Renewable Energy 88 (2016) 51e57

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Preparation and catalytic performance of N-[(2-Hydroxy-3-

trimethylammonium) propyl] chitosan chloride /Na2SiO3 polymer-
based catalyst for biodiesel production
Mengzhu Liang, Benqiao He*, Yixuan Shao, Jianxin Li, Yu Cheng
State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University,
Tianjin 300387, China

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

Article history: A novel polymer-based alkaline catalyst was prepared with sodium silicate (Na2SiO3) and N-[(2-
Received 3 March 2015 Hydroxy-3-trimethylammonium) propyl] chitosan chloride (HTCC), interlinked by epichlorohydrin
Received in revised form (ECH), for biodiesel production. The structure and properties of the catalyst were studied by Fourier
1 October 2015
transform infrared spectroscopy, thermogravimetry-mass spectrometry and transmission electron mi-
Accepted 9 November 2015
Available online 19 November 2015
croscopy. The effects of the variables on the transestericaton of soybean oil to biodiesel were investi-
gated. It is found that Na2SiO3 was bridged on HTCC chains through ECH and well dispersed in HTCC
matrix in nano size. The transesterication conversion reached at 97.0% under the reaction conditions of
Keywords:
Biodiesel
methanol/oil molar ratio of 6:1, catalyst loading of 4.0 wt.% at 55
C for 60 min. After the second run, the
Transesterication catalytic activity kept stable, which was contributed to the stability and dispersion of Na2SiO3 in the
Organiceinorganic hybrid catalyst catalyst.
Sodium silicate 2015 Elsevier Ltd. All rights reserved.
Chitosan

1. Introduction
Biodiesel is biodegradable and renewable because vegetable
oils, animal fats or algal oil are the main raw materials of biodiesel,
which emits less sulfur compounds, particulate matter and un-
burned hydrocarbons than traditional fuel [1e3]. The most com-
mon way to produce biodiesel is through transesterication of
triglyceride with alcohol to yield fatty acid alkyl esters (i.e., bio-
diesel) and glycerol. The transesterication reaction can be alkali
catalyzed, acid catalyzed or enzyme catalyzed. The alkali catalyst
has received more attention because of its higher catalytic ef-
ciency compared to acidic and enzyme catalyst [4e6]. The alkali
catalysts can be classied into homogeneous and heterogeneous
catalysts [5,6]. The homogeneous alkali catalysts, such as NaOH,
KOH and NaOCH3, are employed in the transesterication at labo-
ratory, pilot and industrial scale levels with mild reaction condi-
tions [7,8]. However, the present processes have some limitations,
such as tedious separation of liquid alkali which in turn causes a
dramatic increase in purication cost and environmental pollution
[9e11]. In recent years, the heterogeneous alkali catalysts, such as
* Corresponding author.
E-mail address: hebenqiao@tjpu.edu.cn (B. He).
alkaline earth metal oxides, transition metal oxides and salts, have
drawn more and more attention because they could be easily
separated from the product, thus reducing the pollution, recycling
the catalysts and avoiding the washing process [12e14]. Kouzu
et al. [14] investigated the transesterication of edible soybean oil
in the presence of calcium oxide (CaO), achieving a yield of 93%. But
Ca soap appeared in the product. Sodium silicate (Na2SiO3) is also
an effective heterogeneous alkali catalyst, exhibiting high catalytic
activity for transesterication of triglyceride with methanol
[15e17]. But it was difcult for Na2SiO3 to reuse in the trans-
esterication of soybean oil, because non-calcined Na2SiO3 can be
hydrolyzed and dispersed into the reactants. And the activity of the
calcined Na2SiO3 with a big particular size also depressed with
runs.
In order to improve the recyclability and dispersity of the solid
catalysts, the solid catalysts were often required to support on some
inorganical materials, such as metal oxides, clays and hidrotalcites.
Su et al. [18] reported that alkaline earth metal oxides (MgO, CaO,
SrO and BaO) supporting copper oxide were used as bi-functional
catalysts for transesterication and selective hydrogenation to
produce biodiesel from highly unsaturated hempseed oil. The Cu/
SrO catalyst maintained the transesterication activity even after
being used for 8 cycles though the biodiesel yield slightly

http://dx.doi.org/10.1016/j.renene.2015.11.036
0960-1481/ 2015 Elsevier Ltd. All rights reserved.
52 M. Liang et al. / Renewable Energy 88 (2016) 51e57
decreased. But prior to each reaction, the catalysts needed to
calcine at 1000
C in vacuum for 5 h [18]. Hydrotreated TiO2 sup-
ported potassium catalysts were studied by Salinas et al. [19].
Raising calcination temperature led to the transformation of the
supported potassium catalyst into a titanate form of oxide, which
was accompanied by a substantial increase in catalytic activity [19].
Dang et al. [20] prepared a kaolin-based catalyst from natural
kaolin. The conversion efciencies of soybean and palm oils to
biodiesel over the catalysts reached 97.0% and 95.4%, respectively,
under optimal conditions. But performance of the catalyst could
deteriorated after one cycle [20]. In general, these solid catalysts
were often prepared through a complicated process and need to
calcine at high temperature. Moreover, the solid catalyst often exist
in a powder form.
Up to now, most work was still focused on the preparation of
novel solid alkali catalysts or the catalysts supported on inorganic
oxides for the biodiesel production. Very few studies were reported
on inorganic alkali catalysts chemically supported onto organic
polymer chains. The advantages of the solid catalysts chemically
supported onto polymer chains are to substantially improve cata-
lytic stability and endow the processing of the catalysts with high
specic surface area [21,22].
In the present work, an organiceinorganic hybrid alkaline
catalyst from Na2SiO3 and N-[(2-hydroxy-3-trimethylammonium)
propyl] chitosan chloride (HTCC) for biodiesel production was
prepared. Na2SiO3 was chemically bridged onto HTCC chains with
an interlinker to improve the stability of Na2SiO3 in the polymer.
The properties of the catalyst were characterized with Fourier
transform infrared spectroscopy (FTIR), thermogravimetry-mass
spectrometry (TG-MS) and transmission electron microscopy
(TEM). The catalytic performance of the catalyst was investigated.
2. Material and methods
2.1. Materials
HTCC with an ammonium substitution degree of 95.6% was
purchased from Nantong Lvshen Bioengineering Co., LTD, China.
Sodium silicate pentahydrate (Na2SiO3$5H2O, 28.0e30.0 wt.% Na2O,
the weight ratio of Na2O/SiO2 1.03 0.03), epichlorohydrin (ECH)
(99.0%) and glutaraldehyde (GA) (50%) were purchased from Ker-
mel Corp., Tianjin, China. Rened soybean oil from Fu-hong Corp.,
Liaoning, China was purchased from local supermarket. The other
chemicals are all analytical reagent grade and used without further
purication.
2.2. Preparation of HTCC/Na2SiO3/ECH catalyst
The preparation procedure of HTCC/Na2SiO3/ECH was shown in
Scheme 1. Six grams of ECH was rstly dropwise added into
Na2SiO3 aqueous solution (14.0 g Na2SiO3$5H2O in 30 ml water) at
65
C for 4 h under stirring to obtain Na2SiO3/ECH aqueous solution.
Next, 10.0 g HTCC and 10 ml sodium hydroxide (NaOH) solution
(0.067 mol/l) were added into Na2SiO3/ECH aqueous solution at
65
C for 6 h to get HTCC/Na2SiO3/ECH aqueous solution. Herein,
NaOH was used to neutralize hydrogen chloride produced during
the reaction of alkyl chlorine in ECH with hydroxyl groups of HTCC
[23]. The HTCC/Na2SiO3/ECH aqueous solution was cast carefully
onto teon plates and dried at 65
C under 1.33 kPa for 24 h in a
vacuum oven to obtain HTCC/Na2SiO3/ECH catalyst. Finally, the
catalyst was rinsed with methanol to remove NaOH and the
unreacted epichlorohydrin and then dried at 65
C under 1.33 kPa
for 24 h in a vacuum oven on standby. The catalyst used in the
following experiment was made by this method if not specially
indicated. Another method was also adopted to prepare the hybrid
catalyst as follows: ECH (or GA) was directly dripped into HTCC/
Na2SiO3 aqueous solution to obtain HTCC/Na2SiO3/ECH catalyst (or
HTCC/Na2SiO3/GA catalyst). The other conditions and procedures
were the same as the above.
2.3. Characterization of the catalysts
FTIR spectra of the samples were measured on a FTIR TENSOR 37
(BRUKER Corporation, Germany) operated by Attenuated Total
Reectance (ATR) in the wavenumber range of 4000e500 cm1.
On-line TG-MS analysis of the gas evolved from the sample was
performed simultaneously using the STA-409CD (NETZSCH, Ger-
many) with Skimmer coupled to a quadruple mass spectrometer
QMA 400 (maximum 512 amu). The TG experiments were operated
from 30 to 800
C at a heating rate of 10
C min1 under a
continuous ow of helium (100 ml min1). A transfer line, specially
designed to connect a vacuum pump in order to optimize the
amount of evolved gases, transferred from the TG to the MS. A mass
analysis was performed each 2 s to record mass fragments between
2 and 300 atomic mass units. The measurement of outlet gas via
mass spectrometric intensities was plotted as a function of
temperature.
The dispersity of Na2SiO3 in the HTCC was measured by trans-
mission electron microscope (TEM Hitachi 7650). Their dilute so-
lutions were cast on the Cu grids to obtain thin lms for TEM
measurement.
2.4. Transesterication of soybean oil with methanol over the
catalysts
Batch experiments were carried out in a 250 ml glass ask with
mechanic agitation at atmospheric pressure. The system contained
a warmer jacket. The soybean oil was fed into the glass ask and
preheated before the catalyst and methanol were added. The
catalyst was cut into pieces to achieve better contact. The basic
reaction conditions were as follows if not specially stated. Meth-
anol/oil molar ratio is 6:1, the reaction time is 60 min, the reaction
temperature is 55
C, the amount of the catalyst with respect to
soybean oil is 4.0 wt.%. After reaction completion, the catalysts and
the excess methanol were recovered by centrifugation and vacuum
distillation, respectively.
2.5. Analysis of the biodiesel samples
The conversion of soybean oil was determined by 1H nuclear
magnetic resonance (1HNMR). Samples dissolved in CDCl3 were
recorded on a DRX-500 spectrometer operating at 300 MHz (Bruck
Co.). The percent conversion is 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. The equation is given by Knothe [24].
2ACH3
C  100% (1)
3ACH2
where C is the conversion of soybean oil; ACH3 is the integration
area of the methyl protons (the strong singlet peak); ACH2 is the
integration area of the methylene protons. The factors 2 and 3
derive from the fact that the methylene carbon possesses two
protons and the alcohol (methanol-derived) carbon has three
protons.
The product obtained was analyzed by GC (Agilent Technologies
6890 N), using a capillary column with a length of 30 m, a inner
diameter of 0.32 mm and a lm thickness of 0.25 mm. Helium was
used as a carrier gas. The chromatography was taken out in
 M. Liang et al. / Renewable Energy 88 (2016) 51e57 53

OH NH OH

OH OCH2CHCH2Cl
O=Si O
O=Si
ONa R n
ONa O
Cl NH OH CH2O
(Na2SiO3/ECH) OCH2CHCH2
O
O O=Si OH
(ECH) n ONa
O

CH2OH
(HTCC/Na2SiO3/ECH)
(HTCC)

R: -CH2CHCH2N(CH3)3Cl or -COCH3
OH

Scheme 1. Schematic of the preparation for HTCC/Na2SiO3/ECH.

constant ow mode with a ow rate of 0.6 ml min1 (6 psi). A split
injector was used with a split ratio of 80:1 and a temperature of
523 K. The ame ionization detector (FID) was operated at 573 K.
The oven was maintained initially at 483 K for 9 min. Then, it was
elevated to 503 K at 20 K min1, and remained for 10 min. Total run
time for this method was 29 min.
(mainly with the hydroxyl groups from hydrolysis of Na2SiO3 [16])
to produce new bond SieOeC. For HTCC/ECH spectrum, a new peak
appeared at 1258 cm1 compared with HTCC, attributing to the
CeOeC stretching from cross-linking structure between ECH and
HTCC. These results suggested that ECH was reacted with HTCC and
Na2SiO3 so as to x Na2SiO3 on HTCC chains as showed in Scheme 1.

3. Results and discussion 3.2. Thermal analysis

3.1. FTIR analysis
The FTIR spectra of HTCC, HTCC/ECH, Na2SiO3$5H2O, Na2SiO3/
ECH and HTCC/Na2SiO3/ECH were measured to characterize the
interaction of ECH with HTCC and Na2SiO3$5H2O as shown in Fig. 1.
For Na2SiO3/ECH, new bands at 2920e2869 cm1 were observed
compared with Na2SiO3$5H2O, which are attributed to asymmetric
and symmetric eCH2 groups from ECH. The asymmetric stretching
vibration absorption peaks of SieOeC appeared at 1105 and
1048 cm1. There is no peak at 927 and 836 cm1, implying that no
epoxy groups existed in Na2SiO3/ECH. And the CeCl group of ECH at
760 cm1 still existed in the spectra of Na2SiO3/ECH. These results
suggested that the epoxy groups of ECH reacted with Na2SiO3
The temperatures of weight loss for the samples were listed in
Table 1. Na2SiO3$5H2O exhibited three main weight losses. The rst
weight loss occurred at around 91.0
C, which was associated with
the loss of physically absorbed water. The other two weight losses
at 136.1 and 160.5
C were due to the loss of the crystal water. The
manifest weight loss for Na2SiO3$5H2O was about 41.6% in the
temperature region of 100e180
C, nearly equal to the theoretical
weight (43.4%) of the crystal water in Na2SiO3$5H2O. For HTCC,
there emerged two weight losses. The rst weight loss centered at
about 95.5
C due to the loss of physically adsorbed water. The
second weight loss at 259.7
C came from the decomposition of
HTCC.
In the hybrid systems, the HTCC/Na2SiO3 displayed three weight
losses. The peaks at 152.3 and 187.8
C were from the crystal water
of Na2SiO3$5H2O. The one at 287.7
C represented the thermal
decomposition of HTCC, which is 28.0
C higher than pure HTCC.
This indicates that the HTCC in hybrid system was more thermo-
stable than pure HTCC.
As to Na2SiO3/ECH, two new weight losses appeared at 351.0 and

Table 1
Temperatures of weight loss for Na2SiO3$5H2O, HTCC, HTCC/Na2SiO3, Na2SiO3/ECH,
HTCC/Na2SiO3/ECH and HTCC/Na2SiO3/GA.

Materials Temp. of max. weight loss (
C)

Na2SiO3$5H2O 91.0, 136.1, 160.5

HTCC 95.5, 259.7
HTCC/Na2SiO3 152.3, 187.8, 287.7
Na2SiO3/ECH 178.4, 351.0, 470.9
HTCC/Na2SiO3/ECHa 138.4, 282.7, 294.1, 358.7, 437.6
HTCC/Na2SiO3/ECHb 137.5, 274.3, 290.7, 350.2, 423.8
HTCC/Na2SiO3/GA 178.9, 246.4, 286.3

ECH: Epichlorohydrin, HTCC: N-[(2-Hydroxy-3-trimethylammonium) propyl] chi-

Fig. 1. FTIR spectra of Na2SiO3$5H2O, Na2SiO3/ECH, HTCC, HTCC/ECH and HTCC/ tosan chloride), GA: glutaraldehyde.
a
Na2SiO3/ECH samples (FTIR: Fourier transform infrared spectroscopy; ECH: Epichlo- Obtained from the rst preparation method of HTCC/Na2SiO3/ECH catalyst.
b
rohydrin; HTCC: N-[(2-Hydroxy-3-trimethylammonium) propyl] chitosan chloride). Obtained from the second preparation method of HTCC/Na2SiO3/ECH catalyst.
54 M. Liang et al. / Renewable Energy 88 (2016) 51e57
470.9
C. Actually, there were no weight losses appeared in this
range for pure Na2SiO3$5H2O and ECH (the boiling point of ECH was
117.9
C). So it was inferred that the two weight losses were orig-
inated from new bonds between Na2SiO3 and ECH, suggesting that
ECH could be reacted with Na2SiO3.
For HTCC/Na2SiO3/ECH catalysts obtained from the two
methods mentioned in section 2.2, both catalysts displayed ve
weight losses as shown in Table 1. The weight loss at 138.4
C was
from the crystal water of Na2SiO3$5H2O, the one at 282.7
C was
associated with the thermal decomposition of HTCC, the one at
294.1
C was attributed to the thermal decomposition of the cross-
linked HTCC by ECH. While the weight losses at 358.7 and 437.6
C
may be from the thermal decomposition of new product from the
reaction between Na2SiO3 and ECH. The residual mass rate was
50.2 wt.%, which means Na2SiO3 loaded in HTCC/Na2SiO3/ECH
catalysts was 50.2 wt.%.
For HTCC/Na2SiO3/GA, there were only three weight losses at
178.9, 246.4 and 286.3
C. The weight loss at 178.9
C was related to
the crystal water of Na2SiO3$5H2O. The weight loss at 246.4
C was
due to the thermal decomposition of HTCC. The one at 286.3
C was
the result from the cross-linked HTCC by GA. But no weight losses
appeared when the temperature was higher than 300
C, different
from HTCC/Na2SiO3/ECH catalyst. It was inferred that there could be
no new bond formation between Na2SiO3 and HTCC or GA.
TGeMS analysis was used to further demonstrate the formation
of new bonds between Na2SiO3 and ECH. Table 2 detailed the mass
to charge ratio (m/z values) of the different species from Na2SiO3/
ECH. The evolved gases were CO2 (m/z 44) and H2O (m/z 18).
The m/z 18 (H2O) was presented four weight losses at 94.4, 178.5,
359.9 and 471.5
C. The rst one was assigned to the adsorbed
water. The second one, more intense, at 178.5
C can be attributed
mainly to the crystal water of Na2SiO3$5H2O. The ones at 359.9 and
471.5
C can be assigned to the loss of the H2O molecules due to the
decomposition of ECH chemically attached to Na2SiO3$5H2O.
Further, the other mass fragments (m/z 15, 31, 39, 42, 43, 44, 57,
58) were almost captured at around 354 and 480
C. These mass
fragments were identical to the MS fragments of ECH. This sug-
gested that the lost matter at about 354 and 480
C was from ECH.
Therefore, it further demonstrated that ECH was chemically
bonded with Na2SiO3, in accordance to the results from FTIR spectra
of Na2SiO3/ECH.
3.3. Dispersity of Na2SiO3 particles in the catalyst
The dispersion of Na2SiO3 in different matrices was investigated
by TEM as shown in Fig. 2. The size of Na2SiO3/ECH particles (about
29e162 nm in Fig. 2b) was larger than Na2SiO3 (about 2e15 nm in
Fig. 2a), since Na2SiO3/ECH was agglomerated. The distribution of
Na2SiO3 was uniform in HTCC/Na2SiO3 as shown in Fig. 2c. Fig. 2d
displayed that Na2SiO3 was also well dispersed in HTCC/Na2SiO3/
ECH catalyst with a smaller size compared to Na2SiO3/ECH, far
Table 2
Analysis of the outlet gases from the decomposition of Na2SiO3/ECH by TG-MS.
m/z Assignment of fragments Temperature of weight loss (
C)
15 $CH3 355.9, 475.5
18 H2O 94.4, 178.5, 359.9, 471.5
31 $CH2OH 363.1, 487.3
39 $C3H3 361.2, 486.0
42 $C2H2O 358.0, 478.1
43 $C2H3O 357.2, 478.1
44 CO2 354.6, 479.2
57 $C3H5O 367.8, 475.5
58 $C3H6O 365.6,474.3
TG-MS: thermogravimetry-mass spectrometry.
smaller than the particles of calcined sodium silicate reported by
Guo et al. [15]. It is suggested that Na2SiO3 had good compatibility
with HTCC and well distributed in HTCC. The compatibility was also
demonstrated by X-ray diffraction spectra (not shown here). The
diffraction peaks of Na2SiO3 crystal almost disappeared in Na2SiO3/
HTCC and HTCC/Na2SiO3/ECH samples because Na2SiO3 crystal-
lizing was destroyed by the interaction of Na2SiO3 and HTCC. This
would help to increase the surface area of catalyst, and nally
enhance the catalytic performance of the catalyst.
3.4. Effects of the factors on the conversion of transesterication
The effect of the HTCC/Na2SiO3/ECH catalyst amount (1.0 wt.%e
6.0 wt.% with respect to oil) on transesterication of soybean oil
was investigated under a reaction time of 60 min, a methanol/oil
ratio of 6:1 and a reaction temperature of 55
C (Fig. 3a). When the
amount of the catalyst is only 1.0 wt.%, the conversion is only 52.3%.
And the conversions rose from 81.8% to 97.0% with an increase in
the amount of catalyst from 2.0 wt.% to 4.0 wt.%. It suggested that
the amount of the catalyst had a markedly effect on the trans-
esterication. The conversion almost kept stable when further
increasing the amount of catalyst. Therefore, 4.0 wt.% catalyst was
suitable to the transesterication of soybean oil with methanol.
During the preparation of HTCC/Na2SiO3/ECH catalyst, NaOH was
employed to neutralize the hydrogen chloride from the reaction
between HTCC and ECH in order to promote the reaction. Hydroxyl
groups (OH) from NaOH might be exchanged with chlorine ion
(Cl) in quaternary ammonium salt to produce quaternary
ammonium base, which could also catalyze the transesterication.
So the catalysts of HTCC/ECH and HTCC (no adding Na2SiO3) after
being treated by NaOH solution were also employed to catalyze the
transesterication under the same conditions as those above. But
the conversions obtained were 10.5% and 9.8%, respectively, similar
to the value (10.0%) obtained without catalyst. It is suggested that
the catalysts of HTCC/ECH and HTCC treated by NaOH solution had
almost no catalytic activity. In fact, OH exchange content of the
HTCC after treatment with NaOH was still very low, about
0.13 mmol/g. Therefore, Na2SiO3 in HTCC/Na2SiO3/ECH catalyst
really plays the dominant role for the catalytic activity.
Fig. 3b shows the effect of reaction time on the conversion of
soybean oil. The catalyst amount is 4.0 wt.% with respect to oil and
the reaction temperature is kept at 55
C. When the reaction time
was prolonged, the conversion increased and reached a maximum
of 97.0% at 60 min, beyond which no considerable change in con-
version was observed.
The molar ratio of methanol to oil is also one of the important
factors, which affects the conversion as well as production cost of
biodiesel. Theoretically, transesterication reaction requires 3 mol
of methanol for each mole of soybean oil. However, in practice, the
molar ratio should be higher than stoichiometric ratio in order to
drive the reaction towards biodiesel production. It is found that the
conversion of soybean oil increased with increasing molar ratios of
methanol to oil (Fig. 3c). When the ratio of methanol to oil is 1:1,
3:1 and 6:1, the conversion was 11.8%, 69.6% and 97.0% under a
reaction time of 60 min, the catalyst amount of 4.0 wt.% and a re-
action temperature of 55
C, respectively. Further increasing the
ratio to 9:1, even 12:1, the conversion slightly rose, achieving 98.0%
and 98.5%, respectively. But excess methanol would increase the
cost in the downstream separation process. Therefore, the ratio of
methanol to oil of 6:1 was selected for production of methyl esters
in this system.
The effects of reaction temperature on the conversion of soy-
bean oil were shown in Fig. 3d. The conversion increased with an
increase in temperatures, reaching 98.0% at 55
C and kept stable
when further increasing temperatures. Considering the energy
 M. Liang et al. / Renewable Energy 88 (2016) 51e57
Fig. 2. Transmission electron microscopy (TEM) images of Na2SiO3 in different matrices: Na2SiO3 (a); Na2SiO3/ECH (b); HTCC/Na2SiO3 (c); HTCC/Na2SiO3/ECH (d). The scale bar is
500 nm.
economy and reaction controllability, it was suitable to choose
55
C as the reaction temperature for the transesterication of
soybean oil.
3.5. Catalytic stability of the catalyst
The catalytic stability of the HTCC/Na2SiO3/ECH catalyst was
evaluated through consecutive batch runs by comparison with
HTCC/Na2SiO3/GA and no cross-linked HTCC/Na2SiO3 catalyst
(Fig. 4). It was seen that all catalysts exhibited good catalytic
properties at the rst run with conversions of above 97.0%. For all
the catalysts, a declination of catalytic activity occurred when the
recycling was continued. For HTCC/Na2SiO3/ECH catalyst, there was
only 4.5% declination in the conversion from the second run to the
seventh run. The conversion still reached at 83.0% at the seventh
run. While the catalytic activity for the HTCC/Na2SiO3/GA and no
cross-linked HTCC/Na2SiO3 catalyst continued to sharply decrease
with the runs. At the seventh run, the conversions was decreased to
55
22.0% and 23.9% for the HTCC/Na2SiO3/GA and no cross-linked
HTCC/Na2SiO3 catalyst, respectively. It implied that the HTCC/
Na2SiO3/ECH catalyst exhibited the best catalytic stability for pro-
ducing biodiesel. This was because Na2SiO3 was chemically xed on
the chains of HTCC through ECH to hinder the loss of Na2SiO3 from
the catalyst. In practice, the conversion could be improved through
prolonging reaction time or increasing the catalyst amount to reach
a higher conversion after several runs.
3.6. Component analysis of the biodiesel product
From gas chromatograph analysis, it is found that the biodiesel
produced from soybean oil contains ve esters: C16:0 (palmitic acid
methyl ester, 10.5%), C18:2 (linoleic acid methyl ester, 61.1%), C18:1
(oleic acid methyl ester, 20.4%), C18:0 (stearic acid methyl ester,
1.5%) and C18:3 (linolenic acid methyl ester, 4.0%). The triglyceride
in the oil was transformed into corresponding esters.
56 M. Liang et al. / Renewable Energy 88 (2016) 51e57

Fig. 3. Effects of the factors on the conversion of transesterication: catalyst amount under methanol/oil molar ratio of 6:1, at 55
C for 120 min (a); reaction time under methanol/
oil molar ratio of 6:1, catalyst loading of 4.0 wt.% at 55
C (b); molar ratio of methanol/oil under catalyst loading of 4.0 wt.% at 55
C for 120 min (c); reaction temperature under
methanol/oil molar ratio of 6:1, catalyst loading of 4.0 wt.% for 120 min (d).

100 and dispersion of Na2SiO3 in HTCC/Na2SiO3/ECH catalyst. The

conversion reached 97.0% under the reaction conditions of meth-
anol/oil molar ratio of 6:1, catalyst loading of 4.0 wt.% at 55
C for
80 60 min. When repeatedly using the seven runs of catalyst, the
HTCC/Na2SiO3/ECH conversion was kept at 83.0% for HTCC/Na2SiO3/ECH catalyst, while
decreased to 22.5% and 23.0% for HTCC/Na2SiO3/GA and no cross-
Conversion (%)

60 HTCC/Na2SiO3/GA
linked HTCC/Na2SiO3 catalysts, respectively. Hence the HTCC/
HTCC/Na2SiO3 Na2SiO3/ECH hybrid catalyst exhibited the better catalytic stability
40 than the others.

Acknowledgments
20
The authors gratefully acknowledge the nancial support by the
0 National Natural Science Foundation of China (Grant No. 21174104
1 2 3 4 5 6 7 and 21076156), the Tianjin Natural Science Foundation of China
Run times (Grant No. 13JCZDJC32700), the Program for Changjiang Scholars
and Innovative Research Team in University (PCSIRT) of Ministry of
Fig. 4. Catalytic stability of HTCC/Na2SiO3/ECH, HTCC/Na2SiO3/GA or HTCC/Na2SiO3 Education of China (Grand No. IRT13084).
membranes under methanol/oil molar ratio of 6:1, catalyst loading of 4.0 wt.% at 55
C
for 120 min.
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