OVERVIEW ON UTILIZATION OF ENGINEERED NANOPOROUS

MATERIALS MEDIATED HETEROGENEOUS CATALYSTS USING IN

BIODIESEL SYNTHESIS
Ullia Nurul Ismala (150712312)

Departement of Chemical Engineering, Engineering Faculty, University of Riau, Pekanbaru, Riau, Indonesia

ABSTRACT

World’s energy needs are majorly dependent on the fossil fuels, including petrochemical sources and coal. The
alternate of these fuels include hydro and nuclear powers. However, all these resources are finite and current rate of
consumption indicates the shortening of the fuels and energy in the near future. Diesel plays a remarkable role in
the economy of the developing and developed countries in industry and other sectors being a basic fuel used in
transportation. The increasing demand of alternate energy based on renewable resources and pollution-free
production is a major concern these days for environmentalists. Biodiesel, in this regard is set to be the best entrant
to acquire the desired alternative of conventional fuels. The production of biodiesel is carried out through
transesterification reaction using edible oil feedstocks, which is not feasible for developing countries. Hence,
utilization of low-grade feedstocks for biodiesel production is the new clinch for the developing countries. In
general, the transesterification reaction is mediated by catalysts and hence, design of an effective catalyst is the key
to produce efficient and commercially viable biodiesel. In this direction, it is necessary to understand the material
chemistry of catalysts and mechanism of the catalytic transesterification reaction. This review enlightens the basics
of transesterification, role of various process parameters and factors affecting biodiesel production from different
feedstocks. In this review we have discussed various nanoporous heterogeneous catalysts investigated for biodiesel
production and mainly focused on the mechanism involved in transesterification using heterogeneous catalysts.

Keywords: Nanoporous materials; Biodiesel; Transesterification; Heterogeneous catalyst; Feedstocks; Yield

INTRODUCTION supported technologies and many palm oil entrepreneurs

Depletion of fossil fuel and its feedstock reserves and also
the growing of concern on environmental issues have
developed many researcher’s interest to find substitute for
fossil fuel. Renewable energy sources are gaining attention
as many research attempt to find the alternative. A clean
renewable fuel, biodiesel has been used in worldwide
recently, it be preferred for its biodegradable, nontoxic and
similar characteristic to fossil diesel [Atabani, 2013].
Biodiesel also has several advantages compared to fossil
fuel [Sivaramakrishnan, 2012] as its emissions are non-
toxic; including lower CO, S, and other hydrocarbons
making it a carbon-neutral fuel. Studies revealed that
biodiesel can lessen total CO2 releases by 78% as
compared to the fossil fuels [Miller dan A., 2013], which
aids towards additional necessity to save the nature from
the harmful side effects of the emerged technologies.
Biodiesel production across the globe in 2016 reached 8.5
billion gallons and it is expected to expand 10.3 billion
gallons in the upcoming ten years [6].. Meanwhile in
Indonesia itself, production of biodiesel is not as great as
the production of vegetable oil sources (such as CPO). The
production of biodiesel in Indonesia is constrained by not
prefer to market raw or crude palm oil due to lower cost
investment than to produce the biodiesel.
BIODIESEL PRODUCTION
Imperative research had been done to develop the
properties and performances from derivates of vegetable
oils and animal fats which is are source of biodiesel. Singh
& Singh (2010) mentioned that substitutes of triglycerides
for diesel fuel are often associated with the problem of
high viscosity, low vitality and polyunsaturated characters.
The problem of high viscosity of vegetable oils has been
approached in several ways such as preheating the oils,
blending or dilution with other fuels, transesterification
and thermal cracking/pyrolysis [Parmanik, 2002].
Demirbas (2009) agreed that transesterification method is
the most viable process adopted known so far for the
lowering of viscosity. Transesterification is defined as the
reaction of a fat or oil with an alcohol in the presence of
catalyst to form esters and glycerol. The byproduct, which
is glycerol, has also commercial value. The physical
characteristics of fatty acid methyl/ethyl ester are very
close to those of petro-diesel fuel and the process is
relatively simple [Talha and Sulaiman, 2016].
Biodiesel chemically is a fatty acid methyl ester, which is
formed by transesterification reaction among the
triglycerides (a major constituent of oils) and alcohols
Figure-1. Transesterification reaction. R1, R2 and R3 represent the fatty acid chains
However, the non-catalytic reactions are very slow and
low yielding processes. Hence the catalyst addition is
needed here [Sharma, et al, 2018]. Herbinet, et al [2010]
mentioned the overall reaction of transesterification
reaction takes in three steps;
(i) conversion of triglycerides to diglycerides
(ii) conversion of diglycerides to monoglycerides
and ultimately
(iii) conversion of mono-glycerides to glycerol
along with the formation of biodiesel
Despite the scientific success in the biodiesel production, it
is still at its infant step in terms of commercial feasibility,
due to its inability to meet the world’s present energy
demand. Researchers are working to create maximize the
yield of biodiesel. An accurate cradle to grave valuation is
required to make this process rapid and energy efficient at
industrial scale. One of them is the utilization of catalyst.
The factors that affecting transesterification are showed in
Figure-2.
(i) Feed Stock
(ii) Type of concentration of catalyst
(iii) Type of alcohol
(iv) Oil to alcohol ratio
(v) Reaction condition
At present, different global regions consume different
feedstock for biodiesel production. For example, US uses
Soybean oil, Canada employs Rapeseed and Canola,
Europe uses Sunflower, and Palm oil dominates in Asia, as
feedstock for biodiesel production. The biodiesel produced
using these edible feedstocks are classified as first
generation biodiesel. However, these expensive feedstocks
make the process less economic for the commercialization
of biodiesel in the developing countries. Hence, recent
studies put forward non-edible oil as an alternative to the
edible feedstocks. Depending upon the seasonal and
geographic availability, the feedstock may vary, but it is
necessary to unanimously standardize the characteristics of
feedstock to maximize the biodiesel yield. These
characteristics may include acid value, saponification
(usually methanol and ethanol). The transesterification
reaction is reversible in nature and can be either catalytic
or non-catalytic. The reactions are showed in Figure-1.
value, moisture content, specific density, pH, and viscosity
of feedstocks.
Types of alcohol used in biodiesel production include
methanol, ethanol, propanol, butanol etc. However, it is
witnessed that long-chained alcohol leads to decrease in
biodiesel yield. Nye, et al [1983] performed an experiment
on the transesterification of used frying oil using 0.4%
KOH at 50°C employing oil : methanol molar ratio of
1.3:5 with different solvents i.e. methanol, ethanol and
propanol and the biodiesel yield was obtained as 73.8%,
46.1%, and 31.9%, respectively [Nye, et al, 1983]. This
suggests that the rise in chain length of alcohol decreases
the yield of biodiesel.
Hence, smallest chained methanol being low cost, and
highly miscible solvent, ensures its applicability in
transesterification process. Oil to methanol ratio also plays
a critical role in the transesterification reaction. Even
though the stoichiometric ratio of oil : methanol ideally
should be 1:3 for complete transesterification process, it is
reported that addition of methanol in excess amount shifts
the reaction towards product (biodiesel) formation
[Ramadhas, et a , 2005]. However, the problem lies in the
optimization of the solvent quantity for a spontaneous
transesterification reaction at higher reaction rate. Studies
suggested that, the lower molar ratio of methanol causes an
incomplete reaction, whereas its higher molar ratio
decreases the efficiency of separation of the glycerol from
the excess methanol and also incurs additional production
cost [Rad, et al, 2018]. This happens due to decrease in the
overall density of glycerol, inhibiting its separation from
methanol. Hence, it is necessary to optimize the molar
ratio of oil : methanol beforehand.
Moreover, the optimum time of transesterification varies
with type of feedstock, catalyst type and concentration,
and various other parameters described in above section.
Agitation speed is also, one of the major factors in
transesterification reaction which plays a crucial role,
when the reactants are immiscible in nature (e.g. oil and
methanol). It should be high enough to break the barrier of
mass transfer between two immiscible liquids. Denser
Figure-2. Schematic representation of factors involved in the transesterification of oils for biodiesel production
CATALYST
In general, there are three categories of catalysts used for
biodiesel production known as alkalis, acids and enzymes
[Canakci, 1999]. As compare to enzyme catalysts, alkali
and acid catalysts are more commonly used in biodiesel
production [Ma and Hana, 1999]. They were then
categorized into homogeneous and heterogeneous
catalysts. However, enzyme catalysts have become more
attractive recently since it can avoid soap formation and
the purification process is simple to accomplish.
Nonetheless, Leung et al. [2010] stated that they are not
commercially used because of the longer reaction times
and higher cost. To reduce the cost, some researchers
developed new biocatalysts in recent years. An advantage
is that no purification is necessary for using these
biocatalysts [Matsumoto, et al, 2001].
HOMOGENEOUS CATALYSTS
Homogeneous catalyst possesses similar physical phase
with that of reactants, i.e. are usually miscible with the
reactants, and are categorized into two forms:
homogeneous base and homogeneous acid catalysts.
Homogeneous base catalysts possess catalysis rate ~ 4000
times higher than that of an acid catalyst, at mild reaction
conditions [Kamel, et al, 2018]. However, they can cause
soap formation, if the free fatty acid content of the
feedstock is > 2%. In a typical base catalyzed
feedstock requires comparatively high agitation rate for
significant biodiesel yield.
transesterification, NaOH and KOH are widely used.
Unlike base catalyst, the homogeneous acid catalyst is
insensitive to the presence of free fatty acids in feedstock
oil, hence are mostly applicable for low-grade feedstock.
However, their catalysis rate is comparatively slower than
that of a base catalyst. H2SO4 and HCl have widely used
acid catalyst in the transesterification reaction [Marchetti,
et al, 2008]. Even though, homogeneous catalysts are
cheap, easily available and give better yield at mild
reaction conditions, yet the drawback includes separation
of catalyst after reaction from the product, corrosion of
reactor and saponification as side reaction. These issues
are well addressed by the introduction of heterogeneous
catalyst in the transesterification reaction. We have
enlightened an expounded elucidation on heterogeneous
catalyst involved in transesterification process and the
entire potential characteristic that nominates them as lead
candidate in this process.
HETEROGENEOUS CATALYSTS
A heterogeneous catalyst remains in a separate phase than
that of the reactants. They are also termed as contact
catalysts as they functions via adsorbing the reactant
entities over their surfaces. In biodiesel production
(transesterification reaction), heterogeneous catalyst
majorly lies in solid phase, whereas oil and methanol are in
liquid phase. Various heterogeneous catalyst have been
investigated for the biodiesel production. It is observed
that overall catalytic activity of these heterogeneous
catalysts can be improved via altering their lattice
parameters through elemental doping step. As discussed
above, they catalyze the reaction through adsorption, and
hence, large surface area is required to proceed the
transesterification reaction. Nanocomposites materials, in
this contrast have been proven as the best candidate
[Trangy, 2017]. Nanoporous materials own good surface
properties for instance, large surface area, nano-scaled
pore size with uniform distribution of pores, required for
transesterification reaction [Baskar, et al, 2018]. These
enhanced properties not only makes them finest entrant for
biodiesel production, but for other applications such as
semiconductors [Ma, et al, 2018], surface modification and
tissue engineering [Roy, et al, 2018], environmental
cleanup [Kaur, et al, 2014] biomedical applications e.g.
drug delivery [Hasan, et al, 2017], antibacterial activity
[Baranwal, et al, 2018], diagnostics [Choudary,et al, 2016]
and energy resources [Chen,, 2018]. The heterogeneous
catalyst concentration can be tuned via designing an
effective nanocomposite with enhanced surface properties
which includes high surface to volume ratio and uniform
Table-1 Performance of heterogeneous acid catalysts in transesterification of edible/nonedible feedstocks for biodiesel
Nonporous
Feedstock
Catalyst T (°C)
[HSO3-
Palm oil 108
BMIM]HSO4
Sulfonated
Palm oil 100
graphene
Carbonaceous
Soybean oil 220
catalysts
MECHANISM OF HETEROGENEOUS CATALYSIS
The essential step in transesterification reaction is
adsorption. Heterogeneous catalysts provide reaction site
for the reactants (adsorbents) to be adsorbed, and thus
catalyzes the reaction. Diffusion is one of the major
problem in heterogeneous catalysis of oil. Hence, to reduce
the diffusion and for a proper adsorption reaction, a
heterogeneous catalyst must possess certain characteristics
such as; hefty surface area, uniform distribution of
numerous pores of optimum pore sizes. Solid-acid catalyst
provides positively charged active site for the adsorption
of fatty acid and solid-base catalysts provide negatively
charged active site for the adsorption of methanol. In solid-
base catalysis, a tetrahedral intermediate is formed due to
the reaction between alkoxide ion to the alkyl group of
triglyceride, followed by its reaction with the alcohol. The
rearrangement of this intermediate produces the ester and
diglycerides. In solid-acid catalysis, a carbocation is
formed, which due to the attack of nucleophile (alcohol)
gives rise to tetrahedral intermediate, which excludes
glycerol and forms a new ester regenerating the catalyst. In
summary, physical adsorption of oil or alcohol under
dispersal of nano-pores. Heterogeneous catalyst reduces
the cost of biodiesel production via several ways, in terms
of, ease of synthesis, mild reaction conditions, reusability,
regeneration capability and ease of separation. Based on
the presence of acidic or basic sites on the surface,
heterogeneous catalysts are majorly categorized into two
types, as discussed in the following sections.
HETEROGENEOUS ACID CATALYSTS
Acid catalyst is significant in the esterification of low-
grade feedstock which has high free fatty acid contents. In
general, solid-acid catalyst provides positively charged
acid site for the fatty acid content of oil to get adsorbed,
initiating transesterification reaction between methanol and
adsorbed triglyceride. Table 1 lists various heterogeneous
acid catalysts utilized in transesterification of
edible/nonedible feedstocks highlighting their reaction
parameters and obtained biodiesel yield. It is perceived
that acid catalysts are majorly prepared using sulfonic acid
precursor, which provides them high esterification activity
for available free
fatty acid content, whereas zirconia and SBA15 act as
carrier support.
Reaction Conditions
Catalyst Biodiesel
Molar Ratio Time
loading (yield %)
M:O (hours)
(W%)
11:1 9.17 6.43 98.93
20:1 10 10 98
12:1 5 5 93.2
optimized conditions takes place at the active sites of the
heterogeneous catalysts depending on the type of catalysts.
Intermediates are formed, which lower the activation
energy barrier and facilitates biodiesel production. There
are various other factors, which governs the adsorption of
the adsorbents at the active site of the adsorbate such as;
concentration of active sites, stability of catalyst on the
basis of its leaching activity and surface poisoning effects,
overall catalyst surface hydrophobicity, and repulsion to
polar compounds. Hence, an ideal heterogeneous catalyst
must possess all these given characteristics to facilitate the
effective and efficient biodiesel production. Alteration in
any of these properties may lead to the failure or delaying
of the transesterification reaction.
CONCLUSION
Biodiesel is proven to be an efficient, eco-friendly and
sustainable substitute to conventional fuels. However, the
economics of its production is a major bottleneck to be
addressed by the research communities. In this direction,
non-edible feedstocks i.e. Jatropha oils and waste cooking
oils etc. are explored as a cheaper raw materials as
compare to the edible oils. Mild reaction conditions and
optimum molar ratio of alcohol are essential for economic
production of biodiesel. Yield of produced biodiesel is still
a major challenge for its economic viability. In this
context, nanoporous materials based heterogeneous
catalysts play a crucial role for the effective and efficient
conversion of feedstocks to biodiesel with an added feature
of reusability. These nanoporous materials enhance the
specific surface area of the catalyst for the maximized
adsorption of oil and methanol and hence manifest the
biodiesel production. Various heterogeneous acid and base
catalysts have been explored using various feedstocks and
different optimum biodiesel yields are reported based on
reaction temperature, time, and catalyst concentrations.
Generally, mild reaction conditions and lower time
intervals are required using solid-base catalysts than that of
solid-acid catalyst. Even though solid-base catalysts are
more efficient for spontaneous transesterification reaction,
yet one of the major concerns while using solid-base
catalyst is reusability, which gets down to many folds after
consecutive reactions. In order to remove these lags,
heterogeneous catalysts must possess both base site as well
as the acid site. This can possibly be achieved by doping of
transition metal ions into the solid-base catalysts.

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