Bioresource Technology 113 (2012) 19–22

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

Short Communication

Continuous biodiesel production in a fixed bed reactor packed

with anion-exchange resin as heterogeneous catalyst
Yanbiao Ren a, Benqiao He a,⇑, Feng Yan a, Hong Wang a, Yu Cheng a, Ligang Lin a, Yaohui Feng a, Jianxin Li a,b,⇑
a
The State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300160, PR China
b
The Laboratory of Membrane Materials and Separation Engineering Technology, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, PR China

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

Article history: A continuous biodiesel production from the transesterification of soybean oil with methanol was inves-
Received 23 August 2011 tigated in a fixed bed reactor packed with D261 anion-exchange resin as a heterogeneous catalyst. The
Received in revised form 27 October 2011 conversion to biodiesel achieved 95.2% within a residence time 56 min under the conditions: reaction
Accepted 28 October 2011
temperature of 323.15 K, n-hexane/soybean oil weight rate of 0.5, methanol/soybean oil molar ratio of
Available online 11 November 2011
9:1 and feed flow rate of 1.2 ml/min. The resin can be regenerated in-situ and restored to the original
activity to achieve continuous production after the resin deactivation. The product obtained was mainly
Keywords:
composed of methyl esters. No glycerol in the product was detected due to the resin adsorbing glycerol in
D261 anion-exchange resin
Biodiesel
the fixed bed, which solved the issue of glycerol separation from biodiesel. It is believed that the fixed bed
Continuous transesterification reactor with D261 has a potential commercial application in the transesterification of triglyceride.
Fixed bed reactor Ó 2011 Elsevier Ltd. All rights reserved.
Heterogeneous catalyst

1. Introduction version of biodiesel was up to 97.25% at a reaction time of over

Biodiesel has become more and more attractive as an alterna-
tive fuel resource due to the advantages of renewability and low
emissions (Srivastava and Prasad, 2000; McNeff et al., 2008). Bio-
diesel prepared by the heterogeneous catalysts is becoming the fo-
cus of current investigation (Kim et al., 2004; López et al., 2005;
Feng et al., 2011). Ion-exchange resin as one kind of heterogeneous
catalysts has greater advantages over the homogeneous catalysts,
enzyme and supercritical methanol in easy recovery and regenera-
tion, high activity and stability, low cost (Kalu et al., 2011; Krohn
et al., 2011). Vicente et al. (1998) firstly investigated the ion-ex-
change resins (anionic: Amberlyst A26 and Amberlyst A27, cat-
ionic: Amberlyst 15) for the transesterification of sunflower oil
with methanol in a batch mode. Unfortunately, the conversions ob-
tained for all ion-exchange resins used did not exceed 1%. Shibasa-
ki-Kitakawa et al. (2007) obtained a high conversion close to 90% in
a batch transesterification of triolein with ethanol with anion-
exchange resin (PA306s resin) as a catalyst. Recently, Long et al.
(2011) prepared N-methylimidazole functionalized anion
exchange resin containing NaOH. The co-catalysis of anion
exchange resin with NaOH enhanced the transesterification of
soybean oil with methanol, superior to NaOH solely used. The con-
⇑ Corresponding authors. Tel./fax: +86 22 83955055.
E-mail addresses: hebenqiao@tjpu.edu.cn, hebq2008@gmail.com (B. He), lijx@
sari.ac.cn, jxli0288@yahoo.com.cn (J. Li).
10 h in a batch mode.
Another important advantage of the resin catalysts is suitable to
continuously produce biodiesel. The continuous esterification of
acidified oil with methanol in a fixed bed reactor packed with cat-
ion exchange resin for biodiesel production was widely investi-
gated and good results were achieved (Santacesaria et al., 2007;
Feng et al., 2011). However, the continuous transesterification of
triglyceride with alcohol is not satisfied up to now. Shibasaki-
Kitakawa et al. (2007) investigated a continuous transesterifictaion
of crude triolein with ethanol in fixed bed reactor. The conversion
to biodiesel of about 80% was achieved at a residence time of
60 min, lower than that in batch mode. Recently, Edric et al.
(2011) studied the transesterification of refined coconut oil with
methanol in a fixed bed reactor. It was found that mass transfer
is the rate-determining step and a conversion of only 78%
was achieved. The result was obtained in a non-homogeneous
phase system, leading to the unsatisfied conversion. Further, the
operation stability of the reactor and the regeneration of resins
were not investigated in the continuous mode.
In our previous work (Feng et al., 2011), a continuous esterifica-
tion processes with a conversion of over 98% within 500 h running
time was achieved in a fixed bed to produce biodiesel. As a follow-
up work, a continuous transesterification of soybean oil with meth-
anol for biodiesel production was investigated with a strongly
basic anion-exchange resin (D261) as a heterogeneous catalyst in
this work. The variable influences (co-solvent, feedstock ratio, flow
rate, water content in soybean oil) on the biodiesel conversion

0960-8524/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.10.103
20 Y. Ren et al. / Bioresource Technology 113 (2012) 19–22
were investigated. The operational stability and the regeneration of
the resin catalyst were examined in order to develop a potential
commercial application of anion resins for continuous transesteri-
fication of triglyceride.
2. Methods
2.1. Materials
The soybean oil was purchased from Tianjin Jiali grainoil Co.
Ltd., China and distilled to remove water before use. Methanol
and all co-solvents including methyl tert-butyl ether (MTBE), n-
hexane, tert-butyl alcohol (TBA) and tetra-hydrofuran (THF) were
analytic reagents and purchased from Tianjin Kermel chemical re-
agent Co. Ltd., China. Anion-exchange resin D261 with quaternary
ammonium groups in a chloride form was purchased from the
Chemical Plant of NanKai University, China (physical properties
of the resin presented in s-Table 1 in supplementary information).
To generate the catalytic activity, the following activated proce-
dure was carried out. The resin was firstly washed with deionized
water to remove impurities. And then, the resin was immersed into
the solution of 5.0 wt.% KOH in methanol for 12 h to transform
from chloride form into hydroxyl form. Finally, the alkaline D261
was washed with methanol to pH  7 and stored in airtight condi-
tion before use.
2.2. Continuous transesterification in a fixed bed reactor
The continuous transesterification was performed in a fixed bed
reactor system. The scheme of the fixed bed reactor system was
shown in Fig. 1. The reactor was composed of a water-jacketed
stainless steel column with an internal diameter of 25 mm and a
height of 450 mm. The column was packed with the activated
D261 resin. Methanol, oil and co-solvent were mixed and pre-
heated in a feedstock tank and then fed to the inlet of reactor using
a peristaltic pump. The reaction temperature was controlled by a
thermostat water bath to keep constant temperature with an error
of ±0.5 K. The temperature difference between the inlet and the
outlet was below 0.5 K during all the runs. Ten milliliters of efflu-
ent was collected at each hour of reaction time when the effluent
outlet
Fixed bed reactor
pump
pump
inlet
feedstock
tank
Thermostat
Water bath
Heater
Fig. 1. Scheme of the experimental apparatus for the continuous transesterification.
solution from the outlet of reactor was introduced into an accumu-
lation tank. Then the effluent was purified by reduced pressure dis-
tillation to remove the excess methanol and co-solvent. Methanol
and co-solvent collected were recycled. The left sample was col-
lected for the conversion and composition measurement.
2.3. Regeneration of the resin packed in the fixed bed reactor
In order to maintain the activity of resin D261 in fixed bed reac-
tor, the resin needs to regenerate when the catalytic efficiency
dropped. Basically, the regeneration procedure consisted of the fol-
lowing steps: (1) flushing with methanol at a flow rate 10 ml/min
for 20 min to remove the organic substances (such as glycerol or
esters) absorbed on the resin particles; (2) washing with the
solution of 5.0 wt.% KOH in methanol at a flow rate of 1.5 ml/min
for 90 min to restore the activity of the resin; (3) washing with
methanol to pH  7. The regenerated D261 resin was available
for the next run.
2.4. Analyses of the samples
The FAME conversion was determined by 1H nuclear magnetic
resonance (1H NMR). Samples prepared in CDCl3 were recorded
on a DRX-500 spectrometer operating at 300 MHz (Bruck Co.).
The percent conversion was calculated by the ratio of the area of
the singlet peak associated with methyl esters at 3.7 ppm and the
peaks at 2.3 ppm representative of the a-methylene protons in
the ester molecule. (Knothe, 2001).
The composition of the product obtained was analyzed by Gas
Chromatography–Mass Spectrometry (GC–MS: 6890 N GC/5973
MS, Agilent Technologies).
3. Results and discussion
3.1. Effect of co-solvents and reaction parameters
Soybean oil and methanol are immiscible and would separate
into two phases if no co-solvent exists. A suitable co-solvent added
into the reactants can make the reactants form homogeneous
phase so as to improve the reaction rate (Kim et al., 2004). In this
accumulation
tank
 Y. Ren et al. / Bioresource Technology 113 (2012) 19–22
study, the influences of four co-solvents (MTBE, n-hexane, TBA and
THF) on the biodiesel conversion were investigated under the con-
ditions: methanol/oil molar ratio of 9:1, co-solvent/oil weight rate
of 0.9, reaction temperature of 323.15 K, resin loading of 80 g, feed-
stock flow rate of 1.2 ml/min (namely, a residence time of 55 min).
The result showed that the four co-solvents all exhibited excellent
co-solubility for the soybean oil/methanol system. High FAME
conversion was achieved, 98.9%, 98.4%, and 96.7% for THF, TBA
and n-hexane, respectively. MTBE seems not to be suitable because
a lower conversion of 85.1% was obtained under the same condi-
tions. However, THF can swell the resin. TBA with a low melting
point of 328.15 K has poorer solubility in soybean oil. Therefore,
n-hexane was chosen as the appropriate co-solvent and used in
the following experiment.
Optimum loading amount of n-hexane can achieve a high FAME
conversion and reduce the production cost of biodiesel. So the
influence of n-hexane loading on the FAME conversion was studied
(see s-Fig. 2 in supplementary information). A quick increase in
FAME conversion from 67.6% to 95.2% with increasing n-hexane/
soybean oil weight rate from 0.3 to 0.5. This is because the homo-
geneous phase state of the system was not formed when the rate is
less than 0.5. Further increasing the rate from 0.5 to 1, FAME
conversion only was slightly raised to 97.8%. Considering the pro-
duction cost, n-hexane/soybean oil weight rate of 0.5 was adopted.
Transesterification is a reversible equilibrium reaction. The
molar ratio of reactants is one of the most important variables
affecting the conversion of ester. It was found from the experiment
that FAME conversion was increased from 89.2% to 95.2% with an
increase in the methanol/soybean oil molar ratio from 3:1 to 9:1.
Further increasing the ratio from 9:1 to 28:1, the conversion
dropped from 95.2% to 87.7%. A low conversion obtained at low
methanol/soybean oil molar ratio was due to the incomplete reac-
tion (Enciner et al., 2002). However, too high methanol/soybean oil
ratio also lead to a low conversion as a result of the diluted soybean
oil concentration in the reaction system (Kim et al., 2004). It was
also found that no trace of glycerol in the effluents was detected
by GC–MS and NMR mentioned below when the methanol/soy-
bean oil molar ratio is below 9:1, which may be related to the low-
er solubility of glycerol in the reactant system and resin adsorbing
glycerol particle. This is an advantage that glycerol separation from
product can leave out. When the methanol/soybean oil molar ratio
is beyond 9:1, especially, 28:1, a large amount of glycerol was col-
lected from the effluent. Therefore, the methanol/soybean oil mo-
lar ratio of 9:1 was believed to be an optimal value in the
present process.
Feed flow rate as a function of the reaction time (or residence
time) is one of the key parameters in a continuous transesterifica-
tion. FAME conversion initially increased from 85.5% to 95.2%
when the feed flow rate increased from 0.6 to 1.2 ml/min. Further
increasing feed flow rate from 1.2 to 1.7 ml/min, a decrease from
95.2% to 70.5% in FAME conversion occurred. The maximum FAME
conversion of 95.2% was achieved at feed flow rate around 1.2 ml/
min. This phenomenon was agreed with the results obtained by
Tepe and Dursun (2008). At a low flow rate, a liquid film formed
on the resin surface improved the resistance of the mass transfer.
Raising feed flow rate helps to reduce the resistance, resulting in
a high conversion (Tepe and Dursun, 2008). When too high flow
rate (1.2–1.7 ml/min) was adopted, the reactants will pass through
the resin column in a shorter time. A shorter residence time results
in a low FAME conversion (Halim et al., 2009).
Generally, water has a negative effect on the transesterification
of oils for homogeneous catalysts due to soap formation (Marchetti
et al., 2007). The effect of water content in the range of 0–5.0 wt.%
related to soybean oil on transesterification was examined in order
to investigate the endurance of the resin to water. The transesteri-
fication experiments run under the following conditions: metha-
21
nol/oil molar ratio of 9:1, co-solvent/oil weight rate of 0.5,
reaction temperature of 323.15 K, resins loading of 80 g, the feed-
stock flow rate of 1.2 ml/min. It was found that the FAME conver-
sion decreased from 95.2% to 87.7% with water content increasing
from 0 wt.% to 1.0 wt.% and keep stable when the water content
further increased from 1.0 wt.% to 5.0 wt.% (see s-Fig. 5 in supple-
mentary information). From the viewpoint of chemical reaction
equilibrium, there is no influence of water on transesterification.
But water could deactivate catalytic active sites (OH ) because
water molecules can bind on the active sites more effectively than
methanol (López et al., 2005). It could hold back the hydrophobic oil
molecules to come into contact with the catalyst to some extent,
which would slow down the reaction rate. When the active sites
were saturatedly bound with water, the more water was not harm
to the reaction anymore and the conversion kept stable though the
water content in feedstock increased. This is different from the
phenomenon observed in the homogeneous transesterification that
the soap will be formed to hinder the transesterification when the
water content is beyond 1.0 wt.% (Banerjee and Chakraborty,
2009). Hence, D261 has a better tolerance to the water com-
pared with the homogeneous catalysts, such as KOH, NaOH. The
transesterification can be directly carried out with D261 as a
catalyst even though less water exists in the reactants. Therefore,
it is believed that D261 should be an ideal candidate catalyst for
transesterification in a continuous process of the esterification
following transesterification because about 5.0 wt.% water is firstly
produced in the esterification (Liu et al., 2009).
3.2. Analysis of reaction product
The reaction product obtained by removing methanol and co-
solvent was analyzed by GC–MS listed in s-Table 2 in supplemen-
tary information. The product mainly contained four esters: C16:0
(palmitic), C18:2 (linoleic), C18:1 (oleic) and C18:0 (stearic) acids
of methyl esters. No trace of glycerol, monoglycerides and diglyce-
rides in product were detected in GC–MS, similar to the result ob-
tained in NMR spectrum. Most likely, the glycerol produced was
adsorbed in the resin column. To be more specific, the amount of
glycerol washed out from the fixed bed by methanol after the
end of the reaction was close to the theoretic value from the con-
version. This should be an advantage that can solve the issue of
glycerol separation from biodiesel, even though the absorbed glyc-
erol can retarded the catalytic activity of the resin.
3.3. Catalytic stability and regeneration of D261
The catalytic stability of the resins is a key parameter in the
continuous transesterification. The catalytic activity of D261 with
the time was investigated at the reaction conditions: methanol/
oil molar ratio of 9:1, resins loading of 80 g, n-hexane/oil weight
rate of 0.5, flow rate of 1.2 ml/min and reaction temperature of
323.15 K. It was found that FAME conversion may keep above
90% when continuously running for 4 h. But the activity of the resin
quickly declined after 4 h. The conversion was only 23.7% at 8 h.
One reason for the resin deactivation was because glycerol
adsorbed on the resins mentioned above covered the active sites
and made the catalyst in a pretend state (Chen et al., 2005;
Shibasaki-Kitakawa et al., 2007). Another reason for the deactiva-
tion was due to the leakage of hydroxyl ion of the resins. This
was testified by the drop of ion exchange capacity (IEC) of D261
from 0.32 to 0.21 mmol/g after reaction for 8 h, which is possibly
because the hydroxyl ions were replaced by the fatty acid groups
during the transesterification reaction (Shibasaki-Kitakawa et al.,
2007). The further research on the deactivation of D261 will
carried out in the future work.
22 Y. Ren et al. / Bioresource Technology 113 (2012) 19–22
According to the above results, it is necessary for the used resin
D261 to regenerate after running for 4 h. It is found that the IEC of
the resins was restored to 0.28 mmol/g from 0.21 mmol/g at a
deactivated state of the resin after flushing by methanol. At the
same time, much glycerol, ester and less triglyceride were col-
lected. Hence the first flushing step is to remove the organic sub-
stances (such as glycerol or esters) covered on the resin surface.
The second step is to wash with the solution of 5.0 wt.% KOH in
methanol to activate the risen. The third step is to wash with meth-
anol to pH  7. After regenerating the resins through the three
steps, the IEC value of the regenerated resin reached to
0.32 mmol/g, equal to the IEC value of the fresh activate resin. Five
cycle experiments of catalysis-regeneration of the resin were car-
ried out (see s-Fig. 7 in supplementary information). It was found
that the deactivated resin was all restored to the initial activity
and the biodiesel conversion can keep above 90% for every run.
This indicates that resin D261 had an excellent chemical stability.
4. Conclusions
In a continuous transesterification of soybean oil with methanol
in a fixed bed reactor, D261 exhibited a high catalytic activity. n-
Hexane as an appropriate co-solvent can highly increase the FAME
conversion. High FAME conversion (95.2%) was obtained under
the optimum conditions. The resin can be regenerated in-situ and
restored to the original activity. GC–MS analysis reveals that the
product is simplex and mainly composed of C16:0 (palmitic),
C18:2 (linoleic), C18:1 (oleic) and C18:0 (stearic) acids of methyl
esters. Glycerol was not detected in GC–MS and NMR due to resin
absorbing, which is an advantage for product separation. It is be-
lieved that D261 has a potential commercial application in contin-
uous transesterification of soybean oil.
Acknowledgements
The authors gratefully acknowledge the financial support by
National High Technology Research and Development Program of
China (‘‘863’’ Program, Grant No. 2009AA03Z223), National Natural
Science Foundation of China (Grant No. 21174104 and 50903091)
and International Cooperation Funding (Grant No. 2010DFA51090).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.biortech.2011.10.103.
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