Alumina-supported potassium compounds as heterogeneous catalysts for biodiesel

production: A review
Abstract:
Alumina-supported potassium oxides are promising catalysts for the
transesterification reaction of vegetable oils for biodiesel production. Various
potassium compounds Al2O3-supported were prepared via impregnation
method. Potassium oxide (K2O) is a good candidate for a solid base catalyst
from an economical point of view. In the present work, we reviewed K2O
catalyst for the vegetable oil transesterification based on a variety of related
research papers. The potassium compounds supported in catalysts, KOH/Al2O3,
KNO3/Al2O3, KI/Al2O3, KF/Al2O3 and K2CO3/Al2O3, were optimized through
various reaction parameters, such as: amount of catalyst, molar ratio of oil to
alcohol, reaction time and temperature. Yields and conversions from various
catalytic systems applied for biodiesel production were also compared. Among
the catalysts studied, the KF/Al2O3 showed higher catalytic activity and a small
amount of catalyst requirement in the transesterification reaction, indicating
that it can be applied as a potential catalyst in the industry.
Introduction:
Biodiesel production has become an area in which many researchers have
increasing interest. This is due to its potential as an alternative fuel that offers
a complementary strategy for

sustainability [1]. Transesterification is the method most used commercially for

biodiesel production. It requires 3 mol of methanol (or a higher alcohol) and 1
mol of triglyceride to produce 3 mol of fatty acid methyl (or alkyl) ester and 1
mol of glycerol - as shown in Scheme 1. Under basic conditions, the exchanging
of glycerol with the desired alkanol occurs according to the following steps [2].
Different types of alcohols, such as methanol, ethanol, propanol and butanol
have been used. However, methanol and ethanol are the most used because of
their short chains [3]. Several vegetable oils have been used in biodiesel
production with different results. The oils used include: soybean [2,46], palm
[79], babassu [7], peanut [10], walnut [10], coconut [9,11], cottonseed [12],
canola [1315], waste cooking [16], linseed [17], rapeseed [2,1820], jojoba
[21], buriti [22], macauba [23], oiticica [24], pequi [25], rice bran [26], olive
[27], passion fruit [28], barley [29], turnip [29], pine [30], osage orange [31],
sesame [32], jatropha curcas [33,34], castor [35], algae [36], microalgae [37]
sunflower [2,38,39] saf- flower [40], salmon [41] and animal fat [42]. The most
common commercial process for biodiesel production is by homogeneous
alkali-catalyzed transesterification of a vegetable oil with methanol [43]. In
general, all the catalysts for the transesterification of vegetable oils can be
placed into three classifications known as: homogeneous, heterogeneous and
enzymatic [44]. The process is usually carried out in the presence of a base or
of the acid catalyst, in order to reduce the reaction temperature and to control
the product selectivity. In the homogeneous-basecatalyzed transesterification,
the process reportedly catalyzed by alkaline metal hydroxides [4547], sodium
or potassium shows high catalytic activity which results in the production of
high quality biodiesel. However, these homogeneous catalysis systems have
many drawbacks, due to the difficulties to separate the catalyst from the
glycerin phase [14] and the necessity to use a large amount of water, which,
consequently, results in a considerable amount of wastewater production .
Alternatively, several authors have suggested a two-step method using acid
catalyst, such as: H2SO4 [48,49] and N2O5 [49]. Two of the major
disadvantages of homogeneous catalysts is that they cannot be reused or
regenerated, because the catalyst is consumed in the reaction, and that the
separation of catalyst from the products is difficult and it requires specialized
equipment, which could result in higher production costs [3]. An alternative
method for biodiesel production is the use of heterogeneous catalysts. Studies
have been carried out to synthesize and develop new solid catalysts for
transesterification reaction in order to overcome disadvantages of the use of
homogeneous catalyst and to reduce the environmental and financials costs of
biodiesel production [3]. The heterogeneous catalysts are not consumed or
dissolved in the reaction and therefore can be easily separated from the
products. As a result, the products do not contain impurities of the catalyst and
the costs of final separation are reduced. These catalysts can be easily
regenerated and reused and are environmentally friendly, since there is no
need of a water treatment to be conducted in the separation step [50]. This

reduction in cost is sufficient to make the biodiesel competitive with the fossil
diesel, because it simplifies the processing of reaction products (washing,
separation and purification) and there is no occurrence of soap formation due
to the neutralization of free fatty acids or saponi- fication of triglycerides [51].
Although research on the use of heterogeneous catalysts to obtain biodiesel is
still in its early stages, there have been some interesting results. The main
characteristic these catalysts share is the high amount of basic sites on the
surface when it comes to basic transesterification. Several catalysts have been
evaluated for the production of biodiesel deposited on supporting materials.
Some efficient materials to do this are: the aluminas [2,5,6,8,9,
14,15,19,20,26,34,39,47,52,53,70,71], the hydrotalcites [8,5457], the zeolites
[8,46,58] and the silicas [46,56,5861]. Zeolites are one of the catalyst
supports that have attracted more attention in the field of catalysis due to their
unique pore system, high surface area and high stability. However, these
materials present severe limitations when large molecules are involved as
reactants, especially in liquid-phase systems, as it is frequently the case in the
synthesis of fine chemicals. This is due to the fact that mass transfer limitations
are very strong in microporous materials [62]. Moreover, the high cost of these
materials make them impractical for the production of biodiesel. Thus, it is
necessary to search for heterogeneous catalysts that are more efficient,
cheaper, of easier preparation and environmentally benign for large scale
production. In this context, the alumina appears to be one of the most suitable
alternatives to be used as support for biodiesel production. Aluminum oxide
(alumina) occurs in nature as a mineral (Corydon), which crystallizes in the
hexagonal or rhombohedral system. This form of aluminum oxide has a
thermodynamically stable structure; which is formed in the thermal
decomposition of the natural or synthetics precursors, usually above 1000 C
[63]. The most common applications of alumina are as catalysts, adsorbents
and catalyst supports, because of their high specific area (above 100 m2 g1).
Alumina-supported potassium oxides (K2O/Al2O3) are derived from salts of
potassium such as nitrate [5,9,15,19,34], iodide [6,15,26,70,71], fluoride
[2,14,15] and carbonate [39,15,64], as well as from hydroxides [8,20,53] and
they are catalytically active to high conversions of triglycerides. Studies by Xie
and Boz et al. [6,15] indicate that the high effi- ciency achieved by KI catalysts
supported by alumina may be related to the basicity present in its solid surface
due to the formation of species of K2O and the groups AlOK, which serve as
active sites for the transesterification of oil with methanol. Scheme 2 shows a
proposed impregnation of potassium iodide on a non-calcined alumina support,
with the formation of the intermediate structure K3AlI6. For every 6 molecules
of KI, 3 K atoms and 6 iodine bind to the aluminum present in the structure of
the alumina. The remaining atoms of K, after subsequent calcination, form the
K2O basic sites. Applications of heterogeneous catalysts for biodiesel
production have been reviewed by a variety of researchers. Zabeti et al. [3]
and Helwani et al. [44] focused mainly on the activity of solid acid and base

catalysts, metal oxides and supported metal oxides for transesterification

reactions. However, particularly in this work, the synthesis of aluminasupported potassium oxides in the transesterification of vegetable oils to
produce biodiesel was reviewed in order to find the most effective parameters
on the catalyst activity. It is also evaluated the influence of changes in the
catalyst and the reaction conditions as catalyst (wt%) relative to oil, molar
ration of methanol: oil, reaction temperature, agitation and others.

2. Preparation of the K2O/Al2O3 catalyst

The alumina loaded with different potassium compounds catalysts were
prepared
by
the
incipient-wetness
impregnation
method
[2,14,5,6,8,9,15,19,20,34,39,53,71].
The
incipient-wetness
impregnation
method utilizes an amount of water that is less than or equal to the amount
required to fill the pores of the supporting material. Impregnation occurs with
the mixture of the aqueous solutions of the corresponding metal salt precursors
with the alumina support. After equilibrating the mixture for 2 h, the paste is
dried in an oven at 393 K, for 24 h, and then the solid is calcined in a muffle
furnace in designated temperatures for different times before using it in the
reaction.
3. Transesterification
alumina

reaction

catalyzed

with

potassium

loaded

Usually, the relational system is prepared using a 250 mL glass flask equipped
with a reflux condenser and a magnetic stirrer. Initially, 50 g of vegetable oil
were added to the system and then heated up to the reaction temperature
while stirring constantly. The reaction is initiated as soon as the mixture of
methanol and the catalyst is added into the reactor. The effects of the reaction
time (19 h) [5,8,14,15,19,34,53,70,71], molar ration of methanol: oil (3:1
18:1) [5,6,8,14,15,19,20,34,53,70,71], catalyst (wt%) relative to oil (110 wt%)
[5,6,8,14,19,20,26,34,53],
reaction
temperature
(333348
K)
[6,14,15,19,20,34,53,71], calcination temperature [2,5,6,9,14,19] reutilization
of solid catalytic [2,14,8,9,34,39,70,71] and agitation [20,34] have been
investigated on the conversion (or yield) of the triglycerides to biodiesel. The
control of these parameters aims at optimizing the reaction conditions that
favor higher conversions of triglycerides. The catalyst is separated by filtration;
the filtrate is then maintained at rest to separate it into two layers. The oil
phase consists of methyl esters and nonreactive triglycerides, while the
aqueous phase mainly contains methanol and glycerol. The residual methanol
is separated from the liquid phase by distillation.
4. Influence of modification of the catalyst
4.1. Influence of wt% of the potassium loading
To observe the effect of the load (wt% potassium) in the biodiesel production,
the catalysts were prepared by varying the loading amount of potassium from
10 to 45 wt% and these were used to catalyze the transesterification reaction
as showed in the Fig. 1. The results show that when increasing the loading
amount of potassium, the biodiesel conversion or yield of the reaction
undergoes a maximum peak in all cases, and this depends on the salt used and
occurs at different points (potassium %) for different salts. The highest yield
(97.7%) is obtained with the KF loading of 15 wt% on Al2O3 [14]. In all cases
studied, the maximum amount of potassium that could be added was 35%.
Above this limit, there is a reduction in the conversion or yield of the reaction,
which results in a loss of efficiency. Some studies [6,8] show that the
agglomeration of the potassium compounds in the active phase or the covering
of the reactive points by one excess of potassium compounds, and hence one
lowering of the surface area of the catalyst, is sufficient to decrease activity.
For others, the basicity formation occurs by formation of the K2O and AlOK
compounds (by the thermal decomposition of the loaded K compounds and by
interactions of the saltsupport, respectively) [5,6,14]. As the KF loading is
decreased, [14] a reduction in the formation of the K2O species and the AlOK
groups occurs, which serve as the active sites for the transesterification
reaction, thus decreasing the yield

4.2. Basicity determination of the catalyst

The KI/Al2O3 has high basicity and better catalytic activity (87.4% conversion)
when compared to other options of catalyst [6]. The catalyst activity is
dependent on the strength of its basic sites and their amount. When comparing
alumina loaded with KI, KF, KOH, K2CO3, Br and KNO3, the order of conversion
reported by the authors [6] was as following: KI/Al2O34KF/Al2O34KOH/
Al2O34KNO3/Al2O34K2CO3/Al2O34KBr/Al2O3. However, in the work of Boz and
Kara [15], when evaluating the influence of different sources of potassium (KF,
KI, K2CO3 and KNO3), the highest conversion of triglyceride (98%) and the
highest yield of methyl esters (ME) (99.6%) were obtained with KF/Al2O3. The
high activity of the catalyst might be due to the formation of a new K2O phase
on the catalyst surface, causing an increase in the basicity (as shown in Tables
1 and 2). In this work, the authors also show that increasing the specific
surface area improves the conversion of triglycerides. The high surface area of
the support is an important factor in the incorporation of the active species in
the catalyst. It can be said, therefore, that the basicity and the surface area are
factors that directly influence the activity of catalysts. As the results showed,
higher catalytic surface area and basicity improved the production of biodiesel.
Clearly, there is no way to compare these catalysts, because they were
prepared and used in different conditions. However, we can estimate a profile
of the best synthesis conditions and applications of the catalyst. In previous
works, Xie and Li [6] and Evangelista et al. [26], worked with similar reaction
conditions, (with the exception of the type of oil), but Xie an Li [6] had better
performance than Ma et al. [20] and Evangelista et al. [26] due to the higher
basicity of the catalyst used. This behavior was also observed in the studies of
Boz et al. [14] and Ma et al. [20], who used KF/Al2O3 as a catalyst. Table 1 and

Table 2 show the catalysts in Al2O3 supported with different potassium

compounds, synthesized in different conditions.

4.3. Influence of reaction conditions in the yield and conversion

Table 1 shows that the K2CO3/Al2O3 presents 99% yield, however, this result
does not truly express the conversion of triglycerides into esters. Similarly,
KF/Al2O3 presents 97.7 [14] and 96% [2] yields. This increase was probably
due to the excess methanol used in the work [14] (15:1), whereas in the work
[2], the proportion used was of only 4:1 (methanol:oil). The studies conducted
[19] show the KNO3/Al2O3 synthesized in the calcination temperature of 873 K,
for 3 h and reaching a 94% yield. In the works of [8] and [53] with the
KOH/Al2O3 catalyst, the same calcination and reaction temperatures were
employed, however, lgen and Akin [53] used more time for both reaction
conditions. These factors, nevertheless, do not provide a higher yield of
reaction. The molar ratio of methanol:oil was the condition that prevailed when
Noiroj et al. [8] used the ratio of 15:1, whereas lgen and Akin [53] used the
ratio 12:1, obtaining yields of 91.07% and 89.40%, respectively. The
transesterification of cottonseed oil with methanol indicates that the ester
yields increased as the percentage of methanol increased, with the best results
being for a molar ratio of 12:1 [53]. Since this is an equilibrium reaction, an
excess of methanol will increase the conversion of oil and Fatty Acid Methyl
Ester (FAME) yield by shifting this equilibrium to the right side. Potassium
nitrate catalyst has been studied by Han and Guan [19] with 3% catalyst, and a

transesterification carried out at a molar ratio of methanol to oil of 12:1,

reaction temperature of 343 K, and reaction time of 3 h, resulting in a 94%
yield. As already noted, the values for the reaction yield are not actual values
for the conversion into biodiesel. Vyas et al. [34], using a quantity of catalyst
two times bigger and also double of the reaction time, in the same molar ratio,
achieved 84% conversion of Methyl Esters (ME). Xie et al. [5] increased the
amount of catalyst, methanol:oil ratio and reaction time, and, as a result, also
increased the conversion to 87%. The results showed high catalyst activity
(potassium nitrate) when Benjapornkulaphong et al. [9] used 10% of catalyst,
molar ratio 65:1 (methanol:oil) and the conversion obtained was 94.7% ME,
noting that the catalyst and methanol excesses shifted the reaction, increasing
the formation of methyl esters. However, the use of excess reagents makes the
cost of the process higher. The use of KI/Al2O3 in the soybean oil
transesterification demonstrated superior catalytic activity when compared to
the other catalysts. When the transesterification was conducted over the
KI/Al2O3 catalyst, the highest yield of 98% was obtained when compared to the
work of Islam et al. [70]. Thus, he needs a smaller amount of catalyst and a
reduction of reaction time to make the process economically viable. Silva et al.
[69] studied the obtainment of biodiesel via a reaction of transesterification of
sunflower oil using the catalyst KNO3/Al2O3 and observed the influence of the
concentration of the catalyst in the conversion of triglycerides to ethyl esters.
The 4% KNO3/Al2O3 catalyst showed better catalytic activity in the
transesterification reaction of sunflower oil under the conditions adopted,
resulting in a conversion of 60% ethyl esters. Our study [26] showed that
increasing the amount of KI/Al2O3, the yield of the reaction increased
significantly. When catalyst quantities smaller than 3 wt%, were used, the
results for the yields were lower (80%). Also, it was observed that 5% of
catalyst seems to be an optimum condition with 95.2% yield of biodiesel,
approaching the quantitative data of TG analysis relative to methyl esters,
which resulted in a 96.2% mass loss. According to Xie and Li [6], the higher
activity of the catalyst is due to the increased amount of basic sites. The
K2CO3/Al2O3 catalyst has showed high yield (99%), and Alonso et al. [39]
explain this homogeneous species as arising from species leached to the
methanol during the reaction. Although these studies were conducted under
different conditions, which does not allow a real comparison, they do not agree
with those given by [6], due to its only 48% conversion, and it can be proposed
that the K2O species, which were possibly formed by thermal decomposition of
the carbonates, were at least partially resulting from catalytically active sites.
Ma et al. [20] utilized a 4 wt% KOH/-Al2O3 catalyst, a methanol:oil ratio of 9:1
and 1 h of reaction time to obtain 84.52% conversion, which is lower than the
one presented by Noiroj et al. [8], who used smaller catalyst amounts (3 wt%),
however, with higher molar ratio of methanol:oil and reaction time, the yield
obtained was of 91.07%. It is noteworthy that this yield is from the biodiesel
formed and residual triglyceride. Potassium hydroxide was much more basic

than other potassium salts studied by previous researchers, resulting in

formation of a more stable chemical bond AlOK [20]. The works conducted
with alumina-loaded potassium fluoride show higher yields. Verziu et al. [2]
used higher reaction temperatures to obtain these results, while Boz et al. [14]
made use of the methanol excess (15:1) and reaction time (8 h). This excess of
methanol dislocated the equilibrium in the direction of ME conversion. Boz and
Kara [15] have obtained higher conversion of triglycerides (98%) in methyl
esters using potassium sources on alumina. This conversion was obtained with
the KF/Al2O3 catalyst at a temperature of 333 K, with a ratio of
methanol:canola oil of 15:1.3 wt% of catalyst amount and reaction time of 8 h.
4.4. Effect of the reaction conditions
The reaction conditions are parameters studied to improve the process by
providing better ways to carry out the reaction. In this case, some parameters
of the transesterification reaction heterogeneously catalyzed have been
studied, such as: catalyst amount, alcohol:oil molar ratio, temperature and
reaction time. Table 1 shows the effect of these parameters in the formation of
biodiesel and the same are discussed below.
4.4.1. Alcohol type and molar ratio of alcohol:oil
In transesterification, as in most reactions, the reaction proceeds until it
reaches equilibrium. This reaction requires a 3:1 alcohol/oil molar ratio, but this
equilibrium can shift towards forming more products and therefore achieving
higher ester conversion, which requires an excess of alcohol for complete
conversion of fatty acid esters. Several studies available in the literature report
the importance of molar ratio of methanol:oil in the formation of biodiesel
[5,6,8,14,15,19,20,34,53,71]. Boz and Kara [15] showed that for methanol and
ethanol in the same reaction conditions, the conversion rate is higher, around
96%, in methyl esters to methanol, while ethanol does not exceed the 64%
ethyl esters. The work of Noiroj [8] indicates that when the molar ratio of
methanol to oil was increased, the biodiesel yield was increased and the
highest yield (91.07%) was obtained at a methanol to oil molar ratio of 15:1.
Kulkarni et al. [66] investigated transesterification of canola oil with methanol,
ethanol, and various mixtures of methanol/ethanol, keeping the molar ratio of
alcohol to oil of 6:1 and KOH as a catalyst. The increased rate in the presence
of mixed alcohols was explained by the better solubility of oil in the reaction
mixture due to better solvent properties of ethanol than methanol. Hanh [67]
reported transesterification of triolein with various alcohols such as methanol,
ethanol, propanol, butanol, hexanol, octanol and decanol at a molar ratio of 6:1
(alcohol:triolein) and at a temperature of 25 C in the presence of base
catalysts (NaOH and KOH). The highest ester conversion is obtained by the
transesterification of triolein with methanol and ethanol. It was found that the
ester conversion depended upon the kind of alcohols; as the J.P. da Costa

Evangelista et al. / Renewable and Sustainable Energy Reviews 59 (2016) 887

894 891 number of carbon in alcohol increased, the rate of the ester formation
tended to decrease.
4.4.2. Temperature, time and agitation of reaction
Two key variables are time and temperature of reaction. In general, the
increase in time or in temperature increases the conversion of triglycerides
proportionally. Recent studies show that the [20,34] speed of agitation is also
important, since alcohol has high polarity and triglycerides are non-polar and
viscous, which makes agitation important when forming a mixture of both. Vyas
et al. [34] examined the stirring speed in the band of 100 700 rpm. With a
stirring of 600 rpm, while keeping the other variables constant, the highest rate
conversion of 84% was obtained.
4.4.3. Type and amount of catalyst
The catalysts most frequently used for transesterification are homogeneous
(basic or acidic). Enzymatic and heterogeneous catalysts are rarely used and,
so far, are more important in terms of research on the topic. The basic catalysts
are much more used than the acidic, because of their higher catalytic activity
and better quality of biodiesel produced. The basic catalysts are more efficient
than the heterogeneous. However, recent research show that the
heterogeneous catalysts may have similar efficiencies [8,68] and are cheaper
(since they can be recycled), simpler and less polluting. For this reason, its use
has begun to be investigated in industrial tests for large scale production.
4.5. Potassium leachability
One of the advantages of the use of heterogeneous catalysts is their ability to
regenerate, which means that they can be reused in other cycles, resulting in
less environmental impact than that of the homogeneous catalysts. Successive
reutilization has demonstrated its competency in fixing the support and it has
also presented high catalytic activity. Despite the good results obtained with
K2O/Al2O3, part of the active phase of the catalyst is entrained by the liquid
phase, which happens to catalysts made from other alkali metals as well. This
phenomenon (leaching) has been studied in order to achieve the catalysts
stability, which is essential to the development of the theme and to its use in
alternative fuels. Some researchers have proposed the reuse of the active
species on the surface where elemental analyzes of the catalysts were
performed to determine the amount of active species leached in the reaction.
Generally, X-ray fluorescence (XRF) or energy-dispersive spectrometer (EDX)
are used to determine the potassium content before and after the reaction, in
order to determine the capacity of the active species to be reused (Table 3).
Part of the K initially deposited on the catalyst surface is leached from the solid,

which reveals a lack of chemical stability of the catalysts under reaction

conditions [47].

This shows that about 4555 wt% of K2O were leached. This dissolution of
active K2O can occur via the following reaction [9]:

OHK 1 Benjapornkulaphong et al. [9]

also studied the elemental
composition of NaNO3/Al2O3 and Ca(NO3)2/Al2O3 before and after their use in
transesterification. The results indicated that 70 wt% of Na2O were leached
during the reaction and that 8 wt% of CaO were lost. This result suggests that
when alkali metal oxides supported by alumina were used as the catalyst, part
of the active sites (alkali metals) are reached. The alkali oxides present two
metal cations (Li2O, Na2O or K2O), with one to react with alcohol to form the
methoxide (Reaction (2)) and the other atom likely to be leached in the liquid
phase. This differs of alkali earth metal oxides, which only have one atom of
metal (MgO or CaO), the reaction below suggests a low (or no) leach ability for
these oxides:

Noiroj et al. [8] suggested that the leaching of active species in the reaction
mixture will reduce activity and reusability of the solid catalyst. Therefore, the
determination of the active species leached on a solid support is important to
their performance, and to the amount of wash water needed in the industry.
4.6. Catalyst reusability

The stability and recyclability of these catalysts is a very important issue. This
has been verified by the performance of the recycled catalysts without any
reactivation and by the chemical analysis of the FAME while looking for leached
elements [39]. The activity measurement results for this reused catalyst were
even lower than the values obtained for the fresh catalyst. This lower activity
can be explained considering the losses during the manipulation of the catalyst
and the leaching of K during the washing with methanol. Alonso et al. [39]
reported the use of K2CO3/Al2O3 in the transesterification reaction for four
times. The observed reduction in catalytic activity were as following: yield of
99% of FAME in the first run, followed by 33% in the second run; 6.5% in the
third run, and only 3.8% in the last test carried out. Vyas et al. [34] reused the
catalyst KNO3/Al2O3 for four times. His results showed that the first run
conversion is of 84%, and the second is of 75%, followed by a third run
conversion of 72%. The fourth run presented a result of 60%. Based on that, we
can assume that the same catalyst can be used for at least three times. Verziu
et al. [2] utilized a KF alumina-supported catalyst for six times and the
conversion and the yield of the products started to decrease. After the fourth
run, the conversion is of 95%, approximately. After the first reaction, the
leaching in Al and K was of less than 80 ppm. However, after the fourth
reaction, the leaching exceeded 1.5%, leading to the significant drop in activity.
The comparison of the stability of catalysts with reduced fluoride content,
namely 10 wt%, also indicated a slight improvement in the stability. The
decrease in the conversion and the yield of the products started in the 6th and
5th runs. Reusability of the KF/Al2O3 catalyst [14] was tested by consecutively
recovering and then reusing the catalyst up to three times. The
transesterification reaction of oil with methanol was carried out repeatedly
under one constant set of operating conditions: (methanol:oil) 15:1, catalyst
amount: 3 wt%; temperature: 338 K; reaction time: 8 h. The biodiesel yields
found were the following: E97.7% (first use), E61.2% (second use) and E60.1%
(third use). Islam et al. [70] reused the catalyst KI/Al2O3 for eleven times. In
the first run, the yield obtained is of 98%, while in the seventh run it decreases
to 84%. In the eleventh run, the yield is of 79%. It showed good mechanical
stability as the support, indicating its potential for use in the industrial context.
Jairam et al [71] reused the catalyst KI/Al2O3 for four runs. For the first three
consecutive runs, the value obtained was of 85%. During the fourth run,
however, the conversion dropped to 51%, which is likely due to the leaching of
KI into the solution or the catalyst deactivation.
5. Conclusion
Although, in some cases, the heterogeneous systems showed lower catalytic
activity than the homogeneous, the objective of those systems is to improve
the methods of synthesis in order to replace the homogeneous catalytic. The
optimization of synthesis conditions and transesterification reaction is essential
to determine the most appropriate conditions. The process of separation of

these catalysts is facilitated because they do not need washing, which reduces
the production of waste water and catalyst disposal at the end of the process.
The recovered catalyst can also be reused. The application of heterogeneous
catalysts can contribute to the decrease of biodiesel production costs and is of
great importance for industrial operations. Different types of aluminasupported
potassium compounds have significant effects on the catalyst activity. The
presence of the basic sites (K2O) formed on calcination of potassium
compounds increases the basicity of the catalysts, providing high conversion to
methyl esters. The most active catalyst is the KF/Al2O3, which is suitable to be
applied in the production of biodiesel. Moreover, its application requires a small
amount. The amounts of methyl ester obtained depend not only on the catalyst
activity but also on the type of oils and the reaction conditions, such as:
catalyst amount; alcohol:oil molar ratio; reaction time, temperature, etc.
Acknowledgments
The authors acknowledge CAPES and CNPq, for their financial support.