b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5

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Utilization of waste freshwater mussel shell as an economic

catalyst for biodiesel production

Shengyang Hu, Yun Wang, Heyou Han*

College of Science, State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070, China

article info abstract

Article history: An economic and environmentally friendly catalyst derived from waste freshwater mussel
Received 28 June 2010 shell (FMS) was prepared by a calcination-impregnation-activation method, and it was
Received in revised form applied in transesterification of Chinese tallow oil. The as-prepared catalyst exhibits
2 May 2011 a “honeycomb” -like structure with a specific surface area of 23.2 m2 g
1. The newly formed
Accepted 6 May 2011 CaO crystals are major active phase of the catalyst. The optimal calcination and activity
Available online 12 June 2011 temperature are 900  C and 600  C, respectively. When the reaction is carried out at 70  C
with a methanol/oil molar ratio of 12:1, a catalyst concentration of 5% and a reaction time
Keywords: of 1.5 h, the FMS-catalyst is active for 7 reaction cycles, with the biodiesel yield above 90%.
Freshwater mussel shell The experimental results indicate that the FMS can be used as an economic catalyst for the
Biodiesel biodiesel production.
Catalyst ª 2011 Elsevier Ltd. All rights reserved.
Chinese tallow oil
Transesterification

1. Introduction catalysts, which can be easily separated from reaction mixture

by filtration or centrifugation and reused for several runs, have
Due to the exhaustion of fossil resources and the increasing been studied intensively. These catalysts are less corrosive,
emissions of pollutant, many studies have being directed safer, and more environment-friendly [12]. At the laboratory
towards the exploitation of alternative renewable fuel [1,2]. scale, several heterogeneous catalysts, such as alkali and
Biodiesel, as a potential substituted energy, has attracted alkali earth metal oxides [13e17], cation-exchange resin [18],
great attentions in recent years [3,4]. However, the high zeolites [19] and magnesiumealuminium mixed oxides
production cost of biodiesel compared with that of diesel fuel [20,21], have been developed for biodiesel production.
derived from petroleum limits its development. An important Unfortunately, the synthesis of highly active heterogeneous
contribution to the high production cost results from the catalysts is complex, costly, and requires special skills to
catalytic transesterification reaction [5]. Current biodiesel operate. Therefore, it is a great challenge to explore an ideal
manufacturing processes primarily employs homogeneous solid basic catalyst that is highly effective, low-cost, and
strong bases [6,7] or acids [8,9] as catalysts due to their high ecologically friendly for the promising biodiesel production.
activity and conversion. However, the separation of catalyst To address the issues, utilization of natural calcium sour-
and the purification of products are time consuming and ces from waste shells as an economic catalyst has been a new
expensive accompanied with a large volume of chemical trend for biodiesel production. Nakatani et al. [22] examined
wastewater [10,11]. transesterification of soybean oil catalyzed by combusted
In order to circumvent most of the economical and envi- oyster shell. The research demonstrated that the biodiesel
ronmental drawbacks of homogeneous process, heterogeneous yield was more than 70% under the optimized reaction

* Corresponding author. Tel./fax: þ86 27 87288246.

E-mail address: [email protected] (H. Han).
0961-9534/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.05.009
3628 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5

conditions of a catalyst concentration and reaction time of 25 tallow oil was obtained from Dawu County, Hubei province.
wt.% and 5 h, respectively. Wei et al [23]. and Boey et al [24]. The fatty acid composition consists of 0.21% myristic acid,
reported that eggshell and crab shell can be utilized as 7.51% palmitic acid, 2.60% stearic acid, 16.50% oleic acid,
a catalyst for biodiesel production, respectively. Recently, 32.75% linoleic acid, 39.36% linolenic acid and traces of other
Vieiya-empikul et al [25]. also investigated the catalytic acids. The analytical grade methanol was purchased from
behaviors of golden apple snail shell and meretrix venus Zhenxing Chemical Co. (Shanghai).
shell for the methyl ester production from palm oil. These
catalysts derived from waste shell exhibit large potential for 2.2. Catalysts preparation
biodiesel production due to low-cost and environment-
friendly characteristics. FMS - catalyst was prepared by calcination-impregnation-
Freshwater mussel is an aquatic bivalve mollusk and is activation method. Scheme 1 illustrated the preparation
similar to their marine clam and oyster. It has two shells con- process of FMS - catalyst. The dried FMS was calcined at
nected by a hinge-like ligament. The freshwater mussel gener- 200e1000  C in a muffle furnace after being ground to
ally inhabits rivers, lakes and ponds. In China, for example, it is 200e400 microns. Those FMS calcined at 900  C for 4 h
estimated that the annual production of freshwater mussel is (quoted as FMS-900) was completely impregnated in
over 1.6 million tons (including shell weight) in 2007, resulting in deionized water and then was activated at 600  C for 3 h.
the production of much FMS waste. A large part of waste shell is The resultant material was called FMS - catalyst (quoted as
commonly disposed in the field without any pretreatment, FMS-900-600).
giving a potential threat to arable farmers. In order to reduce the
amount of FMS waste, a great deal of effort has been conducted 2.3. Catalysts characterization
for the application of shell as value-added products. Until now,
the application has been limited to a low-cost adsorbent for The thermal stability of FMS-catalyst was examined using
extracting metal ions [26] and a desulphurization agent to NETZSH TG 209C from room-temperature to 900  C under an
remove SO2 [27]. The inorganic constituent of FMS is mainly inert nitrogen atmosphere and a heating rate of 10  C min
1.
calcium carbonate (ca. 95%), which may assume either of two XRD analysis was carried out with a Rigaku D/MAX-RB
principal crystalline forms, calcite and aragonite. The calcium- diffractometer under the following conditions: FeKa radiation
rich shell is easily converted into calcium oxide by high- (l ¼ 1.9373 Å), tube voltage of 36 kV, a tube current of 20 mA and
temperature calcination in air. Therefore, it is possible to utilize the count time of 0.2 s per 0.02 in the range of 15e90 . SEM
calcined FMS as a low-cost solid catalyst for biodiesel production. micrographs were obtained on a JEOL JSM-6390 to observe the
The present studies aimed at exploring the possibility of morphology of samples. BET was measured with a Quantach-
utilizing FMS waste as a catalyst in catalytic process of bio- rome Autosorb-1-C chemisorptionephysisorption analyzer.
diesel production. Scanning electron microscope (SEM) and Laser Raman spectroscopic measurements were performed on
X-ray diffractometer (XRD) were employed to characterize the a Renishaw invia Raman spectrometer equipped with an
microstructures and crystalline phase of catalyst. Thermog- intergral microscope (Olympus). The excitation source was Ar
ravimetric analysis (TGA) was used to determine the suitable laser (633 nm), focused with a 50  long-local-length objective
calcination and activation temperature. The catalytic behavior microscope and providing a power of 20 mW on the sample.
was evaluated by transesterification of Chinese tallow oil (CTO)
and methanol. The influence of various experimental vari- 2.4. Reaction procedure
ables, such as calcination temperature and activation
temperature, on the catalytic activity was also investigated. The transesterification was performed using different catalyst
concentration and molar ratio of methanol to oil. All experi-
ments were carried out in a 100 mL glass reactor equipped
2. Experimental with a condenser and a mechanical stirrer. It was charged
with 25 g Chinese tallow oil (molecular mass was ca.
2.1. Materials 896 g mol
1) and varied amounts of anhydrous methanol and
catalyst. The mixture was refluxed at 70  C, with mechanical
FMS was collected as waste from the local field. The shell was stirring for a specified time. After the reaction, the catalyst
rinsed with water and dried in a 105  C oven. Inedible Chinese was separated by filtration. The content of fatty acid methyl

Scheme 1 e Preparation procedure of catalyst derived from FMS.

 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5 3629

variables in present study is explained by the following

Table 1 e Levels of for the central composite design.
second-order polynomial model:
Variables Symbols Real values of coded levels
Y ¼ b0 þ b1 X1 þ b2 X2 þ b3 X21 þ b4 X1 X2 þ b5 X22 (1)
ea
1 0 þ1 þa
where Y is the dependent variable (biodiesel yield); X1 and X2
Catalyst X1 3.59 4 5 6 6.41
concentration are the independent variables; b0, b1, b2, b3, b4 and b5 are
(wt.%) intercept, linear, quadratic and interaction constant coeffi-
Molar ratio of X2 7.76:1 9:1 12:1 15:1 16.24:1 cients, respectively.
methanol
to oil

3. Results and discussion

ester in samples was analyzed in similar method reported by 3.1. Characterization of FMS-catalyst
Kansedo et al. [28]. Column temperature and temperature
program were set as follows: the initial temperature was set Fig. 1 shows the TGA curves of natural shell, FMS-900 and FMS-
at 190  C, and then was increased to 280  C with a rate of 900-600. For the natural shell (curve c), at a temperature lower
10  C min
1. The temperatures of the injector and detector than 380  C (1st stage), there is ca. 3.1% weight loss owing to the
were set at 300 and 280  C, respectively. The flow velocity of removal of organics and evaporation of moisture by
H2, N2 and air were kept at 40, 25 and 400 mL min
1 .The physisorption and chemisorption. When the temperature is
yield of biodiesel was calculated according to the method above 380  C, the crystalline phase of CaCO3 is transformed
reported by He et al. [29]. from aragonite to calcite. A weight loss of 0.8% is recorded in
the temperature range of 380e464  C (2nd stage). The major
weight loss (41.3%) occurs in the temperature range of
2.5. Statistical design for experimental 631e765  C (3rd stage), which is attributed to the
decomposition of CaCO3. When the calcination temperature
The experimental design in the present study is a central is above 800  C, the weight loss remains almost constant.
composite design, where the catalyst concentration and Therefore, the suitable calcination temperature is above
molar ratio of methanol to oil are selected as variables. The 800  C to transform CaCO3 to CaO. Compared with TGA curve
central composite design (CCD) consists of 13 experiments of FMS-900, there are two new weight lost peaks in TGA
with four factorial points, five central points and four axial curve of FMS-900-600. One at 339e465  C, corresponded to
points. The distance of the axial points encoded þa and the release of H2O molecular derived from decomposition of

a from the center point is a ¼ 2k/4, where k is the number of Ca(OH)2 and incidental formation of “honeycomb” -like
independent variables. The independent variables and their structure, which is accompanied by a weight loss of 23.5%.
levels in coded and actual values are shown in Table 1. The And another at 560e637  C which is attributed to phase
experimental matrix for the central composite design is transition of CaO [30] and there is only a weight loss of 1.4%.
summarized in Table 2. All experiments are conducted in As presented in TGA curve of FMS-900-600, 500  C should be
a random order. Experimental data is analyzed with the temperature high enough for full decomposition of
software SAS version 8.1 (SAS Institute Inc., Cary, NC, USA). Ca(OH)2. In fact, a higher activation temperature is required
The association between dependent and independent to enhance the catalytic activity of catalyst. It was proved by
the subsequent experimental results.
The FMS - catalyst was further probed by XRD (Fig. 2). The
composition of FMS-catalyst is two principal crystalline
CaCO3, calcite and aragonite (JCPDS card NO. 29-0306 and
Table 2 e Experimental matrix and experimental results
for the central composite design.
Run Type Variables Coded variables Response
no. Y (%)
C M X1 X2

1 Factorial 4 9:1
1
1 62.4

2 Factorial 4 15:1
1 þ1 85.9
3 Factorial 6 9:1 þ1
1 73.5
4 Factorial 6 15:1 þ1 þ1 95.4
5 Center 5 12:1 0 0 95.5
6 Center 5 12:1 0 0 95.0
7 Center 5 12:1 0 0 96.2
8 Center 5 12:1 0 0 94.7
9 Center 5 12:1 0 0 94
10 Axial 6.41 12:1 þa 0 93.2
11 Axial 5 16.24:1 0 þa 95.8
12 Axial 5 7.76:1 0 ea 60.1
13 Axial 3.59 12:1 ea 0 78.6 Fig. 1 e TGA profiles of catalysts before (a) and after (b)
impregnation, and natural shell (c).
3630 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5

Fig. 3 e Raman spectra of natural shell, pure CaCO3, and

Fig. 2 e XRD patterns of natural shell and catalysts catalysts obtained by calcining natural shell at 400, 700,
obtained by calcining natural shell between 200e1000  C. 900  C.

41-1475) when the FMS-catalyst is calcined at a temperature (curve e). Curves bed show the Raman spectra of catalysts
lower than 400  C. The diffraction patterns of FMS-catalyst calcined at 400  C, 700  C and 900  C, respectively. Obviously,
calcined at the temperature range of 400e600  C are the Raman spectra of catalyst calcined at 400  C is similar to
characteristic of calcite. When the calcination temperature that of natural shell (curve a). While the FMS-catalyst
is above 800  C, the diffraction patterns of FMS-catalyst are calcined at 900  C displays the vibration bands of CaO
characteristic of CaO (JCPDS card NO. 82-1691), caused by (1263.1, 1499.9 cm
1) (curve d), according to the standard
the decomposition of CaCO3 from the natural shell. While Raman spectra of CaO (unshown). When the catalyst is
the FMS-catalyst calcined at 700  C contains calcite as the calcined at 700  C, the vibration bands of CaCO3 and CaO are
major phase and CaO as a minor phase. observed in the same Raman spectrum. The results are well
Fig. 3 presents the Raman spectra of FMS calcined at consistent with those of XRD.
different temperatures. For natural shell (curve a), the The morphology of FMS calcined at different temperature
vibration bands of 711.7 and 1085.8 cm
1 correspond to was examined by SEM (Fig. 4). The natural shell displays
CaCO3, according to the standard Raman spectra of CaCO3 a typical layered architecture [31]. With the calcination

Fig. 4 e SEM images of natural shell, and catalysts obtained by calcining natural shell at 400, 700, 900  C.
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5 3631

Table 3 e BET surface area (SBET) and catalytic activity of

FMS-catalyst
Catalyst SBET (m2g
1) Yield (%)
a
Lab-CaO 4.5 92
Natural shell 0.9 No reaction
FMS-900 1.5 71%
FMS-900-600 23.2 96%

a Laboratory CaO was calcined at 600  C.

temperature rising from 200 to 900  C, the microstructures of

natural shell are changed significantly from layered
architecture to porous structure. When the FMS-900 is
further impregnated in deionized water and then activated
at 600  C, the resultant catalyst (FMS-900-600) shows
Fig. 6 e The influence of molar ratio of methanol to oil on
a “ honeycomb ” -like porous surface (Fig. 4e). This is
biodiesel yield. Catalyst concentration: 4%; reaction
probably due to the fact that a large number of gaseous
temperature: 70  C.
water molecular from the decomposition of Ca(OH)2 is
released from catalyst. The gaseous water molecular creates
high porosity, i.e. they act as porogens in the catalyst. appropriate to transform fully calcium carbonate to calcium
During preparation process of catalyst, the specific surface oxide. However, the FMS calcined at 900  C (FMS-900) is
area also is different obviously (Table 3). Among the further impregnated in deionized water and then is
catalysts, the FMS-900-600 exhibits the largest specific activated at 600VC. A higher yield of 96% is achieved under
surface area (23.2 m2 g
1). The both steps of impregnation follows reaction: a molar ratio of methanol to oil of 12:1,
and activation play an important role in improving specific a catalyst concentration of 5 wt.% and a reaction
surface of catalyst. It is evident that large specific surface temperature of 70  C for 1.5 h (Fig. 5b). Compared to the
results in high catalytic activity. As also summarized in published literature [22], the catalyst concentration and
Table 3, the activity of catalysts decreases in the order FMS- reaction time are reduced obviously. The high catalytic
900-600 > CaO > FMS-900 > natural shell. activity is also explained by the BET surface area of
23.2 m2 g
1 for FMS-900-600 versus only 10.5 m2 g
1 for FMS-
900. According to our experiment results, the appropriate
3.2. Influence of preparation conditions on catalytic
activity temperature should be 600  C.
activity

To investigate the influence of preparation conditions on 3.3. Influence of single variable on biodiesel yield
catalytic activity, a series of catalysts were prepared at
different conditions, including calcination and activity The effect of single variable on the biodiesel yield, such as
temperature, and they were used for transesterification of catalyst concentration and molar ratio of methanol to oil,
Chinese tallow oil and methanol. Fig. 5a demonstrates the were examined. For the following experiments, FMS-900-600
results concerning influence of calcination temperature on was used as low-cost catalyst to catalyze the trans-
the catalytic activity. The catalysts calcined below 600  C esterification of Chinese tallow oil and methanol.
almost have no catalytic activity. And a yield of ca.60% is The molar ratio of methanol to oil is an important variable
obtained at 700  C. When the calcination temperature is affecting the yield of biodiesel. The stoichiometric molar ratio
above 800  C, the biodiesel yield is 71%. In terms of energy of methanol to oil for transesterification is 3:1. In practice, the
consumption, the calcination temperature of 900  C is molar ratio should be higher in order to drive the reaction

Fig. 5 e The influence of (a) calcination temperature; (b) activation temperature on catalytic behavior. Molar ratio of methanol
to oil:12:1; catalyst concentration: 5%; reaction temperature: 70  C; reaction time 1.5 h.
3632 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5

Fig. 7 e The influence of catalyst concentration on biodiesel yield. Molar ratio of methanol to oil:12:1; reaction temperature:
70  C.

towards completion and gain more products. Fig. 6 describes 3.4. Statistical analysis
the influence of the molar ratio on the yield of biodiesel. The
yield of transesterification initially increased with the The experimental results corresponding to the central
increase of methanol/oil molar ratio, and then reached composite design are also shown in Table 2. The RSREG
a maximum of 88% at 12:1. When the molar ratio exceeded procedure from SAS is employed to fit the polynomial Eq. (1)
12:1, the yield remained nearly constant. The excessive to the experimental data. The obtained regression model in
methanol is helpful for full contact of reagents and catalyst, terms of the coded variables is given in Eq. (2)
so as to accelerate the reaction rate. However, a higher
molar ratio of methanol to oil is not favorable for the Y ¼ 94:88 þ 5:16X1 þ 11:99X2
5:15X21
0:40X1 X2
purification of product in the following separation process.


9:12X22 R2 ¼ 99:05% (2)
Also, recovery of the excessive methanol will consume large
amounts of energy. Therefore, a methanol/oil molar ratio of The fitted model is analyzed using analysis of variance (Table
12:1 is adopted in our experiment. 4), where the P-values are applied to establish the corresponding
Another key parameter to be optimized is the catalyst coefficient significance. The P-value of model is very low
concentration. Fig. 7 exhibits the results regarding the (<0.0001), indicating the second-order polynomial regression
influence of catalyst concentration on the yield of biodiesel. model is highly significant. The determination coefficient (R2)
Experimentally, the yield varies proportionately to the is shown as 0.9905, which demonstrates that the accuracy and
catalyst concentration. A maximum yield of 96% is obtained general availability of the polynomial model are very good,
at a catalyst concentration of 5 wt.%. However, the yield and the response trends can be analyzed compatibly and well
does not increase when the concentration is above 5 wt.%. by the model. The coefficient values of the regression equation
Getting the reactants to and from the catalyst become the are listed in Table 5. The results reveal that the catalyst
rate determining step (mass transport limitation) which is concentration is the most important variable in the biodiesel
why adding more catalyst is not favorable for increase of yield response, followed by the molar ratio of methanol to oil.
biodiesel yield [23]. Thus, the optimal catalyst concentration Both variables have a positive effect on the yield of biodiesel.
should be 5 wt. % in this system. However, the interaction between the catalyst concentration
the molar ratio of methanol to oil is insignificant.

Table 4 e Analysis of variance for the fitted second-order

polynomial model.
Source DF Sum of squares F Value Pr > F Table 5 e Results of regression analysis for a full second-
order polynomial model.
Linear 2 1361.960228 242.11 <0.0001
Term DF Coefficient t-value Pr > F
Quadratic 2 689.590963 122.59 <0.0001
Cross-product 1 0.640000 0.23 0.6479 Intercept 1 94.880317 126.50 <0.0001
Total model 5 2052.191191 145.92 <0.0001 b1 1 5.156329 8.70 <0.0001
Lack of fit 3 16.980809 8.36 0.0338 b2 1 11.986785 20.21 <0.0001
Pure error 4 2.708000 b3 1
5.146984
8.09 <0.0001
Total error 7 19.688809 b4 1
0.400000
0.48 0.6479
R2 ¼ 99.05% b5 1
9.123185
14.34 <0.0001
 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5 3633

Fig. 8 e Mechanism of FMS catalyst catalyzed transesterification.

The response surface corresponding to the regression CaOeH þ, producing CaO and another alkoxycarbonyl
model (Eq. (2)) is shown in Fig. 10, which exhibits the effects of intermediate (step 3). Finally, the intermediate rearranges and
two independent variables on the biodiesel yield. From divides into biodiesel (methyl ester) and diglyceride (step 4) [32].
a response surface plot, the optimal reaction conditions for
the catalyst concentration and molar ratio of methanol to oil
are 5.3 wt.% and 13.4:1, respectively. Under the optimal
reaction conditions, the theoretical biodiesel yield obtained
from the second-order polynomial regression model (Eq. (2))
is 99.8%. The accuracy of the model is validated with
triplicate experiments under the aforementioned optimal
reaction conditions. The experimental yield of biodiesel is
97.5%, which is in close agreement to the theoretical yield,
indicating the model has a high predictive ability.

3.5. Catalytic mechanism

CaO is major active phase of FMS-catalyst. Fig. 8 shows the

possible mechanism of catalyst in transesterification
reactions. The formation of the methoxide anion is the first
step of the reaction, arising from the reaction between CaO
and methanol (step 1). Next, the methoxide anion attacks the Fig. 9 e Reusability performance of catalyst derived from
carbonyl carbon of triglyceride to form an alkoxycarbonyl FMS in the transesterification reaction. Molar ratio of
intermediate (step 2). The alkoxycarbonyl intermediate methanol to oil:12:1; catalyst concentration: 5%; reaction
contests subsequently a hydrogen proton derived from temperature: 70  C; reaction time 1.5 h.
3634 b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 3 6 2 7 e3 6 3 5

Acknowledgment

The work was supported by the National High Technology

Research and Development Program of China (863 Program,
No. 2007AA100703).

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