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Research article
Program in Petrochemistry, Faculty of Science, Chulalongkorn University, Patumwan, Bangkok 10330, Thailand
Fuels Research Center, Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Patumwan, Bangkok 10330, Thailand
Center of Excellence on Petrochemical and Materials Technology (PETROMAT), Chulalongkorn University, Patumwan, Bangkok 10330, Thailand
a r t i c l e
i n f o
Article history:
Received 18 November 2015
Received in revised form 21 February 2016
Accepted 21 February 2016
Available online 2 March 2016
Keywords:
Biodiesel
Transesterication
Fixed-bed reactor
Calcium oxide
Catalyst extrudate
a b s t r a c t
We studied the production of biodiesel as fatty acid methyl esters (FAMEs) via transesterication of rened
bleached deodorized palm oil with methanol in a xed-bed reactor, using a new heterogeneous base catalyst
in extrudate form. The catalyst extrudates were prepared using a dissolutionprecipitation method from enamel
venus shells (Meretrix meretrix) in the presence of zinc nitrate and alumina as binder precursors. The effects of
addition of hydroxyethylcellulose as a plasticizer and of the extruder type on the extrusion process and physicochemical properties of the extrudates were studied. The as-prepared catalyst extrudate was a mixture of Ca, Zn,
and Al compounds. Calcination at 400 C generated CaO as the major active phase, which was dispersed on the
surface of an alumina support (ZSAH-400). The maximum FAME yield obtained over ZSAH-400 was 65% in a
xed-bed reactor operated at a methanol:oil molar ratio of 30:1, 65 C, and ambient pressure. The effects of
premixing the catalyst extrudates with methanol, vegetable oil, and commercial methyl esters (CMEs) with different fatty acid chain lengths were investigated to improve FAME formation. The ZSAH-400 extrudate premixed
with different CME types gave a stable FAME yield of ~96.5% throughout the operation. The promotion effect provided by premixing with methanol or oil was much less pronounced. A three-phase diagram, thermogravimetry,
and solubility parameters suggest that the CME-rich layer covering the extrudate surface reduces the mass
transfer limitations caused by immiscibility of the reactants.
2016 Elsevier B.V. All rights reserved.
1. Introduction
Biodiesel is a renewable fuel that has several advantages in terms of
exhaust gas cleanliness, non-toxicity, lubricity, biodegradability, and
petroleum-diesel-like fuel properties. Biodiesel, in the form of fatty acid
methyl esters (FAMEs), is commercially produced via transesterication
of triglycerides, which are present in vegetable oils and fats, with methanol, using homogeneous base catalysts. Although the homogeneous
process provides a high reaction rate under mild conditions, it requires
successive steps for catalyst removal and product purication, resulting
in a lower FAME yield and discharge of a large amount of wastewater
[1]. Heterogeneous catalysis is a more promising route for producing
environmentally friendly biodiesel together with the production of
high-purity crude glycerol as a potential biobased building block for
various value-added chemicals.
http://dx.doi.org/10.1016/j.fuproc.2016.02.031
0378-3820/ 2016 Elsevier B.V. All rights reserved.
Ca-based catalysts are highly basic and give a high reaction rate in
transesterication under mild conditions [214]. In the past decade, a
large number of Ca-based catalysts consisting of single [29] and mixed
[1014] metal compounds have been investigated for the
transesterication of triglycerides with methanol to produce FAMEs. All
these catalysts are in powder form, and are only appropriate for stirredtank reactors operated under batch conditions. Transesterication in
xed-bed reactors [1520] is of industrial interest because biodiesel and
glycerol can both be continuously produced at a high throughput.
However, powder catalysts cannot be used in xed-bed reactors because
of product contamination with ne particles and a large pressure drop. To
overcome these problems, powder catalysts are formulated as larger
particles with various shapes, e.g., extrudates, pellets, spheres, and
monoliths [21,22].
Ca-based oxides are hard but brittle materials. Their formulation
requires the addition of binders [15,16] and plasticizers [15]. Inorganic
binders (MgO, alumina [15,16], aluminum phosphates [23], clay
(sepiolite) [24], and boehmite [25]) enhance powder contact and the
mechanical strength of the shaped particles obtained after calcination.
Plasticizers (hydroxyethylcellulose (HEC) [15,23], methylcellulose
68
[24], and MgO [26]) are used to adjust the viscosity and lubricity of the
catalyst paste to facilitate processing. When a catalyst powder is mixed
with binders and/or plasticizers and then pressed to give a specic
shape, its textural properties and active site content are usually
adversely affected, resulting in a decrease in catalytic performance
[21]. The formulation conditions should therefore be carefully adjusted
to optimize the mechanical, physical, and chemical properties of the
resulting shaped catalysts.
The transesterication of triglycerides with methanol over solid catalysts suffers from serious mass transfer limitations related to immiscibility of the reactants and the number of accessible active sites. Several
techniques have been developed to improve the catalytic performances
of Ca-based oxides used in transesterication [25,15]. CaO has been activated by mixing with methanol prior to the reaction to promote the
formation of methoxide species on its surface [2]. Premixing of CaO
with glycerol in reuxing methanol creates calcium glyceroxides
(Ca(C3H7O3)) as a new catalytically active phase [2]. A small amount
of water added directly to the reaction enhances the FAME yield [2,3].
Tetrahydrofuran [4] and FAME [15] have been added as co-solvents to
improve mass transfer in the reaction system. Premixing CaO with
FAME further increases the reaction rate [5]. The FAME coating on the
catalyst surface prevents deactivation caused by adsorption of atmospheric moisture and CO2 on the active sites [5].
In the present study, we prepared heterogeneous base catalysts in
the form of extrudates via a dissolutionprecipitation method, using
waste seashells as a renewable Ca source. Zinc nitrate and alumina
were used as binder precursors; these were partly converted to spinel
ZnAl2O4 after calcination. The catalyst paste was shaped manually and
with a single-screw extruder. The effects of adding HEC as a plasticizer
on extrusion and the characteristics of the resulting extrudates were
studied. A catalyst extrudate obtained under suitable conditions was
evaluated for its catalytic properties in the transesterication of palm
oil with methanol in a continuous-ow xed-bed reactor at 65 C and
ambient pressure. The effect of premixing the catalyst extrudates with
methanol, vegetable oil or commercial methyl esters (CMEs) with
different fatty acid chain lengths on the transesterication was also
investigated.
2. Experimental
2.1. Preparation of Ca, Zn, and Al mixed compound catalysts in extrudate
form
Enamel venus shells (Meretrix meretrix) were washed, ground, and
sieved to particle sizes of b 10 m, followed by calcination in a mufe
furnace at 800 C for 2 h. Zn(NO3)26H2O (commercial grade, PPM
Chemical) was dissolved in deionized water, and the solution pH was
adjusted to 1 by adding 1 M HNO3 (AR grade, JT Baker). The calcined
seashells were vigorously agitated in the acidied Zn(NO3)2 solution
using an overhead stirrer for 2 h. Al2O3 (commercial grade, PPM
Chemical) was added to the mixture, and stirring was continued for
1 h. The mass ratio of calcined seashell: Zn(NO3)26H2O:Al2O3 was
1:0.6:0.4. HEC (commercial grade, Thai Specialty Chemical Co., Ltd.)
was added to the white slurry. The amount of HEC was varied between
0 and 5 wt.% based on the total solid mass. The resulting mixture was
continuously stirred and heated to remove water until a paste was
formed. The catalyst paste was shaped into continuous rods using a
manual extruder equipped with a 2-mm hole die or a Bonnot singlescrew catalyst extruder equipped with a 3.5-mm hole die. For the
single-screw extruder, the screw speed and frequency were set at
40 rpm and 40 Hz, respectively. The extruded rods were dried at
100 C for 2 h and cut to 5 mm lengths. Finally, the extrudates were
calcined at 400 C for 2 h at a heating rate of 3 C min1 using a mufe
furnace. The catalysts were denoted by ZSAH or ZSAH-400 to represent
the as-prepared extrudate or the extrudate calcined at 400 C,
respectively.
69
the plasticity of the catalyst paste, and facilitate extrusion [23]. The mechanical strengths of the extrudates obtained after calcination at 400 C
were signicantly lower than those of the dried extrudates. In particular, the extrudates were destroyed or easily broken at high HEC loadings
(Fig. S2(C) and (D): SI). Ketcong and coworkers found that burning off
the HEC in the extrudates by calcination in air increased the porosity
and reduced the mechanical strength [15]. The extrusion using a
single-screw extruder gave denser and harder extrudates because of
the higher pressure applied to catalyst paste. The high-shear mixing
provided by the screw extruder also breaks down particle agglomerates,
giving smaller particles, each of which is entirely coated with a liquid
layer [22]. The extrudates prepared using a single-screw extruder
showed better shape retention than those obtained using a manual extruder after calcination. The addition of HEC also prevented phase separation between solid particles and liquid media during extrusion with
the single-screw extruder, otherwise heat was generated. Formulation
of the extrudate form of the catalyst was therefore subsequently performed using 3 wt.% HEC and a single-screw extruder.
3.2. Catalyst characterization
XRF spectroscopy showed that the raw seashells consisted of 68.6%
CaO, 0.5% MgO, 0.8% SiO2, and 0.1% Fe2O3. Before calcination, the Ca
compounds present were CaCO3 and Ca(OH)2 (Fig. S3(a): SI). TGA
showed that the amounts of CaCO3 and Ca(OH)2 were 62.1% and
37.8%, respectively (not shown). After calcination of the raw seashells
at 800 C, these Ca phases were completely converted to CaO
(Fig. S3(b): SI). The XRF and XRD results indicate that the seashells calcined at 800 C could be used as a CaO precursor for the preparation of
Ca-based mixed compound catalysts.
The thermal decomposition pattern of ZSAH prepared without adding
HEC is shown in Fig. 1. The corresponding phase composition is summarized in Table 2. Decomposition of the as-prepared ZSAH occurred in multiple steps. The assignment of each step was made by comparing the
decomposition pattern with those of authentic samples and related
data in the literature [9,10,2731]. The major phase was Ca(OH)2
(36.4 wt.%). Some Zn2+ was precipitated as Zn5(OH)8(NO3)22H2O. The
ZnO generated by heating Zn5(OH)8(NO3)22H2O at N 300 C showed
low activity in transesterication [27,29]. The weight loss at 280 C
corresponded to dehydration of Al(OH)3 to Al2O3 [28]. The presence of
CaZn2(OH)62H2O and Ca(NO3)2 in the as-prepared catalyst indicated
that Ca2+ was dissolved from CaO in the calcined seashells.
CaZn2(OH)62H2O was formed via coprecipitation of Ca2+ and Zn2+ at
pH 1113 [31]. It was converted to a mixture of CaO and ZnO at 400 C
Manual
Single screw
a
b
HEC amount
(wt.%)
Extrusion
0
3
5
0
3
5
Faileda
Easy
Easy
Difcult
Easy
Easy
Extrudate characteristics
Dried at 100 C
Calcined at 400 C
Not determined
Hard
Hard
Dense and hard
Dense and hard
Hard
Not determined
Very brittle
Brokenb
Hard
Hard
Very brittle
Fig. 1. Weight loss and DTG curves of uncalcined ZSAH prepared without adding HEC.
70
Table 2
Phase compositions, identied using TGA, of uncalcined ZSAH and ZSAH-400 prepared
without HEC addition.
Weight loss
temperature
(C)
Uncalcined ZSAH
Phase
Composition Phase
(wt.%)
0100
100160
160220
220340
340450
450590
590760
H2O (moisture)
Zn5(OH)8(NO3)22H2O
CaZn2(OH)62H2O
Al(OH)3
Al2O3 a
Ca(OH)2
Ca(NO3)2
CaCO3
Total
3.5
5.1
7.8
4.8
16.8
36.4
14.0
10.1
98.5
ZSAH-400
ZnO
CaO/ZnO
Al2O3
Composition
(wt.%)
4.1
1.8/5.1
24.7
CaO
34.5
Ca(NO3)2 17.3
CaCO3
12.5
100
Fig. 2. XRD patterns of uncalcined ZSAH (a) and ZSAH-400 (b) prepared with 3 wt.% HEC
using a single-screw extruder (symbols: = CaCO3, = CaO, = ZnO, = Ca(OH)2,
= ZnAl2O4, and = CaZn2(OH)62H2O).
Since the FAME added into the reaction improved the mass transfer
of the reaction system as a co-solvent effect [15], the miscibility of the
methanoloilCME system was investigated in this work. A threephase diagram for methanol, palm kernel oil, and C12C14 CMEs is
shown in Fig. 5. The C12C14 CMEs were miscible with either methanol
or palm oil in all proportions, but mixing only methanol and palm oil together always gave separate phases. The addition of the CMEs at high
loading to a mixture of methanol and oil induced a miscible phase in
the system. This could be because the molecular structure of methyl esters, in which the ester groups are hydrophilic and the long hydrocarbon chains of fatty acids are hydrophobic, enables them to dissolve
well in both triglycerides and methanol. A FAME can behave like a
surfactant [33], which promotes the formation of microemulsions in
triglycerides-in-methanol and methanol-in-triglycerides systems [5].
The solubility of oil in methanol or that of methanol in oil is therefore
enhanced by CME addition.
Fig. 3. OM images of uncalcined ZSAH side view (A) and cross section (B), and ZSAH-400 side view (C) and cross section (D).
Fig. 4. SEM images of uncalcined ZSAH side view (A) and cross section (B), and ZSAH-400 side view (C) and cross section (D).
71
72
Table 3
Physicochemical properties of catalysts.
Catalyst
Type
Bulk density
(g cm3)
Crushing strengtha
(MPa)
Vpc
(mm3 g1)
Dpd
()
Total basicitye
(mol g1)
FAME yieldf
(wt.%)
ZSAH
ZSAH-400
ZSAH-400
Extrudate
Extrudate
Powder
1.01
0.96
1.15
0.13
4.23
6.40
n.d.
6.5
9.0
n.d.
52.8
42.7
n.d.
n.d.g
9.3
27.0
49.9
97.9
99.9
a
b
c
d
e
f
g
Fig. 6 shows the FAME yields for transesterication of palm oil with
methanol over the ZSAH-400 extrudates in the xed-bed reactor. The
feed of methanol and palm oil at a molar ratio of 30:1 corresponded to
a mixture composition of 50 vol.%, at which a separate phase appeared.
The efuent was collected and analyzed to determine the FAME yield
after a time-on-stream of 120 min. The FAME yield gradually increased
from 39% to 65% within 240 min, during which the liquid inside the reactor and the efuent were transformed from methanoloil separate
phases to a miscible liquid. This indicates that the FAME generated
from the reaction enhanced the methanoloil solubility, and promoted
contact between the reactant molecules and the catalyst surface.
The ZSAH-400 extrudate premixed with methanol gave an initial
FAME yield of 40.1 wt.%. This is similar to the reaction performed on
the extrudates without premixing, because the reaction in the pristine
case was started up in the presence of methanol. Premixing with methanol enhanced the FAME yield to 96.8% at 360 min. This result should be
related to the promoting effect of methoxide species formed on the surface of the catalyst premixed with methanol overnight. The formation of
surface methoxides over CaO immersed in methanol was conrmed by
solid state 13C NMR spectroscopy [17]. Even at room temperature, the
generation of methoxide on the CaO surface occurs easily [34]. Although
a larger amount of surface methoxides over the premixed catalyst could
be expected, the initial stage of the reaction is essentially controlled by
diffusion of bulky triglyceride molecules to the hydrophilic catalyst
Fig. 5. Ternary diagram of methanol, palm kernel oil, and C12C14 CMEs, based on volume
fraction.
73
Fig. 7. Weight loss and DTG curves of ZSAH-400 extrudates premixed with methanol (A), palm kernel oil (B), and C12C14 CMEs (C), and extrudates premixed with C12C14 CMEs followed
by immersion in methanol (D) or palm kernel oil (E).
subsequent experiment, ZSAH-400 extrudates previously mixed overnight with C12C14 CMEs were immersed in methanol or palm kernel
oil. The decomposition patterns of these two samples are shown in
Fig. 7(D) and (E), respectively. The weight losses corresponding to
C12C14 CMEs disappeared concomitantly with the appearance of patterns derived from methanol or palm kernel oil. These results indicate
that the CMEs adsorbed on the ZSAH-400 extrudates could be replaced
by methanol and vegetable oil, possibly because of the high solubilities
of these reactants in methyl esters (Fig. 5). It should be noted that this
replacement mainly occurred at the early stage of the operation since
the CMEs used in premixing disappeared after 120 min. Subsequently,
a large amount of FAME generated from the reaction promoted contact
between the reactant molecules and the catalyst surface by increasing
the miscibility of methanol and oil.
The compatibility of methanol and palm kernel oil with the CME
layers coated on the catalyst extrudates was explained by considering
the solubility parameters () of these organic compounds; these can
be calculated using Eq. (1) [35]:
G
;
M
where VM is the total volume of the mixture and v is the volume fraction
of component 1 or 2 in the mixture. Based on thermodynamic considerations, the change in Gibbs free energy on mixing (GM) depends on the
magnitude of HM, as follows:
GM H M TSM ;
74
Scheme 1. Simplied model of diffusion of triglycerides and methanol to surface of catalyst extrudates without premixing (top) and for premixing with CMEs (bottom).
(dipoledipole and dipoleinduced dipole) interactions (p), and hydrogen bonding (h) were included in the total solubility parameter
(t) developed by Hansen (Eq. (4)) [36]. The calculation indicates that
the total solubility parameter of methanol is 14.5 (cal cm3)1/2 [37],
which is 1.7-fold higher than the solubility parameter of C12C14
CMEs. As revealed in the three-phase diagram (Fig. 5), a high miscibility
of methanol and CMEs in all proportions should be attributed to hydrogen bonding between the hydroxyl group of methanol and the ester
group of CMEs.
2t 2d 2p 2h :
promotes contact between the reactant molecules and the catalyst surface. As a result, a stable FAME yield (96.5%) is achieved throughout the
operation.
4. Conclusions
The Ca, Zn, and Al mixed compound catalysts in extrudate form were
successfully prepared by dissolutionprecipitation method. Although
the addition of HEC enhanced the plasticity of the catalyst paste and facilitated extrusion, its decomposition generated microscale fractures,
which decreased the crushing strength of the resulting extrudate. However, the mechanical strength, textural properties, and basicity of the
catalyst extrudate were sufcient for biodiesel production via
transesterication of palm oil with methanol in a xed-bed reactor
under mild conditions. Because triglycerides and methanol are immiscible, the reaction on the catalyst extrudate premixed with either methanol or oil suffered from mass transfer problems. Premixing the catalyst
extrudate with different types of CMEs resulted in a stable FAME yield
of ~ 96.5% throughout the operation. This benecial effect arises from
the high solubilities of both reactants in the CME layer covering the catalyst extrudate.
Acknowledgements
The authors are grateful to the Chumporn Palm Oil Industry PLC and
the Thai Oleochemicals (TOL) Co., Ltd. for donating palm oil and CMEs
with different fatty acid chain lengths, respectively. This research was
funded by Chulalongkorn University through the Ratchadapiseksompoch
Endowment Fund (2013), project no. CU-56-912-EN. Financial and technical supports from the Thailand Research Fund (TRF) under the project
no. IRG5780001 (Faculty of Science, Chulalongkorn University), the Center of Excellence on Petrochemical and Materials Technology
(PETROMAT), Chulalongkorn University, and the PTT Public Company
Limited, are also acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.fuproc.2016.02.031.
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