Preparation and Properties of Biodiesel from

Cynara carduncul us L. Oil

J ose M. Encinar,* J uan F. Gonzalez, Eduardo Sabio, and Mara J . Ramiro
Departamento deI ngeniera Qumica y Energetica, Universidad deExtremadura, 06071 Badajoz, Spain
A study was made of the reacti on of transesteri fi cati on of Cynara cardunculus L. oi l by means
of methanol , usi ng sodi um hydroxi de, potassi um hydroxi de, and sodi um methoxi de as catal ysts.
The objecti ve of the work was to characteri ze the methyl esters for use as bi odi esel s i n i nternal
combusti on motors. The operati on vari abl es used were methanol concentrati on (5-21 wt %),
catal yst concentrati on (0.1-1 wt %), and temperature (25-60 C). The evol uti on of the process
was fol l owed by gas chromatography, determi ni ng the concentrati on of the methyl 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, Ramsbottom carbon resi due,
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 15% methanol , sodi um methoxi de as
catal yst (1%), and 60 C temperature. Thi s bi odi esel has very si mi l ar properti es to those of di esel
no. 2.
Introduction
Energy consumpti on i n devel oped countri es has been
i ncreasi ng conti nuousl y over the past decades and i s set
to conti nue i n the future. One possi bl e al ternati ve to
fossi l fuel s i s the use of fuel s of pl ant ori gi n.
1
Such fuel s
al l ow for a bal ance to be sought between agri cul ture,
economi c devel opment, and the envi ronment. Thei r
undoubted advantages i ncl ude mai ntai ni ng cul ti vati on
cropl ands that otherwi se woul d be abandoned, poten-
ti al l y devel opi ng new i ndustri al acti vi tes, reduci ng
dependence on oi l , and i mprovi ng the envi ronment by
causi ng a reducti on i n net CO
2
emi ssi ons. 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. Thei r mai n drawback i s pri ce, whi ch i s
hi gher than for oi l -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.
Among the fuel s of agri cul tural ori gi n, the vegetabl e
oi l s can be an al ternati ve to di esel s for use i n di esel
engi nes.
2-5
Whi l e thei r heati ng val ue i s si mi l ar to that
of fossi l di esel , 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. The vi scosi ty of vegetabl e oi l 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.
Thi s can therefore cause seri ous engi ne deteri orati on,
so i t i s absol utel y necessary to subject the vegetabl e oi l s
to treatments that di mi ni sh the vi scosi ty. There are four
possi bl e treatments: di l uti on, mi croemul si fi cati on, py-
rol ysi s, and transesteri fi cati on,
3
among whi ch the l ast
has doubtl ess been the most commonl y empl oyed.
The transesteri fi cati on reacti on consi sts of transform-
i ng, by means of the acti on of an al cohol , tri gl yceri des
(96-98% of the oi l ) i nto fatty aci d esters, wi th gl yceri n
remai ni ng as byproduct. The resul t i s that tri gl yceri de
mol ecul es, whi ch are l ong and branched, are trans-
formed 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.
6
The overal l transesteri -
fi cati on reacti on can be represented by
Transesteri fi cati on consi sts of a sequence of consecu-
ti ve reversi bl e reacti ons where the tri gl yceri de i s suc-
cessi vel y transformed i nto di gl yceri de, monogl yceri de,
and fi nal l y i nto gl yceri n. Stoi chi ometri cal l y, 3 mol 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 i s al so i mportant due to i ts numerous
appl i cati ons i n di fferent i ndustri al processes.
The al cohol s most frequentl y empl oyed are short-
chai n al cohol s, such as methanol , ethanol , and butanol .
These al cohol s present sl i ght di fferences i n sui tabi l i ty
for transesteri fi cati on. Whi l e both methanol and ethanol
can be easi l y obtai ned from pl ant materi al s, ethanol has
the drawback that the ethyl esters are l ess stabl e and
l eave a greater carbon resi due. As methanol i s al so
cheaper, i t i s the most commonl y empl oyed al cohol . The
catal yst used has a determi nant effect on the reacti on,
rai si ng the rate notabl y. I t i s known that basi c catal ysts
(al kal i hydroxi des or methoxi des) requi re short ti mes
(30 mi n) to compl ete the reacti on even at room temper-
ature, 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).
5,7,8
Cardoon (Cynara cardunculus L.) comes ori gi nal l y
from the Medi terranean area. I t was known to the
anci ent Egypti ans, Greeks, and Romans. Nowadays i t
can be found growi ng spontaneousl y i n the countri es
borderi ng the Medi terranean, both conti nental and the
i sl and. I t i s al so found i n South Portugal , the Canary
I sl ands, and the Azores. Natural i zed cul ti vars are al so
found i n Cal i forni a, Mexi co, and the southern South
Ameri ca, where i t i s known as cardo de casti l l a
(Casti l l i an thi stl e). The speci es i s al so natural i zed i n
* Correspondi ng author. Phone: 34 924 289384. Fax: 34
924 271304. E-mai l : jenci nar@unex.es.
tri gl yceri de (TG) + 3ROH
98
catal yst
3RCO
2
R +
gl ycerol (1)
2927 I nd. Eng. Chem. Res. 1999, 38, 2927-2931
10.1021/i e990012x CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 07/15/1999
Austral i a. I t bel ongs to the Asteraceae fami l y (Com-
posi tae), whi ch al so i ncl udes the arti choke, the sun-
fl ower, and the saffl ower. I n the I beri an Peni nsul a, thi s
thi stl e 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 to 20-30 tons dry matter per ha/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 combusti 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 seed oi l i s si mi l ar i n
composi ti on to sunfl ower oi l ,
9
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%).
These reasons l ed us to study the transesteri fi cati on
process of refi ned C. cardunculus L. oi l usi ng methanol
to characteri ze the methyl esters obtai ned, wi th a vi ew
to i ts use as bi odi esel for i nternal combusti on engi nes.
Experimental Section
Materials. The C. cardunculus L. oi l was obtai ned
i n our l aboratory i n a mechani cal press and then
refi ned. Anhydrous methanol , sodi um methoxi de, so-
di um hydroxi de, and potassi um hydroxi de were suppl i ed
by Panreac. Methyl esters of pal mi ti c, steari c, ol ei c,
l i nol ei c, and l i nol eni c aci ds (empl oyed as standards i n
the chromatographi c determi nati on) were suppl i ed by
Merck and Si gma. Al l reagents were of anal yti c grade.
Transesterification. The transesteri fi cati on process
was carri ed out i n a 250 mL spheri cal reactor, provi ded
wi th a thermostat, mechani cal sti rri ng, and condensa-
ti on systems. Thi s i nstal l ati on i s basi cal l y coi nci dent
wi th that descri bed i n the l i terature.
10
The system was
preheated to 60 C, to el i mi nate moi sture, and then 150
g of C. cardunculus L. oi l was added. When the system
reached 60 C agai n, the methanol 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 mL of sampl e was wi thdrawn for l ater
chromatographi c anal ysi s. Each experi ment was pro-
l onged for 120 mi n, by whi ch ti me the conversi on to
esters i s practi cal l y compl ete. Once the system had
cool ed to room temperature, the gl yceri n was decanted
off and the methyl esters were puri fi ed by di sti l l i ng the
resi dual methanol 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.
Analysis. The anal yti c methods used to determi ne
the characteri sti cs of the bi odi esel are basi cal l y those
recommended by the European Organi zati on for Nor-
mal i zati on (CEN). Thi s organi zati on 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.
11
The methyl ester content was assayed
by gas chromatography i n a HP 5890 chromatograph
provi ded 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.
The fol l owi ng parameters were determi ned i n the fi nal
bi odi esel pr oduct: densi ty (pycnometr y), vi scosi ty
(Broockfi el d di gi tal vi scosi meter), hi gh heati ng val ue
(Parr-1351 bomb cal ori meter, accordi ng to 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), Rams-
bottom 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 on vari abl es empl oyed were methanol /oi l
rati o (5-21%wei ght), catal yst type (sodi um hydroxi de,
potassi um hydroxi de, sodi um methoxi de), catal yst con-
centrati on (0.1-1% wei ght), and temperature (25-60
C). Oi l mass (150 g), reacti on ti me (120 mi n) and
al cohol type (methanol ) were fi xed as common param-
eters i n al l the experi ments.
Influenceof Methanol Concentration. The alcohol/
oi l mol ar rati o i s one of the most i mportant vari abl es
affecti ng the ester yi el ds. As noted above, the reacti on
stoi chi ometry requi res 3 mol of al cohol per mol e of
tri gl yceri de. I n the present work, assumi ng an average
mol ecul ar wei ght of 879.5 for cynara oi l , mol ar rati os
between 1.35/1 and 5.67/1 were used. Fi gure 1 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,
the ester yi el ds i ncrease as the percentage of methanol
ri ses, the best resul ts bei ng for val ues between 15 and
21%, whi ch correspond to mol ar rati os between 4.05/1
and 5.67/1, respecti vel y. For percentages of methanol
l ess than 15%, the reacti on i s i ncompl ete, and at 21%
the separati on of gl yceri n i s di ffi cul t, si nce the excess
methanol hi nders the decantati on by gravi ty so that the
apparent yi el d of esters decreases because part of the
gl yceri n remai ns i n the bi odi esel phase. Hence, the best
resul ts are obtai ned for an i ntermedi ate concentrati on
of methanol of 18%, whi ch corresponds to a mol ar rati o
of 4.86/1. Hi gher rati os woul d make gl yceri n recovery
more di ffi cul t and i ncrease the cost of methanol recov-
ery.
5
Ki neti cal l y, the reacti on i s very fast. As can be
observed i n Fi gure 1 and al so i n Fi gure 2, where the
evol uti on of the four mai n esters over the course of the
reacti on i s shown, the fi nal methyl ester concentrati on
i s al most reached i n 10 mi n and the curves have an
asymptoti c tendency wi th ti me.
Tabl e 1 shows the i nfl uence of methanol concentrati on
on some of the most characteri sti c parameters of the
process. As can be observed, the l owest vi scosi ty val ues
are obtai ned for methanol concentrati ons between 15
and 21%, the opti mum val ue bei ng 18%, for whi ch the
densi ty i s al so a mi ni mum. Wi th regard to cl oud and
pour poi nts, the l atter remai ns al most constant, whi l e
the fi rst markedl y i mproves as the methanol concentra-
Figure 1. Ester concentrati ons vs ti me. I nfl uence of methanol /
oi l rati o (T ) 60 C, [NaOH] ) 1%).
2928 I nd. Eng. Chem. Res., Vol . 38, No. 8, 1999
ti on ri ses. On the other hand, the hi gh heati ng val ues
and fl ash and combusti on poi nts, i n the cases i n whi ch
they were determi ned, are basi cal l y i ndependent of
methanol concentrati on. I n general , i n al l cases, the
val ues of the parameters are si mi l ar to those found by
other authors for pal m oi l , sunfl ower oi l and soybean
oi l .
12,13
Influence of NaOH Concentration. Four experi -
ments were carri ed out varyi ng the NaOH concentrati on
between 0.1 and 1 wt % referred to the starti ng oi l
wei ght. Al so, an experi ment wi thout catal yst (0%NaOH)
was carri ed out, al though i n thi s case the ester conver-
si on was 0%after 120 mi n, so 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 these fi ve experi ments.
As can be observed, the best resul ts are reached for a
concentrati on of 0.5%. For hi gher val ues the yi el ds are
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 hydroxi de, or any other
al kal i ne catal yst, compensates for thi s aci di ty and
bl ocks catal yst deacti vati on.
4,5
The addi ti on of an exces-
si ve amount of catal yst, however, 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, hence, reduce the apparent
ester yi el d. The resul t of these two opposi ng effects i s
an opti mal catal yst concentrati on, that i n thi s case i s
0.5% of NaOH.
Tabl e 2 shows the i nfl uence of NaOH concentrati on
on the more representati ve parameters of the process.
Basi cal l y, i t can be observed that as the catal yst
concentrati on ri ses there i s an excel l ent reducti on i n
both vi scosi ty and cl oud poi nt. There i s al so a reducti on,
al though to a l esser extent, i n densi ty. The mi ni mum
for al l three parameters occurs for a concentrati on of
0.5%NaOH. The pour, fl ash, and combusti on poi nts and
hi gh heati ng val ue do not vary si gni fi cantl y. I n sum, i n
the case of sodi um hydroxi de the best concentrati on
seems to be 0.5%.
Influence of Catalyst Type. As was noted above,
al kal i ne catal ysts are the most effecti ve i n the trans-
esteri fi cati on processes. Reports i n the l i terature i ndi -
cate that the al koxi des of al kal i ne metal s are more
effecti ve than the correspondi ng hydroxi des, al though
for economi c reasons sodi um hydroxi de i s more often
used.
5
I n the present work, we al so studi ed sodi um
methoxi de and potassi um hydroxi de, varyi ng thei r
concentrati on i n the range between 0 and 1 wt %
referred to the starti ng oi l wei ght. The trends found
when changi ng the amounts of these two catal ysts are
basi cal l y the same as those found for sodi um hydroxi de,
al though the opti mal concentrati ons are di fferent for
each one. Tabl e 3 l i st the bi odi esel parameters obtai ned
wi th the opti mal concentrati on for each of the three
catal ysts i ncl udi ng for compari son the characteri sti cs
of a typi cal di esel (di esel no. 2) accordi ng to the data of
Schwad et al .
3
As can be observed, there i s a good approxi mati on of
the di fferent bi odi esel s to the characteri sti cs of di esel
no. 2. The greatest di fferences are i n the fl ash and
combusti on poi nts and the vi scosi ty, whi ch are al l l ower
i n di esel no. 2. On the contrary, the cetane i ndex i s
hi gher i n the bi odi esel s. Thi s parameter guarantees that
there wi l l be a good control of the combusti on, i ncreasi ng
performance and i mprovi ng col d starts, whi ch gi ves ri se
to l ess contami nant exhaust gases.
12
I n the producti on
Figure2. Evol uti on of methyl ester concentrati ons wi th ti me (T
) 60 C, [NaOH] ) 1%, [methanol ] ) 18%).
Table 1. Influence of Methanol Concentration on
Characteristic Parameters of the Process (T ) 60 C,
[NaOH] ) 1%)
% of methanol by wei ght
parameter 5 10 15 18 21
densi ty (25 C), kg m
-3
904 893 877 872 880
vi scosi ty (30 C), cSt 19.89 8.95 6.37 5.31 6.47
HHV, MJ kg
-1
39.17 39.23 39.54 39.65 39.78
cl oud poi nt, C 7 2 0 -1 -1
pour poi nt, C -4 -4 -3 -3 -3
fl ash poi nt, C 174 175
combusti on poi nt, C 182 182
yi el d of esters, % 40.3 70 89 92 88
Figure 3. Ester concentrati ons vs ti me. I nfl uence of [NaOH] (T
) 60 C, [methanol ] ) 15%).
Table 2. Influence of NaOH Concentration on
Characteristic Parameters of the process (T ) 60 C,
[Methanol] ) 15%)
% of NaOH by wei ght
parameter 0 0.1 0.25 0.5 1.0
densi ty (25 C), kg m
-3
917 888 884 875 877
vi scosi ty (30 C), cSt 74.9 10.1 7.9 5.7 6.37
HHV, MJ kg
-1
33.0 39.3 39.6 39.8 39.5
cl oud poi nt, C -7 9 2 -1 0
pour poi nt, C -10 -5 -4 -4 -3
fl ash poi nt, C 350 175 176 175 174
combusti on poi nt, C 177 184 182 182
yi el d of esters, % 0 72.2 86.8 93.9 89
I nd. Eng. Chem. Res., Vol . 38, No. 8, 1999 2929
of di esel fuel s, the cetane number i s an i mportant
i ndi cator of the qual i ty of the fuel 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 ati 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.
14,15
The energy con-
tent of the esters, based on thei r heati ng val ue, i s
around 90%of di esel no. 2 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 i s because the esters contai n 10
wt % of oxygen that can be used i n the combusti on
process, di mi ni shi ng the external ai r requi rements.
Compari son of the three bi odi esel s shows them to have
very si mi l ar characteri sti cs, al though i n the experi ment
where sodi um methoxi de was empl oyed as catal yst the
val ues of vi scosi ty and carbon resi due are the l owest,
whi l e the ester yi el d i s greatest. Neverthel ess, gi ven the
smal l ness of the di fferences found, and taki ng the pri ce
i nto account, one mi ght say that sodi um hydroxi de i s
the most sui tabl e catal yst.
Tabl e 4 l i st the properti es of sunfl ower, rape, and
soybean methyl esters,
3,6
together wi th the resul ts
obtai ned i n thi s work empl oyi ng 1% sodi um methoxi de
as catal yst. As can be seen, the resul ts are very
homogeneous, and the compari son wi th those of di esel
oi l no. 2 (Tabl e 3) makes i t cl ear that any of these methyl
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 di esel no. 2 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 Temperature. The methyl esteri fi ca-
ti on of cynara oi l was carri ed out at 25, 40, 55, and 60
C i n order to determi ne the effect of reacti on temper-
ature on the methyl ester formati on. I n al l these
experi ments, a concentrati on of 15% i n methanol and
1% i n NaMeO (as catal yst) was used. Fi gure 4 shows
the temporal evol uti on of the resul ts. As can be ob-
served, for the same fi nal reacti on ti me, the percentage
of esters obtai ned i ncreases wi th temperature. Never-
thel ess, one must consi der the rates of the process: the
yi el ds obtai ned at 2 mi n of the reacti on were 72, 80, 81,
and 82% for 25, 40, 55, and 60 C, respecti vel y, and at
120 mi n, 87, 90, 92, and 94%, respecti vel y. Hence, there
i s an i ni ti al peri od where the reacti on i s very fast, and
then a second peri od, much l onger than the fi rst, i n
whi ch the composi ti on evol ves sl owl y toward equi l i bri -
um. 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.
3,5
Tabl e 5 l i sts the resul ts for the i nfl uence of temper-
ature on the more representati ve parameters of the
process. They are si mi l ar to the data shown i n Fi gure
4. There i s a sharp fal l i n vi scosi ty and an i ncrease i n
yi el d as the temperature ri ses, whi l e the remai ni ng
vari abl es basi cal l y remai n constant. We may therefore
state that the temperature i s l i nked to reacti on ti me
and that the fi nal properti es of the product depend 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
Table 3. Influence of Catalyst Type on Characteristic
Parameters of the Process and Comparison with
No. 2 Diesel
parameter
0.5%
KOH
1%
MeONa
0.5%
NaOH
di esel
no. 2
densi ty (25 C), kg m
-3
884 880 875 847
vi scosi ty (40 C), cSt 5.37 3.56 4.56 2.39
HHV, MJ kg
-1
39.7 39.8 39.8 45.2
cl oud poi nt, C -2 -1 -1 -19
pour poi nt, C -3 -3 -4 -23
fl ash poi nt, C 177 175 175 85
combusti on poi nt, C 184 179 182 92
yi el d of esters, % 92.5 94 93.9
cetane i ndex 48.9 48.6 47.8 46
di sti l l ati on, C
0% 333 315 325
20% 346 345 344
40% 347 348 346
50% 349 350 348 258
60% 350 351 350
Ramsbottom resi due, % 0.27 0.26 0.36 0.14
sul fur (% mass) <0.01 <0.01 <0.01 0.25
Table 4. Comparison of Methyl Esters of Cynara,
Sunflower, Rape, and Soybean Oils
parameter sunfl ower cynara rape soybean
densi ty (25 C), kg m
-3
880 880 893 884
vi scosi ty (40 C), cSt 4.20 3.56 4.80 4.08
HHV, MJ kg
-1
40.1 39.8 40.0 39.8
cl oud poi nt, C 0-3 -1 -3 2
fl ash poi nt, C 164 175 153 141
combusti on poi nt, C 183 179 171
cetane i ndex 47-51 48.6 52 47
di sti l l ati on, C
50% 364 350 336
60% 369 342
Ramsbottom resi due, % 0.05 0.26 0.3
sul fur (% mass) 0.01 0.01 <0.01 0.01
Figure4. Ester concentrati ons vs ti me. I nfl uence of temperature
([NaMeO] ) 1%, [methanol ] ) 15%).
Table 5. Influence of Temperature on Characteristic
Parameters of the Process ([NaMeO] ) 1%,
[Methanol] ) 15%)
temperature, C
parameter 25 40 55 60
densi ty (25 C), kg m
-3
885 881 880 878
vi scosi ty (30 C), cSt 6.21 5.10 4.90 4.55
HHV, MJ kg
-1
39.60 39.73 39.80 39.78
cl oud poi nt, C 0 -1 -1 -1
pour poi nt, C -2 -3 -3 -3
fl ash poi nt, C 177 176 176 175
combusti on poi nt, C 182 180 180 179
yi el d of esters, % 86 90 93 94
2930 I nd. Eng. Chem. Res., Vol . 38, No. 8, 1999
temperature at whi ch thi s percentage has been ob-
tai 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 ng and l ower the process cost.
Conclusions
The mai n concl usi ons of the present work are the
fol l owi ng:
(a) C. cardunculus L. oi l has sui tabl e characteri sti cs
for transesteri fi cati on. The process yi el ds a bi odi esel
wi th si mi l ar properti es to those of di esel no. 2. Conse-
quentl 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, consti tut-
i ng a seri ous possi bi l i ty for renewabl e energy sources.
(b) The methanol /oi l mol ar rati o i s one of the vari abl es
that has most i nfl uence on the process. I n thi s present
work, wi thi n the range of mol ar rati os empl oyed, the
best resul ts were obtai ned for a 5/1 rati o, whi ch corre-
sponds to a methanol concentrati on of approxi matel y
18 wt % referred to the starti ng oi l wei ght.
(c) Of the catal ysts tested, sodi um methoxi de gave the
hi ghest ester yi el d, al though the yi el ds wi th sodi um
hydroxi de and potassi um hydroxi de were not much
l ower. There was an opti mal concentrati on for the three
bi odi esel s, whi ch we found to l i e i n the range 0.5-1%
i n wei ght referred to the i ni ti al oi l wei ght.
(d) The i nfl uence of temperature i s i mportant ki neti -
cal l y. The best resul ts were obtai ned at 60 C, very near
to the methanol boi l i ng poi nt. Neverthel ess, the trans-
esteri fi cati on progresses sati sfactori l y even at room
temperature, whi ch coul d be very i nteresti ng for i ndus-
tri al scal e producti on due to the energy savi ngs that i t
woul d i mpl y.
(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 presented val ues that were si mi l ar to, or even
better than, those of di esel no. 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 no. 2, consti tute a guarantee of
securi ty from the poi nt of vi ew of handl i ng and storage.
Acknowledgment
The authors woul d l i ke to 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
PRI 97D082.
Literature Cited
Strub, A. The Commi si on of the European Communi ti es, R&D
Programme Energy from bi omass. Thermochemical Processing
Biomass; Bri dwater, A. V., Ed., Butterworth: London, 1984; pp
1-10.
Shay, E. G. Di esel fuel from vegetabl e oi l s: status and opportuni -
ti es. Biomass Bioenergy 1993, 4, 227.
Schwad, A. W.; Bagby, M. O.; Fri edman, B. Preparati on and
properti es of di esel fuel s from vegetabl e oi l s. Fuel 1987, 66,
1372.
Freedman, B.; Butterfi el d, R. O.; Pryde, E. H. Transesteri fi cati on
ki neti cs of soybean oi l . J . Am. Oil. Chem. Soc. 1986, 63, 1375.
Freedman, B.; Pryde, E. H.; Mounts, T. L. Vari abl es affecti ng the
yi el ds of fatty esters from transesteri fi ed vegetabl e oi l s. J . Am.
Oil. Chem. Soc. 1984, 61, 1638.
Qui ck, G. R.; Woodmore, P. J.; Wi l son, B. T. Engi ne eval uati ons
of l i nseed oi l and deri vati ves. I n Vegetable Oils Diesel Fuel:
Seminar I I I , ARM-NC-28, Bagby, M. O., Pryde, E. H., Eds.;
1983, p 138.
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.; 1983; p 78.
Harri ngton, K. J.; DArcy-Evans, C. Transesteri fi cati on i n si tu of
sunfl ower seed oi l . I nd. Eng. Chem. Prod. Res. Dev. 1985, 24,
314.
Benjel l oun-Ml ayah, B.; Lopez, S.; Del mas, M. Oi l and paper pul p
from Cynara carduncul us: prel i mi nary resul ts. I nd. CropsProd.
1997, 6, 233.
Ma, F.; Cl ements, L. D., Hanna, M. A. Bi odi esel fuel from ani mal
fat. Anci l l ary studi es on transesteri fi cati on of beef tal l ow. I nd.
Eng. Chem. Res. 1998, 37, 3768.
Mordret, F. Qual i fy control of methyl esters used as bi ofuel s.
Speci fi cati ons and methods of anal ysi s. Ol., Corps Gras, Lipides
1994, 1, 33
Reed, T. B.; Graboski , M. S.; Gaur, S. Devel opment and com-
merci al i zati on of oxygenated di esel fuel s from waste vegetabl e
oi l s. Biomass Bioenergy 1992, 3, 11.
Freedman, B.; Bagby, M. O. Heats of combusti on of fatty esters
and tri gl yceri des. J . Am. Oil. Chem. Soc. 1989, 66, 1601.
OConnor, C. T.; Forrester, R. D.; Scurrel l , M. S. Cetane number
determi nati on of syntheti c di esel fuel s. Fuel 1992, 71, 1323.
Kri snangkura, K. A si mpl e method for esti mati on of cetane i ndex
of vegetabl e oi l methyl esters. J . Am. Oil. Chem. Soc. 1986, 63,
552.
Received for review January 4, 1999
Revised manuscript received May 7, 1999
Accepted May 21, 1999
I E990012X
I nd. Eng. Chem. Res., Vol . 38, No. 8, 1999 2931