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Applied Energy 108 (2013) 333339

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Biodiesel production by transesterication catalyzed by an efcient


choline ionic liquid catalyst
Mingming Fan, Jianglei Huang, Jing Yang, Pingbo Zhang
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Basic ionic liquid choline hydroxide


shows good catalytic activity in
biodiesel synthesis.
 Technological parameters of the
transesterication reaction are
optimized.
 Choline hydroxide catalyst can
catalyze the transesterication
without soap formation.
 The mechanism has been investigated
using quasi in situ IR.

a r t i c l e i n f o a b s t r a c t

Article history: The catalytic synthesis of biodiesel from soybean oil by transesterication over basic ionic liquid catalysts
Received 14 January 2013 had been studied at atmospheric pressure. Choline hydroxide (ChOH) catalyst exhibited better catalytic
Received in revised form 9 March 2013 activity compared with other basic ionic liquid catalysts, and methanol is the best alcohol for biodiesel
Accepted 23 March 2013
synthesis. The suitable molar ratio of methanol and soybean oil was 9:1, and the optimum catalyst dosage
Available online 11 April 2013
existed for catalytic activity, which was about 4 wt.% (without soap formation). The study also revealed
that the appropriate reaction temperature was about 60 C, and the suitable reaction time was 2.5 h on
Keywords:
the basis of biodiesel yield. The reusability test showed that ChOH catalyst had perfect utility for repeated
Biodiesel
Soybean oil
use. By basicity test, it was found that the basic ionic liquid ChOH possessed better basicity in methanol
Basic ionic liquid solution. The catalytic reaction mechanism was illuminated by the interaction between the methoxyl
Transesterication group after activating and the carbonyl group of the triglyceride, which has been investigated using quasi
in situ infrared spectroscopy.
2013 Elsevier Ltd. All rights reserved.

1. Introduction necessary to develop alternative clean and renewable energy


sources. Biodiesel, obtained from renewable biomass feedstock
Biodiesel has drawn more and more attention in recent years such as vegetable oil, can be used in diesel engines or blended at
because of rapidly increasing crude oil prices, limited fossil fuels, various proportions with petroleum diesel as fuel [3]. Several
and intensied environment pollution [1,2]. So it is increasingly methods for biodiesel production have been developed so far,
e.g., direct use and blending of raw oil [4], micro-emulsication
[5], pyrolysis [6]. A particularly promising method of producing
Corresponding author. Tel.: +86 510 85917090.
biodiesel is transesterication route [7]. Transesterication is the
E-mail address: pingbozhang@126.com (P. Zhang).

0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.03.063
334 M. Fan et al. / Applied Energy 108 (2013) 333339

chemical reaction that involves triglycerides and alcohol in the 2. Materials and methods
presence of a catalyst to form esters and glycerol. Most of hetero-
geneous catalysts are often used in transesterication reaction, be- 2.1. Catalyst preparation
cause catalysts can be easily removed from the reaction mixture by
ltration and recycled in the new process. Therefore, the loss of Preparation of choline hydroxide (ChOH). As shown in reaction
catalyst can be avoided [8]. Several different heterogeneous basic (1), equimolar choline chloride and KOH were dissolved in ethanol.
catalysts have been proposed for the biodiesel synthesis by transe- Thereafter, the solution was kept under vigorous stirring at 60 C
sterication reaction, such as alumina/silica supported K2CO3 cata- for 24 h. After cooling to room temperature, KCl was removed by
lysts [9], KOH/Al2O3 and KOH/NaY catalysts [10], cinder supported ltration, and ethanol was evaporated away from the mixture to
K2CO3 catalysts [11], KOH/bentonite catalysts [12], KNO3/Al2O3 so- obtain basic ionic liquid catalyst ChOH.

lid catalysts [13], Li-doped MgO catalysts [14], CaO catalysts [15 Preparation of choline methoxide (ChOMe). As shown in reac-
17], modied CaO catalysts [18], KF/CaO catalysts [19], KF/CaO tion (2), equimolar choline chloride and NaOCH3 were dissolved
MgO catalysts [20], and KF/CaOFe3O4 catalysts [21]. However, in ethanol, and then ChOMe could be prepared by the same exper-
vegetable oils may contain small amounts of water and free fatty imental steps with ChOH.

acids (FFA). For a base-catalyzed transesterication, the basic cata- Preparation of choline imidazolium (ChIm). As shown in reac-
lyst will react with the FFA to form soap which will lower the yield tion (3), iminazole was added into a vigorously stirring solution
of the biodiesel. The water produced during the saponication of equimolar NaOH in methanol at room temperature and the solu-
reaction will lead to the hydrolysis of the esters to form more tion was stirred for 45 min. With this solution, equimolar choline
FFA [7]. chloride and a certain amount of ethyl ether were added, and kept
Recently, ionic liquids have been reported as the promising cat- under vigorous stirring at room temperature for 24 h. After cooling
alysts for transesterication reaction for biodiesel synthesis. Acidic to room temperature, NaCl was removed by ltration, and the sol-
ionic liquids have drawn much more attention because of their vents were evaporated away from the mixture to obtain basic ionic
excellent catalytic activity, but high reaction temperature is liquid catalyst ChIm.
needed [2224]. On this point, it may be interesting to explore no-
vel basic ionic liquid catalysts for biodiesel synthesis from the

transesterication route with no soap formation. A survey of liter- 2.2. Catalytic performance
ature showed that there had been little references about the use of
basic ionic liquid as catalysts for biodiesel synthesis by transeste- Weighed amounts of soybean oil, methanol and the prepared
rication of soybean oil and methanol. In the present paper, several catalysts were added to a ask having a reux condenser, and a
basic ionic liquid catalysts based on choline chloride were pre- magnetic stirring apparatus. In typical experiment, a measured
pared for biodiesel production. The purpose of this paper is to ex- amount of catalysts (from 2 wt.% to 10 wt.% based on the weight
plore effective and stable ion liquid catalysts and optimum of reactantsmethanol/oil mixture) and weighed amounts of
reaction conditions for biodiesel synthesis from soybean oil. methanol and soybean oil (molar ratio of methanol to soybean
M. Fan et al. / Applied Energy 108 (2013) 333339 335

oil = 6:1, 9:1, 12:1, 15:1, 18:1) were introduced into the reactor. 3. Results and discussion
The reaction was carried out at 3065 C for 0.54.5 h. Then the
reaction mixture became biphasic, the upper phase was mainly 3.1. Choice of various basic catalysts
the desired biodiesel, and the lower phase, ionic liquid, methanol
and glycerol. The inuence of various catalysts is summarized rstly in Table
For biodiesel analysis, the upper phase was mixed with 1. ChOH, ChOMe, ChIm, NaOH and KOH are selected as the repre-
0.05 ml methyl salicylate (internal standard) in a 2 ml tube, fol- sentative catalysts for biodiesel synthesis. As shown in Table 1,
lowed by the addition of hexane (1.5 ml). Then, the treated sam- the biodiesel yield of ChIm catalyst is only 76.9%, and ChOMe cat-
ple (0.2 lL) was injected into the GC-122 gas chromatograph, alyst shows an increase in biodiesel production compared with
which was equipped with a SE-54 capillary column ChIm catalyst, but it is still not the best choice for the present
(0.32 mm  30 m). The column temperature was kept at 160 C study. ChOH catalyst effectively enhances the biodiesel production,
for 2 min, raised to 220 C at a rate of 10 C/min, then to the biodiesel yield reaches 95.0%, which is found to be even higher
260 C at a rate of 8 C/min, and nally maintained at this tem- than that of traditional basic catalysts NaOH (93.1%) and KOH
perature for 10 min. In our work, the mass concentration of bio- (92.2%). It is worth to mention that there is no soap formation
diesel was obtained by the GC and the yield of biodiesel was when ChOH catalyst dosage is 210 wt.% based on the weight of
calculated by the following equation: the reactants, however, soap will appear when catalyst dosage is
over 2.5% for NaOH and KOH under same reaction conditions. Thus,
ChOH is selected as the catalyst in the following work.
mactual C esters  n  V esters
Yield   100%
mtheoretical moil
C esters  n  V oil C esters  n 3.2. Effect of n(Methanol)/n(Soybean Oil)
  100%   100% 4
moil qoil
The relation between molar ratio of methanol to soybean oil
n(Methanol)/n(Soybean Oil) and the catalytic performance of
where both mactual (g) and mtheoretical (g) are the actual mass and ChOH catalyst is investigated. The yield of biodiesel is shown in
theoretical mass of biodiesel; moil (g) is the mass of soybean oil; n Fig. 1 as a function of n(Methanol)/n(Soybean Oil). As can be seen
is the diluted multiple of biodiesel; Cesters (g/mL) is the mass con- in Fig. 1, the yield of biodiesel steeply increases at a low n(Metha-
centration of biodiesel; qoil (g/mL) is the density of soybean oil; nol)/n(Soybean Oil), followed by a gradual decrease at n(Metha-
Vesters (mL) and Voil (mL) are the volumes of biodiesel and soybean nol)/n(Soybean Oil) > 15:1. The increase in the amount of
oil, respectively [21,25,26]. methanol will produce two different effects to the reaction. On
To investigate the reusability of ChOH, the lower phase was rst the one hand, the increase of the reactant methanol can enhance
distilled and then separated by solvent extraction to purify the cat- the conversion rate of soybean oil, hence increasing the biodiesel
alyst. The separation procedures are explained in detail as follows. yield, which is advantageous to the reaction and dominant at
Because the lower phase contained the ionic liquid catalyst, glyc-
erol and excess methanol, rst the excess methanol
Table 1
(b.p. = 64.8 C) can be separated from the mixture by distillation. Catalytic performances of different basic catalysts.
Then the ionic liquid was separated from glycerol by solvent
Entry Catalyst Catalyst dosage (wt.%) Yield of biodiesel (%)
extraction. 2 ml n-butanol and 4 ml water were added into the
above mixtures, which was fully mixed and placed for form two 1 ChOH 4 95.0 1.7
2 ChOMe 4 88.3 1.8
phases. The lower phase contained glycerol and water. The desired
3 ChIm 4 76.9 1.9
ionic liquid was presented in the upper 1-butanol phase. 1-Butanol 4 NaOH 2 93.1 1.1
(b.p. = 117.7 C) was removed by vacuum distillation in order to 5 KOH 2 92.4 1.2
gain the desired ionic liquid. The recovery of the ionic liquid was
Reaction conditions: 60 C, 2.5 h, methanol: soybean ratio of 9:1.
above 95%.

2.3. Characterization

The basicity of the catalysts in methanol solution was deter-


mined by pH meter (Sartorius PB-10).
Quasi in situ IR measurements were carried out with an ABB Bo-
mem FTLA2000-104 spectrometer with 4 cm1 resolution and
5004000 cm1 scanning ranges, using KBr pellets. Under the reac-
tion condition, the reactant and the catalyst was mixed and reacted
for 160 min. Then a drop of sample from the reaction system was
coated in KBr pellets for the observation of reaction intermediates
formed during the reaction.

2.4. Properties of soybean oil

The soybean oil (average molecular weight = 871.16 g/mol) as


analyzed before the initiation of the transesterication reaction
at the preliminary stage exhibited acid value of 0.49 mg KOH g1 Fig. 1. Effect of n(Methanol)/n(Soybean Oil) on biodiesel production. (Reaction
of oil, and saponication index (Sv = 193.68 mg KOH g1). conditions: 60 C, 2.5 h, catalyst dosage 4 wt.%.)
336 M. Fan et al. / Applied Energy 108 (2013) 333339

Fig. 2. Effect of catalyst dosage on biodiesel production. (Reaction conditions: 60 C,


2.5 h, methanol:soybean ratio of 9:1.) Fig. 3. Effect of reaction temperature on biodiesel yield. (Reaction conditions: 2.5 h,
methanol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)

n(Methanol)/n(Soybean Oil) < 9:1. On the other hand, the increase


of the reactant methanol may lead to a relative decrease in the con-
centration of soybean oil and the catalyst, although the absolute
amount of catalyst increases slightly, which is disadvantageous
to the reaction and dominant at n(Methanol)/n(Soybean
Oil) > 15:1. Under the present reaction conditions, the optimum
n(Methanol)/n(Soybean Oil) for the biodiesel synthesis is about
9:1 considering both factors of biodiesel yield and reactant meth-
anol consumption.

3.3. Effect of catalyst dosage

The inuence of catalyst dosage on biodiesel synthesis is sum-


marized as shown in Fig. 2, and the catalyst dosage represents
the mass ratio of ChOH catalyst and the reactants (methanol/oil
mixture), m(catalyst):m(reactants). As can be observed from
Fig. 2, there are distinct increasing trends in biodiesel yield as
the catalyst dosage increases. The biodiesel yield was steeply in-
creased from 73.8% to 95.0% with an increase of catalyst dosage
from 1 wt.% to 4 wt.%, followed by a gradual leveling off at a cata- Fig. 4. Effect of biodiesel production with reaction time. (Reaction conditions:
lyst dosage >4 wt.%. Thus, it should be pointed out that the optimal 60 C, methanol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)

catalyst dosage 4 wt.% was chosen for the production of biodiesel.


2.5 h to 4.5 h, the yield of biodiesel remained almost unchanged.
3.4. Effect of reaction temperature Conclusively, 2.5 h could be the optimal reaction time for the
reaction.
Fig. 3 gives the effect of reaction temperature on the biodiesel
yield at atmospheric pressure. As can be seen, the biodiesel yield
increases with the change of reaction temperature from 30 C to 3.6. Effect of different alcohols
60 C and then decreases. Fig. 3 suggests that increasing reaction
temperature will improve catalytic activity in a certain extent The biodiesel yields for the different alcohols (methanol, etha-
but higher reaction temperature may result in methanol evaporat- nol, propanol, isopropanol, butanol) are shown in Fig. 5. The type
ing quickly, which is an unfavorable factor for improving the con- of alcohols used affects the synthesis reaction for biodiesel very
version of soybean oil. Thus, an optimum reaction temperature obviously, which is perhaps because of the different dissociation
exists for catalytic activity, which is about 60 C. degree of the ve alcohols in oil phase. For alcohols, the more
substituted alkyl the alcohol gets, the weaker dissociation degree
3.5. Effect of reaction time the alcohol has. Therefore, the acidity decreased as the alkyl group
substitution increased [27]. Methanol can be easier to form alkox-
Fig. 4 shows the effect of reaction time in the range of 0.54.5 h ide ions compared with the other four counterparts, which is help-
on the biodiesel yield at atmospheric pressure. As expected, reac- ful to the transesterication reaction. From Fig. 5, it is interesting
tion time affects the synthesis reaction for biodiesel very clearly. that only 10.6% of biodiesel is produced when isopropanol is em-
Only 85.2% of biodiesel is produced at the reaction time of 0.5 h, ployed, it is supposed that the higher steric hindrance of isopropa-
but its formation is increased with the increase of the reaction time nol inhibits the ester exchange process to a great extent. In
from 0.5 h to 2.5 h. When the reaction time was increased from summary, methanol is the best alcohol for biodiesel synthesis.
M. Fan et al. / Applied Energy 108 (2013) 333339 337

Table 2
The basicity of different basic catalysts a.

C (mol/L) pH
0.1 0.3 0.6
ChOH 12.92 13.76 13.80
ChOMe 11.94 12.30 12.55
ChIM 12.47 12.74 12.94
NaOH 12.15 12.34 12.51
KOH 12.40 12.83 13.16
a
Determining conditions: solvent: methanol, T = 25 C.

facilitated the enhancement of catalytic activity. It may be as


new environment friendly catalyst to take the place of traditional
basic catalyst like NaOH, KOH and so on.

3.9. The proposed reaction mechanism

Fig. 5. Catalytic performances of different alcohols. (Reaction conditions: 60 C, The transesterication of soybean oils with methanol to biodie-
2.5 h, alcohol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)
sel is a typical nucleophilic substitution reaction. It was that nega-
tively charged nucleophiles attack the positively charged carbonyl
carbon of the original. The proposed reaction mechanism of ionic
liquids catalysts is illustrated in Scheme 1, based on the present
experimental observations. As known, the OH of basic ionic liquid
acted as active center on biodiesel synthesis through transesteri-
cation of methanol. In our case, the ionic liquids catalysts have two
OH groups. It is suggested that both OH groups as active centers
interact with isolated electron pair at O atom in methoxyl group.
Firstly, the methoxyl group from methanol is activated by the
active species OH. The methoxyl group after activating is attacked
by carbonyl group of triglyceride. The intermediate with methoxyl
group translated into diglyceride group with producing methyl es-
ter. Further, when methanol as reactants entered the catalysts sys-
tem, the intermediate products diglyceride group react rapidly
with nucleophilic reagent (CH3OH) to produce methoxyl group
and diglyceride. Finally, the other carbonyl group of diglyceride
is also attacked by methoxyl group after activating with producing
methyl ester in the same way. In the reaction system, the extrac-
tion of glycerol from the reaction intermediate facilitates the bio-
diesel production. It was supposed that the catalytic activity of
Fig. 6. Reusability of ChOH catalyst. (Reaction conditions: 60 C, 2.5 h, methanol: ChOH ionic liquid catalysts for the transesterication of triglycer-
soybean ratio of 9:1, catalyst dosage 4 wt.%.) ide with CH3OH depends strongly on their capability of activating
the methoxyl group by the active species OH of basic ionic liquid,
which was not only related with the basicity, but also with the
3.7. Reusability of ChOH catalyst
intermiscibility in the reactants.

The experiments were done to test the reusability of ChOH cat-


alyst, and the results were summarized as shown in Fig. 6. From 3.10. Structure characterization
Fig. 6, the yield of biodiesel is appreciably lower than that for the
fresh catalyst. The biodiesel yield remains 90.1% when the ChOH In order to prove the proposed reaction mechanism, the reac-
is employed for the second time, and the ChOH catalyst still yields tion intermediates were characterized by quasi in situ IR. Infrared
82.5% after four successive uses. Therefore, it can be concluded spectra of the mixture of methanol and ChOH catalyst were re-
from the results that ChOH catalyst not only exhibits a favorable corded to aid the interpretation of the reaction intermediates pre-
catalytic performance during the transesterication reaction but sented under reaction conditions. Spectra of methanol, ChOH
also has perfect utility for repeated use. catalyst and the mixture of methanol and ChOH catalyst at 60 C
are shown in Fig. 7, respectively. A strong band in the spectrum
of methanol is seen at 1026 cm1, which is attributable to metha-
3.8. Basicity test nol in liquid phase. After a contact time of 30 min, bands appear at
1014 cm1, due to the CAO stretching vibrations of the methoxyl
The pH values for methanol solution containing different con- group [28,29], which is likely due to methoxyl group formed dur-
centrations of basic catalysts were shown in Table 2. As seen in Ta- ing the initial reaction stage. It is reasonable to suppose that the
ble 2, the pH values of three ionic liquids were high, which have methoxyl group from methanol is activated by the active species
shown strong basicity. It was suggested that ionic liquids had ion- OH and formed.
ization ability in methanol solution. The basicity of ionic liquids The infrared spectrum of the mixture at 60 C is shown in Fig. 8.
was near the traditional alkali. Among them, the ionic liquid ChOH Bands are seen at 1750 cm1 due to the anti-symmetric and sym-
gave better ionization ability in methanol solution, which metric C@O stretching vibrations of carbonyl group for ester. A
338 M. Fan et al. / Applied Energy 108 (2013) 333339

Scheme 1. The proposed reaction mechanism of ChOH ionic liquids catalysts.

evidenced by the progressive increase in the intensities of the


bands at 1171, and 1198 cm1. From Fig. 8, the intensities of two
bands at 1439 and 1461 cm1 increased with the reaction from D
to F, which was related to the deformation of CH2 and CH3 groups
when the oil converted to biodiesel.

4. Conclusion

In this work, the basic ionic liquid catalysts for synthesis of bio-
diesel from soybean oil were evaluated in terms of yield of biodie-
sel. The ChOH catalyst showed better catalytic performance when
n(Methanol)/n(Soybean Oil) was 9:1 and catalyst dosage was
4 wt.%. The appropriate reaction temperature was 60 C, and the
favorable reaction time was 2.5 h. The reusability test showed that
ChOH catalyst had perfect utility for repeated use. The basic ionic
liquid ChOH possessed better basicity in methanol solution, which
promoted the catalytic performance. The reaction intermediates
methoxyl group formed has been proved using quasi in situ infra-
red spectroscopy. These pathways are supported by experiments
Fig. 7. IR of methanol, ChOH and the mixture under 60 C. (A: ChOH; B: Methanol;
involving the formation of fatty acid methyl ester.
and C: the mixture of Methanol and ChOH under 60 C for 30 min.)

Acknowledgements

The nancial supports from the Specialized Research Fund for


the Doctoral Program of Higher Education (New Teachers) (Grant
No. 20100093120003), the National Natural Science Foundation
of China (NSFC) (Grant No. 21106054) and the Fundamental Re-
search Funds for the Central Universities (JUSRP211A07) are grate-
fully acknowledged.

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