
extracti on sol vent i s preferabl e to methanol because of
i ts much superi or di ssol vi ng power for oi l s, i t al so i s
often used as an appropri ate al cohol for the transes-
teri fi cati on of vegetabl e oi l s.
9
Produci ng ethyl esters
rather than methyl esters i s of consi derabl e i nterest
because i t al l ows producti on of an enti rel y agri cul tural
fuel , and the extra carbon atom brought by the ethanol
mol ecul e sl i ghtl y i ncreases the heat content and the
cetane number. Another i mportant advantage i n the use
of ethanol i s that the ethyl esters have cl oud and pour
poi nts that are l ower than the methyl esters. Thi s fact
i mproves the starts col d.
Al kal i ne al koxi des and hydroxi des are the most effec-
ti ve transesteri fi cati on catal ysts compared to the aci d
catal ysts. Transesteri fi cati on occurs at a faster rate i n
the presence of an al kal i ne catal yst than i n the presence
of the same amount of aci d catal yst.
10
Sodi um al koxi des
(sodi um methoxi de for exampl e), KOH, and NaOH are
the most effi ci ent catal ysts used for thi s purpose. They
requi re onl y short ti mes (30 mi n) to compl ete the
reacti on even at room temperature, whi l e aci d catal ysts,
such as sul furi c aci d, requi re hi gher temperatures (100
C) and l onger reacti on ti mes (3-4 h)
5,11,12
The commerci al devel opment of a transesteri fi cati on
process requi res abundant and i nexpensi ve raw mate-
ri al to be avai l abl e. One possi bi l i ty i s to use foodstuff
oi l s such as sunfl ower, soybean, etc., but these oi l s are
very expensi ve. Another i s to produce the oi l s (the
bi omass i n general ) di rectl y, i .e., to cul ti vate nonfood
crops for energy. Thi s l atter possi bi l i ty has been con-
si dered by the authori ti es of the European Uni on as a
sol uti on to the abandonment of tradi ti onal cropl ands.
One of the crops used to produce woody bi omass and
oi l i s the cardoon, Cynara carduncul us L. Thi s pl ant i s
bei ng studi ed experi mental l y i n Spai n i n order to
determi ne i ts opti mal growth condi ti ons. The cardoon
i s a thi stl e nati ve to the Medi terranean area. I t bel ongs
to the Asteraceae fami l y (Composi tae), whi ch al so
i ncl udes the arti choke, the sunfl ower, and the saffl ower.
I n the I beri an Peni nsul a i t i s wel l adapted to the cl i mate
and can be found growi ng wi l d. Total cul ti vated bi omass
producti on can reach 20-30 tons dry matter per ha per
year, i ncl udi ng 2000-3000 kg of seeds. I t i s used as
fodder, or as bi omass for energy producti on by combus-
ti on, pyrol ysi s, and gasi fi cati on. I ts seeds have a hi gh
protei n content, cl ose to 15%, and an oi l content of
around 25%. Thi s oi l i s si mi l ar i n composi ti on to
sunfl ower oi l ,
13
the four pri nci pal fatty aci ds bei ng
pal mi ti c (11-14%), steari c (3%), ol ei c (25%), and l i nol ei c
(56%). At thi s ti me, the cul ti vati on of Cynara i n Spai n
i s under devel opment i n several regi ons. The Spani sh
Government (Offi ci al Bul l eti n of the State 121 of May
20, 2000), and the Commi ssi on of Agri cul ture of the
European Uni on (Regul ati on CE 246/99, code NC
06029059), have authori zed the cul ti vati on of Cynara
i n substi tuti on of tradi ti onal cropl ands.
Wi th these consi derati ons, and as the conti nuati on
of previ ous work,
14
we carri ed out a study of the
transesteri fi cati on process of refi ned Cynara carduncu-
l us L. oi l usi ng ethanol , to characteri ze the ethyl esters
obtai ned wi th a vi ew to thei r use as bi odi esel for
compressi on i gni ti on engi nes.
Experimental Section
Materials. The Cynara carduncul us L. oi l was obtai ned i n
our l aboratory by mechani cal compressi on and then refi ned.
Anhydrous ethanol , sodi um hydroxi de, and potassi um hydrox-
i de were suppl i ed by Panreac. Ethyl esters of pal mi ti c, steari c,
ol ei c, l i nol ei c, l i nol eni c, and eruci c aci ds (empl oyed as stan-
dards i n the chromatographi c determi nati on) were suppl i ed
by Merck and Si gma. Al l reagents were of anal yti cal grade.
Transesterification. The reacti on of transesteri fi cati on
was carri ed out i n a 500 mL spheri cal reactor, provi ded wi th
thermostat, mechani cal sti rri ng, sampl i ng outl et, and conden-
sati on system. Thi s arragement i s basi cal l y the same as that
descri bed i n the l i terature.
15
The procedure fol l owed (modi fi ca-
ti on of that used i n previ ous work
14
) i s descri bed next. The
system was preheated to 75 C, to el i mi nate moi sture, and
then 200 g of Cynara carduncul us L. oi l was added. When the
system reached 75 C agai n, the ethanol and the catal yst were
added, i n the amounts establ i shed for each experi ment, and
the sti rri ng system was connected, taki ng thi s moment as ti me
zero of the reacti on. At evenl y spaced i nterval s, 2 cm
3
of sampl e
were wi thdrawn for l ater chromatographi c anal ysi s. Each
experi ment was prol onged for 120 mi n, by whi ch ti me the
(8) Marckl ey, K. S. Fatty Acids, 2nd ed.; I ntersci ence: New York,
1960.
(9) Lago, R. C. A.; Szpi z, R. P.; Jabl onka, F. H.; Perei ra, D. A.;
Hartman, L. Oleagineux 1985, 40, 147-152.
(10) Formo, M. W. J . Am. Oil. Chem. Soc. 1954, 31, 548-559.
(11) Nye, M. J.; Southwel l , P. H. Esters from Rapeseed Oi l as Di esel
Fuel . I n VegetableOils Diesel Fuel: Seminar I I I , ARM-NC-28; Bagby,
M. O., Pryde, E. H.; Eds.; U.S. Department of Agri cul ture: Peori a, I L,
1983; p 78.
(12) Harri ngton, K. J.; DArcy-Evans, C. I nd. Eng. Chem. Prod. Res.
Dev. 1985, 24, 314-318.
(13) Benjel l oun-Ml ayah, B.; Lopez, S.; Del mas, M. I nd. Crops Prod.
1997, 6, 233-236.
(14) Enci nar, J. M.; Gonzal ez, J. F.; Sabi o, E.; Rami ro, M. J. I nd.
Eng. Chem. Res. 1999, 38, 2927-2931.
(15) Ma, F.; Cl ements, L. D.; Hanna, M. A. I nd. Eng. Chem. Res.
1998, 37, 3768-3771.
444 Energy & Fuels, Vol. 16, No. 2, 2002 Encinar et al.
conversi on to esters was compl ete. After cool i ng, 25% of
gl yceri n based on the wei ght of oi l was added, whi ch resul ted
i n the formati on of an upper phase consi sti ng of ethyl esters
and a l ower phase contai ni ng the l i berated and added gl yceri n,
the excess of ethanol , the unreacted sodi um, or potassi um
hydroxi de together wi th the soaps formed duri ng the reacti on
and some entrai ned ethyl esters and parti al gl yceri des. After
separati ng the two l ayers by sedi mentati on, the ethyl esters
were puri fi ed by di sti l l i ng the resi dual ethanol at 80 C. The
remai ni ng catal yst was extracted by successi ve ri nses wi th
di sti l l ed water. Fi nal l y, the water present was el i mi nated wi th
CaCl 2 fol l owed by fi l trati on. The l ower phase was aci di fi ed wi th
a cal cul ated amount of sul furi c aci d, to neutral i ze any unre-
acted sodi um or potassi um hydroxi de and to decompose the
soaps formed duri ng the transesteri fi cati on. The resul ti ng
mi xture was subjected to a di sti l l ati on at 80 C under a
moderate vacuum (absol ute pressure of 150 mmHg) to recover
the excess of ethanol . Thi s faci l i tated the separati on of gl yceri n
from entrai ned ethyl esters and fatty aci ds deri ved from soaps.
Analysis. The European Organi zati on for Normal i zati on
(CEN) speci fi es the cri teri a that shoul d be sati sfi ed by a
bi odi esel of hi gh qual i ty, or di esel and bi odi esel mi xtures, for
use i n motor vehi cl es.
16
The anal yti cal methods used i n thi s
work to determi ne the characteri sti cs of the bi odi esel are
basi cal l y those recommended by the ci ted organi zati on. The
ethyl ester content was assayed by gas chromatography i n an
HP 5890 chromatograph equi pped wi th a FI D, empl oyi ng a
si l i ca capi l l ary col umn of 50 m l ength and 0.22 mm i .d.
(phase: BPx70). Hexane was used as sol vent and the carri er
gas was ni trogen. Ethyl esters of pal mi ti c, steari c, ol ei c,
l i nol ei c, l i nol eni c, and eruci c aci ds were anal yzed by thi s
procedure. The fol l owi ng parameters were determi ned i n the
fi nal bi odi esel product: densi ty (pycnometry), vi scosi ty (Brook-
fi el d di gi tal vi scosi meter), hi gh heati ng val ue (Parr-1351 bomb
cal ori meter, I SO 1928 norm), cetane i ndex (ASTM D 976
norm), cl oud poi nt (I SO 3015 norm), pour poi nt (I SO 3016
norm), Ramsbottom carbon resi due (I SO 4262 norm), di sti l -
l ati on characteri sti cs (I SO 3405 norm), and fl ash and combus-
ti on poi nts (ASTM D-92 norm).
Results and Discussion
The operati ng vari abl es empl oyed were temperature
(25-75 C), catal yst type (sodi um hydroxi de and potas-
si um hydroxi de), catal yst concentrati on (0.25-1.5 wt %
referred to the total mi xture, i .e., oi l and ethanol ), and
ethanol /oi l mol ar rati o (3:1 to 15:1). Oi l mass (200 g),
reacti on ti me (120 mi n), and al cohol type (ethanol ) were
fi xed as common parameters i n al l the experi ments.
Influenceof Temperature. Al kal i ne al cohol ysi s of
vegetabl e oi l s i s normal l y performed near the boi l i ng
poi nt of the al cohol . Neverthel ess, the reacti on may be
carri ed out at room temperature.
1,5
We studi ed the
ethanol ysi s of the refi ned Cynara carduncul us oi l s at
25, 50, and 75 C i n order to determi ne the effect of
reacti on temperature on the ethyl ester formati on. I n
al l experi ments, an ethanol /oi l mol ar rati o of 9:1 and
1% NaOH (as catal yst) were used. Fi gure 1 shows the
temporal evol uti on of the resul ts. After 2 mi n, the esters
present i n the 75, 50, and 25 C runs were 79, 76.5, and
75.5%, respecti vel y, showi ng the i nfl uence of tempera-
ture on ester conversi on. However, after 2 h, ester
formati on was basi cal l y i denti cal for the three runs
(93.1, 92.5, and 91.6%, respecti vel y). Ki neti cal l y, the
reacti on was very fast. As can be observed i n Fi gures
1, the fi nal ethyl ester concentrati on was al most reached
i n 10 mi n and the curves have an asymptoti c tendency
wi th ti me.
Fi gure 2 show the evol uti on of the si x mai n ethyl
esters over the course of the reacti on i n an experi ment
carri ed out at 75 C. The mai n ethyl ester i s the l i nol eate
wi th a percentage of 55%. Ol eate (25%), pal mi tate (10%),
and stearate (5%) fol l ow i n i mportance. Fi nal l y, the
ethyl esters correspondi ng to the l i nol eni c and eruci c
aci ds are present at percentages l ess than to 1%. Thi s (16) Mordret, F. Ol., Corps Gras, Lipides 1994, 1, 23-24.
Figure1. Ester concentrati ons vs ti me. I nfl uence of temper-
ature ([NaOH] ) 1%, ethanol /oi l ) 9:1).
Figure 2. Evol uti on of ethyl ester concentrati ons wi th ti me
(T ) 75 C, [NaOH] ) 1%, ethanol /oi l ) 9:1).
Biodiesel Fuels fromVegetableOils Energy & Fuels, Vol. 16, No. 2, 2002 445
composi ti on i s very si mi l ar to that of soybean oi l ,
17,18
wi th the excepti on of the l i nol enate whose percentage
i n that oi l i s 8%. On the other hand, rapeseed oi l
19
has
a very di fferent composi ti on, wi th the ol eate (60%) bei ng
the mai n ester. I t appears that the reacti on i s very rapi d
because the ethyl ester conversi on i s near the maxi mum
val ue after onl y 5-10 mi n, and stabi l i zes at the maxi -
mum val ue after 20-30 mi n. These resul ts agree wi th
those obtai ned by Fi l l i e`res et al .
19
Those authors
i ndi cate that at equi l i bri um there are di - and monogl y-
ceri des wi th concentrati ons of 2 and 4%, respecti vel y.
Thi s equi l i bri um can be sl i ghtl y di spl aced i f the gl yceri n
l ayer i s wi thdrawn from the reacti on medi um after 10-
15 mi n and new ethanol and catal yst are added.
After the i ni ti al peri od where the reacti on was very
fast, there was a second peri od, much l onger than the
fi rst, i n whi ch the composi ti on evol ved sl owl y toward
equi l i bri um. I n consequence, as was i ndi cated above,
thi s shows that the transesteri fi cati on may take pl ace
sati sfactori l y at room temperature, i n agreement wi th
resul ts descri bed by other authors.
1,5
Tabl e 1 l i sts the resul ts for the i nfl uence of temper-
ature on the most representati ve parameters of the
process. As was to be expected, si nce the yi el ds i n the
three experi ments were very si mi l ar, the di fferences
between the val ues of the parameters were not very
si gni fi cant. There was a sharp fal l i n vi scosi ty and an
i ncrease i n yi el d as the temperature nose, whi l e the
other vari abl es basi cal l y remai ned constant. Therefore
we may state that the temperature i s l i nked to reacti on
ti me and that the fi nal properti es of the product
depended on the degree of conversi on, i .e., on the ti me
requi red to obtai n a gi ven percentage of ester rather
than on the temperature at whi ch thi s percentage was
obtai ned. Hence, the same yi el d may be obtai ned at
room temperature as at hi gher temperatures by si mpl y
extendi ng the reacti on ti me. I ndustri al l y, thi s coul d
mean energy savi ngs and l ower process costs.
Influence of Catalyst Type and Concentration.
As was noted above, al kal i ne metal al koxi des and
hydroxi des are the most effecti ve transesteri fi cati on
catal ysts, al though for economi c reasons sodi um hy-
droxi de i s more often used.
5
An al kal i ne catal yst con-
centrati on i n the range of 0.5-1 wt % yi el ds 94-99%
conversi on of vegetabl e oi l i nto esters.
20
Further i n-
crease i n catal yst concentrati on does not i ncrease the
conversi on and l eads to extra costs because i t i s neces-
sary to remove i t from the reacti on medi um at the end.
As has been i ndi cated, aci d catal ysts, such as sul furi c
aci d, requi re hi gher temperatures and l onger reacti on
ti mes. There i s one cl ear advantage i n usi ng an aci d
catal yst i nstead of an al kal i ne catal yst: i f the vegetabl e
oi l had a free fatty aci d content of >1%, the al kal i ne
catal yst woul d be destroyed, whereas the aci d catal yst
woul d sti l l be effecti ve. Neverthel ess, for refi ned oi l such
as that empl oyed i n thi s work, wi th free fatty aci d
contents of <1%, al kal i ne catal ysts are preferred for the
i ndi cated reasons. Moreover i n the l i terature there are
exampl es of uses of other catal ysts such as p-tol uene
sul foni c aci d,
21
heterogeneous catal ysts consi sti ng of
mi xtures of CaO, MgO, and ZnO,
22
and natural catal ysts
such as coconut ash or pal m ash.
23
I n a previ ous work,
14
where sodi um hydroxi de, potas-
si um hydroxi de, and sodi um methoxi de were compared,
i t was demonstrated that the resul ts obtai ned wi th
these three catal ysts were basi cal l y the same. I n the
present work, on account of the economi c arguments,
onl y two catal ysts were tested: sodi um and potassi um
hydroxi des, varyi ng thei r concentrati on i n the range
between 0.25 and 1.5 wt %. Al so, an experi ment wi thout
catal yst was carri ed out, al though i n thi s case the ester
conversi on was 0% after 120 mi n so that the properti es
of the fi nal oi l were the same as those of the i ni ti al oi l .
I n Fi gure 3, the percentages of esters obtai ned are
pl otted versus reacti on ti me for the experi ments i n
whi ch the concentrati on of sodi um hydroxi de was
vari ed. As can be observed, the best resul ts were
achi eved for a concentrati on of 1.0%. For hi gher val ues
the yi el ds were l ower. Thi s fact seems to be rel ated to
the free aci di ty of the oi l . When there i s a l arge free
fatty aci d content, the addi ti on of more sodi um hydrox-
i de, or any other al kal i ne catal yst, compensates thi s
aci di ty and avoi ds catal yst deacti vati on.
4,5
Neverthel ess,
for refi ned oi l wi th free fatty aci d contents of <1%, the
addi ti on of an excessi ve amount of al kal i ne catal yst
gi ves ri se to the formati on of an emul si on, whi ch
i ncreases the vi scosi ty and l eads to the formati on of gel s.
These hi nder the gl yceri n separati on, and as a resul t
there i s a di l uti on of the ethyl esters, and the apparent
ester yi el d di mi ni shes. The resul t of these two opposi ng
effects i s an opti mal catal yst concentrati on that i n thi s
(17) Chang, D. Y. Z.; Van Gerpen, J. H.; Lee, I .; Johnson, L. A.;
Hammond, E. G.; Marl ey, S. J. J . Am. Oil. Chem. Soc. 1996, 73, 1549-
1555.
(18) Cl ark, S. J.; Wagner, L.; Schrock, M. D.; Pi ennaar, P. G. J . Am.
Oil. Chem. Soc. 1984, 61, 1632-1638.
(19) Fi l l i eres, R.; Benjel l oun-Ml ayeh, B.; Del mas, M. J . Am. Oil.
Chem. Soc. 1995, 72, 427-432.
(20) Kri snamgkura, K.; Si mamaharnnop, R. J . Am. Oil Chem. Soc.
1992, 69, 166-169.
(21) Ful s, J.; Hugo, F. J. C. Third I nternational Confernceof Energy
UseManagement, Berl i n, 1981; Pergamon Press: El msford, NY, 1981;
p 1595.
(22) Peterson, G. R.; Scarrah, W. P. J . Am. Oil Chem. Soc. 1984,
61, 1593-1597.
(23) Grai l l e, J.; Lozano, P.; Pi och, D.; Geneste, P. Oleagineux1985,
40, 271-276
Table 1. Influence of Temperature on Characteristic
Parameters of the Process ([NaOH] ) 1%,
Ethanol/Oil ) 9:1)
temperature, C
parameter 25 50 75
densi ty (25 C), kg m
-3
870 870 870
vi scosi ty, cSt
15 C 8.61 8.48 8.30
20 C 7.47 7.04 7.35
25 C 6.89 6.32 5.77
30 C 6.32 5.60 4.57
40 C 4.59 4.17 3.43
HHV, MJ kg
-1
39.9 40.0 40.0
cl oud poi nt, C -3 -4 -3
pour poi nt, C -7 -7 -6
Fl ash poi nt, C 185 185 188
combusti on poi nt, C 196 190 194
yi el d of esters, % 91.6 92.5 93.2
cetane i ndex 49.2 49.2 49.1
di sti l l ati on, C
0% 295 285 295
10% 345 310 346
20% 348 348 350
30% 349 351 352
40% 350 353 353
50% 351 355 354
Ramsbottom resi due, % 0.32 0.33 0.29
sul fur (% mass) <0.01 <0.01 <0.01
446 Energy & Fuels, Vol. 16, No. 2, 2002 Encinar et al.
case i s 1.0% of NaOH. One way or another, the mi ni -
mum concentrati on of catal yst requi red i s hard to
eval uate because a compromi se must be made between
durati on of reacti on and catal yst concentrati on. I ndeed,
the curves of Fi gure 3 suggest that at very l ong reacti on
ti mes the same equi l i bri um conversi on woul d be reached
i n al l runs. However, the ti me of reacti on woul d i ncrease
when the catal yst concentrati on decreases. These re-
sul ts were qual i tati vel y si mi l ar to those obtai ned i n the
ethanol ysi s of rapeseed oi l .
19
Tabl e 2 l i sts the resul ts for the i nfl uence of NaOH
concentrati on on the most representati ve parameters
of the process. Basi cal l y, i t can be observed that as the
catal yst concentrati on i ncreased there was a bi g reduc-
ti on i n both vi scosi ty and cl oud poi nt. There al so was a
reducti on, al though to a l esser extent, i n densi ty. The
mi ni mum for these three parameters occurred for a
concentrati on of 1.0% NaOH. Al so, the maxi mum yi el d
i n ethyl esters occurred for a concentrati on of 1%NaOH.
The pour, fl ash, and combusti on poi nts, cetane i ndex,
hi gh heati ng val ue, and Ramsbottom resi due di d not
vary si gni fi cantl y. On the other hand, the val ues of the
previ ous parameters were very si gni fi cant i n the run
performed wi thout catal yst (0%of NaOH). Among these
parameters, the vi scosi ty had val ues 10 ti mes hi gher
that i n the other experi ments. I n summary, i n the case
of sodi um hydroxi de the best concentrati on was 1.0%.
The trends found when varyi ng the concentrati on of
KOH from 0% to 1.5 wt % were basi cal l y the same as
those found for sodi um hydroxi de. The opti mal concen-
trati on for thi s catal yst al so was 1%. Fi gure 4 shows
the temporal evol uti on of the resul ts. Qual i tati vel y thi s
evol uti on was very si mi l ar to that commented on for
Fi gure 3. Neverthel ess, on thi s occasi on, the yi el ds
reached for the concentrati ons of 0.25 and 0.5% of
catal yst were very l ow. The other parameters evol ved
i n a si mi l ar way to that i ndi cated i n Tabl e 2 for the case
of NaOH.
Tabl e 3 l i sts the bi odi esel parameters obtai ned wi th
the opti mal concentrati on of the two catal ysts, i ncl udi ng
for compari son the characteri sti cs of a typi cal di esel (no.
2 di esel ) accordi ng to Schwab et al .s data
3
and a
bi odi esel obtai ned by means of transesteri fi cati on of
Cynara oi l wi th methanol .
14
As can be observed, there
was a good approxi mati on of the di fferent bi odi esel s to
the characteri sti cs of no. 2 di esel . The greatest di ffer-
ences were i n the cl oud and pour poi nts, fl ash, and
Figure3. Ester concentrati ons vs ti me. I nfl uence of [NaOH]
(T ) 75 C, ethanol /oi l ) 9:1).
Table 2. Influence of NaOH Concentration on
Characteristic Parameters of the Process (T ) 75 C,
Ethanol/Oil ) 9:1)
% NaOH by wei ght
parameter 0 0.25 0.50 0.75 1.0 1.5
densi ty (25 C), kg m
-3
917 890 880 870 870 877
vi scosi ty, cSt
15 C 115 14.72 10.29 8.58 8.30 8.48
20 C 95 12.85 9.71 8.00 7.35 7.75
25 C 85 11.30 9.00 7.43 5.77 6.78
30 C 74.9 9.60 7.88 6.86 4.57 5.72
40 C 57 7.83 6.14 5.00 3.43 4.51
HHV, MJ.kg
-1
33.0 39.2 39.7 39.8 40 39.7
cl oud poi nt, C -7 2 0 -1 -3 -2
pour poi nt, C -10 -6 -7 -8 -6 -7
fl ash poi nt, C 350 186 187 192 188 190
combusti on poi nt, C 355 191 192 197 194 196
yi el d of esters, % 0 77.5 84.5 85 93.2 88.9
cetane i ndex 51 49.3 49.2 49.4 49.1 49.2
di sti l l ati on, C
0% 245 298 300 304 295 301
10% 269 346 348 349 346 347
20% 276 349 350 353 350 351
30% 280 350 351 354 352 353
40% 283 351 352 355 353 354
50% 285 352 353 355 354 354
Ramsbottom resi due, % 0.42 0.32 0.32 0.30 0.29 0.31
sul fur (% mass) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
Figure 4. Ester concentrati ons vs ti me. I nfl uence of [KOH]
(T ) 75 C, ethanol /oi l ) 9:1).
Biodiesel Fuels fromVegetableOils Energy & Fuels, Vol. 16, No. 2, 2002 447
combusti on poi nts, the vi scosi ty, and Ramsbottom resi -
due whi ch were al l l ower than no. 2 di esel . On the
contrary, the cetane i ndex was hi gher i n the bi odi esel s.
Thi s parameter guarantees that there wi l l be good
control of combusti on, i ncreasi ng performance and
i mprovi ng col d starts, whi ch wi l l l ead to l ess contami -
nanti ng exhaust gases.
24
I n the producti on of di esel
fuel s, the cetane number i s an i mportant i ndi cator of
the qual i ty of the product and i s usual l y measured by
usi ng a standard engi ne test (ASTM D613). However,
i t i s rel ati vel y di ffi cul t to measure and has rarel y been
determi ned for vegetabl e oi l s and fatty aci d esters. I n
thi s present work, the ASTM Standard D976 was
appl i ed, usi ng boi l i ng poi nt and densi ty for the cal cul a-
ti on of the cetane i ndex. Thi s method i s very wel l sui ted
to the routi ne testi ng of smal l vol umes or when rapi d
i ndi cati ons are requi red of the qual i ty of a di esel fuel ,
and yi el ds si mi l ar resul ts to those obtai ned usi ng more
sophi sti cated methods.
25,26
The energy content of the
esters, based on thei r heati ng val ue, was around 90%
of no. 2 di esel taki ng the mass as reference, and 95%
taki ng the vol ume as reference. Thi s not very si gni fi cant
di fference was because the esters contai ned 10 wt % of
oxygen that coul d be used i n the combusti on process,
di mi ni shi ng the external ai r requi rements. Compari son
of the two ethyl esters wi th the methyl ester shows that
al l three had very si mi l ar characteri sti cs. Onl y sl i ght
di fferences were observed i n the fl ash and combusti on
poi nts, whi ch were l ower i n the methyl ester, and i n
the pour poi nt, whi ch was hi gher i n the methyl ester.
These characteri sti cs represent advantages of ethyl
esters over methyl esters si nce they i mprove col d starts
and safety i n handl i ng.
Tabl e 4 l i sts the properti es of sunfl ower, rape, ground-
nut, and soybean ethyl esters
3,9,24
together wi th the
resul ts obtai ned i n thi s work empl oyi ng 1% of sodi um
hydroxi de as catal yst. As can be seen, the resul ts are
very homogeneous, and the compari son wi th those of
no. 2 di esel oi l (Tabl e 3) makes i t cl ear that any of these
ethyl esters mi ght be used as an al ternati ve to fossi l
fuel s. Some characteri sti cs, such as the hi gh fl ash poi nt
and the l ow sul fur content, are better than no. 2 di esel
oi l from the vi ewpoi nt of handl i ng safety and the
emi ssi on of contami nant gases duri ng combusti on.
Moreover, due to thei r pl ant ori gi n, these fuel s woul d
contri bute to mai ntai ni ng atmospheri c CO
2
equi l i bri um.
Influence of Ethanol/Oil Molar Ratio. Another
i mportant vari abl e affecti ng the yi el d of ester i s the
mol ar rati o of al cohol to vegetabl e oi l . As noted above,
the reacti on stoi chi ometry requi res three mol es of
al cohol per mol e of tri gl yceri de to yi el d three mol es of
fatty esters and one mol e of gl yceri n. Because thi s i s
an equi l i bri um reacti on, an excess of al cohol wi l l
i ncrease the ester conversi on by shi fti ng thi s equi l i bri -
um to the ri ght. However, the hi gher mol ar rati o of
al cohol to vegetabl e oi l i nterferes wi th the separati on
of gl yceri n because there i s an i ncrease i n sol ubi l i ty. The
excess of al cohol seems to favor conversi on of di -to
monogl yceri des, but there i s al so a sl i ght recombi nati on
of esters and gl yceri n to monogl yceri des because thei r
concentrati on keeps i ncreasi ng duri ng the course of the
reacti on, i n contrast to reacti ons conducted wi th l ow
mol ar rati os.
19
Kri snangkura and Si mamaharnnop
20
al so observed that when gl yceri n remai ned i n sol uti on
i t hel ped dri ve the equi l i bri um back to the l eft, l oweri ng
the yi el d of esters. I n the present work, we used mol ar
(24) Reed, T. B.; Graboski , M. S.; Gaur, S. Biomass Bioenergy, 1992,
3, 111-115.
(25) OConnor, C. T.; Forrester, R. D.; Scurrel l , M. S. Fuel 1992,
71, 1323-1327.
(26) Kri snangkura, K. J . Am. Oil. Chem. Soc. 1986, 63, 552-553.
Table 3. Influence of Catalyst Type on Characteristic Parameters of the Process: Comparison with a No. 2 Diesel and
Methyl Esters of Cynara Oil
parameter
ethyl esters of
Cynara oi l [NaOH])1%
ethyl esters
of Cynara oi l [KOH])1%
methyl esters
of Cynara oi l
a
no. 2 di esel
densi ty (25 C), kg m
-3
870 870 880 847
vi scosi ty (40 C), cSt 3.43 4.59 3.56 2.39
HHV, MJ kg
-1
40.0 40.0 39.8 45.2
cl oud poi nt, C -3 -2 -1 -19
pour poi nt, C -6 -8 -3 -23
fl ash poi nt, C 188 185 175 85
combusti on poi nt, C 194 193 179 92
yi el d of esters, % 93.2 90.4 94
cetane i ndex 49.1 48.3 48.6 46
di sti l l ati on, C
0% 295 308 315 258
20% 350 350 345
40% 353 353 348
50% 354 355 350
Ramsbottom resi due, % 0.29 0.28 0.26 0.14
sul fur (% mass) <0.01 <0.01 <0.01 0.25
a
Catal yst: sodi um methoxi de; concentrati on of catal yst ) 1 wt %; methanol /Cynara oi l ) 5:1.
Table 4. Comparison of Ethyl Esters of Cynara,
Sunflower, Rape, Groundnut, and Soybean Oils
parameter Cynara
sun-
fl ower rape
ground-
nut
soy-
bean
densi ty (25 C), kg m
-3
870 873 902 906 881
vi scosi ty, cSt
20 C 7.35 6.97
21 C 6.60
38 C 14.1 17.0
40 C 3.43 4.55 4.41
HHV, MJ kg
-1
40.0 38.9 38.7 38.3 40.0
cl oud poi nt, C -3 -1 8 23 1
pour poi nt, C -6 -8 -4
fl ash poi nt, C 188 187 191 195
combusti on poi nt, C 194 192
cetane i ndex 49.1 49.4 48.2
di sti l l ati on, C
40% 353 352 336
50% 354 353 344
60%
90%
Ramsbottom resi due, % 0.27 0.30 0.69
sul fur (% mass) <0.01 <0.01 0.1
448 Energy & Fuels, Vol. 16, No. 2, 2002 Encinar et al.
rati os of ethanol to Cynara oi l between 3:1 and 15:1.
Fi gure 5 shows the ester percentages obtai ned versus
the reacti on ti me for the fi ve experi ments carri ed out.
As can be observed, wi th a stoi chi ometri c amount of
al cohol , the conversi on to esters was near 62%after 2h.
Under these condi ti ons, the separati on of the gl yceri n
l ayer was fast, compared to reacti ons conducted wi th a
l arge excess of ethanol where the separati on takes ti me,
i s not compl ete, and i ncreases the cost of al cohol
recovery. The ester yi el ds i ncreased as the mol ar rati o
i ncreased up to a val ue of 12:1. The best resul ts were
for mol ar rati os between 9:1 and 12:1. For mol ar rati os
l ess than 6:1, the reacti on was i ncompl ete. For a mol ar
rati o of 15:1 the separati on of gl yceri n i s di ffi cul t and
the apparent yi el d of esters decreases because part of
the gl yceri n remai ns i n the bi odi esel phase. Conse-
quentl y, mol ar rati os hi gher that 9:1 do not i ncrease the
ester yi el ds consi derabl y. Therefore, i t does not seem
recommendabl e-to-use rati os of 12:1 si nce the extra
consumpti on of al cohol i s not compensated by the
i ncrease i n reacti on yi el d. Moreover, an i ncrease i n
al cohol compl i cates recovery of the gl yceri n, si nce thi s
i s parti al l y sol ubl e i n ethanol . Al so, the separati on of
the esters and the recovery of the al cohol woul d be more
expensi ve. Therefore, the mol ar rati o 9:1 seems to be
the most appropri ate.
As has been i ndi cated, the reacti on i s very fast. Val ues
near the fi nal conversi on were reached i n the fi rst 10
mi n. As i s seen i n Fi gure 5, further di spl acement of the
equi l i bri um toward the formati on of esters became very
sl ow, so that, even when there was an excess of al cohol ,
thi s di d not i mprove the equi l i bri um conversi on sub-
stanti al l y. One way of i mprovi ng the process woul d be
to wi thdraw the gl yceri n from the reacti on medi um as
soon as i t i s formed, and to carry out successi ve
transesteri fi cati ons unti l reachi ng compl ete conversi on
to ethyl esters. Thi s mul ti stage transesteri fi cati on
process woul d al l ow one to work wi th smal l er ethanol /
oi l mol ar rati os.
Tabl e 5 l i sts the resul ts for the i nfl uence of the
ethanol /oi l mol ar rati o on some of the most character-
i sti c parameters of the process. As can be observed, the
l owest vi scosi ty val ues were obtai ned for an ethanol /oi l
mol ar rati o between 9:1 and 12:1. Wi th regard to the
cl oud and pour poi nts, the l atter remai ned al most
constant whi l e the former markedl y i mproved as the
ethanol /oi l mol ar rati o i ncreased. However, the hi gh
heati ng val ues, and fl ash and combusti on poi nts were
basi cal l y i ndependent of the mol ar rati o. Therefore, the
behavi or of these parameters al so seems to rati fy that
the mol ar rati o 9:1 i s the most appropri ate for the
transesteri fi cati on of cardoon oi l .
Final Considerations. I n thi s work, the vari abl es
affecti ng the ethanol ysi s of Cynara carduncul us L. oi l
were studi ed. The study was carri ed out under l abora-
tory-scal e condi ti ons. Consequentl y, i t i s hard to choose
the opti mum operati on process condi ti ons. An ethanol /
oi l mol ar rati o 9:1 or 12:1, 1% of NaOH, and 75 C gave
the best resul ts. Neverthel ess, these condi ti ons are not
necessari l y the same for l arger-scal e operati ons, and
economi c compromi ses must be made i n choosi ng the
parameters for operati on.
A very i mportant vari abl e i n the transesteri fi cati on
processes i s the ethanol /oi l mol ar rati o. Thi s mol ar rati o
affects the separati on and recovery of the gl yceri n. A
mol ar rati o of 6:1 i s general l y consi dered the most
appropri ate, al though i n thi s present work, as has been
i ndi cated, we found a mol ar rati o between 9:1 and 12:1
to be the best. Neverthel ess, the resul ts are quanti ta-
ti vel y very si mi l ar to those of the l i terature.
19
For
exampl e, i n the ethanol ysi s of rapeseed oi l , yi el ds
between 91 and 94% are obtai ned for ethanol /oi l mol ar
rati o between 12:1 and 6:1. We have obtai ned yi el ds
between 88.2 and 94.5 for mol ar rati os between 6:1 and
12:1. The ethanol /oi l mol ar rati o al so affects the di stri -
buti on of the catal yst between the ester l ayer and
Figure5. Ester concentrati ons vs ti me. I nfl uence of ethanol /
oi l mol ar rati o (T ) 75 C, [NaOH] ) 1%).
Table 5. Influence of Ethanol/Oil Molar Ratio on
Characteristic Parameters of the Process (T ) 75 C,
[NaOH] ) 1%)
ethanol /oi l mol ar rati o
parameter 3:1 6:1 9:1 12:1 15:1
densi ty (25 C), kg.m
-3
893 870 870 870 872
vi scosi ty, cSt
15 C 15.35 11.44 8.30 8.01 9.65
20 C 13.91 10.30 7.35 7.01 8.50
25 C 11.25 8.58 5.77 6.29 7.10
30 C 10.32 7.44 4.57 5.15 6.30
40 C 8.43 5.72 3.43 4.58 4.69
HHV, MJ kg
-1
39.6 39.8 40 39.9 39.8
cl oud poi nt, C 1 -1 -3 -3 -3
pour poi nt, C -7 -9 -6 -7 -6
fl ash poi nt, C 195 184 188 190 187
combusti on poi nt, C 199 191 194 197 193
yi el d of esters, % 62.1 88.2 93.2 94.5 89.8
cetane i ndex 49.2 49.0 49.1 48.4 49.0
di sti l l ati on, C
0% 283 301 295 297 300
10% 325 347 346 344 345
20% 327 351 350 348 349
30% 328 353 352 351 352
40% 332 354 353 354 354
50% 334 355 354 354 355
Ramsbottom resi due, % 0.32 0.30 0.29 0.31 0.31
sul fur (% mass) <0.01 <0.01 <0.01 <0.01 <0.01
Biodiesel Fuels fromVegetableOils Energy & Fuels, Vol. 16, No. 2, 2002 449
gl yceri n l ayer. Junek and Mi ttel bach
27
show that for a
3:1 stoi chi ometri c ethanol /oi l mol ar rati o most of the
catal yst i s drawn i nto the gl yceri n l ayer i n contrast wi th
an excess of al cohol where the catal yst i s evenl y
di stri buted i n the ester l ayer and gl yceri n l ayer.
The objecti ve of thi s work was to characteri ze the
ethyl esters for use as di esel fuel substi tute. One
i mportant property i n bi odi esel fuel i s the content of
unreacted vegetabl e oi l i n the form of gl yceri n or
gl yceri des. The determi nati on of these products i s
compl ex. As has been i ndi cated, the l i terature
19
reports
that i n the fi nal equi l i bri um of the ethanol ysi s of
rapeseed oi l there i s a 2 and 4% of di - and monogl yc-
eri des when the ethyl ester yi el d i s 94%. Al though i n
thi s work Cynara carduncul us oi l has been used, the
quanti ti es of di - and monogl yceri des shoul d be very
si mi l ar. I n thi s si tuati on the equi l i bri um can be shi fted
to the ri ght by carryi ng out a mul ti stage transesteri fi -
cati on process. Thi s i dea i s the basi s of the Henkel
i ndustri al process for methyl ester producti on, whi ch
i s carri ed out i n a two-stage reacti on wi th separati on
of the gl yceri n after each stage.
28
Conclusions
The mai n concl usi ons of the present work are the
fol l owi ng:
(a) Cynara carduncul us L. oi l has sui tabl e character-
i sti cs for transesteri fi cati on. The process yi el ds a bi odi e-
sel wi th si mi l ar properti es to those of di esel no. 2.
Consequentl y, cul ti vati on of thi s pl ant can be consi dered
as a potenti al al ternati ve for abandoned cropl and, and
i s a seri ous candi date for a renewabl e energy source.
(b) The i nfl uence of temperature i s i mportant ki neti -
cal l y. The best resul ts were obtai ned at 75 C, very near
to the ethanol boi l i ng poi nt. Neverthel ess, the transes-
teri fi cati on progresses sati sfactori l y even at room tem-
perature, whi ch coul d be very i nteresti ng for i ndustri al
scal e producti on due to the energy savi ngs that i t woul d
i mpl y.
(c) Of the catal ysts tested, sodi um hydroxi de gave the
hi ghest ester yi el d, al though the yi el ds wi th potassi um
hydroxi de were not much l ower. The opti mum concen-
trati on for both catal ysts was near 1%. The addi ti on of
an excessi ve amount of catal yst, however, gave ri se to
the formati on of an emul si on, whi ch i ncreased the
vi scosi ty and l ed to the formati on of gel s. The addi ti on
of l ower quanti ti es l ead to a decrease i n the yi el d.
(d) The ethanol /oi l mol ar rati o i s one of the vari abl es
that had most i nfl uence on the process. Wi thi n the
range of mol ar rati os empl oyed i n the present work, the
best resul ts were obtai ned for a 9:1 rati o. Smal l er rati os
di mi ni sh the conversi on. Larger rati os cause probl ems
i n the separati on of gl yceri n and the recovery of ethanol .
(e) Of the parameters determi ned i n the bi odi esel s,
the densi ty, vi scosi ty, cetane i ndex, and hi gh heati ng
val ue were si mi l ar to, or even better than, those of di esel
n. 2. However, the cl oud poi nt and pour poi nts were
hi gher, whi ch mi ght poi nt to potenti al di ffi cul ti es i n col d
starts. On the other hand, the fl ash and combusti on
poi nts, whi ch were hi gher than those of di esel n. 2,
consti tute a guarantee of safety from the poi nt of vi ew
of handl i ng and storage.
Acknowledgment. The authors express thei r grati -
tude to the Junta de Extremadura for the fi nanci al
support recei ved to perform thi s study, by means of the
project I PR98B038.
EF010174H
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(28) Assmann, G.; Bl asey, G.; Gutsche, B.; Jeromi n, L.; Ri gal , J.;
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450 Energy & Fuels, Vol. 16, No. 2, 2002 Encinar et al.