Optimization of Alkali-Catalyzed Transesterification of

Brassi ca Cari nata Oil for Biodiesel Production

M. Pi l ar Dorado,*
,
Evari sto Bal l esteros,

Franci sco J. Lopez,

and
Marti n Mi ttel bach
#
Department of Mechanics and Mining Engineering, EUP deLinares, Universidad deJ aen,
C/ . Alfonso X el Sabio, 28, 23700 Linares (J aen), Spain, Department of Physical and
Analytical Chemistry, EUP deLinares, Universidad deJ aen, C/ . Alfonso X el Sabio,
28, 23700 Linares (J aen), Spain, Department of Agricultural Engineering, ETSI AM,
Universidad deCordoba, Avda. Menendez Pidal s/ n, 14080 Cordoba, Spain, I nstituteof
Chemistry, Karl-Franzens-Universitat Graz, Heinrichstrasse28, A-8010 Graz, Austria
Received May 27, 2003. Revised Manuscript Received October 5, 2003
Envi ronmental concerns are dri vi ng i ndustry to devel op vi abl e al ternati ve fuel s from renewabl e
resources. On the other hand, to reduce food surpl us, the Agri cul tural Pol i cy of the European
Uni on (EU) obl i ges the European farmers to l eave a percentage of the arabl e l and as set-asi de,
where can be grown, as an excepti on, vegetabl es for nonfood purposes, i .e., energeti c ones.
Currentl y, fossi l fuel s are used i n di esel engi nes and are essenti al i n i ndustri al i zed pl aces. I n
addi ti on, petrol eum-based di esel i ncreases envi ronmental pol l uti on. To sol ve these probl ems,
transesteri fi ed vegetabl e oi l that has been grown i n set-asi de l ands can be consi dered to be a
renewabl e energy resource. I n thi s sense, thi s work descri bes the opti mi zati on of the parameters
i nvol ved i n the transesteri fi cati on process of Brassica carinata oi l . Gas chromatography was used
to determi ne the fatty aci d composi ti on of Brassica carinata oi l and i ts esters. Resul ts reveal ed
that the free fatty aci d content i s a notori ous parameter to determi ne the vi abi l i ty of the vegetabl e
oi l transesteri fi cati on process. I n thi s sense, i t was not possi bl e to perform a basi c transesteri -
fi cati on usi ng Brassica carinata oi l wi th a hi gh eruci c aci d content. The transesteri fi cati on process
of Brassica carinata wi thout eruci c aci d requi red 1.4% KOH and 16% methanol , i n the range of
20-45 C, after 30 mi n of sti rri ng. Our resul ts suggest that the greater the presence of KOH,
the l esser the methanol requi rements. However, thi s i s val i d onl y under certai n l i mi ts. Al so, i f
the presence of KOH or methanol i s l ower or hi gher than the opti mal val ues, the reacti on ei ther
does not ful l y occur or l eads to soap producti on, respecti vel y. Based on thi s fi el d tri al , bi odi esel
from Brassica carinata oi l coul d be recommended as a di esel fuel candi date i f l ong-term engi ne
performance tests provi de sati sfactory resul ts.
Introduction
More than 350 oi l -beari ng crops have been i denti fi ed,
among whi ch mai nl y sunfl ower, saffl ower, soybean,
cottonseed, rapeseed, and peanut oi l s are consi dered to
be potenti al al ternati ve fuel s for di esel engi nes.
1
Nev-
erthel ess, other unknown ol eagi nous crops, whi ch are
bei ng grown i n l ess-favored countri es, coul d perform
wel l as an adequate fuel wi th chemi cal and physi cal
properti es si mi l ar to those of di esel fuel .
I n addi ti on, the set-asi de rul es of the European Uni on
(EU) Agri cul tural Pol i cy speci fy a mi ni mum area of
obl i gatory set-asi de l and of the total arabl e area (10%
i n 2001), but al so permi t up to 50% of the total cl ai med
area to be put i nto the vol untary set-asi de category.
However, i ncreasi ng the set-asi de area coul d l ead to
erosi on probl ems and may have an i mpact on arabl e
l and. Neverthel ess, an excepti on has been i ntroduced
i nto the rul es for managi ng set-asi de l and, whi ch al l ows
farmers to cul ti vate crops for nonfood purposes. I n thi s
sense, Brassica carinata (Ethi opi an mustard) i s an
adequate oi l -beari ng crop that i s wel l -adapted to mar-
gi nal regi ons (i .e., Andal usi a (Spai n), whi ch i s one of
the poorest regi ons of the EU). I n fact, thi s crop, whi ch
i s ori gi nal l y from Ethi opi a, i s drought-resi stant and
grown i n ari d regi ons such as Andal usi a.
2,3
Moreover,
nonfood cul tures i n set-asi de l ands can si gni fi cantl y
decrease the enormous amount of subsi di es spent for
agri cul tural overproducti on i n Europe, whi ch l eads to
an i ncrease i n farmer i ncomes as wel l as the creati on
of new empl oyment. For these reasons, Brassica cari-
nata consti tutes an i nteresti ng al ternati ve to di esel fuel
i n l ess-favored regi ons.
* Author to whom correspondence shoul d be addressed. E-mai l :
mpdorado@ujaen.es.

Department of Mechani cs and Mi ni ng Engi neeri ng.

Department of Physi cal and Anal yti cal Chemi stry.

Uni versi dad de Cordoba.

#
Karl -Franzens-Uni versi tat Graz.
(1) Peterson, C. L. Trans. ASAE 1986, 29, 1413-1422.
(2) Ki mber, D. S.; McGregor, D. I . The Speci es and Thei r Ori gi n,
Cul ti vati on and Worl d Producti on; I n Brassica Oilseeds: Production
and Utilization; Ki mber, D. S., McGregor, D. I ., Eds.; CAB I nterna-
ti onal : Wal l i ngford, Oxon, U.K., 1995; pp 1-7.
(3) Mendham, N. J.; Sal i sbury, P. A. Physi ol ogy: Crop Devel opment,
Growth and Yi el d; I n Brassica Oilseeds: Production and Utilization;
Ki mber, D. S., McGregor, D. I ., Eds.; CAB I nternati onal : Wal l i ngford,
Oxon, U.K., 1995; pp 11-64.
77 Energy & Fuels 2004, 18, 77-83
10.1021/ef0340110 CCC: $27.50 2004 Ameri can Chemi cal Soci ety
Publ i shed on Web 11/13/2003
However, vegetabl e oi l s are composed pri mari l y of the
fatty esters of gl ycerol (tri gl yceri des), wi th a chemi cal
structure that di ffers from di esel fuel . I n fact, vegetabl e
oi l s used as fuel report several probl ems that have been
i denti fi ed, i .e., the hi gh vi scosi ty and hi gh mol ecul ar
wei ght cause poor fuel atomi zati on (whi ch l eads to i n-
compl ete combusti on) and l ow vol ati l i ty, respecti vel y.
4,5
I n thi s sense, the transesteri fi cati on of vegetabl e oi l s
consti tutes an effi ci ent method to provi de a fuel wi th
chemi cal properti es that are si mi l ar to those of di esel
fuel . Thi s chemi cal reacti on resembl es the conversi on
of an organi c aci d ester i nto another ester of the same
aci d (Scheme 1).
Al though i t i s a wel l -known process si nce, i n 1864,
Rochl eder descri bed gl ycol preparati on through the
ethanol ysi s of castor oi l ,
6
the proporti on of reagents
affects the process, i n terms of conversi on effi ci ency,
7
and thi s factor di ffers accordi ng to the vegetabl e oi l .
Several researchers have i denti fi ed the most i mportant
vari abl es that i nfl uence the transesteri fi cati on reacti on,
namel y, the reacti on temperature, the type and amount
of catal yst, the rati o of al cohol to vegetabl e oi l , the
sti rri ng rate, the reacti on ti me, etc.
8-12
I n thi s sense, i t
i s i mportant to characteri ze the oi l (i .e., fatty aci d
composi ti on, water content, and peroxi de val ue (PV)) to
determi ne the correl ati on between them and the feasi -
bi l i ty to convert the oi l i nto bi odi esel .
12,13
The fatty aci d composi ti on of the oi l s seems to have
an i mportant rol e i n the performance of bi odi esel i n
di esel engi nes. Accordi ng to Knothe and Dunn,
14
satu-
rated hydrocarbon chai ns are especi al l y sui tabl e for
conventi onal di esel fuel . I n thi s sense, Ethi opi an mus-
tard presents up to 6% saturated hydrocarbon chai ns
(Tabl e 1), whereas sunfl ower oi l , canol a oi l , and soybean
oi l methyl esters present up to 4.8%-12.1%, 5%-7%,
and 4.7%-17% saturated chai ns, respecti vel y.
Based on the fatty aci d composi ti on and many other
parameters, the EU i s about to approve the fatty aci d
methyl esters requi rements and test methods (European
Standard EN 14214). Accordi ng to thi s prenorm, the
maxi mum amount of l i nol ei c aci d methyl ester can be
12%. Al so, the i odi ne val ue i s l i mi ted to 120. These
parameters excl ude the use of the bi odi esel from sun-
fl ower oi l , whi ch i s one of the mai n ol eagi nous crops that
are grown i n Spai n and other southern countri es of the
EU. I n fact, research rel ated to bi odi esel from sunfl ower
oi l has been seri ousl y cri ti ci zed. However, some re-
searchers have found that bi odi esel from sunfl ower oi l
performs adequatel y i n di esel engi nes.
15-17
Thi s obser-
vati on i ndi cates that more research i s needed before the
approval of the future EU standard for bi odi esel .
Because the chemi cal properti es of the esters deter-
mi ne thei r feasi bi l i ty as fuel , the i ntent of thi s work i s
to i nvesti gate and opti mi ze the parameters i nvol ved i n
the transesteri fi cati on of Brassica carinata oi l for fuel
use, to devel op a l ow-cost chemi cal process, and to deter-
mi ne the i nfl uence of the chemi cal properti es of the oi l
i n the transesteri fi cati on. Transesteri fi cati on tests were
(4) Goeri ng, C. E.; Schwab, A. W.; Daugherty, M. J.; Pryde, E. H.;
Heaki ng, A. J. Trans. ASAE 1982, 25, 1472-1483.
(5) Bagby, M. O. VegetableOils for Diesel Fuel: Opportunities for
Development; Ameri can Soci ety of Agri cul tural Engi neers: St. Joseph,
MI , 1987; ASAE Paper No. 87-1588.
(6) Formo, M. W. J . Am. Oil Chem. Soc. 1954, 31, 548-559.
(7) Freedman, B.; Pryde, E. H.; Mounts, T. L. J . Am. Oil Chem. Soc.
1984, 64, 1638-1643.
(8) Peterson, C. L.; Reece, D. L.; Cruz, R.; Thompson, J. A Com-
pari son of Ethyl and Methyl Esters of Vegetabl e Oi l as Di esel Fuel
Substi tute: Li qui d-Fuel s from Renewabl e Resources; Proceedings of
Alternative Energy Conference; Ameri can Soci ety of Agri cul tural
Engi neers, 1992; pp 99-110.
(9) I si gi gur, A.; Karaosmanogl u, F.; Aksoy, H. A. Appl. Biochem.,
Biotechnol. 1994, 45, 103-112.
(10) Muni yappa, P. R.; Brammer, S. C.; Noureddi ni , H. Bioresour.
Technol. 1996, 56, 19-24.
(11) Zheng, D.; Hanna, M. A. Bioresour. Technol. 1996, 57, 137-
142.
(12) Coteron, A.; Vi cente, G.; Marti nez, M.; Araci l , J. Recent Res.
Dev. Oil Chem. 1997, 1, 109-114.
(13) Anggrai ni , A. A. Wi ederverwertung von Gebrauchten Spei seol en/
-fetten i m Energeti sch-Techni schen Berei ch -ei n Verfahren und
Dessen Bewertung; Dep. AgrarTechni k, Uni versi tat Gesamthochschul e
Kassel : Wi tzenhausen, Germany, 1999; p 193.
(14) Knothe, G.; Dunn, R. O. Bi ofuel s Deri ved from Vegetabl e Oi l s
and Fats. I n Oleochemical Manufactureand Applications; Gunstone,
F. D., Hami l ton, R. J., Eds.; Sheffi el d Academi c Press: Sheffi el d, U.K.,
2001; pp 107-163.
(15) Ful s, J.; Hawki ns, C. S.; Hugo, F. J. C. J . Agric. Eng. Res. 1984,
30, 29-35.
(16) Kaufman, K. R.; Zi ejewski , M. Trans. ASAE 1984, 27, 1626-
1633.
(17) Harri ngton, K. J.; DArcy-Evans, C. J . Am. Oil Chem. Soc. 1985,
62, 1009-1013.
Scheme 1. Transesterification Process Table 1. Chemical and Physical Properties of Brassica
Oils
hi gh-eruci c
Brassica carinata
oi l
b
Brassica carinata
oi l wi thout
eruci c aci d
b
fatty aci ds (%)
a
pal mi ti c C16:0
(t 4.118 mi n)
5.3 ( 0.1 5.4 ( 0.1
pal mi tol ei c C16:1
(t 4.545 mi n)
steari c C18:0
(t 5.53 mi n)
0.20 ( 0.01
ol ei c C18:1
(t 6.167 mi n)
10.0 ( 0.2 43.2 ( 0.9
l i nol ei c C18:2
(t 7.275 mi n)
24.6 ( 0.5 36.0 ( 0.7
l i nol eni c C18:3
(t 8.8 mi n)
16.5 ( 0.3 15.2 ( 0.3
eruci c C22:1
(t 13.86 mi n)
43.6 ( 0.8
Other Properti es
b
free fatty aci d (%) 10.81 ( 0.31 2.2 ( 0.2
peroxi de val ue (meq) 8.9 ( 0.1 22.5 ( 0.4
densi ty (kg/m
3
) 914 ( 1 921 ( 1
ki nemati c vi scosi ty at
40 C (mm
2
/s)
118.8 ( 0.9 68.1 ( 0.8
ki nemati c vi scosi ty at
20 C (mm
2
/s)
48.6 ( 0.9 32.1 ( 0.6
water content (%) 0.25 ( 0.02 0.20 ( 0.01
a
Other fatty aci ds (myri sti c, margari c, margarol ei c, arachi di c,
gadol ei c, and beheni c) were present i n amounts of <1%.
b
Medi um
val ue ( standard devi ati on (n ) 3).
78 Energy & Fuels, Vol. 18, No. 1, 2004 Dorado et al.
conducted i n a sti rred tank reactor that was equi pped
wi th a temperature control l er and a refl ux condenser,
to avoi d methanol l osses.
Materials and Methods
1. Characterizationof theOil. Hi gh-eruci c and l ow-eruci c
Brassica carinata oi l seeds were col l ected and processed by
mechani cal col d-press extracti on. At thi s poi nt, the crude oi l
was not refi ned any further. The fatty aci d composi ti on of
the oi l was anal yzed usi ng gas chromatography (GC)
(Hewl ett-Packard, model 5890 GLC). The chromatograph was
equi pped wi th a fl ame i oni zati on detector (FI D) and a 30 m
0.25 mm Supel col wax-10 gl ass col umn that was packed
wi th pol y(ethyl ene gl ycol ) (fi l m thi ckness of 0.25 m). Ni trogen
was used as a carri er gas at a fl ow rate of 1 mL/mi n. The
i njector and detector temperatures were mai ntai ned at 250
C. The col umn temperature was i ncreased from 165 C (2 mi n)
to 180 C at a rate of 4 C/mi n (3 mi n), then to 200 C at a
rate of 5 C/mi n, and fi nal l y to 260 C at a rate of 15 C/mi n;
thi s l ast temperature was mai ntai ned for 2 mi n. ChemStati on
software (HP-3365) was used for data acqui si ti on.
18
The
chemi cal and physi cal properti es of Brassi ca oi l s are gi ven i n
Tabl e 1.
2. Transesterification Process. The reacti on vessel was
charged wi th a gi ven amount of Brassica carinata oi l (100 g),
whi ch was sti rred at 1100 rpm and preheated at di fferent
temperatures. Meanwhi l e, the sol uti on of methanol (CH3OH)
and KOH was added. The mi xture was sti rred and heated.
The ti me of reacti on was vari ed, to obtai n a l arge range of
methyl ester yi el ds. Heati ng and sti rri ng were then stopped,
and the product was al l owed to settl e, to al l ow the two phases
to be separated. The top phase consi sted of bi ofuel , whereas
the l ower phase contai ned a mi xture of i mpuri ti es. The upper
l ayer was puri fi ed usi ng di sti l l ed water and then dri ed over
anhydrous sodi um sul fate (Na
2SO4) (see Scheme 2). I n thi s
sense, 0.5 g of anhydrous Na2SO4 were added for every 100
mL of ester, sti rred for 15 mi n, and then was al l owed to settl e
and be decanted. To remove sol i d traces from bi ofuel after the
puri fi cati on step, a fi l trati on process was needed. Thi s step
was performed wi th the hel p of a vacuum pump and a 27-m-
di ameter fi l ter paper (No. 1305, from ALBET (Fi l tros Anoi a
SA, Barcel ona, Spai n)). For each oi l sampl e, three repl i cati ons
were performed.
The opti mum of each parameter i nvol ved i n the process was
determi ned whi l e the rest of them remai ned constant. After
each opti mum was attai ned, thi s val ue was accepted and
consi dered to be constant duri ng the opti mi zati on of the next
parameter. Ester yi el d resul ts (gi ven as percentages) were
rel ated to the wei ght of oi l at the start (wei ght of ester/wei ght
of oi l ).
Fi nal l y, bi odi esel fuel properti es were determi ned wi th the
hel p of the standard tests and compared to those of di esel fuel ,
accordi ng to the EN-590 standard and European Standard EN
14214 for bi odi esel .
Results and Discussion
1. Oil Properties. Accordi ng to Tabl e 1, the free fatty
aci d (FFA) content was i n the range of 2.2% (for
Brassica carinata oi l wi thout eruci c aci d) to 10.8% (for
hi gh-eruci c Brassica carinata oi l ). Hi gh-eruci c Brassica
carinata oi l showed a si gni fi cantl y hi gh FFA val ue,
compared to sampl es wi thout eruci c aci d, probabl y
because of the presence of the eruci c aci d. These FFA
contents shoul d make transesteri fi cati on of the oi l s
possi bl e; FFA contents of >3% decrease the conversi on
effi ci ency consi derabl y.
13
However, Dorado et al .
19
found
that transesteri fi cati on woul d not occur i f oi l s wi th an
FFA content of >3%were used. I n thi s work, i t was not
possi bl e to perform transesteri fi cati on of hi gh-eruci c
Brassica carinata oi l ; i t l ed to soap formati on. I t seems
that the presence of eruci c aci d was responsi bl e for the
observed hi gh FFA content, and we feel confi dent that
i t was the mai n obstacl e to accompl i shi ng transesteri -
fi cati on of the hi gh-eruci c Brassica carinata oi l . On the
other hand, i t can be noti ced that the absence of eruci c
aci d i n the noneruci c Brassica carinata oi l has l ed to
an i ncrease i n the presence of ol ei c and l i nol ei c aci ds
(see Tabl e 1).
(18) Bal l esteros, E.; Cardenas, S.; Gal l ego, M.; Val carcel , M. Anal.
Chem. 1994, 6, 628-634.
(19) Dorado, M. P.; Bal l esteros, E. A.; de Al mei da, J. A.; Schel l ert,
C.; Lohrl ei n, H. P.; Krause, R. Trans. ASAE 2002, 45, 525-529.
Scheme 2. Process to Obtain Biofuel
Transesterification of Brassica Carinata Oil Energy & Fuels, Vol. 18, No. 1, 2004 79
The peroxi de val ue (PV) i ndi cates oi l autoxi dati on,
whi ch i s a property that coul d l ead to catal yst i nacti vi ty
duri ng the transesteri fi cati on process. Accordi ng to
Tabl e 1, the PV ranged from 8.9 meq/kg for hi gh-eruri c
Brassica carinata oi l to 22.5 meq/kg for noneruci c
Brassica carinata oi l . However, Anggrai ni
13
found that,
for transesteri fi cati on purposes, val ues up to 30-35
meq/kg coul d be tol erated. I n the present work, the
ki nemati c vi scosi ty was si gni fi cantl y hi gher for hi gh-
eruci c Brassica carinata oi l than that for noneruci c
Brassica carinata oi l . Neverthel ess, i n both cases, the
ki nemati c vi scosi ty val ue was too hi gh to al l ow the use
of strai ght Brassica carinata oi l s as fuel s. On the other
hand, the water content was very si mi l ar i n both cases
(<1%), whi ch prevents saponi fi cati on or the hydrol ysi s
of gl yceri des and makes transesteri fi cati on possi bl e.
13
I n thi s fi el d tri al study, onl y Brassica carinata oi l
wi thout eruci c aci d was successful l y transesteri fi ed,
thus i ndi cati ng that the FFA content was the more
offensi ve parameter.
2. Catalyst Optimization. To avoi d corrosi on prob-
l ems i n engi ne components that are due to the presence
of aci d traces, basi c catal ysts i nstead of aci d catal ysts
were sel ected.
20
I n thi s sense, two basi c catal ystssKOH
and NaOHswere tested under the same condi ti ons
(1.26%catal yst and an excess of al cohol , tested at room
temperature). However, no ester formati on was ob-
served usi ng NaOH, unl ess the reacti on ti me was
consi derabl y i ncreased (up to 14 h), compared to KOH
(up to 1 h). For thi s reason, KOH was sel ected. The
effect of KOH concentrati on was studi ed i n the range
of 0%-2.3%(wei ght of KOH/wei ght of oi l ). Resul ts usi ng
KOH (al cohol over the stoi chi ometri c amount) are
shown i n Fi gure 1.
Onl y noneruci c Brassica carinata oi l was successful l y
transesteri fi ed. As shown i n Fi gure 1, the maxi mum
yi el d of ester was obtai ned by addi ng 0.8% of KOH.
However, the ester was opaque, whi ch i ndi cated the
presence of unreacted gl yceri des.
21
The opti mum was
achi eved usi ng 1.4% of KOH, whi ch produced a 91.9%
yi el d of reddi sh, crystal l i ne, and transparent ester. Thi s
amount was greater than the amounts of catal yst used
by other researchers.
10,22
Ester formati on started after
20-40 s of sti rri ng. KOH amounts greater than 1.4%
produced a smal l er ester yi el d, because of the presence
of soaps, whi ch prevents ester l ayer separati on, as found
by Coteron et al .
12
3. Alcohol Optimization. Prel i mi nary tests were
conducted usi ng both methanol (50% v/v) and ethanol
(50% v/v). Under the same condi ti ons (1.4% catal yst,
room temperature), i t was not possi bl e to achi eve ester
formati on usi ng ethanol (even usi ng an anhydrous
al cohol , whi ch l ed to the formati on of soap and gel ati -
nous l ayers. I nstead, usi ng methanol , both the ester and
gl ycerol l ayers were easi l y separated. Anyway, trans-
esteri fi cati on usi ng ethanol occurred sl ower than that
usi ng methanol , as reported by Du Pl essi s et al .
23
I n
the present work, methanol was the al cohol sel ected.
The effect of methanol presence was studi ed i n the
range of 0%-20% (wei ght of methanol /wei ght of oi l ).
Resul ts usi ng methanol are shown i n Fi gure 2.
The methanol :tri gl yceri de mol ar rati o that i s requi red
by the stoi chi ometry shoul d be 3:1. However, as shown
i n Fi gure 2, the maxi mum yi el d of ester was obtai ned
by addi ng 16% methanol (wei ght of methanol /wei ght of
oi l ), whi ch i s equi val ent to a mol ar rati o of 1:4.6 (oi l :
methanol ). I n contrast, other researchers have found i t
necessary to i ncrease the mol ar rati o up to 1:6, or even
to 1:12, to achi eve the maxi mum yi el d of monoester
product from saffl ower oi l or soybean oi l .
9,21
Our fi ndi ngs
are probabl y due to the greater amount of catal yst used
i n the present work, compared to that i n the work of
other researchers.
9,21
Ester formati on started after 30
s of sti rri ng. I n thi s work, methanol amounts of >20%
(20) Bal l esteros, E.; Gal l ego, M.; Val carcel , M. Anal. Chim. Acta
1993, 282, 581-588.
(21) De Fi l i ppi s, P.; Gi avari ni , C.; Scarsel l a, M.; Sorrenti no, M. J .
Am. Oil Chem. Soc. 1995, 72, 1399-1404.
(22) Trent, W. R. Process of Treati ng Fatty Gl yceri des. U.S. Patent
462,370, 1945.
(23) Du Pl essi s, L. M.; de Vi l l i ers, J. B. M.; Hawki ns, C. S. Methods
of Preparing and Purifying Methyl and Ethyl Fatty Acid Esters from
Sunflowerseed Oil; SAE: Pretori a, Republ i c of South Afri ca, 1983; p
9.
Figure1. Percentage yi el d of ester rel ati ve to oi l at start (w/w
%), usi ng di fferent amounts of KOH and al cohol over the
stoi chi ometri c amount.
Figure2. Percentage yi el d of ester rel ati ve to oi l at start (w/w
%), usi ng di fferent amounts of methanol and 1.4% KOH.
80 Energy & Fuels, Vol. 18, No. 1, 2004 Dorado et al.
made gl ycerol separati on di ffi cul t, thus decreasi ng ester
yi el d formati on, whi ch was opaque. I n thi s case, ester
formati on started after 80 s of sti rri ng. The addi ti on of
<5% methanol resul ted i n the creati on of a uni que and
foamy l ayer. Methanol amounts up to 10%produced two
l ayers, al though the l ower l ayer was gel ati nous and the
upper l ayer was opaque, because of the presence of
unreacted tri gl yceri des, thus i ndi cati ng that methanol
was i nsuffi ci ent to perform a compl ete reacti on.
4. ReactionTemperatureOptimization. The maxi -
mum yi el d of ester was obtai ned at room temperature.
Resul ts reveal ed that the ester yi el d sl i ghtl y decreases
when other reacti on temperatures are used, especi al l y
when the temperature i s >50 C. However, other
researchers achi eved better resul ts usi ng temperatures
above 50 C, up to 70-80 C.
9,23
I n fact, several
researchers found that the temperature i ncrease i nfl u-
ences the reacti on i n a posi ti ve manner.
24
Al though a refl ux condenser was used to avoi d meth-
anol l osses, the ester yi el d si gni fi cantl y decreased at
temperatures of >50 C, probabl y because of a negati ve
i nteracti on between temperature and catal yst concen-
trati on, due to si de reacti ons, such as soap formati on.
12
Al so, Trent
22
found that reacti on temperatures of >60
C shoul d be avoi ded, because they tend to accel erate
the saponi fi cati on of the gl yceri des by the al kal i ne
catal yst before compl eti on of the al cohol ysi s. Because
of thi s observati on, as wel l as economi c reasons, room
temperature was sel ected duri ng transesteri fi cati on.
5. Reaction Time and Stirring Time Optimiza-
tion. To achi eve perfect contact between the reagents
and the oi l duri ng transesteri fi cati on, they were mi xed
together.
21
The ester yi el d sl i ghtl y i ncreased as the
reacti on ti me i ncreased. Resul ts reveal ed that, after 1
min of stirring, a suitable phase separation was achieved.
The maxi mum yi el d of ester was reached after 30 mi n
of sti rri ng, whereas other researchers requi red up to
4 h.
23
6. SettlingTime Optimization. After the transes-
teri fi cati on was fi ni shed, the reacti on products were
pl aced i n a cl osed vessel , to be decanted. A successful
reacti on produces two l i qui d phases: ester (upper l ayer)
and gl ycerol (l ower l ayer). When room temperature was
>38 C, whi ch i s the usual temperature i n most pl aces
i n Andal usi a (Spai n) duri ng the summer, separati on
between the phases occurred wi thi n 1-3 h. However,
when room temperature decreased to 10-15 C, several
days were requi red for compl ete settl i ng to occur. To
i ncrease the pouri ng-off rate, a temperature i ncrease
was requested, i .e., wi th the hel p of a doubl e boi l er at
40 C. I n thi s case, compl ete settl i ng coul d be reached
i n <3 h, probabl y because of the posi ti ve i nfl uence of
the settl i ng temperature. I n fact, i t was noti ced that,
after a few days of settl i ng, the opaque ester sampl es
turned crystal l i ne, and a sl i ght gl ycerol l ower phase
appeared. Thi s coul d be expl ai ned by a certai n confl i ct
between gl ycerol sol ubi l i ty and l ow temperatures. I n
concl usi on, thi s probl em coul d be resol ved by i ncreasi ng
the settl i ng temperature or settl i ng ti me.
7. Purification StepOptimization. I t i s i mportant
to remove i mpuri ti es that are present i n the ester l ayer,
i .e., soaps, KOH traces, methanol traces, and free
gl ycerol . Otherwi se, a hi gh content of free gl ycerol can
resul t i n separati on of the gl ycerol , causi ng probl ems
duri ng storage, i n the fuel system or produce hi gher
al dehyde emi ssi ons.
25
I n the present work, washi ng wi th
di sti l l ed water, gentl e sti rri ng for 4 mi n, and settl i ng
i n a vessel (to al l ow decanti ng) was appl i ed to remove
mi neral contami nants i n the ester. After thi s step, two
l ayers were formed. The upper l ayer was made of
bi ofuel , and the l ower l ayer was made of water and
i mpuri ti es. Thi s process was repeated unti l the l ower
phase had a pH val ue that was si mi l ar to that of
di sti l l ed water, thus i ndi cati ng that onl y water was
present and that the i mpuri ti es were removed i n the
former washi ng. Prel i mi nary tests were conducted by
addi ng 2, 4, or 15 mL of di sti l l ed water to the ester (2.27,
4.55, or 17.01 wt % of ester, respecti vel y) and al l owi ng
the mi xture to settl e i n a vessel , to be poured off. After
the settl i ng was compl eted, the ester l ayer appeared
opaque, and a second washi ng process was performed
to achi eve a more sui tabl e and crystal l i ne sampl e of
ester (Fi gure 3). However, by addi ng 10 mL (11.36%)
or 15 mL (17.01%) of di sti l l ed water, no more washes
were needed. For economi c reasons, washi ng one ti me
usi ng 11.36%of di sti l l ed water at 25 C was consi dered
to be the best choi ce. Al so, washi ng more than one ti me
above room temperature i s not economi cal l y sound,
because of the addi ti onal cost, al though other research-
ers found i t necessary to wash several ti mes or use wash
water at temperatures up to 90 C.
23,24,26,27
I n Fi gure 3,
on the x-axi s, the fi rst addend of each sum i ndi cates the
percentage of di sti l l ed water used duri ng the fi rst step
of the washi ng process. The second addend i ndi cates the
percentage of di sti l l ed water used duri ng the second step
of the washi ng process, whi ch i s needed to achi eve a
pH val ue of the l ower l ayer that i s si mi l ar to the
pH val ue of the di sti l l ed water, thus i ndi cati ng that
no i mpuri ti es were present i n the ester l ayer after
the previ ous washi ng step. As i n Du Pl essi s et al .,
23
l osses of esters duri ng the washi ng process were<6%
(2%-3%).
8. Fuel Specifications. The fuel properti es of the
bi odi esel from Brassica carinata oi l wi thout eruci c aci d
were determi ned wi th the ai d of standard tests. The
bi odi esel properti es were determi ned to be si mi l ar to
those of di esel fuel (accordi ng to standard EN-590) and
were especi al l y si mi l ar to those of the EN 14214
standard, thus i ndi cati ng that methyl esters from
Brassica carinata oi l wi thout eruci c aci d have adequate
val ues, compared to di esel fuel (Tabl e 2). The i odi ne
val ue does not meet the EN 14214 standard. However,
thi s parameter (whi ch i s rel ated to bi ofuel storage
performance) has not been accepted by the Spani sh
government, because i t excl udes sunfl ower oi l (whi ch
i s one of the mai n Spani sh ol eagi nous crops) from bei ng
used as bi odi esel . I n thi s sense, to determi ne the
i mpl i cati ons of thi s parameter, research concerni ng the
performance of di esel engi nes i s needed.
The col d fi l ter pl uggi ng poi nt (CFPP), pour poi nt (PP),
and cl oud poi nt (CP) are three i mportant parameters
that are associ ated wi th the engi ne behavi or i n col d-
weather operati ng condi ti ons. However, i nstead of the
(24) Karaosmanogl u, F.; Akdag, A.; Ci gi zogl u, K. B. Appl. Biochem.,
Biotechnol. 1996, 61, 251-265.
(25) Mi ttel bach, M. Bioresour. Technol. 1996, 56, 7-11.
(26) Purcel l , D. L.; McCl ure, B. T.; McDonal d, J.; Basu, H. N. J .
Am. Oil Chem. Soc. 1996, 73, 381-388.
(27) Canakci , M.; Van Gerpen, J. Trans. ASAE 1999, 42, 1203-1210.
Transesterification of Brassica Carinata Oil Energy & Fuels, Vol. 18, No. 1, 2004 81
CP and PP, the European Standard EN 14214 onl y
i ncl udes the CFPP determi nati on. I n thi s sense, non-
eruci c Brassica carinata oi l methyl ester provi des a
sui tabl e fuel for col d-weather use. The CP and PP val ues
for noneruci c Brassica carinata oi l methyl ester are al so
more appropri ate than those for cottonseed methyl ester
(PP ) -4 C), soybean methyl ester (CP ) +2 C, PP )
-1 C), sunfl ower methyl ester (CP ) 0 C, PP ) -4
C), or rapeseed methyl ester (CP ) -2 C, wi th an al so
appropri ate PP val ue of -9 C).
14
Accordi ng to the Conradson carbon resi due (CCR)
content, whi ch represents the carbon-formi ng tendency
of fuel s, the bi odi esel from Brassica carinata oi l exhi b-
i ted a val ue over the No. 2 di esel fuel speci fi cati on (EN
590). Thi s coul d l ead to the formati on of deposi ts at the
i njector and combusti on probl ems. For thi s reason, a
l ong-term performance test shoul d be performed to
veri fy the formati on of abnormal carbon deposi ts or any
probl ems rel ated to i ncompl ete combusti on that coul d
requi re a more frequent cl eani ng.
Fi nal l y, regardi ng to the l ow presence of free gl ycerol ,
i t can be seen that the gl ycerol removal was successful l y
performed (see Tabl e 2), thus i ndi cati ng that the
puri fi cati on step was adequate.
Conclusions
A l ow-cost transesteri fi cati on process of Brassica
carinata oi l has been descri bed. An oi l :methanol mol ar
rati o of 1:4.6, the addi ti on of 1.4% of KOH, a reacti on
Figure 3. Ester pH after washi ng one and two ti mes wi th di sti l l ed water (percentage of ester wei ght).
Table 2. Fuel Specifications of Nonerucic Brassi ca Cari nata Oil Methyl Esters, Diesel Fuel (EN-590), and Biodiesel
European Standard (EN 14214)
Val ue
parameter test method
bi odi esel , European
Standard EN 14214
di esel fuel ,
EN-590
noneruci c Brassica carinata
oi l methyl esters
Di sti l l ate Properti es
di sti l l ate content at 250 C (vol %) ASTM-D-86 <65 0
di sti l l ate content at 350 C (vol %) ASTM-D-86 >85 83.60
temperature, 95 vol % (C) ASTM-D-86 360 357.2
Other Properti es
densi ty at 15 C (kg/m
3
) EN I SO 3675 860-900 820-860 888.8
ki nemati c vi scosi ty at 40 C (mm
2
/s) ASTM D445*I P-71*BS188 3.5-5.0 2-4.5 4.83
i odi ne val ue UNE 55.013 <120 138
fl ash poi nt (C) ASTM-D-2709 >120 >55 163
cetane number, CN
a
ASTM-D-613 >46
cetane i ndex, CI
a
ASTM-D-4737/96a >51.0 56.9
water content (mg/kg) ASTM-D-1744 <500 <50
col d fi l ter pl uggi ng poi nt, CFPP (C) I P-309/96 depends on the cl i mate -9
cl oud poi nt, CP (C) ASTM-D-2500 -9
pour poi nt, PP (C) ASTM-D-97 -6
Conradson carbon resi due (wt %) ASTM-D-4530 0.15 1.73
copper corrosi on (3 h, 50 C), degrees ASTM-D-130 Cl ass 1 1 1a
gross heati ng val ue (MJ/kg) I SO 1928 39.55
aci d val ue (mg KOH/g) EN 12634 <0.5 0.1
free gl ycerol (wt %) NF-T-60-704 0.0008 <0.02
a
The equati ons for predi cti ng the cetane number (CN) are not appl i cabl e to bi odi esel . As an al ternati ve method, the cetane i ndex (CI )
i s used for bi odi esel .
82 Energy & Fuels, Vol. 18, No. 1, 2004 Dorado et al.
temperature i n the range of 20-45 C, and 30 mi n of
sti rri ng are consi dered to be the best condi ti ons to
devel op a l ow-cost method to produce bi odi esel from
Brassica carinata oi l . The i mpuri ti es, i ncl udi ng gl ycerol
traces, are removed after the bi ofuel i s washed wi th
11.36% of di sti l l ed water at 25 C. Resul ts show that
the presence of eruci c aci d i ncreases the free fatty aci d
(FFA) content and prevents the conversi on of Brassica
carinata oi l i n i ts methyl ester. Al so, our resul ts suggest
that there i s a correl ati on between the amount of
methanol requi red to perform the transesteri fi cati on of
the oi l and the amount of KOH. I n thi s sense, the
greater the presence of KOH, the l esser the methanol
requi rements. However, thi s i s val i d onl y under certai n
l i mi ts. I n fact, i f the presence of KOH or methanol i s
l ess than the opti mal val ues, the reacti on does not ful l y
occur. Si mi l arl y, amounts of KOH or methanol that are
greater than the opti mal val ues l ead to soap producti on,
whi ch prevents separati on of the ester l ayer. Al so, a
certai n confl i ct between gl ycerol sol ubi l i ty and l ow
temperatures was observed. Thi s i s an i mportant factor
to consi der whi l e promoti ng the separati on of bi odi esel
and gl ycerol . Fi nal l y, based on thi s fi el d tri al , bi odi esel
from Brassica carinata oi l coul d be recommended as a
di esel fuel candi date, i f l ong-term engi ne performance
tests provi de sati sfactory resul ts.
Acknowledgment. The authors thank KOI PESOL
(Spai n), whi ch provi ded Brassica carinata oi l sam-
pl es for testi ng, and REPSOL-YPF, whi ch performed
anal yti cal anal ysi s to determi ne the bi ofuel speci fi ca-
ti ons.
EF0340110
Transesterification of Brassica Carinata Oil Energy & Fuels, Vol. 18, No. 1, 2004 83