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Top Catal (2010) 53:721736

DOI 10.1007/s11244-010-9460-5

ORIGINAL PAPER

Advancements in Heterogeneous Catalysis for Biodiesel Synthesis


Shuli Yan Craig DiMaggio Siddharth Mohan
Manhoe Kim Steven O. Salley K. Y. Simon Ng

Published online: 14 April 2010


Springer Science+Business Media, LLC 2010

Abstract Heterogeneous catalysts are promising for the


transesterification reaction of vegetable oils to produce
biodiesel and have been studied intensively over the last
decade. Unlike the homogeneous catalysts, heterogeneous
catalysts can be easily separated from reaction mixture and
reused for many times. They are environmentally benign and
could be easily operated in continuous processes. This
review classifies the solid catalysts into two categories based
on their catalytic temperature, i.e. high temperature catalysts
and low temperature catalysts. The nature of the catalysts can
be specified into solid bases and solid acids. Three aspects,
catalyst activity, catalyst life and oil flexibility, will be
reviewed. Two kinds of heterogeneous catalysts, reported by
IFP Inc. and by WSU, respectively, show a high catalytic
activity, long catalyst life and low leaching of catalyst
components. These two catalysts also show ability to
simultaneously catalyze esterification and transesterification, and can be used in half-refined or crude oil system
which provide a potential for greatly decrease the feedstock
cost.
Keywords Biodiesel  Heterogeneous catalyst 
Transesterification  Esterification  Solid base  Solid acid

increasingly important to search for sustainable alternative


fuels. Among the many possible sources, biodiesel derived
from vegetable oil attracted early attention as a promising
fuel for substitution or blending with petroleum based
diesel fuel, because biodiesel and petroleum diesel share
similar physical and chemical properties [1]. Thus, pure
biodiesel or biodiesel blends can be used in conventional
compression-ignition engines without the need for engine
modifications [2]. Furthermore, certain properties of biodiesel, such as flash point, cetane number, ultralow sulfur
content, lubricity, biodegradability, and smaller carbon
footprint were all superior to petroleum diesel [3, 4].
1.1 Biodiesel Chemical Background
Biodiesel is an industry adopted term for a mixture of fatty
acid alkyl esters, that are a product of the transesterification
reaction of triglycerides with methanol. In that reaction,
three alkyl esters are produced from one triglyceride molecule. A second product, glycerol, is also produced in a
molar ratio of 1:1 glycerol:triglyceride, further adding to
the value of processing oils. These reactions are represented by:

1 Introduction
Due to growing worldwide demand for energy and its
resulting impact on the environment, it is becoming

S. Yan  C. DiMaggio  S. Mohan  M. Kim 


S. O. Salley  K. Y. S. Ng (&)
Department of Chemical Engineering and Material Science,
Wayne State University, Detroit, MI 48202, USA
e-mail: sng@eng.wayne.edu

This well established process, introduced in the nineteenth century, has been used to exploit the fatty acid and
triglyceride content of a variety of natural oils for biodiesel

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722
Fig. 1 Reaction mechanism of
base catalyzed
transesterification [17, 19]

Top Catal (2010) 53:721736

(1)

ROH

R O

+B

OR

(2)

R2

OH

R1

R O

R2

R1

O
O

R3

R3
O

O
OR

(3)

R2

OH

O
O

R1

R2

R3

R3
O

(4)

O
-

R2

O
O

B H

R2

OH

fuel over the years. Among these renewable oils and fats
are soybean oil [5], rapeseed oil [6], cotton seed oil [7],
sunflower seed oil [8], jojoba oil [9], waste cooking oil
[10], chicken fat [11], lard [12], and beef tallow [3].
Typical alcohols used as the reactant in this biodiesel
process include methanol [5], ethanol [13] and butanol
[14], with methanol being the most widely used because of
its lower cost.
Some of the first industrial processes to create biodiesel
relied on either strong base or strong acid homogeneous
catalysts for this transesterification reaction. Examples of
the base catalyst are potassium hydroxide [9, 13] and
sodium hydroxide [14, 15], while sulfuric acid has been
used as an acid catalyst [16]. The reaction mechanism for
strong base catalyzed transesterification is shown in Fig. 1
[1719]. Lee et al. [19] described the first step in the
synthesis of alkyl esters as the formation of an alkoxide ion
(RO) through proton transfer from the alcohol using the
base catalyst; the alkoxide ion then attacks a carbonyl
carbon on the triglyceride molecule and forms a tetrahedral
intermediate ion (step 2). This ion rearranges to generate a
diglyceride ion and alkyl ester molecule (step 3). The
diglyceride ion reacts with the protonated base catalyst,

O
R3

123

OR

R1

R3
O

which generates a diglyceride molecule and returns the


base catalyst to its initial state (step 4). The resulting
diglyceride is then ready to react with another alcohol
molecule, thereby starting the next catalytic cycle until all
the glyceride molecules have been converted to alkyl esters
(biodiesel).
Strong acid catalyzed transesterification is illustrated in
Fig. 2 [20]. This process can simply be described as the
protonated carbonyl group nucleophilicly attacks the alcohol, forming a tetrahedral intermediate; the proton then
migrates, and the intermediate decomposes forming a new
ester. This process can be extended to di- and mono-glycerides as well. Additionally, research shows that heterogeneous catalysis, both base and acid, also follow the above
mentioned mechanism for alkyl ester production [19].
1.2 First Generation Homogeneous Catalysts and Their
Limitations
Traditional or first generation homogeneous catalysts enjoy
certain advantages over other catalysts including costeffectiveness, high activity, and easily attained reaction
conditions (25130 C, atmospheric pressure). However,

Top Catal (2010) 53:721736


Fig. 2 Reaction mechanism of
acid catalyzed
transesterification [17, 20]

723
+

OH

(1)

R2

R1

O
H

R1

R2

O
O

O
R3

R3

O
+

OH
O

(2)

R2

R1

HO

R4

R2

R4 OH

R1

O
R3

R3
O

HO

(3)

R2

H
O
R4

R1

OH

R2

O
O

R4
R1

O
R3

R3
O

these same homogeneous catalysts, by virtue of the associated production process, face a variety of technical hurdles that limit their use for biodiesel production and
eventually may cause the demise of the early biodiesel
producers. Homogeneous catalysts are normally limited to
batch-mode processing [21]. In addition, other steps in the
biodiesel production process also require time consuming
and costly processing. These steps include oil pretreatment,
catalytic transesterification, separation of fatty acid/methyl
ester (FAME) from crude glycerin, neutralization of waste
homogeneous catalyst, distillation of accessory methanol,
water washing of the FAME phase, and vacuum drying of
the desired products [22]. Each of these steps introduce
additional processing time and cost. As an example, separation of the products from the spent waste catalyst
require a post treatment with large volumes of water to
neutralize the used catalyst in the product mixture. This
creates an additional process burden by generating waste
water that must be treated before release into the environment [22].
Other difficulties with using homogeneous catalysts
center on their sensitivity to free fatty acid (FFA) and water
in the source oil. FFAs react with basic catalysts (NaOH,
KOH) to form soaps when the FFA and water content are
above 0.50 and 0.06%, respectively [5, 23]. This soap
formation complicates the glycerol separation, and reduces

the FAME yield. Water in the feedstock results in the


hydrolysis of FAME in the presence of strong basic or
acidic catalyst. Thus, some inexpensive oils, such as crude
vegetable oils, waste cooking oil, and rendered animal fats,
which generally contain a high content of FFA and water,
cannot be directly utilized in existing biodiesel facilities
with homogeneous catalysts. Likewise, the cost of oil
feedstock in 2006 accounted for up to 80% of biodiesel
production cost [24, 25]. So when petroleum diesel prices
fell in 2008, the relatively expensive soybean derived
biodiesel could not ompete, forcing many biodiesel facilities to close. Therefore, part of the current solution is to
develop a second generation technology based on heterogeneous catalysts that are capable of effectively processing
less costly feedstocks high in FFAs and water content with
a simpler less costly processing method.
1.3 Second Generation Heterogeneous Catalyst
Advancements
Recent developments in heterogeneous catalysis for biodiesel production has the potential to offer some relief to the
biodiesel producers by improving their ability to process
alternative cheaper feedstocks, and to use a shortened and
less expensive manufacturing process. Whereas homogeneous based process required batch mode operation,

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heterogeneous processes can be run in either batch or continuous mode giving the producers the option to continue
with their current batch reactors or retrofit their operations
with a packed bed continuous flow reactor operation. Heterogeneous catalysts in either mode are in a separate phase
from the reaction products, thereby removing costly and
time consuming water washing and neutralization steps to
separate and recover the spent catalyst. Additionally, contaminated water from that process is greatly reduced and the
need for waste water treatment minimized.
The greatest advantage of the heterogeneous approach
over the homogeneous method is the prolonged lifetime of
the heterogeneous catalysts for FAME production. This
attribute is generally related to the stability of the microcrystal structure of the catalyst surface. Poisoning and
leaching of catalyst components can change the bulk and
surface structure of the catalyst and cause catalyst deactivation quickly if the catalyst is not formulated properly.
The above three factorscatalytic activity, catalyst life
and oil flexibilityhave a tremendous impact on the cost
of biodiesel. Because of this, we have undertaken a review
of the past and current heterogeneous catalyst technology
with these aspects as the focus. In this paper, the reported
heterogeneous catalysts are separated into two categories
based on their operation temperature. For reaction temperatures lower than the flash point of biodiesel (130 C),
we refer to this type of catalyst as a low temperature catalyst. For reaction temperatures greater than 130 C, we
classified these catalysts as high temperature catalysts.
These catalysts are characterized by the need for additional
safety considerations and require more energy intensive
operations. To further reduce the field of catalysts for this
review, only heterogeneous catalyst technologies which
provide the potential for decreasing the biodiesel process
cost and feedstock cost will be discussed.

2 Low Temperature Catalysts


As previously stated, studies of solid base catalysts began
burgeoning in the 1970 s. Most dealt with common single
metal oxides such as alkaline oxides and rare earth metal
oxides. Subsequently, studies were expanded to include
alkali metal exchanged zeolites, alkali metal ion-supported
catalysts, and clay minerals such as hydrotalcites.
2.1 Solid Base Catalysts
2.1.1 Alkaline Metal Salts on Porous Supports
Alkali metals are the most common source of super basicity and are frequently selected as the active species for
biodiesel production. The loading of many kinds of

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Top Catal (2010) 53:721736

alkaline salts on supports have been reported as a way to


prepare basic catalysts, such as NaOH [2, 2629], KOH
[30, 31], K2CO3 [32], KI [33, 34], KNO3 [35, 36], KF [37
40], and LiNO3 [41, 42]. The supports for these catalysts
include Al2O3 [33, 39], Zeolite [43], ZnO [41] and SiO2
[34].
An example of a commercialized super base catalyst is
Na/NaOH/Al2O3. It is used for the alkylation of cumene,
and the isomerization of safrole, dimethyl butene and vinylbicyclo heptene [44]. Kim et al. [29] also tested its
activity for soybean oil transesterification with methanol
and found almost the same activity as homogeneous NaOH
catalyst under optimized reaction conditions (FAME yield
was 94% with a reaction temperature of 60 C, reaction
time of 2 h, stirring speed 300 rpm, co-solvent n-hexane
10 mL, amount of catalyst 1 g). The basicity is believed to
be associated with the Lewis base concept according to the
O 1s XPS results presented. Table 1 shows the effect of
preparation on catalyst basicity. The oxygen 1s binding
energy shifts downward as the Na and NaOH impregnation
onto the c-Al2O3 support progresses, indicating that the
basicity increases together with the degree of impregnation.
Consistent with O 1s binding energy, the catalysts FAME
activity also proportionally increases.
Xie et al. [35] and Vyas et al. [36] investigated the
activity of KNO3/Al2O3. Xie et al. [35] pointed out that the
active phase was K2O derived from KNO3 at high temperature, and the surface AlOK groups were the main
active sites. Cui et al. [39] prepared KF/c-Al2O3 and found
there were two types of basic sites on the catalyst. The
strong basic sites (super basic) promote the transesterification reaction at low temperature (65 C), while the basic
sites with medium strength require a higher temperature to
process the reaction. Later, Boz et al. [40] prepared KF
catalysts loaded on nano-c-Al2O3 and Wang et al. [45]
loaded KF on malodorous CaOMgO. They both found
that the catalysts FAME activity is closely related to the
basic nature of the catalyst and also to the high surface to
volume ratio and porosity of the catalyst.

Table 1 XPS analysis of O 1s orbital of four catalysts


Catalyst

Binding energy
of O 1s (eV)

Biodiesel yield
(%)

c-Al2O3

538.8

NaOH/ c-Al2O3

538.5

60

Na/ c-Al2O3

537.5

70

Na/NaOH/ c-Al2O3

535.5

78

Reaction conditions: Methanol/oil molar ratio is 6:1, reaction temperature is 60 C, and stirring speed is 300 rpm. All data are taken
from literature [29]

Top Catal (2010) 53:721736

However, in spite of the high activity of the supported


alkaline catalysts, they have important limitations. First,
these catalysts like their homogeneous alkaline hydroxide
counterparts have a low tolerance to FFA and water in raw
materials. At this time, there is no report of using this kind
of catalyst for directly processing crude oils which have a
high total acid number (TAN). Only refined oils can be
used with these catalyst systems. Secondly, some
researchers have observed lixiviation of catalyst components into reaction mixtures. Arzamendi et al. [46] found
that 55% of K2CO3, 20% of Na2CO3 and 15% of Na3PO4
dissolved into the reaction mixtures and catalyzed the
transesterification reaction. Also, Xie et al. [35] found
KNO3/Al2O3 catalysts have a high solubility in water and
were therefore unstable in the transesterification system.
However, Noiroj et al. [47] found that the type of support
strongly affected the activity and leaching of the active
species of the catalyst. In this case, the amount of leached
potassium of the KOH/Al2O3 was higher than that of the
KOH/NaY catalyst. And they found that the interaction
between active phase and support affected the leaching
results. Additionally, Ramos et al. [48] prepared sodium
hydroxide on a zeolite support and hypothesized the presence of a homogeneous-like mechanism where the alkali
methoxide species were leached out.
2.1.2 Alkaline Earth Metal Oxide Catalysts
Much attention has been paid to alkaline earth metal oxides
since they have shown less solubility in reaction mixtures
and less corrosion in comparison to supported alkaline
catalysts. As solid super base can be synthesized from
alkaline metal oxides, researchers started from pure alkaline metal oxides. In fact, alkaline metal oxides have
already been used as base catalysts in many organic reactions. For example CaO is widely used for as the isomerization of 5-vinylbicyclo [2.2.1] hept-2-ene (VBH) to
5-ethylidenebicyclo [2.2.1] hept-2-ene (ENB) [49, 50],
synthesis of 1, 3-dialkylurea from ethylene carbonate and
amine [51] and the synthesis of monoglyceride [52]. With
respect to biodiesel production, the basicity of this type of
metal oxide catalyst has been shown to have an influence
on its activity for FAME generation. The basic strength of
the Group II metal oxides follows the order: MgO \
CaO \ SrO \ BaO. Corresponding research has demonstrated the catalysts activity for transesterification of oil
with methanol follows the same order [5355]. But, compared to a homogeneous NaOH catalyst, the above alkaline
earth metal oxides show a relatively low transesterification
activity. In particular, MgO exhibits almost no activity in
transesterification of vegetable oils into biodiesel. Pure
CaO reacts at a slow rate and requires about 624 h to
reach a state of reaction equilibrium [5658]. BaO is not

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suitable for biodiesel production because it dissolves in


methanol and forms some noxious species [59, 60]. Conversely, SrO, has a high activity and is insoluble in methanol, but will react strongly with CO2 and water in the air
to form unreactive SrCO3 and Sr(OH)2. Furthermore, these
strontium compounds are difficult to regenerate by calcining, requiring temperatures above 1200 C [17]. As a
partial solution to these limitations, recent work has
focused on using mixed metal oxides to enhance the
basicity of CaO or MgO-based catalysts and elevate their
respective selectivity for FAME.
2.1.2.1 Supported CaO Catalysts Although earlier work
showed weak FAME activity for pure CaO catalysts, more
recent research has shown that the smaller particle size of
CaO catalysts can increase the total amount of base sites
and base strength, which leads to an improved activity in
the oil transesterification reaction. Reddy et al. [61] tested
the activity of nanocrystalline CaO and found it active even
at room temperature. However, as Gryglewics [6, 62] and
Martyanov and Sayari [63] pointed out, pure CaO converted to a form of suspensoid due to its poor mechanical
strength, which would lead to difficulties in separating the
waste catalyst from biodiesel and glycerol products after
transesterification. Since these findings could have a
potential impact on industrial applications, many
researchers have tried to solve this problem by applying
CaO on different metal oxide supports.
In particular, CaO has been combined with ZnO [64],
MgO [46, 65], Al2O3 [65, 66], zeolite [48, 65], SiO2 [65,
67], and La2O3 [68] with improved base characteristics,
activity and catalytic life. Rubio-Caballero et al. [64] used
the calcined calcium zincate as a solid catalyst for the
methanolysis of sunflower oil to FAME resulting in yields
higher than 90% after 45 min of reaction. The reaction
conditions of the heterogeneous process (60 C, methanol:
sunflower oil molar ratio of 12, 3 wt% catalyst) were very
similar to those observed under homogeneous conditions
(KOH dissolved in methanol). Yan et al. [65] investigated
the effects of a second metal oxide by impregnating CaO
on basic oxides such as MgO, neutral oxides such as SiO2,
and acidic oxides such as Al2O3 and zeolite HY. In this
work, the best results were obtained for a catalyst with
16.5% of CaO loading on MgO. The same catalyst also
possessed the strongest base strength and largest number of
base sites. The conversion of rapeseed oil using this catalyst reached 92% at 64.5 C. Further work by Yan et al.
revealed the active centers of the CaO/MgO catalyst. CO2TPD profiles of CaO/MgO showed that there were two
types of basic sites each with a different strength. The
desorption peaks of CO2 at *600 C were attributed to the
strong basic sites corresponding to unbounded O2- anions,
while CO2 desorption peaks at low temperature (*350 C)

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were attributed to the weak basic sites related to oxygen in


both Ca2?O2- and Mg2?O2- pairs. Yan et al. [17, 65, 68]
also quantified the effects of base property on oil transesterification. They found that the activity of CaO/MgO linearly
increased with base amount, and base amount linearly
increased with CaO loading when the CaO loading was lower
than 16.5%. Later, Yan et al. [70] combined CaO with the
basic oxide La2O3, and used the Hammett method to determine the base properties of catalysts. They found that the
binary metal oxides had a higher base strength and a wider
base site distribution than pure CaO and La2O3 catalysts
individually, and they also had a higher reactivity than CaO
and La2O3 individually. Using this binary metal oxide catalyst with a 3:1 of molar ratio of Ca to La, they found the
FAME yield reached 94.3% within 60 min at just 58 C.
This suggested a reaction rate much closer to that of a
homogeneous NaOH catalyzed processes and that heterogeneous catalysts were capable of attaining the same activities as homogeneous catalysts.
Equally important here, this work indicated that CaO
type heterogeneous catalysts also showed a high tolerance
to water and FFA which is present in unrefined raw oil
feedstocks. This implies these heterogeneous catalysts have
a potential for biodiesel production. Until now, many CaObased catalysts were reported to be more tolerant than the
supported alkaline catalysts. Yan et al. [65] reported that
conversion of rapeseed oil by CaO/MgO reached as high as
98% when the water content of the raw oil was in the range
of 02 wt% and the total acid number was below 7.4 mg
KOH/g (FFA content around 3.7%). Later, Yan et al. [70]
reported that CaOLa2O3 was active when the oil contained 10% of water and when the FFA content was lower
than 3.5%. They then tested the basicities of the catalysts
which had adsorbed small amounts of FFA and water,
respectively, naming the catalysts Ca3La1FFA and
Ca3La1water. Yan and co-workers found that the basic
properties of the Ca3La1water catalyst are much closed to
the fresh CaOLa2O3 catalyst; therefore, it can be assumed
that CaOLa2O3 shows a high tolerance to small amounts
of water, while the basic property of the Ca3La1FFA
catalyst notably decreased both the base strength and sites,
indicating CaOLa2O3 has a low tolerance for FFA in oils.
Further characterization results indicated that there are
Lewis base sites and Bronsted base sites on the surface of
fresh CaOLa2O3 catalysts and both of these base sites are
active centers for oil transesterification with methanol. In
fact, the addition of small quantities of water can change
the Lewis base sites into Bronsted base sites suggesting
Ca3La1water is still active in transesterification. Conversely, FFA will react with and bind to both base sites
resulting in poisoning of the catalyst. Therefore, Ca3La1
FFA shows a low activity for FAME production. Further
work by Yan et al. [70] using CaOLa2O3 for processing

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crude soybean oil, crude palm oil and waste cooking oil,
which satisfy the limitation of water content lower than
10% and FFA lower than 3.5%, showed a FAME yield in
excess of 95% within 3 h. For the oils with a high FFA
content, dilution with refined oil will lower the FFA content of the mixture again allowing the use of a CaOLa2O3
catalyst to produce a high FAME yield.
Equally important to the usefulness of a catalyst is its
lifetime. Reddy et al. [61] found that nanocrystalline calcium oxide particles deactivated after eight cycles with
soybean oil and after only three cycles with higher FFA
content poultry fat. Similarly, Kawashima et al. [57, 58]
found evidence of decreased FAME activity with CaTiO3
and CaZrO3 catalysts after as few as three cycles.
To overcome these limitations, therefore, it is important
to understand the mechanism of catalyst deactivation. In
general, there are three pathways by which catalyst deactivation can occur: poisoning, blocking of reactant fragments and lixiviation. Many studies have already paid close
attention to poisoning due to high levels of either FFA or
water present in raw materials [65, 70], so they will not be
discussed here. But little research has been performed that
focuses on the effects of exposing a stored catalyst to CO2,
moisture, and O2 present in the air. As stated by Busca
[69], base catalysts can easily react with these components
of ambient air to form very stable surface species like
carbonate, hydroxide, and epoxide which cover the basic
sites and deactivate the base catalysts. Yan et al. [70] found
that when comparing the activity of a fresh CaOLa2O3
catalyst to one exposed to air for 12 h, the yield of FAME
sharply decreased from 96.8 to 34.5%, and the total base
amount decreased from 14.0 to 1.5 mmol CO2/g. They
later attributed this decrease in activity to moisture and
CO2 in air restructuring the surface of CaOLa2O3 catalyst
from metal oxides to hydroxide and carbonate. Other
research groups have found that the reused base catalysts
have a lower basic strength and a lower activity than fresh
the catalysts [71, 72]. This was explained by the blockage
of active surface sites on the catalyst by strongly adsorbed
intermediates or product species. In particular, Martyanov
and Sayari [63] studied reused catalysts (CaO, Ca(OCH3)2)
and found that surface adsorbed butyric acids were the
most likely species responsible for the catalyst deactivation
in their experiments.
Catalyst lixiviation or leaching is another frequently
encountered pathway for catalyst deactivation. Many
researchers have studied the leaching of catalyst components into reaction mixtures. Kouzu et al. using a pure CaO
catalyst [71] found that the calcium concentration would be
as high as 3065 ppm in the FAME when waste cooking oil
was used as the source oil. Later Kouzu et al. [72] showed
calcium in the products of transesterified refined soybean
oil. In that case, he found that the calcium content in

Top Catal (2010) 53:721736

glycerol was about 2000 ppm and calcium content in


FAME was around 10100 ppm. Similarly, Granados et al.
[73, 74] studied the leaching of species from solid CaO and
the role of these species in the catalytic reaction. He
pointed out that CaO can react with glycerol to form Ca
diglyceroxide which is more soluble than CaO and active
in oil transesterification. He found that the solubility of
CaO in alcohol is around 0.6 mg/mL and when CaO was
less than 1 wt% the major reaction mechanism is homogeneous. When the catalyst loading is greater than 1 wt%
CaO, the total homogeneous contribution is much smaller
than that arising from the heterogeneous sites [74]. Thus, it
is very apparent that determining the homogeneous contribution to the FAME yield of a CaO-based catalyst system, and other like catalysts, is as important as quantifying
the heterogeneous component.
2.1.2.2 Supported MgO Catalysts One of the drawbacks
of using a CaO-based catalyst is the low BET surface area
associated with the catalyst. Because activity is closely
related to surface area for many catalyst systems, loss of
active surface area through deactivation can have a proportionally larger effect on the product yield. Therefore,
one solution would be simply to use more catalyst in your
industrial application design. However, this introduces
additional cost into the plant design and material usage. To
avoid these concerns some research groups have turned to
metal oxide catalysts from hydrotalcites which are welldispersed, have a high surface area, and are characterized
by a strong base property. One such example is a MgO
based catalyst. Cantrell et al. [55] reported on a supported
MgOAl2O3 catalyst which was active in transesterification of glyceryl tributyrate using methanol. He found that
the BET surface area was as high as 166 m2/g. Using the
same catalyst, Xie et al. [75] found that the Mg/Al molar
ratio also had an effect on FAME activity. Using a Mg/Al
ratio of 3, 773 K calcination temperature, 15:1 M ratio of
soybean oil: methanol, and a catalyst dosage of 7.5 wt%,
oil conversion was found to be 67% after 9 h. Other work
by Li et al. [76], using mixed oxides from MgCoAlLa
hydroxide, found those catalysts maintained its activity for
7 recycles in a batch reactor. Additional work on the MgO
Al2O3 catalyst, by Fraile et al. [77], found that the reaction
mechanism relied on the residual alkaline ions as the main
source of strong basicity and catalytic activity in the
transesterification of sunflower oil with methanol.

727

various commercial resin catalysts. They found that the


anion-exchange resins, such as Diaion PA308, PA306s,
HPA25 (Mitsubishi Chemical C., Ltd, Tokyo, Japan),
exhibited much higher catalytic activity than the cationexchange resins like PK208 (Mitsubishi Chemical C., Ltd,
Tokyo, Japan). The anion-exchange resins characterized by
a lower cross-linking density and a smaller particle size
produced both a high reaction rate and conversion. The
best catalytic performance was obtained on Diaion PA306s
resin, which yielded over 80% conversion of soybean oil to
ethyloleate after 3 h reaction at 323 K. However, other
groups have found less satisfactory results using base resin
catalysts. In particular, Aracil and coworkers [81] used an
anion-exchange resin in the transesterification of sunflower
oil to biodiesel and found the conversion was less than 1%
after 8 h at a typical reaction temperature of 333 K. Kim
et al. [82] found that trace amounts of CH3ONa, functioning as a homogeneous catalyst, exhibited a synergetic
effect with the resin catalyst for conversion.
2.1.4 Biont Shell Based Catalysts
Recently, catalysts derived from renewable materials, such
as shrimp shell [83, 84], turtle shell [83], crab shell [83],
oyster shell [85] and egg shell [86] have been employed for
conversion of oils to FAME. Previously, these catalysts were
generally considered as waste. The major components of
these biont shells are chitin, protein and CaCO3. Normally,
disposal of these waste materials from seafood processing
are an economic or environmental problem for entrepreneurs
and local governments. However, biodiesel production catalysts prepared from these wastes are a promising
green technology. Xie et al. [83] first reported preparing
biont shell supported KF catalysts for biodiesel production
and found methylester yields from rapeseed oil as high as
97.5% within 3 h under optimal reaction conditions. Yang
et al. [84] reported, a three step preparation procedure for a
shrimp shell catalyst which included incomplete carbonization of the shrimp shells, loading KF onto the altered
shells, and activation. In a different approach, Nakatani et al.
[85] and Wei et al. [86] prepared CaO catalysts by simple
calcination of oyster shells and egg shells, high in CaCO3
(95%), at 7001000 C. Although these catalysts proved
active for biodiesel synthesis, further work is required to
limit the amount of Ca leaching to improve the catalyst life
and tolerance to water and FFA in oil feedstock.

2.1.3 Base Resin Catalysts

2.2 Solid Acid Catalysts

Not only inorganic bases, but also some organic bases were
also tested for biodiesel production [78, 79], especially for
base resin catalysts. Shibasaki-Kitakawa et al. [80] investigated the transesterification of triolein with ethanol using

Even though many heterogeneous base catalysts have been


reported as highly active for biodiesel synthesis, they still
cannot tolerate acidic oils with FFA content [3.5%, such
as yellow and brown grease. However, sulfur based acidic

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728

homogeneous catalysts such as H2SO4 show a much higher


tolerance to FFA and water than the basic homogeneous
NaOH and KOH catalysts, suggesting these catalysts may
be more suited for processing acid oils. Using this line of
reasoning, some research turned to investigating sulfur
based heterogeneous acid catalysts for converting acidic
oils into biodiesel.
2.2.1 Sulfated Zirconia Based Catalysts
Sulfated metal oxides show superacid properties because of
the interaction between the sulfate group and the metal
oxide centers. These kinds of catalysts, including sulfated
zirconia [8789] and sulfated tin oxides [90] have been
widely used in esterification and transesterification reactions under mild conditions. Kiss et al. [87] studied several
solid acid catalysts (zeolites, ion-exchange resins, and
mixed metal oxides) as catalysts for the esterification of
dodecanoic acid with 2-ethylhexanol, 1-propanol, and
methanol. That work revealed that sulfated zirconia was
the most active for esterification. Later, Garca et al. [91]
investigated the activity of sulfated zirconia for soybean oil
transesterification. That group found that the catalyst
preparation method had a significant effect on the resulting
catalyst activity. Under optimized conditions (120 C, 1 h
and 5 wt% of catalyst) and using sulfated zirconia prepared
by a solvent-free method, the methanolysis of soybean oil
was 98.6% and ethanolysis was 92.0%. The sulfated zirconia prepared by standard methods [88] was poor for
soybean oil methanolysis (conversion of 8.5%) and conventional zirconia even less so. Similarly, Suwannakarn
et al. [89] studied the activity and stability of a commercial
sulfated zirconia catalyst for transesterification of tricaprylin with a series of aliphatic alcohols at 120 C. He
found that the catalytic activity decreased as the number of
carbons in the alkyl chain of the alcohol increased. In
addition, the sulfated zirconia catalyst exhibited significant
activity loss with subsequent reaction cycles. Characterization of the recycled catalysts showed that the concentration of the SO42- moieties in the sulfated zirconia had
permanently decreased. Essentially, the SO42- species
were leached out. As explained by Yadav and coworkers
[92, 93], the sulfate groups leached out as H2SO4 and
HSO4-, which in turn gave rise to a homogeneous acid
catalysis which interfered with activity measurements of
the intended heterogeneous catalyst.
2.2.2 Heteropolyacid Catalysts
A series of heteropolyacid (HPAs) catalysts have also
attracted much attention due to their high activity in

123

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biodiesel formation reactions, both transesterification and


esterification. Alsalme et al. [94] studied some HPA catalysts
and compared them with some homogeneous and heterogeneous catalysts such as H2SO4, Amberlyst-15, and zeolites
HY and H-Beta. The intrinsic catalytic activity, expressed as
turnover frequency (TOF), of the HPA catalyst is significantly higher than that of the conventional acid catalysts in
these reactions. They also tested the catalytic activity and
acid strength of several kinds of HPA catalysts. The TOF
values decreased with decreasing catalyst acid strength
in the order: H3PW12O40 & Cs2.5H0.5PW12O40 [ H4SiW12
O40 [ 15%H3PW12O40/Nb2O5, 15%H3PW12O40/ZrO2, 15%
H3PW12O40/TiO2 [ H2SO4 [ HY, H-Beta [ Amberlyst-15.
They found that Cs2.5H0.5PW12O40 exhibits high catalytic
activity as well as high resistance to leaching. The other types
of supported HPA catalysts suffered from leaching and
exhibited a significant homogeneous component to the catalysts activity caused by the leached HPA. Pesaresi et al.
[95] studied the catalytic mechanisms of CsxH4-x
SiW12O40 (x = 0.84) in the transesterification of C4 and C8
triacyglycerides and esterification of a C16 FFA. The catalyst
material, loading C1.3 Cs per Keggin, provided an insoluble,
heterogeneous catalyst active for both transesterification and
esterification, with reactivity correlating with the number of
accessible H? sites residing within the mesopore structure.
For loadings B0.8 Cs per Keggin, transesterification activity
arises from the homogeneous contribution. Narasimharao
et al. [96] investigated structure related activity for CsxH3xPW12O40 (x = 0.93). Materials with the Cs content in the
range x = 2.02.7 were well dispersed, having a high surface areas *100 m2/g-1 and high Bronsted acid strength.
CsxH3-xPW12O40 was active in both esterification of palmitic acid and transesterification of tributyrin. Further work
showed an optimum performance occurs for Cs loadings of
x = 2.02.3, correlating with the accessible surface acid site
density. These catalysts were recovered for three times and
leaching of soluble heteropolytungstate wasnt observed.
Other HPAs were also reported. Katada et al. [97] found
that H4PNbW11O40, H3PW12O40 and the heteropolyacidderived solid acid catalyst, H4PNbW11O40/WO3Nb2O5,
were highly active for the transesterification of triolein with
ethanol. But, H4PNbW11O40 and H3PW12O40 dissolved into
the reaction mixture; H4PNbW11O40/WO3Nb2O5 was
insoluble to the reaction mixture. Further study showed
that the activity of H4PNbW11O40/WO3Nb2O5 was sensitive to calcination temperature, and calcination around
773 K provided a highly active catalyst. The activity
was observed in the co-presence of water (3.9 wt%) and
oleic acid (5 wt%). In a fixed-bed continuous-flow reaction,
it maintained the yield of FAME around 2540% for
4 days.

Top Catal (2010) 53:721736

2.2.3 Organically-Functionalized Acid Catalysts


The purpose of preparing organically-functionalized acid
catalysts is to overcome the shortcomings of other acid
catalysts, such as leaching and low surface area. Some
attempts have been made with the sulfonic acid ionicexchange resins, such as Poly (DVB) resin sulfonated with
H2SO4 [98], Amberlyst-35(Rohm & Haas) [98], Amberlyst-15 (Rohm & Haas) [94, 99], and Nafion SAC-13[100].
Rezende et al. [98] prepared different polymer supports
based on styrene and divinylbenzene which were conveniently functionalized with sulfonic acid. In order to obtain
an appropriated triglyceride conversion at low temperature
(65 C), it was necessary to use a high ratio of methanol to
oil (50:1300:1) and high catalyst dosage (2550%). Under
the optimal conditions FAME yields reached a maximum
value over 90% using a sulfonated poly (DVB) ionexchange resin which had 442 m2/g of specific surface area
and 3.4 meqH? g-1 of acid capacity. Some polymer based
catalysts were claimed to be active for both oil transesterification and fatty acid esterification reaction in unrefined
oil systems. As an example, Soldi et al. [101] prepared
sulfonated polystyrene compounds where sulfonation was
between 5.0 and 6.2 mmol SO3H/g of dry polymer. That
work showed conversion of beef tallow, with a
53 mg KOH/g acid number, reached 70% within 18 h.
2.2.4 Natural Based Catalysts
A novel type of renewable catalyst has been prepared from
various carbohydrates such as D-glucose, sucrose, cellulose
and starch [102104]. These catalysts were made by
incomplete carbonization of carbohydrates followed by
sulfonation. The incomplete carbonization of D-glucose
leads to a rigid carbon material consisting of small polycyclic aromatic carbon sheets in a three dimensional sp3bonded structure [103]. Sulfonation has been demonstrated
to provide a highly stable solid with a high density of active
SO3H sites. This type of catalyst was found to be physically robust without leaching of SO3H groups during use.
This resulted in remarkable catalytic performance for
FAME formation reactions for both transesterification and
esterification [103, 105, 106]. In studies by Lou et al. [106],
carbohydrate-derived acid catalysts had been successfully
applied to biodiesel production with higher fatty acid oils,
such as waste oils with high acid values. Variables such as
starting material, carbonization temperature and time, and
sulfonation temperature and time for catalyst preparation
all had a significant impact on the catalytic and textural
properties of the prepared solid acids. Under optimal
reaction conditions (80 C, 20: 1 of molar ratio of methanol to oil, 10 wt% of catalyst loading, over a starch-derived
sulfonic acid catalyst), the FAME yield was measured at

729

about 92% after 8 hs reaction. Furthermore, the starchderived solid acid catalyst proved exceptionally stable
under reaction conditions.

3 High Temperature Catalysts


Even though solid acid catalysts exhibit improved activity
for converting acid oils into FAME, most of them show a
relative low reaction rate and deactivate quickly in comparison to solid base catalysts. Intensifying reaction conditions, by increasing reaction temperature and pressure,
has been shown to effectively accelerate the reaction rate
and prolong the catalyst lifetime. Some of the more successful examples of these catalysts that function at higher
temperature and pressure, including both solid base and
acid catalysts, were tested in subcritical or supercritical
methanol flow conditions (240 C, 8 MPa) and reported
below.
3.1 Solid Base Catalysts
Several strong base catalysts have been tested at high
reaction temperatures. One of which, CaO investigated by
Demirbas [107], was operated under supercritical methanol
conditions. When the temperature was 252 C, transesterification was completed within 6 min with 3 wt% CaO
and 41:1 methanol/oil molar ratio. In other work on Ca
based catalysts, Suppes et al. [108] found that CaCO3 was
active when the temperature was greater than 200 C and
required about 18 min to essentially convert all the oil;
FFA in the oil was esterified by CaCO3 and did not appear
to inhibit the catalyst; Also, no decrease in activity of the
calcium carbonate was observed after weeks of utilization
suggesting little leaching or deactivation.
Separately, Barakos et al. [109] used both non-calcined
and calcined MgAlCO3 hydrotalcite catalysts in refined
cottonseed oil, acidic cottonseed oil, and crude animal fat
feedstock. MgAlCO3 hydrotalcite catalysts were active
in both transesterification and esterification. The activity of
the calcined catalyst was lower than the non-calcined catalyst. But, the non-calcined catalyst showed evidence of
deactivation when recycled. However, additional information regarding catalyst leaching and stability was not presented in this work.
3.2 Solid Acid Catalysts
3.2.1 Sulfate Salts
As with the low temperature catalysts, the activity of the
sulfated salt family of catalysts is based on the presence

123

730

of sulfonic acid sites, which can be considered as the


heterogeneous counterpart of sulfuric acid. Also, the acid
strength of the catalyst still has an important role in the
transesterification reaction. Some factors, such as the
preparation technology and suitable selection of support,
greatly influenced the acid site distribution on the catalyst. For instance, Jothiramalingam and Wang [21]
reported that catalysts prepared from a stronger acid
precursor containing benzene sulfonic acid groups had a
higher acid strength and were more active than those
containing only propylsulfonic acid groups. Chen et al.
[110] presented evidence that good catalytic performance
of the sulfated silica-zirconia material was attributed to
an improved preparation process which resulted in a
higher dispersion of zirconia, thus creating a higher acid
site density.
The carriers for sulfonic acid include not only some
inorganic metal oxides (zirconia oxide [21, 110], tin oxide
[111], stannia [112]), but also some mesostructured silica
[113] and carbon materials such as multi-wall carbon
nanotubes [114, 115] and asphalt [115]. In their work,
Jitputti et al. [112] evaluated the activities of sulfated
zirconia and stannia for crude palm kernel oil and coconut
oil conversion to biodiesel. They showed minor activity at
200 C, which subsequently decreased with additional
recycling. They associated the decrease in activity to both
sulfate leaching and active site poisoning. In other work,
Melero et al. [113] prepared propylsulfonic acid SBA-15
material and found it highly active for the conversion of
refined and crude palm oil and soybean oil. The catalytic
performance was attributed to the large surface area and
pore diameter of the mesoporous support. However, they
also found a slight decrease of activity in recycled catalyst testing. To remedy this, they pointed out that further
work would be performed to enhance the strength of acid
sites and control the surface properties of the silica support in order to enhance the durability of these sulfonated
mesostructure catalysts. Shu et al. [115] prepared sulfonation of carbonized vegetable oil asphalt and sulfonated
multi-walled carbon nanotubes (s-MWCNTs). They found
that the asphalt-based catalyst showed higher activity than
the s-MWCNTs for the production of biodiesel and that
this behavior might be correlated to the high acid site
density of asphalt catalysts resulting from its loose
irregular network and large pores. Using the asphalt based
catalyst, the conversion of cottonseed oil achieved
89.93% when the methanol/cottonseed oil molar ratio was
18.2, reaction temperature 260 C, reaction time 3.0 h,
and a catalyst/cottonseed oil mass ratio of 0.2%. Also, the
asphalt based catalyst can be re-used. Shu et al. [114,
115] thought that the sulfonated polycyclic aromatic
hydrocarbons provided an electron-withdrawing function
to keep the acid sites stable.

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Top Catal (2010) 53:721736

3.2.2 Heteropolyacid Catalysts


Sunita et al. [116] compared the activities of zirconia
supported isopoly and heteropolytungstate catalysts. Zirconia-supported heteropolytungstate possessed a high total
acidity and showed superior catalytic performance compared to zirconia-supported heteropolytungstate catalysts.
Under their reaction conditions of 200 C, methanol/oil
molar ratio 15, and 15% WO3/ZrO2 calcined at 750 C the
ZrO2 catalyst achieved 97% conversion of oil. Kulkarni
et al. [117] impregnated tungstophosphoric acid on four
different supports such as hydrous zirconia, silica, alumina
and activated carbon, and used them for converting low
quality canola oil containing about 20 wt% FFA to biodiesel. The hydrous zirconia supported tungstophosphoric
acid was found to be the most active. At 200 C, 1:9 oil to
alcohol molar ratio, and 3 wt% catalyst loading a maximum ester yield of 90 wt% was observed.
3.2.3 Other Catalysts
Except for the above two types of catalysts, other weaker
solid acid catalysts were also tested for activity in biodiesel
formation reactions. These included many types of zeolite
and phosphate based catalyst systems. For instance, Brito
et al. [118] studied the activity of several commercialized
Y-type zeolites in a continuous tubular reactor at atmospheric pressure and within a temperature range of 200
476 C. The results showed that higher temperature
accelerated transesterification reaction rate. With used fry
oil, they found that the optimal reaction conditions for
transesterification with methanol could be achieved with
zeolite Y530 at 466 C, 12.35 min residence time, and a
methanol/oil molar ratio of only 6.
In other work, some phosphate salts have also been
reported active for biodiesel formation. One such example is
by Li and Xie [119] who prepared Fe3?-vanadyl phosphate.
When the transesterification reaction was performed at a
molar ratio of methanol to oil of 30:1, reaction temperature
of 473 K, reaction time of 3 h, and a catalyst loading of
5 wt%, the maximum conversion of soybean oil was found
to be 61.3%. The importance of this work is that it showed
the activity of this catalyst was not significantly affected by
the presence of free fatty acids and water in the reactant
mixture. In addition, the catalyst also exhibited catalytic
activity for the esterification of free fatty acids with methanol. Unfortunately, the same catalyst slowly deactivated
after 5 recycles. Serio et al. [120] suggested that the deactivation of vanadyl phosphate catalyst was strongly affected
by reaction temperature. In effect, higher reaction temperatures accelerated the deactivation process. However, catalyst leaching at higher temperatures was not the root cause of
deactivation. Instead, surface characterization work showed

Top Catal (2010) 53:721736

that deactivation was primarily due to the progressive


reduction of surface vanadium from V5? to V3? by methanol
where V5? and intermediate V4? species were active and
V3? was inactive. Further work revealed that the deactivation was reversible and catalyst activity could be restored by
simple oxidation.
Yet another catalyst technology based on FeZn doublemetal cyanide complexes was tested by Sreeprasanth et al.
[121]. The catalysts were hydrophobic, and contained only
Lewis acidic sites. Bronsted acid sites as well as basic sites
were absent. These catalysts proved active for both the
transesterification and esterification of unrefined and waste
cooking oils. Thus Lewis acidic sites were found to be
active centers for both the transesterification and esterification reactions and the surface hydrophobicity of these
catalysts improved their tolerance to water.
3.3 Amphoteric Metal Oxide
Some amphoteric metal oxides, such as PbO, PbO2, and
ZnO, have attracted attention from researchers because of
their adjustable basic and acid properties. Singh and Fernando [122] found that the FAME yield reached 89% using
amphoteric PbO and PbO2. However, further testing
showed Pb content in the glycerol and biodiesel products
was as high as 2000 ppm which implied some dissolution
of the catalyst. With respect to ZnO based catalyst systems,
two candidates appear to offer the best next generation
catalyst solution for improved biodiesel synthesis. One is a
catalyst composed of zinc aluminum oxides from Institut
Francais Du Petrole (Vernaison, France); the other is a
catalyst of zinc lanthanum oxides from Wayne State University (MI, USA).
3.3.1 ZincAluminum Catalyst for the Esterfif-HTM
Process
The Esterfif-HTM process was developed by the French
Institute of Petroleum (IFP) and commercialized by Axens.
It was first used in an industrial context in 2006, by Sofiproteol in Se`te [123]. This process uses a heterogeneous
catalyst, a spinel mixed oxide of zinc and alumina metals.
The use of heterogeneous catalysts eliminates the need for
catalyst recovery and washing stepsand associated waste
streamsrequired by processes using homogeneous catalysts such as sodium hydroxide or sodium methylate. The
process chart is shown in literature [22]. The catalyst
section includes two fixed bed reactors (CSTR), fed with
vegetable oil and methanol at a given ratio. Excess methanol is removed after each reactor by partial evaporation.
Then, esters and glycerol are separated in a settler. The
remaining glycerol is collected and the residual methanol
removed by evaporation.

731

A patent [124] awarded to IFP described an acid catalyst


with a formula of ZnAl2O4, xZnO, yAl2O3 (with x and y
being in the range of 02) which originated from a hydrotalcite precursor. The BET surface area is between 50
and 200 m2/g and a pore volume is greater than 0.3 cm3/g.
In the continuous process, the reaction temperature is
required to be between 210 and 250 C, pressure between
30 and 50 bar, and VVH (volume of injected oil/volume of
catalyst/hour) from 0.3 to 3. Using these conditions, they
showed a FAME yield of 91% based on a catalyst with a
surface area of 65 m2/g, pore volume of 0.63 cm3/g under
the conditions of 240 C, 50 bar, 160 min of contact time.
This patent also addressed the catalyst lifetime. They found
that on the 14th day, the FAME yield decreases to 30.9% at
240 C, 50 bar, 1 VVH. The structure of the deactivated
catalyst is not reported in this patent. A subsequent IFP
patent [125] states that this catalyst is quite sensitive to
water. In fact they maintained the water concentration
below 1000 ppm, which implies that the oil feedstocks
used in Esterfif-HTM process must be well refined.
3.3.2 Zinc Lanthanum Catalysts
A series of zinc and lanthanum containing catalysts were
developed by Yan et al. [68, 126, 127]. This type of catalyst exhibits weak basic properties and is composed of
ZnO, La2CO3 and LaOOH. Chief among its attributes are
activity, longevity, FFA and water tolerance, and oil
flexibility.
The ZnLa catalysts demonstrate high catalytic activity.
When using refined soybean oil, FAME yields as high as
95% under reaction conditions of 60 min, 200 C, 500 psi,
36:1 M ratio of methanol to oil, and 2.3 wt% catalyst
dosage in a stirred batch reactor.
Yan et al. [127] reported the Zn3La1 catalyst which had
a 3:1 M ratio of zinc to lanthanum was recycled 17 times in
a batch reactor without loss of activity and maintained a
high FAME yield (*92.3%) for 70 days in a continuous
tubular flow reactor (Fig. 3a, b). Additional testing showed
the catalyst still active after more than 100 days of use
[128]. At this point, there is no report of any other heterogeneous catalyst with a longer catalyst life than this
Zn3La1 catalyst for biodiesel production.
As part of the above work, food-grade soybean oils
combined with 5.20%, 10.13%, 15.21% and 30.56% of
oleic acid and 1.03%, 3.12% and 5.07% water were tested.
The results (Tables 2 and 3) show that all the oils were
converted within 150 min to FAME (*96%) even with
FFA content as high as 30.56% or water content as high as
5.07%. This suggests that by properly controlling the
temperature of the reaction, hydrolysis reactions in the
presence of water can be minimized, which will allow for
higher FAME yields from higher FFA and water content

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732

Top Catal (2010) 53:721736


Table 3 Yield of FAME in the presence of different water addition

100

Water addition
(%)

Yield of FAME at different reaction time (%)


20 min

60 min

90 min

150 min

70

52

88

93

94

60

1.03

50

80

90

96

3.12

22

74

89

93

5.07

13

57

78

90

90

Yield of FAME %

80

50
40

Reaction conditions: catalyst amount of Zn3La1 is 2.3 wt%, molar


ratio of methanol to oil is 36:1, reaction temperature is 200 C. All
data are taken from literature [68]

30
20
10
0

100
0

10

12

14

16

18

FAME content %

Recycle times
100

Yield of FAME (%)

80

80

60

40

20
60

0
0

20

40

60

80

100

120

140

160

180

200

Reaction time min

40

Crude coconut oil


Waste cooking oil
Crude soybean oil
Crude palm oil
Crude algae oil
Crude corn oil from DDGs
Food grade soybean oil
NaOH
H2SO4

20

Food grade soybean oil with 3 % water and 5 % FFA addition

0
0

10

20

30

40

50

60

70

80

Time (day)

Fig. 3 FAME yield (a) in the batch reactor using the recycled
Zn3La1 catalyst. Note the catalyst was reused for 17 times. The
average yield of soybean methyl esters is 93.7% (b) in the continuous
reactor. Note that this catalyst has run for 70 days, and the average
yield of FAME during stable stage is 92.3% [127]

Table 2 Yield of FAME in the presence of different FFA addition


FFA
addition (%)

Yield of FAME at different reaction time (%)


5 min

10 min

20 min

40 min

10

16

52

83

88

93

5.20

38

72

83

95

92

10.13

73

83

88

92

92

15.21

89

95

98

92

30.56

75

85

93

95

01

60 min

90 min

Reaction conditions: catalyst amount of Zn3La1 is 2.3 wt%, molar


ratio of methanol to oil is 36:1, reaction temperature is 200 C. All
data are taken from literature [68]

123

Fig. 4 FAME yield of crude corn oil from DDGs, crude algae oil,
crude coconut oil, crude palm oil, crude soybean oil, waste cooking
oil, food grade soybean oil and food grade soybean oil with 3% water
and 5% oleic acid addition. Reaction conditions: 126 g of oil, 180 g
of methanol, 3 g of catalyst, 200 C, 500 psi, in the batch stir reactor.
Note that all of these oils was converted into FAME within 3 h [127]

feedstocks. Furthermore, this catalyst was found to be


relatively insensitive to species in air such as CO2, moisture and O2 in air, which poison base catalysts.
Zn3La1 was used to process multiple unrefined and
waste oils, i.e. crude corn oil from DDGs, crude algae oil,
crude coconut oil, crude palm oil, crude soybean oil, waste
cooking oil, food grade soybean oil with 3% water and 5%
FFA addition. Figure 4 shows that all the oils were completely converted to FAME within 3 h in a batch reactor.
This is an impressive result considering the fatty acid
composition and total acid number (TAN) of these oils
(Table 4). Here, it should be noted that crude corn oil from
DDGs contains 93% triglycerides and has a TAN as high as
25.19 mg KOH/g. Similarly, crude algae oil contains only
80% triglycerides, and has a TAN of 26.38 mg KOH/g,
while crude coconut oil has a TAN of 8.48 mg KOH/g.
After reaction, the TAN of all the oils is significantly

Top Catal (2010) 53:721736

733

Table 4 Fatty acid composition and TAN of food grade soybean oil, crude soybean oil, crude palm oil, waste cooking oil, crude corn oil from
DDGs, crude algae oil and crude coconut oil [127]
Crude soybean
oil (%)

Crude palm
oil (%)

Waste cooking
oil (%)

Crude corn oil


from DDGs (%)

Crude algae
oil (%)

Crude coconut
oil (%)

C 12:0

49.13

C 14: 0

0.27

0.21

2.72

19.63

13.05
0.39

41.92
0.23

20.91
10.62

10.12
1.79

C 16: 0
C 16: 1

11.07
0.09

11.58
0.18

11.50
0

C 18: 0

3.62

4.17

3.85

4.26

4.77

6.95

2.83

C 18: 1

20.26

22.75

42.44

24.84

26.26

33.33

7.59

C 18: 2

57.60

52.78

11.30

53.55

56.20

18.45

2.75

C 18: 3

7.36

6.59

0.04

5.60

1.27

1.16

0.15

Others

6.86

6.01

TAN

0.03

6.62

0.48

7.56

26.38

8.48

100

600

Yield of FAME %

80

500
400

Yield of FAME
La content in FAME phase
Zn content in FAME phase

60

300

40

200
100

20

0
0
0

10

20

30

40

50

60

70

80

Time (day)

100

1800

80

1400

1600

Yield of FAME %

reduced. For instance, the TAN of algae oil after reaction is


0.94 mg KOH/g and that of corn oil from DDGs is
1.32 mg KOH/g. This implies that during the reaction
process, esterification of FFA with methanol is simultaneously performed with the transesterification of triglycerides with methanol. Where traditional homogeneous
catalysts would have been deactivated using these high
TAN/FFA feedstocks, the Zn3La1 shows a remarkably
high activity for biodiesel formation reactions with a
variety of feedstocks.
Unlike previously reported solid catalysts, the Zn3La1
catalyst is very stable. Yan et al. pointed out that the Zn
and La contents in the FAME product are only 6 and
2 ppm. The Zn and La contents in the glycerine phase were
measured at only 8 and 4 ppm after a short induction
period when the yield of FAME stabilized (Fig. 5a, b). The
low level of Zn and La in FAME and glycerin products
suggests that Zn3La1 is a true heterogeneous catalyst with
a very stable crystal structure that does not deactivate under
reaction conditions.
Figure 6 illustrates the reaction pathway for biodiesel
formation. Where other catalysts have failed, this catalyst
can successful handle all the components of a crude feedstocks. In particular, there are three major components to
these inexpensive oils: triglyceride, FFA, and water. Thus,
there are four major reactions: transesterification of triglyceride with methanol, which results in the formation of
FAME; esterification of FFA with methanol, which results
in FAME; hydrolysis of FAME, which consumes FAME;
and hydrolysis of triglycerides, which results in FFA. The
transesterification and esterification reactions will lead to
higher yields of FAME. However, hydrolysis reactions will
lead to lower FAME yields. With appropriate control of the
reaction temperature, Yan et al. [68] was able to maximize
the transesterification and esterification reactions while de
emphasizing the oil and biodiesel hydrolysis reactions.

25.19

Zn and La content (ppm)

Food grade
soybean oil (%)

1200

Yield of FAME
La content in glycerine phase
Zn content in glycerine phase

60

1000
800
600

40

400
200

20

Zn and La content (ppm)

Fatty acid
components

0
-200

0
0

10

20

30

40

50

60

70

80

Time (day)

Fig. 5 Zn and La contents in a FAME product and b glycerine


product. Note that after 3 days metal contents in FAME product
reached a low level; after 7 days metal contents in glycerine product
reached a low level [127]

4 Summary and Future Opportunity


The use of heterogeneous catalysts for biodiesel production
is an emerging research field which has been quickly
growing over the last 10 years. Most of the reported

123

734

Top Catal (2010) 53:721736

Fig. 6 Reactions pathways of


transesterification,
esterification, and hydrolysis of
unrefined and waste oils [68]

Unrefined or Waste Oils

Triglyceride

Transesterification

Water

Hydrolysis

FFA

Esterification

Hydrolysis

Fatty Acid Methyl Esters

catalysts can be divided into two types, solid base and solid
acid catalysts, according to their active center. Both Lewis
acidbase sites and Bronsted acidbase sites have the
ability to catalyze the oil transesterification reaction.
Therefore, catalyst activity is closely related to the acid/
base strength. Other texture properties of the catalyst also
impact the catalysts activity, such as specific surface area,
pore size, pore volume and active site concentration.
Modification of reaction conditions, such as increasing
reaction temperature (130250 C), pressure (100
1000 psi), catalyst quantity (310 wt%), and methanol/oil
molar ratio (10:142:1) is effective for obtaining high
FAME yields. Reported catalysts, operating at high temperature, exhibit a low base or acid strength which many
research groups have demonstrated is the basis for
improved activity, improved tolerance to FFA and water,
and extended catalyst lifetimes. Within these high temperature catalysts, two catalysts stand out as leading technologies: one is the ZnOAl2O3 catalyst from IFP and the
other is the ZnOLa2O3 catalyst developed at Wayne State
University. Additional work is still required to find ways to
rejuvenate or re-active catalysts that have failed because of
poisoning, leaching, or loss of surface area. Finally, the
most recognized drawbacks of heterogeneous catalysts are
their slow reaction rates in comparison to homogeneous
catalysts. Perhaps, by enhancing the number and type of
active sites and intensifying reaction conditions, to minimize mass transfer limitations, these catalysts may be able
to overcome this limitation as well.

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