Bioresource Technology 100 (2009) 23082310

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Preparation of biodiesel from waste oils catalyzed by a Brnsted acidic ionic liquid
Minghan Han *, Wulang Yi, Qin Wu, Ying Liu, Yongchun Hong, Dezheng Wang
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

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

Article history: Preparation of biodiesel from waste oils catalyzed by a novel Brnsted acidic ionic liquid with an alkane
Received 7 August 2008 sulfonic acid group was investigated. The acidity and the activity of the ionic liquid were very low at
Received in revised form 17 October 2008 lower temperature when the ionic liquid was crystalloid; they recovered at higher temperature when
Accepted 18 October 2008
the crystallized ionic liquid was liqueed. When methanol:oils:catalyst molar ratios were 12:1:0.06,
Available online 13 December 2008
the yield of fatty acid methyl esters can reach 93.5% after the reaction of acidic oil with methanol had
taken place at 170 C for 4 h. In addition, the ionic liquid had a good reusability and can be easily sepa-
Keywords:
rated from the biodiesel by simple decantation.
Biodiesel
Brnsted acidic ionic liquid
2008 Elsevier Ltd. All rights reserved.
Waste oil
Transesterication
Esterication

1. Introduction In recent years, room-temperature ionic liquids have attracted

With rapidly increasing crude oil prices, limited fossil fuels, and
intensied environment pollution, it is increasingly necessary to
develop alternative clean and renewable energy sources. Biodiesel,
as an alternative diesel fuel, is a biodegradable and renewable fuel.
Biodiesel, consisting of fatty acid methyl esters (FAME), is usually
produced by transesterication of vegetable oil or animal fat with
methanol in the presence of a catalyst. Conventionally, the catalyst
is homogeneous base catalysts, such as potassium hydroxide, so-
dium hydroxide, or their alkoxide (Crabbe et al., 2001; Al-Widyan
and Al-Shyoukh, 2002; Felizardo et al., 2006).
Although the raw materials used to produce biodiesel are avail-
able from a wide variety of sources, only inexpensive materials
(such as waste oils) are valuable for the production of biodiesel
in China. However, waste oils contain large amount of fatty acids
and cannot be used to prepare biodiesel catalyzed by an alkali;
otherwise there will be a serious saponication.
In order to make use of waste oils as raw materials, fatty acids
should be converted into FAME by the esterication of fatty acids
with methanol. The esterication is usually catalyzed by an acidic
catalyst, such as sulfuric acid or benzene sulfonic acid. However,
sulfuric acid and benzene sulfonic acid catalysts are corrosive
and are not easily recovered, leading to the release of environmen-
tal unfriendly efuents, which inevitably leads to a series of envi-
ronmental problems. Because of the detrimental effects of these
catalysts, great efforts directed toward the development of envi-
ronmental friendly catalysts have been made.
* Corresponding author. Tel.: +86 10 62781469; fax: +86 10 62772051.
E-mail address: hanmh@tsinghua.edu.cn (M. Han).
much interest as relatively clean and promising catalysts and alter-
native solvents that possess important attributes, such as wide li-
quid range, negligible vapor pressure, high catalytic activity,
excellent chemical and thermal stability, potential recoverability,
design possibilities, and ease of separation of the products from
reactants (Seddon, 1997; Welton, 1999; Wilkes, 2002). Many or-
ganic reactions involving alkylation (Xin et al., 2005; Piao et al.,
2004), esterication (Xing et al., 2005), nitration (Qiao and Yokoy-
ama, 2004), hydrogenation, epoxidation, or DielsAlder have been
performed in room-temperature ionic liquids with excellent yields
and selectivity (Gordon, 2001; Zhao et al., 2002). Nevertheless, an
example of direct using ionic liquids as catalyst for the esterica-
tion of waste oils to biodiesel is absent from the literature except
our groups (Han et al., 2006; Wu et al., 2007a).
In this study, a novel Brnsted acidic ionic liquid with an alkane
sulfonic acid group was prepared and used for the preparation of
biodiesel from waste oil. It was characterized by infrared (IR) spec-
troscopy and thermogravimetry (TG). The effects of varying reac-
tion conditions on the production of biodiesel were studied.
2. Methods
2.1. Preparation of SO3H functional Brnsted acidic ionic liquid
(Yoshizawa et al., 2001; Cole et al., 2002)
Pyridine was stirred solvent free with 1,4-butane sulfone,
respectively, at 40 C for 1 day. The zwitterion produced, which
was a white solid, was washed three times with toluene to remove
unreacted material and dried in a vacuum. A stoichiometric

0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.10.046
 M. Han et al. / Bioresource Technology 100 (2009) 23082310 2309

Table 1 zation, the ionic liquid losses a H2O and forms a sulfonate, that is
Sources and basic properties of waste oils. the reason that the crystallization of the ionic liquid can not be ob-
Source Acid number/ Fatty acid content/ served when it contains a sufcient amount of water.
mgKOH
g 1 wt.%
Cottonseed oil Yiyang 4.8 2.2 3.1.2. TG analyze of the ionic liquid
Swill oil Beijing 73 35.5 According to the weight loss curve of the ionic liquid, the ther-
Sewer oil Beijing 100 4050 mal decomposition temperature was 320 C. The weight loss curve
Soybean oil Daqing 122 62
sediment
also proved the ionic liquid possessed high thermal stability and
Acidic oil Xingtai 168 84 wide liquid range, which is about 300 C.

3.2. Effect of the acid number of waste oils

amount of concentrated sulfuric acid was added dropwise to the
zwitterion, and the mixture was stirred at 40 C for 23 days until The main components of the waste oils are triglycerides and
liqueed, resulting in the formation of the ionic liquid. The ionic li- fatty acids, the acid numbers of the waste oils will increase with
quid was washed repeatedly with toluene and ether to remove the increase of the fatty acid contents. The experimental results
unreacted material and dried under vacuum. The purity of the ionic listed in Table 2 showed that the conversion increased with the in-
liquid was more than 95% as characterized by NMR spectroscopy crease of the acid number of the waste oils, this is the reason that
(Wu et al., 2007b). the esterication of fatty acids with methanol took place much
quicker than the transesterication of triglycerides with methanol,
2.2. Characterization of the ionic liquid catalyst that is that the waste oils which contains more fatty acid can be
easily converted into FAME.
The structure of the ionic liquid was analyzed by NMR spectros-
copy (Wu et al., 2007b) and IR spectroscopy. IR spectra were re- 3.3. Effect of the reaction conditions on the reaction
corded on a Nicolet Nexus 670 FTIR spectrometer using KBr
windows suitable for Fourier transform infrared (FTIR) transmit- As shown in Fig. 1, the FAME content increased with an increase
tance technology to form a liquid lm. The thermal decomposition in reaction temperature every 20 C from 80 to 180 C. However,
temperature was determined by TG analysis. although the temperature interval of the increase is equal, the cor-
responding increased FAME content was reduced gradually. These
2.3. Preparation of biodiesel from waste oils and analysis results indicate that the effect of reaction temperature on the reac-
tion became smaller with an increase in temperature. On the con-
The source and basic properties of the waste oils used in the trary, the pressure increase in the reactor rises greatly with the
experiments are listed in Table 1. Methanol was obtained from Bei- increase of reaction temperature. Thus the preferred reaction tem-
jing Chemical Co., Ltd. The reaction was carried out in a 250 mL perature is between 170 and 180 C.
cylindrical stainless steel reactor, equipped with a thermostat,
mechanical stirring, and a sampling outlet. Waste oil, methanol
and ionic liquid catalyst with different molar ratios were quantita- Table 2
Effect of acid numbers on the yield of FAME.
tively introduced into the reactor successively. The reaction was al-
1
lowed to proceed for 15 h with vigorous stirring and heating at Acid number/mgKOH
g Yield of FAME/wt.%
the desired temperature. After the reaction, the reactor was cooled Cottonseed oil 4.8 45.0
to room-temperature and two phases were formed. The lower Swill oil 73 58.5
phase consisted of the produced methyl esters, and the upper Sewer oil 100 66.5
Soybean oil sediment 122 72.1
phase contained the ionic liquid catalyst, water and excess metha-
Acidic oil 168 78.0
nol. The lower phase containing the methyl esters was simply sep-
arated from the upper phase by decantation. Reaction conditions: n (methanol):n (oil):n (catalyst) = 12:1:0.057; 65 C; 5 h.
The biodiesel products were analyzed by a Shimadzu LC-10AT
HPLC using an ultraviolet detector. An ODS-2 column (4.6 mm 
5 lm  150 mm) was used and the mobile phase was acetone/ace- 100
tonitrile mixture (50:50 v/v) at a ow rate of 1.0 mL/min. The col-
umn temperature was 40 C and the detection wavelength was
210 nm. The biodiesel samples were diluted with acetone (HPLC 80
grade).
Methyl ester
3. Results and discussion 60
Content (wt.%)

Diglyceride
Monoglyceride
3.1. Characterization of the ionic liquid catalyst Triglyceride
40

3.1.1. Property variation of the ionic liquid at different temperatures

The crystallization of the ionic liquid which contained 1% H2O 20
was observed after stored at 5 C for 24 h, but the crystallization
can not be observed after stored at 5 C for more than a month
when its water content is more than 15%, the crystallized ionic li- 0
quid can be liqueed at 40 C. The crystallized ionic liquid had al-
80 100 1 20 140 1 60 180
most no acidity and activity, its acidity and activity recovered after o
Reaction temperature / C
liquefaction. The IR spectra of the crystallized ionic liquid and the
liqueed ionic liquid showed that some groups of crystallized ionic Fig. 1. Effect of reaction temperature on the reaction. Reaction conditions:
liquid and the liqueed ionic liquid were different. After crystalli- n(methanol):n(swill oil):n(catalyst) = 12:1:0.1; 3 h.
2310 M. Han et al. / Bioresource Technology 100 (2009) 23082310
Table 3
Effect of the molar ratio of ionic liquid/methanol to oil on the reaction.
Molar ratio of ionic Methyl ester Molar ratio of Methyl ester
liquid to oil content, wt.%* methanol to oil content, wt.%**
0.03 67.5 3 70
0.034 83.2 6 81.5
0.06 93.5 12 91
0.115 95.8 18 92.5
*
Reaction conditions:n (methanol):n (acidic oil) = 12:1; 170 C; 4 h.
**
Reaction conditions:n (ionic liquid):n (Cottonseed oil) = 0.06:1; 170 C; 5 h.
The effect of the molar ratio of ionic liquid to oil on the reaction,
listed in Table 3, illustrated that with an increase in the molar ra-
tio; the reaction rate was enhanced, resulting in a higher FAME
content. This was attributed to the increase in acidity in the reac-
tion system. In addition, when the molar ratio was less than 0.06, it
had a signicant effect on the catalytic performance. The FAME
content obviously increased from 67.5% to 93.5% in 4 h when the
dosage of the ionic liquid was increased from 0.03 to 0.06. How-
ever, when the molar ratio was more than 0.06, it had a slight ef-
fect on the catalytic performance. A slight increase in the FAME
content was observed when the molar ratio was increased from
0.06 to 0.115. Thus, considering the reaction rate and the cost of io-
nic liquid, the optimum molar ratio of ionic liquid to oil is 0.06.
In addition, as the molar ratio of methanol to oil increased, the
FAME content was rapidly increased. Since transesterication and
esterication in biodiesel production are reversible reactions,
increasing the amount of methanol is benecial to the forward
reactions. In addition, since the ionic liquid catalyst was readily
soluble in methanol, increasing the amount of methanol will en-
hance the contact area between the catalyst and the oil, resulting
in a higher rate of reaction. When the molar ratio of methanol to
oil was less than 12, the amount of methanol had a signicant ef-
fect on the catalytic activity. The FAME content was obviously in-
creased from 70% to 91% in 5 h when the molar ratio of
methanol to oil increased from 3 to 12. However, if this ratio was
further increased, the concentration of catalyst will be greatly di-
luted, resulting in a slight increase in the rate of reaction. There-
fore, when the molar ratio of methanol to oil was more than 12,
the amount of methanol had a slight effect on the catalytic perfor-
mance. A slight increase in the FAME content was observed as the
molar ratio of methanol to oil increased from 12 to 18. Moreover, a
higher molar ratio of methanol to oil will cause a larger amount of
methanol to be separated from the ionic liquid during recycling.
For this reason, the optimal molar ratio of methanol to cottonseed
oil 12 is preferable.
3.4. Economic evaluation
Obviously, the above reaction conditions are hardly competitive
with those of the common process using hydroxide or alkoxide, the
operation cost using the ionic liquid is higher than that using
hydroxide or alkoxide. As we know, the cost of the raw material
(animal/plant oils) is more than 80% total cost of biodiesel, only
inexpensive materials (such as waste oils) are valuable for the pro-
duction of biodiesel in China. However, waste oils contain large
amount of fatty acids and cannot be used to prepare biodiesel cat-
alyzed by an alkali, otherwise, there will be a serious saponica-
tion, so hydroxide or alkoxide can not be used for the
preparation of biodiesel from waste oils.
Eventhough the price of the ionic liquid is about 15 times as
that of potassium hydroxide which is a common catalyst for the
preparation of biodiesel, the ionic liquid can be reused repeatedly.
For the used ionic liquid which consists of water, methanol and
little glycerin, water must be removed from it by distillation. After
distillation, the ionic liquid can be reused again for another run
repeatedly. Our experiments showed that the yield of FAME de-
creased slightly after nine runs. The decrease of the yield is due
to the ionic liquid lost gradually in the operations which include
phase separation, decantation and so on. Therefore, we can con-
clude that the catalytic activity of the ionic liquid was almost not
changed after repeated reuses; the ionic liquid is a very promising
catalyst for the preparation of biodiesel from waste oils in industry.
4. Conclusion
The acidity and activity of the Brnsted acidic ionic liquid with
an alkane sulfonic acid group are very low at lower temperature
when the ionic liquid is crystalloid; they recover at higher temper-
ature when the crystallized ionic liquid is liqueed.
From various parametric studies, such as dosage of the ionic li-
quid, molar ratio of methanol to oil, and reaction temperature, an
optimum reaction condition was established. When metha-
nol:oils:the ionic liquid molar ratio was 12:1:0.06, the yield of fatty
acid methyl esters can reach 93.5% after the reaction of acidic oil
with methanol had taken place at 170 C for 4 h.
The ionic liquid can be reused repeatedly, so it has potential
application in the production of biodiesel.
Acknowledgements
This work is supported by the State Key Program of National
Nature Science Foundation of China (20436050) and National Basic
Research Program of China (Nos. 2004CB719706, 2009CB219901).
References
Al-Widyan, M.I., Al-Shyoukh, A.O., 2002. Experimental evaluation of the
transesterication of waste palm oil into biodiesel. Bioresource Technol. 85,
253256.
Cole, A.C., Jensen, J.L., Ntai, L., Tran, K.L.T., Weaver, K.J., Forbes, D.C., Davis, J.H., 2002.
Novel bronsted acidic ionic liquids and their use as dual solvent-catalysts. J. Am.
Chem. Soc. 124, 59625963.
Crabbe, E., Nolasco-Hipolito, C., Kobayashi, G., Sonomoto, K., Ishizaki, A., 2001.
Biodiesel production from crude palm oil and evaluation of butanol extraction
and fuel properties. Process Biochem. 37, 6571.
Felizardo, P., Correia, M.J.N., Raposo, I., Mendes, J.F., Berkemeier, R., Bordado, J.M.,
2006. Production of biodiesel from waste frying oil. Waste Manage. 26, 487
494.
Gordon, C.M., 2001. New developments in catalysis using ionic liquids. Appl. Catal.
A: Gen. 222, 101117.
Han, M.H., Wu, Q., Chen, H., Wang, J.F., Jin, Y., 2006. A method for biodiesel
preparation, China Patent 200610083300.6.
Piao, L.Y., Fu, X., Yang, Y.L., Tao, G.H., Kou, Y., 2004. Alkylation of diphenyl oxide with
at-dodecane catalyzed by ionic liquids. Catal. Today 93, 301305.
Qiao, K., Yokoyama, C., 2004. Nitration of aromatic compounds with nitric acid
catalyzed by ionic liquids. Chem. Lett. 33, 808809.
Seddon, K.R., 1997. Ionic liquids for clean technology. J. Chem. Tech. Biotechnol. 68,
351356.
Welton, T., 1999. Room-temperature ionic liquids, solvents for synthesis and
catalysis. Chem. Rev. 99, 20712083.
Wilkes, J.S., 2002. A short history of ionic liquids from molten salts to neoteric
solvents. Green Chem. 4, 7380.
Wu, Q., Chen, H., Han, M.H., Wang, D.Z., Wang, J.F., 2007a. Transesterication of
Cottonseed oil catalyzed by bronsted acidic ionic liquids. Industrial &
Engineering Chemistry Research 46 (24), 79557960.
Wu, Q., Dong, B., Han, M., Zuo, Y., Jin, Y., 2007b. Synthesis and characterization of
novel Brnsted acidic ionic liquids. Spectroscopy and Spectral Analysis 27 (10),
20272031.
Xin, H.L., Wu, Q., Han, M.H., Wang, D.Z., Jin, Y., 2005. Alkylation of benzene with 1-
dodecene in ionic liquids [Rmim]+Al2Cl6X (R = butyl, octyl and dodecyl,
X = chlorine, bromine and iodine). Appl. Catal. A: Gen. 292, 354361.
Xing, H.B., Wang, T., Zhou, Z.H., Dai, Y.Y., 2005. Novel Brnsted-acidic ionic liquids
for esterications. Ind. Eng. Chem. Res. 44, 41474150.
Yoshizawa, M., Hirao, M., Ito-Akita, K., Ohno, H., 2001. Ion conduction in
zwitterionic-type molten salts and their polymers. J. Mater. Chem. 11, 1057
1062.
Zhao, D., Wu, M., Kou, Y., Min, E., 2002. Ionic liquids: applications in catalysis. Catal.
Today 74, 157189.