C H A P T E R

16
Applications of Heterogeneous Catalysts
in the Production of Biodiesel by Esterification
and Transesterification
Luiz P. Ramos*, Claudiney S. Cordeiro, Maria Aparecida F. Cesar-Oliveira,
Fernando Wypych, Shirley Nakagaki
Research Center in Applied Chemistry, Department of Chemistry, Federal University of Paraná, Curitiba, Paraná, Brazil
*Corresponding author email: [email protected]

O U T L I N E

Introduction 255 Layered Materials 265

Layered Double Hydroxides 265
Heteropolyacids 257
Layered Hydroxide Salts 265
Zeolites 258 Layered Carboxylates 266
Layered Materials as Heterogeneous Catalysts in
Clay Minerals 260
(Trans)Esterification Reactions 266
Clay Minerals Improving Acidity 262
Acid-Activated Clay Minerals in Biodiesel Polymeric Catalysts 269
Production 263
Concluding Remarks 272
Case 1 263
Case 2 263 References 272
Case 3 264

INTRODUCTION economy theory proposed by Trost (1991), in which the

majority of the atoms present in chemical reagents
It is well known that most of the products derived must be incorporated into useful products.
from the chemical industry involve a catalyst in at least Many traditional processes based on homogeneous
one step of synthesis (Figueiredo and Ribeiro, 1987). catalysis have been reviewed in order to minimize waste
However, traditional processes for chemical conversion generation. In addition, many researchers have shown
have numerous inconveniences such as the generation that heterogeneous catalysts are excellent alternatives
of undesirable by-products and environmental pollu- to generate lower amounts of waste streams and also
tion. For this reason, civil groups as well as govern- to improve the quality of coproducts, which may
mental agencies are pressing the industrial sector to contribute with additional revenue for the overall pro-
overcome these problems by developing alternative duction process.
processes in which waste generation is minimized or The biodiesel industry is another important sector
even eliminated. This concept is also part of the atom that is following the same strategic pathway (Cordeiro

Bioenergy Research: Advances and Applications 255

http://dx.doi.org/10.1016/B978-0-444-59561-4.00016-4 Copyright Ó 2014 Elsevier B.V. All rights reserved.
256 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

et al., 2012; Di Serio et al., 2008). Biodiesel is a biodegrad- system is easily purified and glycerin is of high purity,
able fuel derived from renewable sources that can be diminishing the investment to achieve a suitable market
obtained by different routes such transesterification specification (Ramos et al., 2003). Many classes of chem-
and esterification. The traditional transesterification ical compounds have been tested as solids for hetero-
process of oils and fats is based on the use of a homoge- geneous catalysis to produce biodiesel by either
neous system, with methanol as the transesterification esterification or transesterification processes. Among
agent and a base catalyst, usually an alkoxide or a these, zeolites, ionic exchange resins, inorganic oxides,
hydroxide (NaOH or KOH) that generates the corre- layered compounds, guanidines and metal complexes
sponding alkoxide in situ (Van Gerpen and Knothe, have been already used (Cordeiro et al., 2011).
2009). Then, the synthetic mono alkyl esters can be In order to have a truly heterogeneous catalytic pro-
used as biodiesel after suitable purification. The main cess, the solid catalyst must not leach into the reaction
problem of these processes is related to the required pu- medium and it also needs to be stable under the reaction
rification steps of the mono alkyl esters as well as glyc- conditions and reusable. While using solid catalysts for
erin, which must be recovered in good condition due to biodiesel preparation, whether by esterification or trans-
their high commercial value. esterification, the most common catalyst classifications
Ideally, the biodiesel fuel must be free of residues are solid Brønsted acids, Brønsted bases or Lewis acids.
formed in the chemical process like free and bonded The same solid catalyst, however, may present more
glycerin, soaps and water, which are normally used in than one of these sites and depending on the acidity or
washing stages for purification. The presence of glycerin basicity of the solid, the catalytic performance can vary
in the resulting biofuel is problematic because this pol- considerably (Sharma et al., 2011).
yol may undergo dehydration during combustion, pro- Recently, in addition to this primary classification, a
ducing a toxic unsaturated aldehyde named acrolein number of other factors have been considered while
that is not only a dangerous atmospheric pollutant but developing solid catalysts for esterification or transester-
also a reactive chemical that can be easily involved in ification reactions. The solids hydrophobicity, for once,
condensation reactions, producing an accumulation of is used to unveil the water tolerance. The knowledge
carbon deposits that may block filters and compromise of the pore and channel system is used to improve the
the engine performance (Mittelbach and Tritthart, mass transfer of the catalytic substrate, which for this
1988). Soaps and free fatty acids (FFAs) cause degrada- kind of reaction presents a relatively high viscosity
tion of engine components and free water can interfere (Wilson and Lee, 2012).
with the biodiesel acid number and induce hydrolysis Metal oxides, mainly calcium (CaO), magnesium
and biological contamination under nonadequate stor- (MgO) and strontium (SrO) oxides, are among the most
age conditions (Ramos et al., 2003). extensively studied solid bases for heterogeneous cata-
The traditional fatty acid esterification processes in lytic processes (Sharma et al., 2011). Among all alkaline
homogeneous media uses Brønsted acids such as sulfu- and alkaline earth metal oxides, CaO is the most widely
ric or hydrochloric as reaction catalysts (Ilgen et al., studied. Many are the reasons to explain this fact,
2007). However, the extensive use of these catalysts including its low cost, low toxicity and low solubility in
may induce corrosion in reactor components and pipe- methanol, which is the most commonly used primary
lines. Also, the purification of the monoesters produced alcohol for the catalytic transesterification of oils and
in this way is also expensive and may require additional fats (Sharma et al., 2011; Kusdiana and Saka, 2001).
washing steps and distillation (Altiparmak et al., 2007). CaO also has a long catalytic life, with high activity in
A traditional sequence for biodiesel production in- many recycling processes under moderate reaction condi-
volves (1) the recovery of vegetable oil by pressing tions (Lopez et al., 2007). Besides these advantages, CaO
and/or solvent extraction, (2) the oil pretreatment to can be obtained from various and sometimes unusual
adjust its properties for transesterification, (3) the trans- natural sources. Naturally occurring minerals such as cal-
esterification process, (4) the purification by several cite (CaCO3) and several calcium salts (Lopez-Granados
stages of water washing and (5) the recovery of reaction et al., 2010) as well as mollusk shells and egg shells
coproducts, especially glycerin. Each of these steps adds (Cho and Seo, 2010) can be used as a source of CaO by
costs to the overall process. Thus, the introduction of calcination.
operation units that are able to reduce the contamination The impregnation of different alkaline salts in zeolites
degree of mono alkyl esters and glycerin may be an followed by appropriate thermal treatment can produce
important measure to make biodiesel more competitive basic zeolites and the resulting solids have shown good
from an economic and environmental point of view. activity as heterogeneous catalysts for transesterifica-
For these reasons, many researches had focused their tion. Studies have shown that the basicity of the resulted
efforts to substitute homogeneous catalysts for heteroge- zeolite can be related to the electropositive nature of the
neous ones. The biodiesel produced in a heterogeneous exchanged alkaline cation (Philippou et al., 2000).
 HETEROPOLYACIDS 257
The infrequent use of acid catalysis in transesterifica- Besides their inherent superacidity (pKHþ > 12)
tion reactions, in comparison to the base catalysis, is in (Mizuno and Misono, 1998), which already ensures the
part justified by the lower catalytic activities of the achievement of relatively high yields, these compounds
acid compounds. On the other hand, acid catalysts are can be devised in such a way to produce a pore architec-
less sensitive to several contaminants such as water ture and a chemical composition that meets the structure
and FFAs, which in many cases can deactivate the base and size of the molecules that are involved in both ester-
catalyst or drive the catalytic reaction to other products ification and transesterification reactions.
(Van Gerpen and Knothe, 2009). Polyoxometalates, frequently named as POMs, are
Notwithstanding this apparent disadvantage of the anionic metal-oxo clusters whose chemical properties
acid catalyst, solid catalysts with Brønsted or Lewis can be modulated by the presence of one or more
acid properties have been recently investigated in het- different transition metal ions and the cation used to
erogeneous processes. These solids are promising solid generate the salt form.
catalysts for the replacement of strong inorganic acids The presence of two different metal atoms per poly-
that, although effective in both esterification and trans- oxometalate molecule generates compounds with mixed
esterification homogeneous catalytic systems, have metals, vanadium and molybdenum being the most
serious adverse factors such as corrosion of the reaction commonly used. Furthermore, the presence of other
vessels. Furthermore, the use of strong inorganic acids atoms in the structure, besides the metal and the oxygen
leads to medium- and long-term environmental prob- atoms, leads to heteropolyoxometalate compounds with
lems (Helwani et al., 2009a). Thus, the possibility of the general formula (XnþMo12O40)(8n), where X can
using solids with acid properties, rather than highly often be as W (V), Si (IV), Ge (IV) and Ti (IV). These an-
corrosive liquids, therefore replacing homogeneous pro- ions can be arranged in typical structures such as
cesses by heterogeneous ones, may be advantageous Keggin and Dawson structures.
since higher catalytic efficiencies may be obtained in The protonated form of heteropolyoxometalate an-
more sustainable conversion processes. These are likely ions is referred to as heteropolyacids, which may be
to outweigh the higher costs that are often associated defined as a condensed structure of different types of
with the rational synthesis and use of suitable solid acids. oxyacids. In water, it is expected that all HPA protons
Furthermore, the research of acid catalysts has also are dissociated. The strength of these acids in acetoni-
been driven by the possible use of waste cooking oil trile was estimated. For instance, the acidity of
and other cheap and widely available raw materials H3PW12O40 in acetonitrile is greater than that observed
for biodiesel production. For such materials, the catalyst for the p-toluenesulfonic acid and H2SO4, two acids usu-
must be suitable for acting in the presence of high water ally used as catalysts for (trans)esterification in homoge-
and acid content, properties that are often found in low neous catalytic systems (Drago et al., 1997).
cost feedstocks. In general, solids with high acid proper- HPAs are generally soluble in water and other polar
ties usually meet these prerequisites (Oliveira et al., media. Therefore, they are usually unsuitable for bio-
2010; Zhao et al., 2012). diesel production by heterogeneous catalysis. However,
The present work presents a discussion about the these anionic compounds are water insoluble when pre-
most important classes of inorganic solids and poly- sented as salts with large cations such as Csþ. Because of
meric materials that have been applied in the synthesis this characteristic, there is a great interest in the applica-
of (m)ethyl monoesters through esterification or transes- tion of this family of solid compounds in heterogeneous
terification. However, biological systems such as immo- process, acting as acid, redox and bifunctional catalysts
bilized lipases are not treated in this book chapter. (Li et al., 2007).
Luckily, highly qualified reviews have been published The (C16TA)H4TiPW11O40 solid, resulting from the
recently on this specific subject (Di Serio et al., 2008; Fjer- combination of a surfactant (C16TA, cetyltrimethylam-
baek et al., 2009; Tana et al., 2010). monium) with an HPA, was recently reported as a
water-tolerant solid for the heterogeneous catalytic
esterification of palmitic acid (Zhao et al., 2012). The
HETEROPOLYACIDS observed high conversion (94.7 wt%) and high efficiency
(91.8 wt% yield) were attributed to the presence of
The heteropolyacid (HPA) solids, related to the class Brønsted and Lewis acid sites, its amphiphilic property
of polyoxometalates, are often remembered when there and high water tolerance. The authors claimed that sub-
is a need for catalysts that are tolerant to the large strate molecules concentrate around the catalyst through
amounts of water. As already discussed above, such hydrophobic interactions with its lipophilic tail while
conditions are usually found in the catalytic conversion methanol molecules are absorbed by HPA through
of low-cost raw materials to liquid biofuels such as hydrogen bonding. The hydrophobic surroundings
biodiesel. also promote the separation and/or repulsion of water
258 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

molecules from the surface of the catalyst. Also, the solid catalytic properties to the resulting material such as
catalyst showed a good recyclability and its heteroge- selectivity.
neous character was proved through several cycles of re- In general, zeolites and other porous materials of
covery and reuse. similar composition and textural properties, named
In order to heterogenize the HPAs and improve their zeolite-like materials and zeotypes, have been prepared
recovery and reuse, their impregnation on zirconia was and used as catalysts in various chemical processes.
also investigated (Oliveira et al., 2010). The H3PW12O40 These solid catalysts present a strong scientific appeal
was immobilized on zirconia at different ratios and for green chemistry applications since they are consid-
calcined at 200  C for 4 h. No decomposition of the Keg- ered environmentally benign when one takes into
gin anion structure was observed under these conditions. account their chemical composition.
The resulting solids were used in the esterification of oleic There are several reports regarding the use of zeolite-
acid with ethanol at a 20 wt% loading, 100  C and 4 h based catalysts for various chemical reactions. Such uses
with an ethanol:acid molar ratio of 6:1, conditions under have been recently reviewed (Martinez and Corma,
which an 88 wt% conversion of oleic acid to ethyl oleate 2011; Rinaldi and Schuth, 2009). This versatility of uses
was obtained. A small leaching (8 wt%) of the catalyst is not only justified for their great variety in chemical
was observed at the end of the reaction, therefore composition but also because of the uniformity of their
affecting the reaction kinetics. The recyclability study pore structure.
indicated that, after being recovered, washed and ther- Due to the presence of pores and channels, catalysts
mally treated, the solid presented conversion values as based on zeolites can present size selectivity that is
high as 70 wt%, that is, 80% of the original value of rarely seen in other solids. This selectivity can be
88 wt%. observed for reactants, products and transition state in-
These examples and many others have shown that termediates that are expected to control a given catalytic
HPA and POWs represent promising catalysts for both reaction (Csicsery, 1984). However, for the same reason,
esterification and transesterification (Giri et al., 2005; these solids not always perform well in catalytic
Caetano et al., 2008; Wee et al., 2010; Leng et al., 2009) processes that are dependent on one of their main chem-
but their heterogenization in different supports still ical properties (e.g. acidity). This occurs mainly for pro-
needs to be improved in order to keep the process totally cesses in which the reactants have dimensions exceeding
heterogeneous. the catalytic channels and pores provided by zeolitic
solid catalyst. Therefore, the structure of a zeolite cata-
lyst must be idealized in order to have not only the
ZEOLITES appropriate chemical property but also the textural
properties that would offer an array of pores and chan-
Zeolites are natural or synthetic materials, classically nels that are adequate for the diffusion of the chemical
defined as crystalline aluminosilicate compounds (Cundy reactants. The strategy to meet these two goals is a chal-
and Cox, 2003). Zeolites can be prepared by different lenge for the catalytic application of these solids.
synthetic routes with different Si/Al molar ratios, crystal The preparation of zeotype materials with mesopores
structures, and proton exchange levels. These modifica- (2e50 nm) appears to be the solution to avoid the mass
tions favor the rationalization of catalytic properties transfer limitations of zeolites in many catalytic pro-
such as pore size, hydrophobicity, strength and distribu- cesses. In this sense, many efforts have been made in
tion of acid sites. When designed in a positive way, all the scientific community to prepare zeolite-like mesopo-
these properties can be interesting and useful for applica- rous materials that are able to address this goal (Tao
tions in heterogeneous catalysis (Corma et al., 1989). et al., 2006).
The catalytic activity of zeolytes can derive from the For applications in the esterification of fatty acids or
properties of the cation that is present in its chemical in transesterification of oils and fats, in which large mol-
composition. Moreover, the exchange of these cations ecules are directly involved in the production of bio-
by protons may generate different degrees of zeolite fuels, it is expected that, apart from their high acidity,
acidity, which is also an interesting property for various the surface of the zeolitic and/or zeotype solids should
catalytic processes (Csicsery, 1984). In fact, acid zeolites be hydrophobic enough to promote the adsorption of
are used in many industrial catalytic applications, the substrate on the catalyst surface. In this regard, the
mainly in the petrochemical industry. adsorption of polar molecules may cause deactivation
Another interesting property is the organized and of catalytic sites, such as in the case of water in esterifi-
uniform pore distribution and the existence of a cav- cation reactions (Helwani et al., 2009a). For example,
ity system of regular molecular dimensions ranging faujasite is a highly hydrophilic zeolite that presents
from <1 nm to over 10 nm, depending on the solid high levels of water adsorption. Hence, this material is
material. This feature may bestow rather important barely adequate for esterification because water may
 ZEOLITES 259
not only inactivate the catalytic sites on the solid surface Ajaikumar and Pandurangan (2007) prepared Al-
but also compromise the reaction yields by interfering MCM-41 materials with different Si/Al ratios (29, 52,
with the reaction mechanism (Nijhuis et al., 2002). 74 and 110) and used these solids in the esterification
The MCM-41 molecular sieves have been used as an of acetic and propionic acids with various alcohols
alternative to zeolite microporous materials. Since its (1-hexanol, 2-ethyl-1-isoamyl alcohol and cyclohexanol).
discovery in the early 1990s, these molecular sieves With a small addition of aluminum, which translates
have been used as catalyst in different chemical reac- into a high Si/Al ratio of 110, these authors observed a
tions (Beck et al., 1992; Climent et al., 1999), including higher hydrophobicity and a higher catalyst hydrother-
in the preparation of biofuels (Twaiq et al., 2003). mal stability of the material concerning the amount of
Similar to the zeolites, these mesoporous compounds water formed during esterification. Furthermore, the
also have a regular and ordered distribution of pores use of more hydrophobic solid materials prevented the
(mesopores) across the solid catalyst, allowing their subsequent hydrolysis of the ester formed. On the other
use for the conversion of larger molecules (Carmo hand, solid catalysts with lower Si/Al ratio promoted
et al., 2009). Moreover, the incorporation of metals in lower levels of alcohol dehydration, which can also be
the structure of mesoporous solids may lead to acidic favored at high temperature. As a result, the selectivity
materials with special characteristics such as a higher of the catalytic reaction is improved toward the ester pro-
hydrothermal stability. For example, the incorporation duction as the accumulation of possible by-products
of aluminum ions in zeolitic materials can lead to a (etherified and dehydrated compounds) is decreased.
decrease in the Si/Al ratio and a subsequent increase Hence, the hydrophobicity achieved at higher Si/Al
in the amount of the solid acid sites, since it is well ratios was an important factor for the best catalytic
known that the lower the framework Si/Al ratio of the performance (catalytic efficiency), whereas the use of
zeolite, the lower the strength of its acid sites, regardless low aluminum contents led to more selective catalytic
of its higher density (Ma et al., 1996; Corma et al., 1989). systems.
Furthermore, the catalyst hydrophobicity can also be Corma et al. (1989) reported that strong Brøn-
changed by modifying the Si/Al ratio. This leads to an stedeLowry acid sites are required for the catalytic
alteration in the ability of the solid to adsorb nonpolar esterification of acetic acid since they are able to proton-
molecules in the catalytic reactions such as esterification ate the acetic acid carbonyl group. Working with proton-
and transesterification, as well as in desorption of polar ated faujazite zeolite after dealuminization, these
molecules such as water (Luque et al., 2007). In general, authors observed that some dealuminized HY zeolites
high Si/Al ratios (or low aluminum contents) leads to with Si/Al ratio less than or equal to 15 had better cata-
high solid hydrophobicity. Thus, since the Si/Al ratio lytic performance. The strong acid sites present in that
modifies the acidity and hydrophobicity of the catalyst, solid, which correspond to those aluminum vacant sites
its influence on the catalytic properties is subtle, mainly or sites occupied by one aluminum atom and the respec-
in esterification reactions. tive nearest neighbors, are more active for the catalytic
The presence of water is an important factor in the esterification of fatty acids. Zeolites with high Si/Al
conversion outcome of esterification reactions. The equi- ratio presented a more hydrophobic surface and this
librium constant for ester formation is very low (3.38 for hydrophobicity became the predominant factor for the
the reaction of acetic acid with ethanol in nonpolar sol- equilibrium shifting toward the production of alkyl
vents) (Corma et al., 1989). So, to obtain high ester yields, esters. Also, the higher the aluminum content of the
the reaction must be displaced toward the products, for zeolite, the higher the observed adsorption effect.
example, by the continuous removal of water from the Carmo et al. (2009) also prepared solids based on
system. Furthermore, the reaction can be shifted toward Al-MCM-41 to investigate the relationship between the
the products when working with a large excess of high availability of acid sites, introduced by increasing
reagents. the aluminum content in the mesoporous solid, and
In order to segregate the water from the reaction envi- the degree of esterification of palmitic acid with meth-
ronment, it is necessary to work with high reaction rates anol, ethanol and isopropanol. However, these authors
and this can be achieved with homogeneous acid cata- restricted their work to solids with low Si/Al ratios
lysts such as sulfuric acid. However, for solid catalysts (8, 16 and 32) whose hydrophobicity was much smaller
such as the zeolitic materials and zeotypes, the proper than the solids described in the previous work. This and
balance between strength and density of the acid sites, most of the data already available in the literature pro-
suitable for a good catalytic performance and water pose the utilization of solid catalysts for esterification
segregation, is often difficult to achieve. The rate of reac- reactions. In general, these studies have been motivated
tions catalyzed by zeolite catalysts and other solid mate- by the technological challenge of developing a suitable
rials is usually very low compared to that of sulfuric acid catalytic system to convert vegetable oils or animal fats
(Ma et al., 1996). of high acid number in biodiesel. Hence, by the catalytic
260 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

esterification of their fatty acid content, these materials and reuse and a good catalytic activity was obtained in
would be neutralized and become suitable for transes- the first and subsequent recycling stages. Similarly, zir-
terification in alkaline media. conia impregnated with tungsten oxide (ZrO2/WO2)
The high aluminum content solid catalysts (Si/Al was also investigated as an acid catalyst for both esteri-
molar ratio of 8) prepared by Carmo et al. (2009) showed fication and transesterification reactions with methanol
relatively modest palmitic acid conversion values. The (Lopez et al., 2007).
highest value achieved in this study was 79 wt% of
methyl ester. The authors did not report the effect of
hydrophobicity on reaction conversion but only the CLAY MINERALS
increased effect of aluminum incorporation in the cata-
lytic activity of the resulting solids. Clay minerals are composed of hydrous layered sili-
Ma et al. (1996) used different zeolitic solids (zeolite cates that are part of the phyllosilicates family. The phyl-
ZSM-5 and three HY zeolites with Si/Al molar ratios losilicates family is broad and is roughly separated by
of 30, 5.1 and 9.3) to evaluate the relationship between layer types, groups, subgroups and species (Brindley
the solid hydrophobicity and its aluminum content and Brown, 1980). Two basic units are important to build
with the observed catalytic efficiency in the preparation the clay minerals, the first is silicon atoms coordinated
of ethyl, n-butyl, isopentyl and benzyl acetates; ethyl tetrahedrically to oxygen atoms (SiO4) and divalent or
and n-butyl benzoates and dioctyl phthalates. For all trivalent metals coordinated octahedrically to hydroxyls
the solid catalysts used in this study, a high selectivity (Mþ2/Mþ3(OH)6). The silicon tetrahedral face can share
for the expected ester was observed without any forma- the three corners with other silicon tetrahedral to build a
tion of ether derivatives. The increase in selectivity hexagonal two-dimensional pattern, the tetrahedral
with decreasing aluminum content was also reported sheet. A similar procedure can be adopted by the octahe-
by Corma et al. (1989). dral, where basically two differences can be obtained
Insoluble inorganic salts and other inorganic solids when Mþ2 or Mþ3 atoms occupy the center of the
based on transition metals can also be used as acid octahedral.
catalysts for transesterification. The application of so- When Mþ2 is used and the octahedral share the edges,
dium molybdate (Na2MoO4) and sodium tungstate all octahedral sites are occupied and a two-dimensional
(Na2WO4) has been recently reported as efficient cata- unit is formed, the so-called octahedral sheet. This unit
lysts for biodiesel production under relatively mild resembles the structure of brucite (Mg(OH)2) and the
experimental conditions (Nakagaki et al., 2008; Santos sheet is called trioctahedral. When Mþ3 is used and the
et al., 2011). In these studies, soybean oil (0.7 mg/g octahedral share the edges, only 2/3 of the octahedral
KOH of acid number), degummed soybean oil contain- sites are occupied and the resulting two-dimensional
ing 180 ppm of phosphatides (1.0 mg/g of KOH), and unit resembles the structure of gibbsite Al(OH)3; in
waste cooking oil (1.5 mg/g KOH) were transesterified this case, the sheet is named dioctahedral. In the ideal
with methanol (methanolysis). At 65e80  C using a condition, the apical oxygen of the tetrahedral sheets
54:1 methanol:oil molar ratio and 5 wt% catalyst for can be linked to one octahedral, building the clay min-
3e5 h, both catalysts reached conversions higher than erals of the 1:1 layer type. The unshared hydroxyls of
92 wt% regardless of the feedstock used for methanoly- the octahedra lie at the center of the tetrahedra at the
sis. The catalytic activity of these compounds was attrib- same “z” level of the shared apical oxygen.
uted to the presence of molybdenum(VI) or tungsten(VI) Under ideal conditions, two clay minerals of the 1:1
strong Lewis acid sites that are probably able to polarize layer type can be obtained. When Mþ2 occupies the center
the methanol OeH bond leading to intermediate species of the octahedral, the structure of chrysotile (Mg3(OH)4
that possibly have high nucleophilic character. Si2O5) is obtained and the replacement of Mþ2 by Mþ3
The heterogeneous nature of the above-mentioned yields the structure of kaolinite (Al2(OH)4Si2O5).
catalysts was investigated through their reuse in several As both sides of the octahedral have hydroxyls to
consecutive reaction cycles. Both compounds could be share, one octahedral sheet can also be combined with
reused for at least three catalytic cycles. However, part two tetrahedral sheets, originating the 2:1 layer-type
of the solid catalysts was lost during the recycling pro- clay minerals. Again, when Mþ2 occupies the center
cesses due to their reduced particle size and noticeable of the octahedral, the structure of talc is obtained
adherence to the walls of the reaction vessel. To circum- (Mg3(OH)2Si4O10) while its replacement by Mþ3 results
vent these problems, both molybdenum (Bail et al., 2013) in the structure of pyrophyllite (Al2(OH)4Si4O10).
and tungsten (Santos et al., 2011) compounds were het- Figure 16.1 shows the lateral (A) and top (B) views of
erogenized in silica obtained by the solegel process the above-cited compounds.
and used in esterification of stearic and oleic acids. Im- In nature, the phyllosilicates are obtained through
provements were observed in the catalysts’ recovery weathering, which is the phenomenon related to the
 CLAY MINERALS 261

FIGURE 16.1 Lateral view (A) and top view (B) of the layered structures of chrysotile (a), kaolinite (b), talc (c) and pyrophyllite (d). (For color
version of this figure, the reader is referred to the online version of this book.)

disintegration and chemical alteration of rocks and min-

erals at the Earth’s surface in direct contact with the at- the cationic exchange capacity and the plastic properties
mosphere, water and organism. Through this process, of these clay minerals, particularly when they are
many different isomorphic substitutions occur either in dispersed in water.
the tetrahedral (Si by Al or Feþ3) or in the octahedral Using the example of talc and pyrophyllite, these
sheets (Al or Mg by Feþ2/þ3, Li, Ti, V, Cr, Mn, Co, Ni, minerals can give origin to trioctahedral saponite
Cu and Zn), mainly in clay minerals of the 2:1 type. ððMþxy $nH2 OÞðM g3y ðA l; F eÞy ÞðS i4x A lx O1 0 ðO HÞ2 ÞÞ,
The isomorphic substitution generates an excess of where Mgþ2 is substituted by Al and Fe and Si, by Al.
negative charge into the layers, which needs to be After this substitution, the excess of negative charges
compensated with the intercalation of hydrated cations in the clay layers are compensated by the intercalation
between the layers. Hence, this substitution generates of hydrated cations ðMþ xy $nH2 OÞ. Another example of
262 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

trioctahedral mineral derived from pyrophyllite is the described in the 1960s (Ryland et al., 1960), when
clay mineral hectorite ððMþ y $nH2 OÞðMg3y Liy ÞðSi4 O10 acid-modified smectites provided high gasoline yields
ðOHÞ2 ÞÞ. In the case of dioctahedral talc, the derived clay when used as a petroleum-cracking catalyst.
minerals are montmorillonite ððMþ Acid activation of clay minerals using mineral acids is
y $nH2 OÞðAl2y Mgy Þ
not new and this procedure causes disaggregation of
ðSi4 O10 ðOHÞ2 ÞÞ, beidellite ððMþ
y $nH2 OÞAl2 ðSi4x Alx Þ clay particles, elimination of impurities and improve-
O10 ðOHÞ2 Þ and nontronite ððMþ þ3
x $nH2 OÞFe ðSi4x Alx Þ ment of their surface area, porosity and catalytic proper-
O10 ðOHÞ2 Þ. ties. Acid-activated clays are broadly spread in different
industrial processes, being especially used as bleaching
agent and catalysts. Although this process was found
Clay Minerals Improving Acidity
to be dependent on several factors such as the type of
Most of the clay minerals have low Brønsted and mineral, its crystallinity, morphology and particle size,
Lewis acidity. The Brønsted acidity and surface area the effects of the selective acid leaching of a 2:1 clay min-
can be slightly improved during drying when interstitial eral, which is a first-order process, can be schematically
and intercalated cation hydration water molecules are seen as shown in Figure 16.2.
removed. Another way to improve the acidity is to The treatment of clay minerals with mineral acids at
exchange the intercalated species with highly polarizing room temperature tends to replace the intercalated cat-
species such M3þ cations, where the hydrolysis of the ions by hydrated protons and/or by the leached cations,
solvated water molecules release protons. improving Brønsted acidity while the structure is mostly
The Lewis acidity is normally associated with preserved (Figure 16.2(b)). By contrast, the thermal acid
exposed Al3þ or Fe3þ at the broken crystalline edges, activation has several effects on the structure of the clay
which can be increased by heating the clay material to minerals, which depend on the temperature, time of
temperatures above 300  C or by acid treatment treatment and concentration and strength of the acid
(Moronta, 2004). As the thermal treatment can lead to used. Under mild temperatures, times and acid con-
the collapse of the clay mineral structure, the acid treat- centration, the first effect is usually the removal of
ment is the most effective way to improve both Lewis acid-soluble impurities and partial leaching of the octa-
and Brønsted acidity. This procedure was already hedral coordinated metals from the octahedral sheet

FIGURE 16.2 Steps of the acid activation. (a) Raw 2:1 clay mineral; (b) original intercalated cations are replaced by hydrated protons;
(c) octahedral structural metals are leached out of the structure; (d) hydrated silica obtained by the collapse of the clay structure. (For color
version of this figure, the reader is referred to the online version of this book.)
 CLAY MINERALS 263
Konwar et al., 2008; Nascimento et al., 2011; Neji et al.,
2011; Zatta et al., 2012, 2013; Rezende et al., 2012; Olowo-
kere et al., 2012), as well as in the transesterification of
oils and fats (Bokade and Yadav, 2009). Some specific
cases will be evaluated in sequence.

Case 1 (Zatta et al., 2012)

Standard Texas Montmorillonite STx-1 with the
chemical formula ((Ca0.27Na0.04K0.01)[Al2.41Fe(III)0.09
Mg0.71Ti0.03]Si8.00O20(OH)4), supplied by the Clay Min-
eral Society repository, was activated using phosphoric,
nitric and sulfuric acids under different conditions of
temperature, time and acid concentrations and the
resulting materials were characterized by X-ray diffrac-
FIGURE 16.3 Possible mechanism for the formation of Brønsted tion (XRD), nitrogen adsorption isotherms and Fourier
and Lewis acid sites after treatment of a 2:1 clay mineral constituted transform infrared spectroscopy. Also, the presence of
basically of Al in the octahedral sites and Si in the tetrahedral sites.
Lewis and Brønsted acid sites in the structure of the cata-
(For color version of this figure, the reader is referred to the online
version of this book.) lyst was characterized by pyridine adsorption. After-
ward, the materials were evaluated as catalysts in the
(Figure 16.2(c)). During this process, not only the Lewis methyl esterification of lauric acid. Blank reactions car-
acidity is generated but also the anions of the acid can be ried out in the absence of any added catalyst presented
incorporated in the structure. conversions of 32.64, 69.79 and 79.23% for alcohol:lauric
As clays having Mg or Fe in their structure are more acid molar ratios of 60:1, 12:1 and 6:1, respectively. In the
easily leached than octahedra occupied by Al, the acid presence of the untreated clay and using molar ratios of
activation must be optimized to extract the best charac- 12:1 and 6:1 with 12 wt% of catalyst, conversions of 70.92
teristic of each clay mineral. Under extreme conditions, and 82.30% were obtained, respectively. For some key
regardless of the type of clay mineral, all the octahedral samples obtained by the acid activation, conversions
metals are removed to produce inactive hydrated up to 93.08% of lauric acid to methyl laurate were ob-
fibrous silica as reported previously (Figure 16.2(d)) tained, much higher than those observed for the thermal
(Wypych et al., 2005). The effect of an effective acid acti- conversion (TC) or using raw montmorillonite. Relative
vation is the broadening of the basal X-ray diffraction good correlations were observed between the catalytic
peak due to the damage of the layers and, finally, to activity and the development of acid sites and structural
the total collapse of the structure. The physical effects and textural properties of the acid-leached materials.
of this activation process are the improvement of the
Case 2 (Zatta et al., 2013)
surface area and pore volumes up to a specific point
from which these properties are decreased. The pore The same sample of montmorillonite STx-1 described
radii are also constantly reduced during the treatment. above was submitted to acid activation using aqueous
For each acid and activation conditions, a new optimiza- solutions of phosphoric acid. The acid treatment was
tion needs to be reported since each clay mineral has a carried out under vigorous stirring at 100  C in a flat-
characteristic that depends not only on the mineralog- bottomed flask connected to a reflux condenser and a
ical classification but also on the mine from which it heating mantle. The mineral clay and the acid solution
was extracted. were mixed in a 1:4 ratio (mass per volume) using acid
As an example for montmorillonites (Wilson and concentrations of 0.5, 1, 2 and 4 mol/l.
Clark, 2001; Zatta et al., 2012), Figure 16.3 shows a After the acid activation process, the samples were
possible mechanism for the formation of Brønsted and repeatedly washed with distilled water until pH close
Lewis acid sites after mineral acid treatment of a 2:1 to 7, dried at 110  C for 24 h and then heated in an
clay mineral constituted basically of Al in the octahedral oven at 250  C for 2 h. To check the influence of other
sites and Si in the tetrahedral sites. acids in the activation of montmorillonite STx-1, this
clay mineral was subjected to activation with hydrochlo-
ric (37% proof), nitric (65% proof) and sulfuric (98%
Acid-Activated Clay Minerals in Biodiesel
proof) acids. The resulting acid-activated clay materials
Production were characterized and subsequently used in the cata-
Just a small number of papers have been devoted so lytic conversion of lauric, oleic and stearic acids, as
far to the use of acid-activated clay minerals in the cata- well as of a complex mixture of fatty acids (tall oil) to
lytic esterification of fatty acids (Vijayakumar et al., 2005; their corresponding fatty acid methyl esters (FAMEs).
264 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

100 100
K10 PA
K10 K10
PA PA PA
95 K10
90 95

85
Conversion (%)

Conversion (%)
80
STX 90
STX
75 TC STX
TC STX TC
TC 85
70
65
80
60
5 10
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1 2 3 4
Experiment
Use cycle
FIGURE 16.4 Comparison among the catalytic activities of the
FIGURE 16.5 Reuse experiments of the best phosphoric acid
best sample obtained after phosphoric acid (PA) activation with those
activated sample. The reactions were carried out at 160  C for 2 h with
of the thermal conversion (TC), raw montmorillonite (STX) and a
a methanol:fatty acid molar ratio of 12:1 and a catalyst loading of
standard commercial Lewis acid catalyst (K10). Experiments 1e4 were
12 wt% in relation to the oil mass.
carried out with stearic acid, 5e8 with lauric acid, 9e12 with oleic acid
and 13e16 with tall oil fatty acids.

an oven at 110  C for 24 h and finally ground until pas-

sage through a 60 mesh sieve. The surface area of the
The results obtained for the best phosphoric acid-
acid-activated clays was improved from 71 m2/g to
activated sample (PA) were compared to those of the
238 m2/g for the VLn sample and from 123 m2/g to
TC and from a standard commercial Lewis acid catalyst
170 m2/g for the BBn sample. The catalytic activity of
(K10) and raw montmorillonite (STX). In all experi-
these compounds was evaluated in the esterification of
ments, conversion of all samples were carried out for
different organic acids, using different acylating agents
2 h at a methanol:fatty acid molar ratio of 12:1 and
and reflux conditions. In the case of methyl and hexyl
160  C with 12 wt% of the catalyst in relation to the oil
esterification of lauric acid (Figure 16.6), the sulfuric
mass.
acid activation of both clays greatly improved their cat-
In general, the PAs and the standard Lewis acid cata-
alytic activity and this was also valid for other acids and
lyst (K10, SigmaeAldrich), which is produced by HCl
acylating agents. As reported in Case 2, acid activation
activation of mineral clays at boiling temperatures, had
led to catalytic activities higher than the standard Lewis
similar catalytic activities. However, in some cases, the
acid catalyst (K10).
catalytic performance of PA was even better than that
of K10 (Figure 16.4). These data were a strong indication
that PA and K10 have similar chemical and physical
100
characteristics, even though part of the layered structure
Vla BBa
is still retained in PA after acid activation. BBa Vla

Tests of reuse of the best PA were performed 80 K10

(Figure 16.5) and no significant losses of activity were
observed during the first four consecutive reaction cy- 60
Ester (%)

cles (see dotted horizontal line in Figure 16.5). This is a K10

very important observation since, from any practical 40 Vln
use in industrial processes, the catalysts must last for BBn

long time before deactivation.

20

Case 3 (Rezende et al., 2012) BBn Vln

Two different clay minerals (namely BBn and VLn), 0
1 2 3 4 5 6 7 8 9 10
mined in Boa Vista District of Paraı́ba (Brazil), were
Experiment
acid-activated using a 10 wt% suspension of clay in
4 mol/l sulfuric acid at 90  C for 2 h to produce the FIGURE 16.6 Comparison between the catalytic activity of two
BBa and VLa solids, respectively. The solids were Brazilian clay minerals (BBn and VLn) and their respective acid-
activated counterparts (BBA and VLa) in the esterification of lauric
filtered under reduced pressure and washed with acid. A standard commercial Lewis acid catalyst (K10) was also used
distilled water until the washing water had the same for comparison. Experiments 1e5 correspond to the use of methanol,
pH of the original material. The material was dried in whereas hexanol was used in experiments 6e10.
 LAYERED MATERIALS 265
In conclusion, clay minerals are cheap inorganic ma- In this work, the chemical composition of a specific
terials that are readily available worldwide, environ- LDH will be condensed as M2þ/M3þ-A. Thus, an LDH
mentally friendly and suitable for the development of whose layers contain Mg and Al and the counterion
reusable acid catalysts for the esterification of fatty acids between the layers is nitrate will be written as Mg/
and the transesterification of oils and fats. The natural Al-NO3.
acidity can be improved by thermal treatment and selec- One peculiar characteristic of LDHs is the memory ef-
tive acid activation. Depending on the clay minerals’ fect. Calcination of Mg/Al or Zn/Al LDHs forms mixed
origin and genesis, different chemical compositions are and nanostructured mixed metal oxides described as
possible and different acid treatments are needed to LDO, which are able to reassemble the LDH structure
optimize the acidic properties. Normally, the catalysts if added back to an aqueous solution containing a salt
can be used in several consecutive reaction cycles and, whose anions will be intercalated between the layers
after deactivation, the residual solids can be easily in order to stabilize the LDH structure (Carlino, 1997).
disposed of or even incorporated in native clays for These anions can be different from the anions found in
the production of ceramic materials, bricks and roofs, the original LDH. This kind of materials can substitute
as well as in the production of porcelains. basic homogeneous catalysts like ammonia, ammonium
salts or amines and offer an option as nonpollutant solid
catalysts that can be easily separated from the reaction
LAYERED MATERIALS system and recovered. Their catalytic activity is related
to the large surface area of LDHs, its solid base character
Apart from clay materials, different types of layered and layered morphology. For instance, Zn/Al LDH con-
compounds have been tested as heterogeneous catalysts taining nitrate, sulfate or orthophosphate anions have
in processes traditionally mediated by homogeneous catalytic activity in esterification reactions (Hu and Li,
catalysts, which are in some cases expensive and highly 2004), while Mg/Al LDH intercalated with t-butoxide
toxic. Reactions such as Michael addition, cyanoethyl- is active in transesterification (Choudary et al., 2000).
ations of alcohols, aldolic condensations and condensa-
tion of nitro compounds with aldehydes and ketones,
and ring openings can be used as examples (Centi and Layered Hydroxide Salts
Perathoner, 2008). Some layered hydroxides can also undergo isomorphic
Layered materials have also been used as solid cata- substitution of hydroxyl groups by other oxo-ions or by
lysts for biodiesel production through esterification water molecules. In the last case, additional anions will
and transesterification. Most applications involving be required to neutralize the excess of positive charge in
this class of compounds refer to the use of layered dou- the layers, keeping the cations unaltered, i.e. only divalent
ble oxides (LDOs), which are derived from layered dou- cations are present in the layers. The resulting compounds
ble hydroxides (LDHs) by controlled calcination. LDHs, are called layered hydroxide salts. According to this
layered hydroxide salts (LHSs) and layered carboxylates description, LHSs can be classified based on the structure
are less commonly used for this purpose. This section of copper hydroxide nitratedCu2(OH)3NO3dand zinc
presents a brief review of the structure of these layered hydroxide nitratedZn5(OH)8(NO3)2$2H2O. The general
materials in addition to the description of their use formula for an LHS is M2þ ðOHÞ2x ðAn Þx=n $mH2 O,
and performance as catalysts.
where M ¼ Mg, Ni, Zn, Cu, Co and A ¼ NO3 ; SO2 4
e Cl (Arizaga et al., 2007).
Layered Double Hydroxides The layers in the copper hydroxide nitrate structure
are formed by octahedrons whose center is occupied
LDHs are compounds whose individual layers are of by Cu2þ cations and these are coordinated to hydroxyl
brucite-like (Mg(OH)2) structure. In brucite, the layers groups and nitrate ions that have substituted ¼ of the
are electrically neutral with magnesium cations located hydroxyl sites. This example is the easiest description
in the center of an octahedron with six hydroxyl groups of an LHS.
in the vertices. The isomorphic substitution of magnesium The structure of zinc hydroxide nitrate has two main
by trivalent cations forms positively charged layers, which characteristics. The first is that ¼ of the Zn2þ cations in
are stabilized by the presence of anions in the interlayer octahedral coordination with hydroxyl groups migrate
space (Bravo-Suárez et al., 2004). LDHs are represented out of the layers, leaving empty octahedrons and form-
m
by the formula ½M2þ 3þ
1x Mx ðOHÞ2 Ax=m $nH2 O, where ing tetrahedrons up and down the empty octahedral
M and M are divalent and trivalent cations and Am
2þ 3þ
sites. Then, each layer is formed by zinc cations in octa-
represents an anion with an m-charge and x usually has hedral coordination with hydroxyl groups and in tetra-
a value between 0.25 and 0.33 (Crepaldi and Valim, 1998). hedral coordination, whose base is formed by three
266 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

hydroxyl groups shared with the main octahedral layer Zinc laurate melts at approximately 137  C, when nearly
and its apex is occupied by water molecules. The result- 30% of the all-trans conformation is lost. As a result, the
ing layers have residual positive charge with com- structure is partially disassembled but the metals still
2þ
3 Zn2 ðOHÞ8 ðH2 OÞ2  , where oct and
position ½Znoct tetr
remain coordinated to oxygen atoms, either bridging
tetr indicate octahedral and tetrahedral sites (Stählin two different carboxylate groups or in a monodentade
and Oswald, 1971). form (Taylor et al., 2006).
The residual positive charge in the layer is neutral- The application of metal carboxylates in the produc-
ized with nitrate ions in the interlayer space in a perpen- tion of biodiesel became more usual since Cordeiro
dicular position to the layers plane. Normally, nitrate et al. (2008) demonstrated that the LHS zinc hydroxyni-
ions do not coordinate directly to the cations in the trate (ZHN, Zn5(OH)8(NO3)2$2H2O) is rapidly trans-
layers; however, part of the nitrate ions can be grafted formed into zinc carboxylates when used in the
to the layers by controlling the pH of the synthesis catalytic conversion of lauric acid to methyl laurate.
(Arizaga et al., 2008). The stacking of layers is stable According to these authors, zinc carboxylates, which
because of the numerous hydrogen bonds that are are produced in situ during a reaction course, is the
formed between OH groups in the layer, nitrate ions actual catalytic species in the reaction system. Recently,
and the interlayer water molecules. Two adjacent layers the transformation of LDHs into metal carboxylates
are shifted by a factor of b/2 along the (001) plane and was also demonstrated during the catalytic esterification
are stacked along the basal axis. of fatty acids (Cordeiro et al., 2012).

Layered Carboxylates Layered Materials as Heterogeneous Catalysts

Layered carboxylates are also known as metal fatty
in (Trans)Esterification Reactions
acid soaps. These carboxylates are used in several appli- The use of LDH as catalysts for transesterification
cations such as fuel additives, cosmetic products, com- reactions is less common if compared to the use of
ponents of lubricants greases, catalysts, among many LDOs derived from LDH by calcination. However, the
others. Carboxylates can be obtained by melting a t-butoxide intercalated Mg/Al LDH (LDH/t-BU) was
selected fatty acid or fatty acid mixture with the oxide shown to be catalytically active for production of
that contains the metal of interest. Temperatures above b-ketoesters by transesterification with primary, second-
200  C and vigorous agitation are usually required for ary and tertiary alcohols (Choudary et al., 2000).
synthesis. However, the precipitation method is more Serio et al. (2006) synthesized Mg/Al LDHs by copre-
commonly used. In this method, fatty acids are neutral- cipitation at pH 10. After washing and drying, the LDHs
ized with sodium hydroxide in ethanol under stoichio- were calcined at 500  C for 14 h to produce the corre-
metric conditions. Afterward, an ion exchange is sponding oxides. Besides, two samples of oxides identi-
promoted by adding a salt solution of the metal of inter- fied as MgO1 and MgO2 were obtained by calcination
est to the sodium carboxylate solution obtained previ- of Mg(OH)2 and (MgCO3)4 Mg(OH)2 at 400  C. All these
ously, also under stoichiometric conditions. As a result, oxides were tested as catalysts for soybean oil methanol-
the desired metal carboxylate is precipitated and subse- ysis. Reactions carried out with 10 wt% catalyst at 100  C
quently recovered by filtration (Barman and Vasudevan, yielded about 80% of products using the LDO solids and
2006). less than 20% with both MgO1 and MgO2. The higher
Zinc is among the metals most commonly used for the activity of LDO, with respect to other catalysts, was justi-
synthesis of carboxylates. However, other cations, fied by the presence of a higher concentration of very
mainly di- and trivalent, have also been used such as strong base sites and large pores that favored the reaction
manganese, nickel, copper and lantanum (Lisboa et al., by rendering the active sites more accessible to the bulky
2012). In the layered zinc(II) carboxylates, the central triglyceride molecules. In another study (Serio et al.,
zinc metal is tetrahedrally coordinated to bridging 2007), an LDO obtained in the same way was used in
bidentate carboxylate groups forming a bilayer of the the methanolysis of soybean oil with and without the
hydrocarbonic chain bridges in a syn-anti arrangement addition of 10 wt% of its weight in oleic acid. The reaction
(Lacouture et al. 2000; Barman and Vasudevan, 2006). was carried out at 180  C for 1 h with 5 wt% catalyst using
Layered carboxylates are isostructural materials and commercial MgO as a reference material. The methanol-
this can be observed through the repeating basal planes ysis of neutral soybean oil was catalyzed with LDO and
of their X-ray diffraction pattern below 20 of 2q (Taylor MgO and the yields were 92% and 75%, whereas the cor-
and Ellis, 2007; Lisboa et al., 2012). In long-chain metal responding values for the acidified soybean oil were
carboxylates such as zinc laurate, methylenic groups of 80.3% and 76.6%, respectively.
the hydrocarbon chains are organized in a zigzag Unlike the direct use of LDOs, Xi and Davis (2008)
conformation, which is also referred to as all-trans. rehydrated the LDO and tested the resulting material
 LAYERED MATERIALS 267
as catalyst for transesterification. The experiments
to O2 is lower than that of Mg bonded to O2. For the
started with the coprecipitation of an Mg/Al LDH
LDH with an Mg:Al molar ratio of three, calcination at
with an Mg:Al molar ratio of four. The material was
500  C led to the optimal basicity for catalytic applica-
calcined at 500  C under nitrogen atmosphere to form
tions in the methanolysis of soybean oil.
the LDO and then rehydrated with vapor under nitro-
Cantrell et al. (2005) reported the use of layered
gen atmosphere. The crystallinity of the resulting rehy-
materials for the catalytic transesterification of glyc-
drated LDH was lower than that of the initial LDH.
erin tributyrate. For this purpose, a series of ½Mgð1xÞ
The absence of CO2 in the rehydration process avoided
formation of carbonate ions. Hence, the counterion in Alx ðOHÞ2 xþ ðCO3 Þ2
x=2 compounds with the x value rang-
the LDH structure was the hydroxyl ion. For this reason, ing from 0.25 to 0.55 were calcined at 500  C for 3 h
the hydrated LDH had more Brønsted sites than a under wet N2 flux (95% humidity). Also, pure Al2O3
typical LDH. This material was subsequently used in and samples of magnesium-impregnated calcined
the methanolysis of tributyrine and the yield of monoes- hydrotalcite were used as reference materials and no
ters was around 80% when the reaction conditions catalytic activity was detected in any of these com-
involved 136.5 g of methanol, 43.0 g of tributyrine and pounds. On the other hand, the LDOs improved their
0.25 g of catalyst at 60  C for 400 min. catalytic efficiency with an increase in their magnesium
Zeng et al. (2008) synthesized various LDHs with content, achieving a maximum ester yield of 74.8% with
different Mg:Al molar ratios by coprecipitation and 25% of magnesium in the LDO structure. The reactions
ripened them at 65  C. The solid LDHs were washed were always performed at the same experimental condi-
and dried at 90  C to be subsequently calcined in a tions (60  C for 3 h), in which pure MgO yielded only
muffle at 673e1073  C for 7 h, with the resulting oxides 11% of esters.
being tested in the transesterification of refined colza oil. In another study, heterogeneous catalytic processes
The catalytic activity was correlated with the tempera- were developed for the alcoholysis of triglycerides using
ture and time of calcination as well as with the Mg:Al LDOs that were impregnated with alkaline metals
molar ratio. The best yield (90.5%) was obtained from (Trakarnpruk and Porntangjitlikit, 2008). Mg/Al-NO3
the oxide with Mg:Al molar ratio of three that was LDHs were synthesized by coprecipitation and calcined
calcined at 500  C for 12 h. In this case, the transesterifi- at 450  C for 35 h. The resulting oxide was added to a
cation was carried out with 1.5% of catalyst in relation to potassium acetate solution in order to impregnate the
the oil mass, a methanol:oil molar ratio of 6:1 and stir- oxide with potassium ions. The material was recovered
ring at 300 rpm for 4 h at 65  C. In addition, the reuse from the solution, dried at 100  C for 12 h and calcined
assays showed that the catalytic activity was kept for again at 500  C for 2 h. The potassium content of the
six cycles with a slight decrease in ester yield after resulting powder was 1.5%. FAMEs with a 96.9% ester
each cycle. content and methyl ester yields of 86.6% were obtained
Mg/Al LDOs were also tested by Xie et al. (2006) in with these solids in reactions carried out at 100  C for
the transesterification of soybean oil with methanol. 6 h, using 7% of catalyst and a methanol:oil molar ratio
The precursor was synthesized by coprecipitation at of 30:1.
pH 7. The material was calcined for 8 h at different tem- Liu et al. (2007) carried out the catalytic conversion
peratures and the obtained LDO was tested in the trans- of chicken fat to methyl esters using oxides that were
esterification of soybean oil with a methanol:oil molar derived from the Mg6Al2(CO3)(OH)16$4H2O hydrotalcite
ratio of 15:1, 7.5% of catalyst and heating under reflux. by calcination at different temperatures (400e800  C) for
The Mg:Al molar ratio of three yielded 67% of ester, 8 h. As a result, the effect of the calcination temperature
which was the best result if compared to other molar on the catalytic performance of the oxide was confirmed,
ratios of 2.0, 2.5, 3.5 and 4.0. The calcination temperature as already described by Xie et al. (2006). High yields of
also influenced the catalytic activity. Actually, the calci- 94 wt% were obtained when the LDH was calcined at
nation temperature affected the basic strength of the 550  C and the reaction was carried out at 120  C for 6 h
oxides as determined by the Hammett method. When with a catalyst loading of 0.04 mg/l. The catalyst activity
the calcination temperature was increased from 300  C decreased slightly in the first recycling stage but dropped
to 500  C, the methyl ester yield reached a maximum to only 60% of the original value after the fourth consec-
of 66%. The highest yield was attributed to the achieve- utive reaction cycle. However, the original activity could
ment of the highest basicity after calcination. According be totally recovered by calcination of the spent catalyst
to XRD, this oxide corresponded to the MgO periclase in air.
phase. Temperatures above 500  C transformed the Antunes et al. (2008) catalyzed the methanolysis of
crystalline phase into spinel with less basicity and also soybean oil with Mg/Al and Zn/Al oxides that were
less catalytic activity. Calcination below 500  C led obtained by calcination of the corresponding LDH at
Al3þ to replace Mg2þ sites and the basicity Al bonded 450  C for 12 h. Transesterification was performed for
268 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

7 h at 70, 100 and 130  C with a methanol:oil molar ratio 20 mmol of glyceryl tributyrate, 600 mmol of methanol
of 55:1. The highest activity was detected at 130  C and and 0.1 g of catalyst. The Li/Al LDO gave yields higher
the yield at this temperature was 80% with MgO, 70% than 98% while the LDOs with Mg/Al and Mg/Fe
with Mg/Al LDO, 63% with Zn/Al LDH, 30% with yielded only 32% and 23.9%, respectively. These results
ZnO, and 11% with Al2O3. were close to the 37.1% yield that was achieved with
Ilgen et al. (2007) used LDOs derived from Mg6- MgO under the same conditions. These authors also
Al2(OH)16CO3$4H2O for the catalytic conversion of observed the influence of the calcination temperature
canola oil into methyl esters. The LDH was prepared on the catalytic performance and concluded that
by coprecipitation of magnesium and aluminum carbon- the optimal temperature to obtain the best synthetic
ate salts at pH 10 and ripened for 18 h. After separation, LDOs is between 450  C and 500  C.
the solid compound was dried at 80  C and then Ngamcharussrivichai et al. (2007) used CaO.ZnO
calcined at 500  C for 16 h. The LDO with particle diam- mixed oxides as heterogeneous catalysts for the metha-
eter of 150e177 mm gave a 63% ester yield when the re- nolysis of palm kernel oil. A layered hydroxide formed
action was carried out at 60  C with methanol:canola oil by a mixture of the divalent cations (Ca2þ and Zn2þ)
molar ratio of 6:1. Higher molar ratios of 9:1, 12:1 and was coprecipitated in alkaline media. The mixed hydro-
16:1 decreased the ester yields to values lower than xide was then subjected to calcination between 600  C
60%, and when LDOs with other particle sizes (125, and 900  C for 2e6 h. Ester yields higher than 94%
125e150 and 150e177 mm) were used, the best perfor- were obtained with this catalyst after 1 h at 60  C using
mance was obtained in the range of 125e150 mm. In a methanol:oil molar ratio of 30:1 and a catalyst loading
the same report, the use of n-hexane as a cosolvent of 10 wt%. Also, the mixed oxide was shown to have a
was shown to be detrimental to methanolysis. Also, Ca:Zn molar ratio of 0.25.
methanol resulted in better ester yields than ethanol. LDHs containing Zn/Al and Mg/Al with different
Barakos et al. (2008) calcined Mg/Al-CO3 at 350  C counterions (nitrate, chlorite and carbonate) and
for 6 h and tested it for methanolysis of cotton oil. Sam- M2þ/M3þ ratios were synthesized by Cordeiro et al.
ples with 95% esters were obtained for reactions carried (2012) and used as catalysts in the esterification of fatty
out at 180  C, using methanol:oil molar ratios of 6:1 wt% acids with methanol. The best conversion of 97 wt%
and 1 wt% of catalyst at 2200 kPa. was obtained with Zn5AlCl for a reaction that was
Albuquerque et al. (2008) prepared calcium and mag- carried at 140  C with a methanol:lauric acid molar ratio
nesium mixed layered hydroxides by coprecipitation of 6:1 and 2 wt% of the solid catalyst. However, all the
from which LDO catalysts were generated. The LDH LDHs tested were converted in situ to layered carboxyl-
was calcined at 800  C and the resulting oxides were ates, which preserved their catalytic activity even after
tested in the catalytic methanolysis of sunflower oil at several consecutive cycles of reuse.
60  C. Higher yields of 92.4% were obtained in methanol- LDH compounds containing Mg2þ, Ni2þ and Al3þ
ysis after 3 h using a methanol:oil molar ratio of 12:1 and were synthesized by Wang and Jehng (2011) and
a 2.5 wt.% of the solid catalyst with a 3.8 Mg:Ca ratio. calcined at 500  C for 10 h to produce heterogeneous
Macedo et al. (2006) prepared (Al2O3)4(SnO) and LDO catalysts for biodiesel production. The best condi-
(Al2O3)4(ZnO) LDOs from the corresponding Sn/Al tion for synthesis involved the use of a methanol:soy-
and Zn/Al LDHs and both present catalytic activity in bean oil molar ratio of 21, 0.3 wt% of catalyst, 105  C
the alcoholysis of soybean oil, even when branched alco- and 1200 rpm for 4 h, when an 87% conversion of soy-
hols were used. Yields higher than 80% were obtained bean oil to methyl esters was obtained. The observed
with methanol after 4 h at 60  C and the recycling tests catalytic efficiency was related to the basicity and Mg
indicated that these materials did not lose their catalytic content of the Mg/Al/Ni catalysts.
activity. Corma et al. (2005) also applied LDOs in the transes-
Shumaker et al. (2008) used LDO catalysts to convert terification of monoesters with glycerol. LDHs were
soybean oil in methyl esters. The LDH precursors initially calcined at 450  C under nitrogen flux for 8 h
(Mg/Al, Fe/Al and Li/Al) were obtained by coprecipi- to produce LDOs that were immediately rehydrated in
tation and subsequently calcined at 450  C for 2 h. The N2 atmosphere to avoid the presence of CO2. MgO
best catalytic performance was obtained with the oxide was also synthesized from magnesium oxalate by calci-
derived from [LiAl2(OH)6](CO3)0,5.nH2O, reaching a nation at 500  C for 6 h and used as a control. The LDOs
conversion of 83.1% in 2 h with a methanol:oil molar containing Li/Al had a performance better than those
ratio of 15:1. Under the same conditions, the LDO containing Mg/Al or MgO due to formation of stronger
derived from the Mg/Al precursor yielded only 13.6% Lewis basic sites, since Liþ ions, which are more electro-
of products. The same catalysts were also tested in the positive than magnesium, increase the charge density of
methanolysis of glyceryl tributyrate. The reactions the oxygen. Based on this, alumina was impregnated
were carried out at 65  C under reflux for 1 h with with KF and the resulting material revealed basicity
 POLYMERIC CATALYSTS 269
even higher than that of the Li/Al LDO. The catalytic esterification, whereas only manganese laurate gave a
conversion of glycerol to glycerin oleate with KF/ reasonable catalytic activity of about 75 wt% with the
Al2O3 was 98% with monoester selectivity of 69%. use of ethanol. In general, the best results were obtained
Cordeiro et al. (2008) showed that the LHS zinc hy- at temperatures around 140  C. Also, the structure of
droxide nitrate [ZHN, Zn5(OH)8(NO3)2$2H2O] can be copper(II) and lanthanum(III) laurates was shown to
used as a heterogeneous catalyst for the esterification be preserved after three consecutive reaction cycles.
of fatty acids and for the transesterification of vegetable
oils. For the transesterification reaction carried out at
150  C for 2 h with 5 wt% of ZHN and a methanol:palm POLYMERIC CATALYSTS
oil molar ratio of 48:1, the resulting ester layer contained
95.7 wt% of methyl esters and the purity of the glycerin This section describes the application of functional-
layer was as high as 93 wt%. Also, when esterification ized polymers as catalysts for esterification and transes-
was carried at 140  C for 2 h with a methanol:lauric terification reactions to produce biodiesel. Polymeric
acid molar ratio of 4:1, the final ester layer contained catalysts consist of functionalized polymeric matrixes
97.4 wt% of methyl laurate. In addition, these authors or polymeric matrixes that can be used as solid supports
were able to demonstrate that ZHN turned into zinc for a variety of catalysts, constituting catalytic systems
laurated(C12H23O2)2Zndduring the reaction course (Coutinho et al., 2004a,b; Guerreiro et al., 2010; Lee
and this new layered material was held responsible for and Saka, 2010; Zieba et al., 2010). These materials
the observed catalytic activity. have long been studied as heterogeneous catalysts in
LDHs containing Zn/Al and Mg/Al with different systems that traditionally employ acid or basic homoge-
counterions and M2þ/M3þ ratios were used as cat- neous catalysts.
alysts in the esterification of fatty acids with methanol. Biodiesel production can be carried out in the pres-
All LDHs were synthesized by coprecipitation and ence of different types of catalysts. In the specific case
high conversion rates were obtained depending on the of polymeric catalysts belonging to the class of function-
reaction condition. For instance, a 97 wt% conversion alized polymers, their use in biodiesel synthesis has
of lauric acid to methyl laurate was obtained using a focused on acid catalysts, such as in the case of ion
methanol:fatty acid molar ratio of 6:1 and 2 wt% of cata- exchange resins (Ma and Hanna, 1999; Guerreiro et al.,
lyst at 140  C for 2 h. However, all LDHs were also 2006; Knothe et al., 2006; Soldi et al., 2009; Rezende
converted in situ into layered carboxylates and this et al., 2008; Helwani et al., 2009b; Lee and Saka, 2010).
new material was responsible for the observed catalytic Acid-catalyzed triacylglycerol transesterification is
activity, which was preserved even after several consec- not commercially applied as often as catalysis in basic
utive cycles of reuse (Cordeiro et al., 2012). medium because acid catalysis in homogeneous me-
Reinoso et al. (2012) used zinc carboxylates (acetate, dium is around 4000 times slower than the base-
laurate, palmitate, stearate and oleate) as catalysts for catalyzed reaction. However, acid catalysts can perform
the methanolysis of soybean oil. Methyl ester conver- esterification and transesterification simultaneously,
sions as high as 98 wt% were obtained for yields in the producing biodiesel directly from oils with high acid
range of 84 wt% when the reaction was carried out for number. These oils are not suitable for biodiesel produc-
2 h with a 30:1 methanol:oil molar ratio and a catalyst tion via alkaline catalysis, since the FFAs promptly react
loading of 3 wt% in relation to the oil mass. with the base, generating soaps that make the separation
Jacobson et al. (2008) developed a solid catalyst by between the ester and glycerin difficult during the
immobilizing zinc stearate in silica using the solegel washing step (Bondioli et al., 1995; Schuchardt et al.,
method. The resulting solids contained 6 wt% of zinc 1998; Ma and Hanna, 1999; Vicente et al., 2004; Lotero
and a total available surface area of 35 m2/g. These et al., 2005; Meher et al., 2006; Rezende et al., 2008; Lee
solids were shown to be catalytically active in the meth- and Saka, 2010).
anolysis of used frying oil with high acid number Several acid catalysts can be used in alcoholysis, espe-
(w15%). High yields of 98 wt% were obtained at cially sulfonic and sulfuric acids (Hayyan et al., 2011).
200  C for 10 h using a methanol:oil molar ratio of 18:1 Although these catalysts afford high yields of mono
and 3 wt% of catalyst in relation to the mass of the start- alkyl esters, they require high temperatures and long
ing material. reaction times to achieve a satisfactory conversion
Lisboa et al. (2012) described the synthesis and char- rate. Another disadvantage is that residual acid cata-
acterization of layered copper(II), manganese(II), lantha- lysts can contaminate the fuel and attack the metal
num(III) and nickel(II) laurates as well as their catalytic parts of the engine, corroding it. To avoid this situation,
activity in the methyl and ethyl esterification of lauric acid catalysts must be completely eliminated from the
acid. Conversions between 80 wt% and 90 wt% were final product, which demands many purification steps
observed for all catalysts when methanol was used for (Canakci and Gerpen, 1999).
270 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

Some types of organic polymers and ion exchange tridimensional, insoluble, and porous; their ability to ex-
resins can be used as polymeric catalysts, behaving as change ions arises from the introduction of adequate
heterogeneous catalysts for esterification and transester- functional groups into the polymeric support (Kunin
ification reactions. Heterogeneous catalysts such as et al., 1962; Akelah and Sherrington, 1981; Fréchet,
these reduce the number of biodiesel purification steps, 1981; Harmer and Sun, 2001; Hart et al., 2002).
facilitates catalyst reuse, and decreases production costs Polymeric matrix functionalization can be achieved in
(Schuchardt et al., 1998; Choudary et al., 2000; Fukuda two ways: (1) monomers containing the desired func-
et al., 2001; Harmer and Sun, 2001; Ramos et al., 2003; tional groups (or precursors of this functional group)
Abreu et al., 2004; Suppes et al., 2004; Chouhan and can be directly polymerized; (2) the polymeric support
Sarma, 2011). can be prepared first, and the functional group is intro-
The pioneering studies of Merrifield on the solid- duced by chemical modification of the polymeric sup-
phase synthesis of polypeptides and subsequent works port (Molinari et al., 1979; Kucera and Jancar, 1998;
have shown that polystyrene (PS) is a suitable polymeric Harmer and Sun, 2001).
support for catalysts and reagents (Merrifield, 1963; Coutinho and Rezende (2001) and Coutinho et al.
Fréchet, 1981). Styrene and divinylbenzene (DVB) are (2004a) showed that supported species can be prepared
among the monomers that are most often employed by chemically modifying the copolymer base (polymeric
to prepare solid polymeric matrixes. Polystyrene- support). These authors reported the sulfonation of a sup-
co-divinylbenzene (PS-DVB), an insoluble copolymer, port consisting of PS reticulated with DVB (Figure 16.7).
results from styrene polymerization in the presence of The aromatic rings on the insoluble PS-DVB copolymer
varied amounts of DVB. The characteristics of this react with concentrated sulfuric acid in the presence of
copolymer depend on the quantity of DVB present in 1,2-dichloroethane; the latter compound expands the
the material (Kapura and Gates, 1973; Xia et al., 2012). polymeric matrix and allows sulfonation of the internal
In many cases, the success of a heterogeneous surface as well. Most of the functional groups introduced
catalyst relies on the features of the polymeric material. into polymeric matrices concentrate inside the resin beads
Bergbreiter (2002) proposed that some physicochemical (Coutinho and Rezende, 2001).
properties should be considered when choosing the Cationic resins can be used as an option for catalytic
catalyst support, including the catalytic activity, surface reactions involving mineral or sulfonic acids. In the
area, porosity, and thermal and mechanical stability of presence of water, the cationic groups on the polymer
the material in the conditions of the catalyzed reaction display different acidity constants, as in the case of com-
(Bergbreiter, 2002; Chouhan and Sarma, 2011). pounds with low molecular mass.
In the field of polymer chemistry, the term resin is The catalytic performance of an ion exchange resin is
indistinctly employed to describe polymers with and associated with the concentration of functional groups
without cross-links (Akelah and Sherrington, 1981; and the physicochemical properties of the support.
Sharma, 1995). Alternatively, in heterogeneous catalysis, Therefore, compared with homogeneous catalysts,
the term resin refers to species consisting of long different factors affect the activity of resins.
polymeric chains interconnected via cross-links, the The use of ion exchange resins as catalysts has
so-called polymeric matrix. Polymeric matrixes are many advantages: (1) despite being equivalent to strong

SO3H

CH2 – CH CH2 – CH CH2 CH2 – CH CH2 – CH CH2

SO3H
ClCH2CH2Cl
+ H 2SO4
94ºC/3,5 h
C H2 C H CH2 – CH CH 2 C H2 C H CH2 – CH CH2

SO3H

FIGURE 16.7 Sulfonation of a polymeric matrix consisting of polystyrene and divinylbenzene.

 POLYMERIC CATALYSTS 271
FIGURE 16.8 PS sulfonation with acetyl sulfate.

mineral acids, resins are less oxidizing and corrosive, FFAs. However, oils with high FFA content are difficult
since most of the catalytic sites are located inside the to transesterify using the commercially available alka-
beadsdtherefore, they do not pose any hazards to the line catalyst (Zhang et al., 2003; Tesser et al., 2005;
operator and are easy to store; (2) resins behave as selec- Marchetti and Errazu, 2008; Sharma et al., 2008; Liu
tive catalysts and enable reaction control; (3) catalysts et al., 2009; Tesser et al., 2010; Chouhan and Sarma,
with high purity are recovered at the end of the reaction 2011; Shahid and Jamal, 2011; Borges and Dı́az, 2012).
by simple filtration; (4) resins do not require neutraliza- Canakci and Van Gerpen (1999, 2001) found the transes-
tion before being separated from the reaction medium, a terification would not occur if the FFA content in the oil
step that usually reduces product yield; (5) resins elimi- was beyond 3%. According to the research paper by
nate the steps and equipment necessary to separate the Kouzu et al. (2011), the promising approach is to esterify
catalyst and purify the product, simplifying continuous FFA into FAMEs with the help of the solid acid catalyst,
or batch procedures based on ion exchange resins; and and there were some research papers studying utili-
(6) if the resins undergo deactivation due to contamina- zation of several types of heterogeneous catalysts
tion or prolonged use, they can be reactivated via a sim- including sulfonated cation exchange resin (Russnueldt
ple procedure that does not release hazardous gases into and Hoelderich, 2009; Tesser et al., 2010; Kouzu et al.,
the atmosphere (Saha and Sharma, 1996; Coutinho and 2011). With respect to utilization of the sulfonated
Rezende, 2001; Harmer and Sun, 2001; Marquardt resin for the preesterification of FFA, some researchers
and Eifler-Lima, 2001; Mitsutani, 2002; Coutinho et al., focused their attention on the macroreticular type but
2003, 2004a,b; Kiss et al., 2006). the use of two types of resins (macroreticular and gelular
The main drawback of ion exchange resins is that types) were also studied by other authors (Ramadhas
their maximum operation temperature is relatively et al., 2005; Soldi et al., 2009; Lam et al., 2010; Melero
low. Literature suggests that they should be used below et al., 2010; Kouzu et al., 2011; Semwal et al., 2011;
125  C to ensure long catalyst lifetime (John and Israel- Li et al., 2012; Xia et al., 2012; Zhang et al., 2012a,b).
stam, 1960; Akelah and Sherrington, 1981; Giménez Feng et al. (2011) investigated the continuous esterifi-
et al., 1987; Coutinho and Rezende, 2001; Rezende cation of FFAs from acidified oil with methanol by cation
et al., 2008). exchange resin in a fixed bed reactor to prepare biodiesel
Aromatic compounds are easy to functionalize, espe- and the operational stability of continuous esterification
cially if they contain acid groups like sulfonic acids. The by resin in the fixed bed reactor was also conducted
sulfonation of organic compounds containing benzene (McNeff et al., 2008; Shibasaki-Kitagawa et al., 2010;
rings, including polymers, has been extensively re- Feng et al., 2011; Cheng et al., 2012).
ported (Ma and Hanna, 1999; Coutinho and Rezende, According to Feng et al. (2010), from the viewpoint of
2001; Coutinho et al., 2003, 2004a,b, 2006; Rezende cost savings, the use of cation exchange resins in hetero-
et al., 2008; Soldi et al., 2009). Figure 16.8 represents geneous catalytic processes may be advantageous over
the sulfonation PS (Soldi et al., 2009). enzymes and supercritical methanol (Feng et al., 2010).
Sulfonation significantly modifies the physical prop- These resins are composed of copolymers of DVB and
erties of linear PS, especially the polarity. Hence, sulfo- styrene containing sulfonic acid groups attached to ben-
nated PS should remain insoluble during biodiesel zene rings and these are the active sites for esterification
production. Soldi et al. (2009) studied methods to sulfo- and transesterification (Marchetti and Errazu, 2008;
nate linear PS and applied the resulting sulfonated Rezende et al., 2008; Russnueldt and Hoelderich, 2009;
material as heterogeneous polymeric catalyst to produce Feng et al., 2010; Kouzu et al., 2011). However, other sul-
soybean methyl esters. Raw materials with different fonated polymeric backbones such as AmberlystÒ , Dow-
moisture degrees and the effect of different variables exÒ and NafionÒ , a perfluorinated ion exchange resin,
on the conversion rate have been investigated; biodiesel all of them having a very strong Brønsted acid character,
production from soybean oil and beef tallow led to have also been used in these type of reactions (Özbay
significantly improved yields. et al., 2008; Talukder et al., 2009; Feng et al., 2010;
Recently, much interest has been taken in utilizing Park et al., 2010; Galia et al., 2011; Yin et al., 2012; Zhang
low-cost plant oil and fat containing a large amount of et al., 2012a). In general, cation exchange resins are
272 16. APPLICATIONS OF HETEROGENEOUS CATALYSTS IN THE PRODUCTION OF BIODIESEL

preferable for esterification (Giménez et al., 1987; Chen Akelah, A., Sherrington, D., 1981. Application of functionalized
et al., 1999; Coutinho et al., 2004b; Coutinho et al., polymers in organic synthesis. Chem. Rev. 81, 557e587.
Albuquerque, M.C.G., Santamarı́a-González, J., Mérida-Robles, J.M.,
2006; Grob and Hasse, 2006), while anionic resins may Moreno-Tost, R., Rodrı́guez-Castellón, E., Jiménez-López, A.,
be applied for transesterification of oils and fats (Shiba- Azevedo, D.C.S., Cavalcante Jr., C.L., Maireles-Torres, P., 2008.
saki-Kitakawa et al., 2007; Ren et al., 2012). MgM (M ¼ Al and Ca) oxides as basic catalysts in trans-
esterification processes. Appl. Catal. A: Gen. 347, 162e168.
Altiparmak, D., Keskin, A., Koca, A., Gürü, M., 2007. Alternative fuel
properties of tall oil fatty acid methyl esterediesel fuel blends.
CONCLUDING REMARKS Bioresour. Technol. 98, 241e246.
Antunes, W.M., Veloso, C.O., Henriques, C.A., 2008. Trans-
Truly heterogeneous catalytic processes are attractive esterification of soybean oil with methanol catalyzed by basic
for many practical applications due to their recyclability, solids. Catal. Today 133e135, 548e554.
structural stability, high selectivity and good catalytic Arizaga, G.G.C., Satyanarayana, K.G., Wypych, F., 2007. Layered
hydroxide salts: synthesis, properties and potential applications.
performance. However, all these properties are hardly Solid State Ionics 178, 1143e1162.
achievable in a single catalytic system. In most cases, Arizaga, G.G.C., Mangrich, A.S., Gardolinski, J.E.F.C., Wypych, F.,
leachable catalytic species migrate to the reaction envi- 2008. Chemical modification of zinc hydroxide nitrate and Zn/
ronment, causing a partial contamination of the final Al-layered double hydroxide with dicarboxylic acids. J. Colloid
product as well as a loss in catalytic activity when the Interface Sci. 320, 68e176.
Bail, A., Santos, V.C., Freitas, M.R., Ramos, L.P., Schreiner, W.H.,
solids are applied in several consecutive reaction cycles. Ricci, G.P., Ciuffi, K.J., Nakagaki, S., 2013. Investigation of a mo-
Moreover, in many situations found in the literature, the lybdenum-containing silica catalyst synthesized by the sol-gel
heterogeneity of catalytic systems is not approached process in heterogeneous catalytic esterification reactions using
with proper analytical methods, resulting in wrong methanol and ethanol. Appl. Catal. B: Environ. 130e131, 314e324.
conclusions and/or classification of the proposed solid Barakos, N., Pasias, S., Papayannakos, N., 2008. Transesterification of
triglycerides in high and low quality oil feeds over an HT2
catalyst. These usually arise from poor data on catalyst hydrotalcite catalyst. Bioresour. Technol. 99, 5037e5042.
recovery and reuse, poor characterization of the catalyst Barman, S., Vasudevan, S., 2006. Melting of saturated fatty acid soaps.
structure and high leaching levels of catalytic species. J. Phys. Chem. B 110, 22407e22414.
Also, in many cases, no attempt is made to fully Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T.,
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new family of mesoporous molecular sieves prepared with liquid
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was nicely demonstrated by Silva et al. (2013) using and ligands. Chem. Rev. 102, 3345e3384.
bismuth-containing mixed oxides. Apart from these ob- Bokade, V.V., Yadav, G.D., 2009. Transesterification of edible and
servations, the lack of suitable reaction controls such nonedible vegetable oils with alcohols over heteropolyacids
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However, many of these will never be able to reach in- approach. Quim. Nova 27, 601e614.
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