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