Renewable and Sustainable Energy Reviews 49 (2015) 50 0 –516

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Renewable and Sustainable Energy Reviews

journal homepage: www.e l sevi e r . c om / l oc a t e / rser

Purification of crude biodiesel obtained

by heterogeneously-catalyzed transesterification
Vlada B. Veljković n, Ivana B. Banković-Ilić, Olivera S. Stamenković
Faculty of Technology, University of Niš, Bulevar oslobodjenja 124, 16000 Leskovac, Serbia

a r t i c l e i n f o ab s t ract

Article history: This review paper presents the methods that have been used to date for the purification of crude
Received 3 April 2014
biodiesel obtained by heterogeneous production processes. At first, a typical biodiesel production
Received in revised form
process using heterogeneous catalysts is shortly described, paying attention to the main processing
11 November 2014
steps. Then, possible impurities and their effects on the biodiesel quality are pointed out. The main part
Accepted 23 April 2015
Available online 16 May 2015 of this review paper deals with the traditional (wet and dry washing) and novel (membrane extraction,
precipitation, complexation, simultaneous ion-exchange and precipitation as well as simultaneous
Keywords: biodiesel synthesis and purification) purification methods. These purification methods are compared
Biodiesel
with respect of their refining efficiency. A special attention is paid to their comparison regarding the
Dry washing Ion-
type of raw materials used in biodiesel production. Furthermore, advantages and disadvantages of the
exchange Membrane
extraction crude biodiesel purification methods are emphasized. Finally, environmental aspects of crude
Precipitation biodiesel purification are highlighted.
Wet washing. & 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
2. Biodiesel production process using heterogeneous catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
2.1. Description of typical biodiesel production processes using solid catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
2.2. Effects of impurities on biodiesel quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
3. Purification of crude biodiesel from heterogeneously-catalyzed transesterification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
3.1. Crude biodiesel purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
3.1.1. Wet washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
3.1.2. Dry washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
3.1.3. Membrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
3.1.4. Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
3.1.5. Ion exchange and precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
3.1.6. Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
3.1.7. Simultaneous biodiesel synthesis and purification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
3.2. Comparison of various crude biodiesel purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
3.3. Comparison of crude biodiesel purification methods regarding oily feedstocks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
3.4. Environmental aspects of crude biodiesel purification methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515

1. Introduction

n
Corresponding author. Tel.: þ 381 16 247 203; fax: þ 381 16 242 Biodiesel has gained world-wide attention in recent years as an
859. alternative fuel that has a number of favorable properties such as
E-mail address: veljkovicvb@yahoo.com (V.B. Veljković).

http://dx.doi.org/10.1016/j.rser.2015.04.097
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 245
516

Table 1
a
Comparison of homogeneous and heterogeneous catalysis for biodiesel production.
246 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516
Type of Advantage
catalyst
Homogeneous Modest reaction conditions
High activity of base catalysts results in high yield in short time
Base catalysts are much more active than acid catalysts
Methoxides are more effective than hydroxides
Acid catalysts can be used for esterification and transesterification
Acid catalysts are insensitive to the presence of FFA and water
Heterogeneous Environmentally friendly, noncorrosive, recyclable and with fewer disposal
problems
Easy separation of products, higher selectivity, longer catalyst life
Acid catalysts can be used for esterification and transesterification
Acid catalysts are insensitive to the presence of FFA and water
Can be used in fixed-bed reactors with continuous operation
Comparatively cheap
a
Adapted from Endalew et al. [6].
high degradability, no toxicity as well as low emission of
carbon monoxide, particulate matters and unburned hydrocarbons.
Biodiesel is a mixture of fatty acid alkyl esters and it can be
used in conventional diesel engines, which need almost no
modification. So far, it has mainly been produced by
transesterification of triacyl- glycerols (TAGs) and/or esterification
of free fatty acids (FFAs) from various natural sources like
vegetable oils and animal fats or waste cooking oils using
homogeneous basic (most frequently sodium or potassium
hydroxide) or acid (sulfuric acid) catalysts, respectively that are
usually dissolved in methanol. Because of high activity of
traditional basic catalysts and mild reaction conditions, the
conver- sion of TAGs into methyl esters completes within 1 h at
atmospheric pressure and relatively temperature (up to 65 1C).
However, these processes have several drawbacks such as soap
formation, reduction of catalytic efficiency caused by the
catalyst consumption, the increase in viscosity and the
formation of gels. In addition, for wet washing of crude biodiesel,
the most frequently used purification method, a large amount of
water is needed in order to remove the residual catalyst and to
clean the biodiesel product, thus producing a huge amount of
wastewater that should be adequately treated. This additional
step in the overall biodiesel production process increases the
overall cost of the process, making it non-competitive to the
diesel production from petroleum. The cost of biodiesel production
is about 1.5–3 times more expensive than petroleum based diesel
[1,2]. Furthermore, homogeneous catalysts cannot be reused,
which is probably their major disadvantage. Finally, homogeneous
base- catalyzed transesterification is limited by availability of
refined oily feedstocks. Despite being readily available and
inexpensive, non- refined feedstocks (crude oils, rendered animal
fat and greases) have limited use in base-catalyzed
transesterification because of high content of FFAs that
unfavorably react with the base catalyst.
An alternative that could eliminate some drawbacks of
traditional homogeneous base-catalyzed biodiesel production
processes is the use of heterogeneous catalysts. First of all,
heterogeneous can be used in batch reactors repeatedly or in
continuous fixed-bed reactors. More- over, the use of solid
catalysts results most probably in simpler and cheaper separation
processes, reduction of the wastewater effluent and capital and
energy costs. For instance, solid catalysts could be retained in the
reactor simply by filtration. Therefore, the operating costs
associated with the additional separation and purification stages
could be avoided. Furthermore, heterogeneous catalysts exhibit a
less corrosive character and can be used in a fixed-bed reactor,
leading to safer, cheaper and more environment-friendly
operation [3]. The benefit with heterogeneous catalysts is their
lower consumption in
Disadvantages
Separation problems after reaction and wastewater treatment
Saponification forms stable emulsion
Catalyst cannot be reused
Basic catalysts are sensitive to the presence of FFA and water
Higher process cost compared with heterogeneous processes
Acid catalysts give very slow reaction rate and are corrosive
Acid catalysts require higher methanol-to-oil molar ratio and
temperatures
Currently less effective than common homogeneous base catalysts
Mass transfer limitations in the multi-phase reaction system
Basic catalysts require oily feedstocks with low FFA and water content
High alcohol-to-oil molar ratio, temperature and pressure can be
required
Higher cost of acid catalysts compared to basic catalysts
Possible leaching into the reaction mixture
the transesterification reaction. For example, 88 t of NaOH is
required to produce 8000 t of biodiesel, while only 5.6 t of
supported MgO are sufficient to produce 100,000 t of biodiesel [4].
The disadvantages of solid catalyst are slow kinetics, incomplete
conversions, severe condi- tions, limited lifetime and high costs
[5]. At last, crude glycerol of higher purity could be obtained in
heterogeneous reaction systems. The main disadvantage of solid
catalysts, namely their lower reaction rate in comparison to the
rate of homogeneous reactions, can be overcome by using higher
methanol-to-oil ratios, temperatures and pressures. Therefore, the
use of efficient heterogeneous catalysts opens up the possibility of
more favorable processes for biodiesel production. Table 1
summarizes the advantages and disadvantages of homoge- neous
and heterogeneous catalysts for biodiesel production.
Both acids and bases are used as heterogeneous catalysts
in transesterification and esterification reactions. Various types of
solid catalysts have been assessed such as alkali earth oxides, alkali
oxides, not metal oxides, metal oxides, cation exchange resins,
metal phosphates and acid supported on different materials
[4]. The chemical nature of solid catalysts determines the rate of
transester- ification reaction. The stronger basicity due to the
presence of more active basic sites improves the catalytic activity in
the transesterifica- tion reaction. Therefore, biodiesel is usually
produced in the presence of a base catalyst, although acid
catalysts have also been used. Despite all the efforts,
heterogeneous catalysts for biodiesel produc- tion have not been
widely exploited at industrial level, yet. So far, only a biodiesel
production process using a mixed oxide of zinc and aluminum has
been carried out commercially [7]. However, this technology is
spreading to different parts of the world [6].
In order to be used the biodiesel produced in heterogeneously
catalyzed processes must comply the prescribed biodiesel stan-
dard specifications such as EN 14214 or ASTM D6751. Hence, once
produced, crude biodiesel (commonly a mixture of fatty acid
methyl esters) should be purified. Various impurities, such as
unconverted TAGs, mono- and diacylglycerols, FFAs, glycerol,
water, catalyst, soaps and others must be removed from crude
biodiesel by the downstream purification steps in order to prevent
the damage of diesel engines [8]. Whereas the development and
use of heterogeneous catalysts for biodiesel synthesis have widely
been described in many publications, a little attention has been
paid to the quality of biodiesel obtained in heterogeneous catalytic
systems [9]. There are only a few studies concerning the purifica-
tion of crude biodiesel obtained by processes using calcium oxide
as the basic catalyst [10–13]. Since today's commercial production
of biodiesel is based on homogeneous catalytic systems, it is not
surprising that the majority as well as on the type of biodiesel production processes (2) separation of the
of publications deals with feedstock and operating using solid catalysts reaction mixture from the
the pur- ification of crude conditions [16]. Mainly, solid catalyst, (3)
biodiesel obtained in inorganic catalysts are A typical biodiesel transesterification of TAGs,
homogeneous catalytic employed because of their production process based on (4) separation of the ester
processes. Surveys on the cheapness, availability, esterification and phase (crude biodiesel) from
methods for purification of stability, durability and transesterification reactions of the methanol/glycerol phase
crude biodiesel produced by easiness of regeneration [6]. oily feedstocks with an and (5) pur- ification of crude
alkali-transesterification of Recent researches have been alcohol in the presence of a biodiesel. Also, the overall
various feed- stocks can be focused towards the solid catalyst comprises the process includes the crude
found in the recent reviews heterogeneous base inorganic following main process glycerol processing through
[8,14,15]. catalysts that are low cost, stages (Fig. 1): (1) acidification and separation
The main objective of eco-friendly and highly esterification reaction of of glycerol from alcohol. The
this review paper is to effective. Among them, the FFAs, purification of crude biodiesel
present the purification CaO-based catalysts that can and the recovery of alcohol
methods that have been used be obtained from natural and glycerol improve the
to date in heteroge- neous sources or wastes appear to biodiesel product quality and
biodiesel production be promising for catalyzing reduce the overall process
processes. At first, a typical transesterification of costs, respectively. The
biodiesel production process various feedstocks. For biodiesel production process
using solid catalysts is instance, quick lime [17], is further briefly described.
shortly described, paying calcium-containing shells Biodiesel production
attention to the main [18,19] and lime mud, a solid process using solid catalyst
processing steps. Then, waste from the paper mill [20] can be con- ducted as a one-
possible impurities and their have been shown to own step or two-step process,
effects on the biodiesel excellent catalytic properties depending on the type of oily
quality are pointed out. The that make them suitable for feedstock. When the oily
main part of this review biodiesel production. The use feedstock, such as refined
paper deals with the of these catalysts not only vegetable oils, contains less
traditional (wet and dry makes the transesterification than 1% FFAs and no
washing) and novel process economic and impurities, an base-catalyzed
(membrane extraction, environmentally friendly but transesterification process is
precipi- tation, complexation, also eliminates the wastes applied. However, when the
simultaneous ion-exchange from the environment. It is oily feedstock, such as non-
and precipita- tion as well as also worth mentioned that edible vegetable and waste
simultaneous biodiesel solid acids favoring cooking oils, contains high
synthesis and purification) esterification and FFA, water and impurities, a
purification methods. In transesterification reactions special attention in the
addition, these purification simultaneously are of special process design and
methods are compared with impor- tance for biodiesel selection of catalysts is
respect of their refining production from low-cost required. Because of the
efficiency. A special feedstocks having high FFA high FFA content and water,
attention is paid to their content. Development of new, the acid- catalyzed
comparison regarding the more effective and cheaper transesterification process is
type of raw materials used in heterogeneous catalysts will preferable for biodiesel
biodiesel production. lead to a lower total production. However, this
Furthermore, the advan- biodiesel production cost process requires relatively
tages and disadvantages of from different oily high tem- peratures, long
the crude biodiesel resources. For instance, reaction times and the
purification meth- ods are improved catalyst equipment made from
summarized. Finally, the performance can be corrosion-resistant materials.
environmental aspects of achieved by utilization To overcome these
crude biodiesel purification macro- and meso-porous problems, the two-step
are highlighted. solids support that enhances process is applied, which
TAG and FFA diffusion to includes an acid-catalyzed
active acid/basic groups and pre- esterification followed by
2. Biodiesel production has beneficial effects on the the base-catalyzed
process using heterogeneous reaction rates [21]. Also, the transesterification to convert
catalysts application of eco-friendly FFAs and TGAs into esters,
technologies such as respectively. Since both reac-
Heterogeneous catalysts microwaves, ultrasound and tions are reversible, an
for membrane reactors can be excess of alcohol is usually
transesterification/esterificati used for solving the operation employed to force the
on can be either chemicals or problems including high reaction towards the methyl
enzymes, the former energy consumption, long ester formation. By using
catalysts being acidic or reaction and low productivity bifunctional catalyst that
basic types. Selection of a that increase the production catalyzes both esterification
heterogeneous catalyst cost [22]. of FFAs and transesterification
depends on its catalytic of TAGs simultaneously, the
activity, cost and availability biodiesel produc- tion can be
2.1. Description of typical
conducted in the one-step
process.
The FFA esterification
stage usually includes a
homogeneous catalyst (most
frequently sulfuric acid),
although solid acid cata- lysts
can be also employed.
Commonly, the esterification
reaction is carried out close
to the alcohol boiling
temperature under vigorous
agitation. After completing
the reaction, the reaction
mixture is neutralized by
adding a base. Finally, the
esterified oil phase
containing esters and TAGs is
separated from the aqueous
phase and is led to the
transesterification reactor.
Both stirred tank reactors and
fixed-bed column reactors are
employed. The reac- tion
conditions depend on the
type of the catalyst applied.
The final reaction mixture
contains esters and glycerol
as the main

Fig. 1. Process
selection for biodiesel
production.
products, acylglycerols, solid catalyst and soaps. Usually, after
the transesterification reaction, the solid catalyst is firstly
collected from the reaction suspension by filtration or
centrifugation. In some cases, a part of the catalyst is leached into
both the ester and alcoholic phase. The collected solid catalyst can
be reused with or without regeneration or must be properly
disposed. Then, crude biodiesel is separated from the
glycerol/alcohol phase. Because of the large difference in
density of the two phases, the phase separation by
gravitational settling is relatively fast and commonly employed in
the practice. However, centrifugation is more effec- tive than
settling and should be considered for the application at large
scale biodiesel production. However, these separation pro- cesses
do not completely remove glycerol and methanol from crude
biodiesel. After being separated, both phases are further
processed to get the products (esters and glycerol) of desired
purity and to recover the excess of methanol. The methods used
for these purposes are the same as those employed in the
processes using homogeneous base catalysts.
After the phase separation stage, methanol is
sometimes removed from crude biodiesel by evaporation, vacuum
flash vapor- ization or stripping. Since crude biodiesel contains
many impurities that must be removed, it is subjected to
purification most fre- quently by water washing, although water-
free agents are also used. In some cases, these processes cannot
remove the leached catalyst (for instance the leached calcium
oxide) completely from the crude biodiesel. Novel methods are
developing for the effective elimina- tion of the leached catalyst
from the crude biodiesel. When water washing is employed,
water-soluble impurities are removed, such as residual
methanol and glycerol, while acylglycerols and FFAs remain in
the biodiesel. Finally, the biodiesel is dried by flash or thin-film
evaporation, commonly under vacuum, or by adsorption onto
appropriate adsorbent materials followed by a filtration.
Usually, wastewater generated in the purification stage is
gravita- tionally separated from the biodiesel phase. This
wastewater must be adequately treated before reuse or disposal
[23].
2.2. Effects of impurities on biodiesel quality
Fuel performances of biodiesel depend on its purity [24]. The
quality standards, for instance ASTM D6751 and EN 14214,
specify the chemical composition and other properties of
biodiesel that can be used as an alternative to diesel fuels.
Therefore, manufac- turing companies are concerned to
produce biodiesel with the physico-chemical properties
fulfilling the biodiesel quality stan- dards. Each commercial
producer aims at producing of biodiesel with no or minimal
amounts of impurities. Major impurities of biodiesel are the
same regardless of type of feedstock, alcohol and catalyst as well
as operational conditions applied in the process production. They
are glycerol, alcohol, catalyst, unreacted TAGs, formed mono-
and diacylglycerols, FFAs, water, soap and salts. Leaching of
solid catalysts can be a source of product contamina- tion, which
should be seriously taken into account when hetero-
geneous processes are applied for biodiesel production.
The biodiesel impurities affect the diesel engine
performance
through a number of negative effects [15]. Methanol reduces
viscosity, density and flash point, corrodes parts of aluminum and
zinc and deteriorates natural rubber seals and gaskets. Glycerol
can cause undesirable storage, engine durability and
environmental problems, such as fuel tank bottom deposits, injector
fouling and higher emission of aldehydes and acrolein. Negative
effects of the present water are numerous: the combustion heat
reduction, the hydrolysis of methyl esters, the microbiological
growth causing the blockage of filters, the ice crystals formation
resulting to fuel gelling and the corrosion of fuel tubes and injector
pumps. If present in the biodiesel, soaps can cause engine
promote corrosion of the engine components. Acylglycerols can
cause crystallization, turbidity, higher viscosity and deposit
formation at pistons, valves and injection nozzles.
3. Purification of crude biodiesel from heterogeneously-
catalyzed transesterification
The purification step is essential for using the produced esters
(crude biodiesel) as a fuel, since only the product satisfying the
standard specifications can be considered as biodiesel. A number
of technologies for the purification of crude biodiesel produced in
homogeneously alkali-catalyzed transesterification of various
feedstocks are available, and novel technologies are also emerging
[8]. However, only a few papers treat the purification of crude
biodiesel from heterogeneously catalyzed processes [10–13].
Among heterogeneous catalytic systems, calcium oxide is one
of the most active solid catalysts used in biodiesel production so
far [10,12,25–37]. It is so active that soybean oil is converted into
methyl esters perfectly at reflux of methanol within 2 h using 8 g
CaO/L of soybean oil and the methanol-to-oil molar ratio of 12:1
[30]. Beside the catalytic activity, the additional advantages of
calcium oxide are the possibility for its repeated use as catalyst,
as well as its easy availability and low cost. A survey on the
literature related to the purification of crude biodiesel obtained
by transesterification of various feedstocks using calcium-based
catalysts is given in Table 2. In addition, the literature review on
the purification of crude biodiesel produced by transesterification
using other types of heterogeneous catalysts (that are not calcium
compounds) is presented in Table 3.
It is worth mentioned that it is not possible to produce
biodiesel satisfying the quality standard specifications by the
heteroge- neously catalyzed transesterification without an
appropriate pur- ification procedure. This was well-demonstrated
by Dias et al. [38], who employed the transesterification of pork
lard, waste frying oil and their mixture catalyzed by calcium
manganese oxide (CaMnOx) or calcium oxide to produce
biodiesel. After completing the reac- tion, the reaction mixture
was filtered under vacuum and left overnight for phase
separation. Afterwards, the ester and alcoholic phases were
separated. Methyl ester content, independently of the raw
material, was not in agreement with the specification according to
EN 14214, as well as iodine value of the waste frying oil biodiesel.
Because of the catalyst leaching, an additional purification step
was, moreover, required to ensure product compliance with the
standard specifications regarding calcium content.
Leaching of calcium ions into the alcoholic and ester phases
not only reduces the number of repeated calcium oxide use but
also generates the increased calcium content in the crude
biodiesel. This leaching may be due to production of water by
transforma- tion of calcium oxide into calcium diglyceroxide [31]:
CaO þ 2C3 H8 O3 sCaðC3 H7 O3 Þ2 þ H 2
O
which then can be subjected to the hydrolysis:
2þ
Ca ðC H O Þ þ 2H O⇄Ca þ 2OH þ 2C3 H8 O3
3 7 3 2 2
corroding, injector damaging, filter plugging and engine weakening.
FFAs reduce the oxidation stability of biodiesel and
The other sources of the soluble calcium are calcium soaps that
can arise from the neutralization of FFAs present in the oily
feedstock or the saponification of the acylglycerols and esters,
which can occur simultaneously during the CaO-catalyzed
transesterification [47,48]. The produced calcium soaps are
scraped from catalyst particles, causing an increase in the
soluble calcium [31]. Beside calcium diglyceroxide and soaps,
the potential components of the calcium dissolved in the ester
phase can also be formed by the hydrolysis of calcium methoxide
and hydroxide [32,49], which are obtained in the reactions of
calcium oxide with methanol and water, respectively.
Calcium oxide solubility in mixtures of biodiesel, glycerol and
methanol is 0.6 mg of equivalent CaO/mL at 60 1C [33]. Hence, the
Table 2
Survey on purification methods of crude biodiesel produced by transesterification catalyzed by calcium-based catalysts.

a
Production Purification Product properties Concluding remarks Ref.
Reactants Catalyst Operating Method Operating conditions
(oil:alcohol (wt% to conditions
molar ratio) oil mass)

Jatropha CaO (1.5) 70 1C, 2.5 h Wet washing: 45 1C, 20 min, stirring Only 58% removal of [13]
curcas oil, Water (water:oil ¼ 1:10) calcium; biodiesel
methanol yield: 69.5%
(1:9) Complexation: Decalcification
EDTA (agent:Ca ¼ 1:1) efficiency: 83.9%;
biodiesel yield: 92.3%
2
Precipitation: ν (20 1C): 7.32 mm /s, ρ Decalcification
Oxalic and citric acid (agent: (20 1C): 878.4 kg/m3, FP: efficiency : 4 92%;
Ca ¼ 1:1) 4 170 1C, CV: o citric acid is the
0.05%, SA: o 0.005%, better agent (96.2%)
SC: ensuring the
0.0036%, CN: 56.1 biodiesel yield of
95.5%
b
Sunflower oil, CaO (0.2) 60 1C, Wet washing: Washing (RT, 500 rpm, 1 h) was Ca-soaps cannot be [10]
methanol 1000 rpm, followed by decanting, separating removed below 5 ppm
(1:14) 5h and outgassing (100 mbar, 70 1C
Distilled water (10 wt%) and FP: 174 1C, WC:
washing 1 h) 200 ppm, AV:
0.06 mg KOH/g,
MEC:
98%, ν (40 1C):
2
4.41 mm /s, ρ (20 1C):
3 2þ
883 kg/m , Ca :
Twice distilled water (10 wt%) 362 ppm
2þ
washing MEC: 98%, Ca :
Twice distilled water (10 wt 320 ppm
2þ
%) washing followed by aq. MEC: 97.3%, Ca :
HCl (0.1 M; 10 wt%) washing 209 ppm
Distilled water (10 wt%)
2þ
washing followed by aq. HCl MEC: 96.5%, Ca :
(0.1 M; 10 wt%) washing 312 ppm
Dry washing: Stirring with resin (2 h) was 2þ
MEC: 97.4%, Ca : Ca-soaps can be
Sulfonic resin (DOWEX DR followed by filtering, decanting, o 1 ppm, removed below
2030; 50 wt% to the distilled water washing (10 wt%, RT, AV: 5 ppm. Ca-soaps are
biodiesel mass) 500 rpm, 1 h), decanting, separating 3.8 mg KOH/g transformed to FFAs
and outgassing (100 mbar, 70 1C
and
1 h)
Ion-exchange/precipitation: Precipitating (biodiesel:methanol
Solid Na2CO3 suspended in mass ratio ¼ 2, 60 1C, 1000 rpm, 4
methanol: h) was followed by distilled water
1 wt% (of biodiesel mass) washing (RT, 500 rpm, 1 h), 2þ
MEC: 92.8%, Ca : Optimal amount of
þ
decanting, separating and 390 ppm, Na : 140 Na2CO3 for Ca
5 wt% outgassing (100 mbar, 343 K, 1 h) ppm removal: 5 wt%
2þ
MEC: 96.7%, Ca :
þ
o 5 ppm, Na : 0 ppm
2þ
10 wt% MEC: 98.3%, Ca :
þ
o 5 ppm, Na : 12 ppm
Sunflower oil, Simultaneous reaction and
2þ
Distilled water washing (10 wt%, RT, MEC: 96.9%, Ca :
methanol ion-exchange/precipitation 500 rpm, 1 h) was followed by þ
o 3 ppm, Na : o 1 ppm
(1:30) with Na2CO3 (5 wt%) decanting, separating and
outgassing (100 mbar, 70 1C and 1 h)
b c 1
Waste CaO BT , 2 h Dry washing: RT, LHSV : 2 h 15DRY and IRC76 [12]
are
cooking oil, (0.78 g/ Cation-exchange resins more efficient in Ca
methanol 100 mL (Amberlyst-15DRY, removal than 200CTNA
(1:20) oil) Amberlite-200CTNA, and 31WET
Amberlite-IRC76 and
Amberlyst-31WET, swelled
and washed with methanol)
Amberlyst-15DRY with no FGC: o 0.01% 51% removal of CaO
methanol
FGC: 0.12% 100% removal of CaO
Amberlyst-15DRY with
methanol (20 vol% to
biodiesel)

b c 1
Soybean oil, CaO (0.8 g/ BT , 2 h Dry washing: RT, LHSV : 0.5 h Removal of Ca: 50% Leaching of the catalyst [31]
methanol 100 mL Cation-exchange resins (carboxylated resin) and is observed (Ca: 22–
oil) (sulfonated or carboxylated) 4 99% (sulfonated resin) 139 ppm)
Table 2 (continued )

a
Production Purification Product properties Concluding remarks Ref.
 Reactants Catalyst Operating Method Operating conditions
(oil:alcohol (wt% to conditions
molar ratio) oil mass)

Soybean oil, Ca 60 1C, Dry washing: Ştirring (6 or 50 wt% to biodiesel Regarding Ca removal, [11]
methanol glyceroxid 1000 rpm, Ion-exchange resin mass, RT, 500 rpm, 1 h) both resin amounts
(1:14) (0.4) 2h were ineffective
2
Membrane extraction: 2.11 mL/min, RT, flux 26.4 L/(m h) Regarding Ca
Ceramic monochannel removal, both
membranes (0.05 and membranes were
0.1 mm) ineffective
Ion-exchange/precipitation Pretreatment (biodiesel:methanol
followed by dry washing, mass ratio ¼ 2, 60 1C, 1200 rpm, 5
membrane extraction or h): precipitating with methanol-
water washing: Na2CO3 (5 wt% to biodiesel mass),
Dry washing using resin (6 wt filtering and settling MEC: 95.7%, WC: Effective Ca removal
%) 367 ppm, Ca: 2.3 ppm in all cases
Membrane extraction using MEC: 94.5%, WC:
ceramic membrane (0.1 mm) 458 ppm, Ca: 1.9 ppm
Water washing MEC: 98%, WC:
125 ppm, Ca: 2.8 ppm
Waste frying Dry washing using resin (6 wt MEC: 95.8%, WC: Effective Ca removal
oil, %) 319 ppm, Ca: 3.4 ppm in all cases. The
methanol Membrane extraction using MEC: 95.7%, WC: values were little
(1:14) ceramic membrane (0.1 mm) 331 ppm, Ca: 3.2 ppm higher than those of
Water washing MEC: 95.4%, WC: the soybean oil
213 ppm, Ca: 4.7 ppm biodiesel

Pork lard, CaMnOx: 50 1C, 8 h No washing Vacuum filtration and overnight WC: 0.04%, AV: 0.25 mg Biodiesel purification is [38]
methanol (3 wt% to separation KOH/g, IV: 68 g I2/100 g, required to ensure
(1:18) oil mass) MEC: 92.5%, ν (40 1C): product compliance
4.59 mm2/s with EN 14214
regarding to Ca content

Waste frying
WC: 0.04%, AV: 0.28 mg
oil (WFO),
KOH/g, IV: 129 g I2/100 g,
methanol
MEC: 94.3%, ν (40 1C):
(1:18)
4.70 mm2/s

Mixture of WC: 0.04%, AV: 0.17 mg

pork lard KOH/g, IV: 117 g I2/100 g,
(22%) and MEC: 92.1%, ν (40 1C):
WFO (78%) 4.74 mm2/s
(1:18)

a
FGC – free glycerol content; AV – acid value, FP – flash point, CV – coking value, SA – sulfate ash, SC – sulfur content, CN – cetane number, MEC – methyl ester
content, and WC – water content.
b
BT – boiling temperature; RT – room temperature.
c
LHSV – liquid hourly space velocity.

leached calcium appears in both the ester and alcoholic phases.
Thereby, the problem is not the calcium concentration in the
alcoholic phase, but the large calcium concentration in the crude
biodiesel phase that must be reduced [10]. The calcium concentra-
tion in the final alcoholic phase of 420 ppm [33] or 534 ppm [10]
is still much lower than the metal ion concentration met in
homo- geneous reaction systems where all of the basic
catalyst is dissolved in the alcoholic phase. Hence, the
purification of crude glycerol obtained in the CaO-catalyzed
transesterification reaction is simpler and with less demanding
washing procedures [10].
The lixiviation of calcium ions to the ester phase also
occurs during the CaO-catalyzed transesterification [31]. Calcium
contents of
15.8 and 35.4 mg/kg of biodiesel were found by Dias et al. [38]
in biodiesels produced using calcium oxide and calcium
manganese oxide, respectively. Kouzu et al. [31] reported higher
calcium content of 139 ppm in the ester phase within 2 h of the
reaction. Thus, the calcium concentration in the crude biodiesel is
higher than the limit value allowed by the biodiesel standard
specifications (less than
5 ppm). For instance, the calcium concentration of 748 ppm
was reported for crude biodiesel obtained using calcium oxide
as the catalyst [10]. While washing with water or acidulated
water is efficient in removing the catalyst form crude biodiesel
obtained by
homogeneously alkali-catalyzed processes [50], these processes
are not suitable for decalcifying the crude biodiesel obtained by the
CaO- catalyzed transesterification [10]. The main difficulty is to
remove calcium soaps from crude biodiesel efficiently [10].
During the CaO-catalyzed methanolysis of sunflower oil, the
ester concentration reaches a maximum value rapidly (in 60 min),
and the calcium concentration increases smoothly, reaching nearly
500 ppm after 5 h [10]. Therefore, it is necessary to compromise on
the reaction time so that it provides as the highest ester
concentration with the lowest calcium soap concentration. Calcium
soaps are dissolved in biodiesel and can precipitate during
prolonged storage, reducing the calcium concentration two and a
half times [10]. This indicates that filtration of crude biodiesel
immediately after separating the alcoholic phase does not result in
total calcium removal, i.e. a period of ageing is needed for more
complete removal of calcium. Therefore, new efficient procedures
for decalcification of crude biodiesel are required that will resolve
the problem of calcium oxide leaching.
3.1. Crude biodiesel purification methods
According to the main mechanism, the purification methods
used to date for refining crude biodiesel can be classified in the
250 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516

Table 3
A review on purification of crude biodiesel produced by transesterification using catalysts other than calcium compounds.
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 251
516

Biodiesel production Biodiesel purification Biodiesel product Concluding remarks Ref.

a
properties
Reactants (oil: Catalyst Operating Method Operating conditions
alcohol molar ratio) conditions

Palm oil, methanol SrO (2 wt% to the Batch stirred reactor, Wet Washing (magnetic Washing significantly Washing of biodiesel [39]
(1:9) oil mass) 65 1C washing: stirrer; 1:1), separating improves the quality of slightly reduces its density,
distilled (48 h), centrifuging the biodiesels showing total AV, moisture and SA
water (3300 rpm, 30 min), good compliance with the content, while it increases
and
drying in an oven (70 1C, standard specifications. viscosity, FP, IV and SV. Sr:
1 h) 1.8 ppm
Batch ultrasonic-
assisted reactor,
45 min

Brown grease, ZnO/ZrO2 (0.8 g) 200 1C, autogenous Wet Washing and drying SC: 302 ppm The product meets the [40]
methanol pressure, 2 h washing: (24 h) ASTM diesel fuel sulfur
(15:10.55 water specification ( o 500
mL/mL) ppm)

Jatropha curcas oil, ρ (15 1C): 887.3

Na/SiO2 (3 wt%) Batch ultrasonic- Wet Washing and drying The product fulfills the [41]
methanol (1:9) 3
assisted reactor washing: over Na2SO4 kg/m , WC: 236 ppm, standard biodiesel
(200 W, 24 kHz), hot water AV: specifications
15 min 0.22 mg KOH/g, CN: 53,
FP: 134, TS: 100 ppm

Crude palm kernel 2

SO4/ZrO2 (1 wt%) 200 1C, 50 bars, 1 h Wet Washing (50 1C) and MEC: 95.8% [42]
oil, methanol (1:6)
washing: drying over Na2SO4
hot distilled (25 wt% to esters)
water
Crude coconut oil,
MEC: 93%
methanol (1:6)

Crude palm oil,

Zirconium Continuous up-flow Wet Washing and drying AF-1 biodiesel: MEC: 97.1, The AF-1 biodiesel meets [43]
category-1 animal functionalized fixed-bed (0.9 cm ID) washing: (40 1C, 0.5 bar, 12 h)
3
ρ (15 1C): 894 kg/m , ν the next standard
fat (AF-1), waste SBA-15, reactor, 209 1C, distilled
2
(40 1C): 5.9 mm /s, FP: specifications: MEC, ρ, FP,
cooking oil, pork agglomerated 70 bar, residence water, twice 160 1C, CN: 64, AV: CN, IV, Na þ K, Ca þ Mg, P,
lard, mixed (28 g) time 30 min 2.4 mg KOH/g, IV: 100.8 g methanol, MAG
animals fats, I2/100 g
methanol (1:50)
Zirconium Batch stirred reactor
functionalized (2000 rpm), 209 1C,
SBA-15, powder 6h
(12.45 wt. %)

Soybean, beef tallow, Sulfonated 64 1C,18 h Dry Evaporation, adsorption MEC: 94% Leaching of sulfonic groups [44]
ethanol (1:100) polystyrene washing: (2 wt%, 65 1C, 20 min, is very unlikely
(20 mol%) Magnesol stirring) and filtration

Yellow grease, MnO (28.1 g) Supercritical two- Distillation: Removal of methanol, The biodiesel product meets [45]
methanol (1:30) step continuous (after first water and glycerol the ASTM standard
process, 260 1C, step) specifications
9 MPa, contact time
25 min

Jatropha curcas oil, Cation – (Diaion Esterification Dry Adsorption (flow rate: MEC: 99.3%; ρ (15 1C): The biodiesel product fully [46]
3
methanol (1:1, PK208LH, 1.2 kg) followed by washing: 0.04–0299 L/h; best 879 kg/m , ν (40 1C): meets the standard
2
based on FFA) and anion – transesterification anion- flow rate: 0.233 L/h) 4.4 mm /s, FP: 139 1C, CN: specifications
(Diaion PA306S, and adsorption, exchange followed by methanol 53, AV: 0.05 mg KOH/g,
1.1 kg) three packed-bed resin evaporation under IV: 95.9 g I2/100 g
exchange resins reactors in series, vacuum
50 1C

a
FGC – free glycerol content; AV – acid value, IV – iodine value, FP – flash point, SA – sulfate ash, SC – sulfur content, CN – cetane number, TS – total sulfur, MEC –
methyl ester content and WC – water content.

following groups: (a) wet washing, (b) dry washing, (c) membrane
extraction, (d) precipitation, (e) complexation and (f) simultaneous
biodiesel synthesis and purification.
3.1.1. Wet washing
Wet washing is the most frequently used method of crude
biodiesel purification because the purified biodiesel obtained by
homogeneously alkali-catalyzed transesterification usually fulfills
the quality biodiesel standard specifications [8]. Water is mostly
used as the wet washing agent for the removal of water-soluble
impurities from crude biodiesel. Frequently, this method includes
washing with acidified water in the first step followed by
washing with pure water. To avoid the soap hydrolysis and
consequently increasing the acidity of the product, Huerga et al.
[51] applied neutral water in the first washing step, acidified
water in the second one and finally washing with pure water.
Wet washing method has also been used for purifying crude
biodiesel produced
by heterogeneous reaction emulsification occurs, sunflower oil cannot be specifications. Water washing
systems. However, the reducing the biodiesel yield. removed by water washing of biodiesel slightly reduced
purification efficiency of wet Contrary, at too low agitation or by exchange of the its den- sity, total acid value,
washing depends on the type speed the purification calcium soaps with aqueous as well as moisture and
of heterogeneous catalyst efficiency is not obvious. protons. sulfated ash contents, while it
applied to catalyze the Zhu et al. [13] observed Contrary to crude increased viscosity, flash
transesterification reaction. that warm water (45 1C, mass biodiesels from CaO- point, iodine and
On the one hand, water ratio of water to jatropha oil catalyzed processes, the saponification values [39]. The
washing processes are not ¼ 1:10) removed only 58.3% biodiesel obtained from residual catalyst (leached
suitable for purifying the of the calcium present in the transesterification using strontium oxide) was also
crude biodiesel from biodiesel containing 1.200 other heteroge- neous removed from the crude
heterogeneous processes mg/mL of calcium ions. The catalyst is in good compliance biodiesel successfully. After
using calcium- based catalysts remaining calcium with the standard water washing, the products
such as calcium oxide [10,13]. concentration of 0.50 mg/mL specifications after water- from jatropha oil [41],
This can be attrib- uted to the (correspond- ing based washing. According to animal fats [43] and yellow
formation of very stable Salamatinia et al. [39] and grease [45] fulfilled the
approximately to 560 mg/kg
Kim et al. [40], water washing
calcium soaps dissolved into of biodiesel) indicated that standard specifications. In
of crude biodiesel obtained
crude biodiesel [10]. On the the quality of the purified addition, the washed
from palm oil and brown
other hand, water washing product did not meet the biodiesel obtained from
grease using strontium oxide
methods are suitable for biodiesel standard brown grease met the ASTM
and ZnO/ZrO2, respec- tively
purifying the crude biodiesel specification (max 5 mg/kg). diesel fuel sulfur specification
after heterogeneous processes In addition, a large amount resulted in the purified [40].
using other catalysts [39–43]. of the purified biodiesel was product satisfying the
Residual glycerol and lost (about 30%), affecting standard
3
methanol are very effectively the overall process .
eliminated from crude economics negatively. 1
biodiesel by water washing According to Alba-Rubio et .
because of high solubility in al. [10], simple water washing 2
water. This method is also of crude biodiesel at room .
successful in removing temperature under stirring (1
residual sodium soaps h) did not result in the D
resulting from the cation-ion purified biodiesel satisfying r
exchange in the novel the calcium content y
washing methods [10,11]. specification as its level (362
Wet washing is performed ppm) was significantly higher w
by distilled water or than the specified limit. All a
acidulated water (aqueous other analyzed properties can s
h
mineral acid solution). Water be easily satisfied with a
i
is used either at room water rinsing step. For n
temperature or as hot [39– comparison, the biodiesel g
43]. Before the wet washing obtained by the homo- Dry washing is
step, the excess of alcohol is geneously alkali-catalyzed developed with the aim of
sometimes separated from transesterification of sunflower replacing water washing by
the ester by distilla- tion or oil met all standard environmentally friendly
evaporation. Since crude specifications after simple water-free purification
biodiesel and water are water washing. With respect methods. It removes the
immiscible, the mixture is to decalcification of crude impurities from crude
vigorously stirred to promote biodiesel, doubled water biodiesel using waterless
the contact between the washing, as well as simple washing agents: adsorbents
phases. After water washing, and double water washing, as and acid resins. These
the washed biodiesel is well as double water washing agents are used either as
dehydrated by convective followed by acid washing suspended in crude biodiesel
heat drying, vacuum flash were also useless because in a stirred vessel or as a
evaporation, hot air bubbling, the calcium concentration in fixed bed in the column
anhydrous salts (sodium the purified biodiesels (320, through which crude
sulfate) or other water 209 and 312 ppm, biodiesel flows. When used as
absorbents. The main respectively) was similar to suspended, the waterless
drawback of water washing that achieved by simple washing agent is collected
is the generation of water rinsing (362 ppm). The after treatment by filtration.
wastewater that should be ester content was not The basic mechan- isms of
adequately treated, thus reduced by double water removing impurities from
increasing the overall costs of washing. However, the ester crude biodiesel by dry
the biodiesel production content decreased from 98.0% washing are filtration,
process. Also, water washing to 96.5% with the additional adsorption, ion exchange and
appears inefficient in acid washing because of the glycerol/soap interac- tion
removing of the leached ester hydrolysis catalyzed by [52]. One or more
calcium oxide [10,13]. the acid. Therefore, very mechanisms can be dominant
Furthermore, the operability stable calcium soaps formed in removing impurities,
of water washing is poor. At during the CaO-catalyzed depending on the process
too high agitation speed transesterification of conditions and the proper-
ties of the waterless washing the homogeneously alkali-
agent. catalyzed transesterification
The waterless washing but more effective than the
agents cannot remove all the Magnesol treatment [53].
methanol and glycerol, which However, a higher biodiesel
should be removed as much as yield was achieved by water
possible during the washing (96%) than by
gravitational separation adsorption using a cation
stage [53]. In order to exchange resin (92%) because
increase the removal a part of biodiesel remained in
efficiency, the purified the column after purification
biodiesel is sometimes [62]. Strong acid resins have
washed with distilled water also been used in purifying
in a stirred tank [10]. The crude biodiesels produced
ester phase is then separated by CaO-catalyzed
from the aqueous phase by transesterification aimed at
decantation and outgassed. dissolved calcium removal
[10,12]. In this process of
decalcification, protons of the
3.1.2.1. Dry washing by
functional groups on the
adsorption. Only the
resin are exchanged by
commercial adsorbent
calcium ions of calcium soaps,
Magnesol (magnesium
glyceroxide, methoxide and
silicate) has been used to
hydroxide that are believed
date for refining of crude
to compose the leached
biodiesel obtained from
catalyst. Thus, the removal of
soybean oil and beef tallow
leached calcium is by
using ethanol and a
absorption into cation-
sulfonic resin as the
exchange resin with the help
catalyst [44]. The crude
of its basicity. According to
biodiesel was treated with
Kouzu and Hidaka [12], the
2 wt% Magnesol at 65 1C.
major driving force for the
After stirring for 20 min, the
calcium removal from
adsorbent was collected by
filtration.
Other types of adsorptive
materials, such as silica
materials [54–59], bleaching
earth [60], activated carbons
obtained from the spent tea
waste [55] and cheap
biosorbents [61], have been
used in refining crude
biodiesels produced by
homogeneously alkali-
catalyzed transesterification.
Doubtless, many of them are
note- worthy in terms of
possible application in the
purification of crude
biodiesels from
heterogeneous processes, and
the corresponding
investigations can be
expected in the near future.

3.1.2.2. Dry washing by

cation exchange. Various
cation-exchange resins are
applied for purifying crude
biodiesel differing in the type
of functional groups (sulfonic
or carboxylic), polymer
matrix (macro- reticular or
gelular) and counter-cation
(H þ or Na þ ). Cation-
exchange resins are equal
to water washing in
removing alkali soaps from
crude biodiesel obtained by
252 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 253
516
crude biodiesel is the ion- decreases, leading to the to reduce the calcium content useful in refining crude
exchange ability. Also, the accelerated internal mass in the crude biodiesel biodiesel with respect to the
strong acid resins are transfer. Calcium removal is obtained from waste cooking calcium content and their
effective in free glycerol also improved by adding oil. The polymeric beads removal efficiency was
removal [12,53]. However, methanol to the crude ranging between 0.5 mm better at the higher
contents of acylglycerols in biodiesel. Methanol reduces and 0.9 mm were used in operating temperature
crude biodiesel are hardly viscosity of the crude the original shape after because of accelerating the
reduced by treating with the biodiesel and enhances swelling with methanol. The internal mass transfer.
strong acid resin [12]. swelling of the polymer crude biodiesel passed Calcium removal efficiencies
through a 15 mm i.d. column
The use of strong acid matrix, both accelerating the of the tested resins were
packed with the swelled
resins can generate a new internal mass transfer. in the following order:
resin. In order to eliminate
problem, arising from the Moreover, methanol dissolves Amberlyst-15DRY ¼
water from the resin,
formation of FFAs through a part of the leached calcium Amberlite-IRC76 4 Amberlyst-
methanol flowed through the
the exchange of calcium ions and intensifies ion- 31WET 4 Amberlite-200CTNA.
column (50 mL/h) for 2 h. The
of calcium soaps by protons exchanging ability of the The higher removal efficiency
crude biodiesel was then
of the acid sites of the resin. resin by its proton- donating of the Amberlyst-15DRY resin
pumped into the column with
This reaction increases the activity. 1
compared to that of the
acid value of the treated Alba-Rubio et al. [10] used the LHSV of 2 h . The Amberlite-200CTNA resin was
biodiesel produced from a sulfonic resin (50% to the purification tests were attributed to the protonated
sunflower oil above the biodiesel mass) to refine the conducted at room form of the former resin.
standard limit [10]. crude biodiesel in a stirred temperature and 50 1C. All Beside the 100% calcium
However, it is possible that tank. The suspen- sion was tested resins were removal, the free glycerol
the protons liberated by the stirred for 2 h at room content was reduced below
resin in the cation exchange temperature and then filtered 0.01 wt%. The acid value of the
react with the anionic species to separate the ester phase purified biodiesel was
generated from the leached from the resin. Then, the 0.2 mg KOH/g, i.e. bellow the
catalyst, without affecting ester phase was washed with standard limit. The calcium
the acid value [12]. For distilled water (10 wt%) in a removal by cation-exchange
instance, calcium stirred tank for an hour at resin was significantly
diglyceroxide reacts with the room temperature. The ester promoted by adding metha-
liberated protons from the and aqueous phases were nol (20 vol%) to the crude
cation exchange forming dec- anted, and the former biodiesel. However, the free
glycerol as a by-product: was outgassed. The calcium glycerol content was not
CaðC3 H7 O3 Þ2 content was reduced from 748 reduced in the presence of
ppm in the crude biodiesel to methanol. The Amberlyste-
þ 2H SO3
less than 1 ppm in the 15DRY resin was
-2C3 H5
purified biodiesel. However, successfully regenerated by
ðOHÞ3 þ Ca
the acid value increased to rinsing with methanol and 1
2SO3
3.8 mg KOH/g, which was M hydrochloric acid flowed
The same type of reaction is above the limit value. FFAs through the cation-exchange
possible with calcium were not removed by water column. About 90% of the
methoxide and hydroxide washing. Also, the ester absorbed calcium was
composed of the leached content in the purified washed off the resin, which
catalyst. Indeed, the biodiesel was 97.4%, which then allowed the 100%
increased free glycerol was compatible with the calcium removal.
content was observed in presence of FFAs. Thus, Ferrero et al. [11] have
the purified biodiesel, rinsing with a strong acid recently purified the
compared to the treated one resin reduces the calcium methanol-free crude
[12]. level satisfactory but it biodiesels produced using the
Calcium removal by a generates another problem calcium glyceroxide catalyst
fixed-bed column depends on by increasing the acid value by dry washing with a
the polymer matrix of the above the specified limit. strong acid resin with
cation-exchange resin, the Kouzu et al. [31] removed sulfonic groups (Purolites
operating temperature and about 50% and more than PD206). The resin has cation-
the methanol addition [12]. 99% of the dissolved calcium exchange and dehydrat- ing
All these factors affect the from the crude soybean oil (desiccant) abilities. When
absorption of the leached biodiesel using carboxylated using the cation-exchange
calcium into the resin by and sulfonated resins, resin, crude biodiesel was
influencing the rate of respectively in a fixed-bed washed with 6 wt% or 50 wt%
internal mass transfer. The resin column operating at of resin (based on the
macro-reticular resin with liquid hourly space velocity biodiesel mass) under
large pores leads to the fast (LHSV) of 0.5 h
1
. In a later magnetic stirring (500 rpm)
internal mass transfer, study, the same research within
compared to the gelular group [12] used four resins 2 h at room temperature.
resin, which enhances (Amberlyst-15DRY, Amberlite- Both resin dosages were
accessibility of the leached 200CTNA, Amberlite-IRC76 ineffective regarding calcium
calcium to the inner active and Amberlyst-31WET) removal which was about 2
sites. With increasing differing in the polymer wt%.
operating temperature, matrix, the acidic func- tional
viscosity of crude biodiesel group and the counter-cation 3
 254 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516
. .
1
.
P
3
r
.
e
c
M i
e p
m i
b t
r a
a t
n i
e o
n
e This purification method
x is based on the use of
t precipitating agents to
r remove calcium ions from
a crude biodiesel. When the
c precipitating agent, such as
t oxalic acid or citric acid, is
i
added to crude biodiesel
o
n containing calcium ions, an
Because of their insoluble compound is formed
thermal, chemical and in the reaction between the
physical stability, ceramic agent and calcium ions while
membranes have high stirring the reaction mixture.
potential in the separation of The reactions of calcium ions
soaps and alcohols [63,64]. with oxalic and citric acid are
They are also considered presented by the following
effective for crude biodiesel stoichiometric equations,
purification by removing respectively:
glycerol [65] or by retaining Ca2 þ þ
the unreacted TAGs [63] or H 2 C2 O 4
soaps [64]. þ H2
Ferrero et al. [11] used O-
two monochannel ceramic CaC2 O4
membranes with a pore H2 O↓ þ
diameter of 0.05 and 0.1 μm, 2H þ
respectively to purify crude
biodiesel by forcing it to 3CaO
recirculate through the þ 2H3
membrane tube (2.11 C6 H 5
mL/min) at room O7
temperature. The crude -Ca3
biodiesel was cross-filtered ðC6 H5
by the ceramic membrane O7 Þ 2 ↓
tube with the flux through þ 6H
the membrane of 26.4 þ

L/m2/h. When the The precipitate can be

volumetric concentrated separated from the purified
factor reached 3, the biodiesel by filtration or
recirculation was stopped. centrifugation. It can be
Calcium removal efficiency of expected that successful
the two membranes was very precipitation will depend on
poor although the calcium concentration,
membrane with higher temperature, pH and rate of
porosity presented better precipitating agent addition.
result (30%) than that with Zhu et al. [13] tested two
lower porosity (22%). The precipitating agents, namely
result agreed with those of oxalic acid and citric acid, at
Wang et al. [64], who different agent-to-calcium
reported inefficient removal
molar ratios for
of the calcium soap by the
ceramic membrane.

3
.
1
.
4
V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 255
516
256 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516
purifying the crude biodiesel obtained from jatropha oil under the
same precipitation conditions (45 1C, 20 min and stirring). Oxalic
and citric acid showed the decalcification efficiency 92.2% and
96.2%, respectively at the agent-to-calcium molar ratio of 1:1,
when the purified biodiesel yield was 90.7% and 95.5%, respec-
tively. The calcification efficiency was reduced by half with
halving the dose of the precipitating agent. However, when the
dose of water was reduced, the decalcification efficiency did not
change obviously. Citric acid has additional advantages over
oxalic acid. Because of agglomeration, citric acid does not
disperse easily in crude biodiesel, does not form emulsion after
adding with water and can be readily separated from biodiesel.
Contrary, oxalic acid disperses easily in crude biodiesel, resulting
in stable emulsion formation that makes the phase separation
difficult.
3.1.5. Ion exchange and precipitation
Alba-Rubio et al. [10] have recently introduced a new method
to eliminate calcium from crude biodiesel. They washed the crude
biodiesel with a suspension of sodium carbonate in methanol at
the boiling temperature. The idea is to exchange calcium ions
from calcium soaps present in the crude biodiesel with sodium
ions from the carbonate and to form insoluble calcium
carbonate
subsequently:
Ca2 þ þ Na2 CO3 -CaCO3 ↓ þ 2Na
þ
Calcium soaps have a more prevalent non-polar end, being less
water soluble and more dissolvable in biodiesel, which increases
separation difficulty. After exchanging calcium by sodium, sodium
soaps might be more easily removed using both wet and dry
washing [34,64].
Methanol is used because it is a reagent in the transesterifica-
tion reaction that prevents the ester hydrolysis. Since sodium
carbonate is slightly soluble in methanol [66], it is solid and can
easily be separated by filtration. Calcium carbonate formed is also
removed by filtration in the same step with sodium carbonate. In
addition, sodium carbonate is an inexpensive chemical with a low
impact on the environment. It is important that the sodium
concentration in the alcoholic phase because of sodium carbonate
dissolution is lower than that observed when sodium hydroxide is
used as a catalyst.
Alba-Rubio et al. [10] treated the crude biodiesel produced
using calcium oxide with sodium carbonate suspended in metha-
nol in a stirred vessel (1000 rpm) at 65 1C for 4 h. Anhydrous
sodium carbonate was suspended in methanol (1, 5 or 10 wt% to
the biodiesel mass). The biodiesel was separated by filtration and
was washed with distilled water (10 wt% to the biodiesel mass)
under stirring (500 rpm) at room temperature for an hour. The
two phases were decanted, and the ester phase was outgassed.
Washing the crude biodiesel with 5 wt% of sodium carbonate
resulted in the purified biodiesel that complied the standard
specifications regarding ester, calcium and sodium contents. When
a higher amount of sodium carbonate (10 wt%) was applied, the
calcium content was reduced below the specified limit but the
sodium content in the ester phase was above the standard limit.
When 1 wt% of sodium carbonate was employed, significant
calcium and sodium concentration remained in the ester phase,
both above the specified limits, and the ester content (92.8 wt%)
was below the standard limit.
Ferrero et al. [11] employed the method of Alba-Rubio and
coworkers [10] as a pretreatment stage followed by the
additional refining stage using the acid resin, ceramic
membrane or water washing. In the pretreatment stage, the
crude biodiesel was treated with methanol (biodiesel:methanol
mass ratio of 2) con- taining anhydrous sodium carbonate (5 wt%
to the biodiesel mass) at 60 1C for 5 h under vigorous magnetic
stirring (1200 rpm). In
this stage, calcium was replaced by sodium, consequently produ-
cing sodium soaps. After removing the solid phase (formed
calcium carbonate and remained sodium carbonate) by filtration,
methanol was separated from the purified biodiesel by gravita-
tional settling. Afterwards, the ester phase was treated at room
temperature by the resin (6 wt%) under stirring (500 rpm, 2 h), the
membrane (0.1 μm pore size) or the water washing in order to
remove sodium soaps. The pretreatment and the additional water
or water-free washing were effective in removing calcium and
sodium, respectively.
3.1.6. Complexation
This method for purifying crude biodiesel uses a complexing
agent to remove calcium ions. So far, only ethylenediaminetetraa-
cetic acid (EDTA) has been used as the complexing agent for
decalcifying crude biodiesel [13]. EDTA forms a complex with
calcium ions in a 1:1 agent-to-calcium molar ratio:
2 2
Ca2 þ þ ½H2 Y ⇄½CaY þ 2H þ
where ½H2 Y 2 is the tetravalent anion of the disodium salt of
EDTA (Fig. 2a). Five membered heterocyclic rings are formed with
EDTA, which are highly stable (Fig. 2b). Since the actual complex-
4
ing species is ½Y , the calcium–EDTA complex will be formed
more efficiently and be more stable in basic solution. Stability of
the calcium–EDTA complex is pH dependent: lower the pH, lesser
the stability of the complex. EDTA is slightly soluble in water,
which limits its use as the decalcifying agent [13]. It is also
hazardous for the environment.
Zhu et al. [13] removed calcium from crude biodiesel obtained
from raw jatropha oil using EDTA at the agent-to-calcium molar
ratio of 1:1. When the aqueous solution of EDTA is added to crude
biodiesel containing calcium ions, the reaction between the agent
and calcium ions occurs while stirring the reaction mixture.
Water-soluble complexes are formed between EDTA and calcium
ions and, although the calcium remains in solution, it fails to give
ionic reactions. The calcium–EDTA complex can be separated from
the purified biodiesel by centrifugation. The purified biodiesel will
be the upper clear liquid, while the calcium–EDTA complex will
be in the lower aqueous layer. Hence, the calcium removal from
crude biodiesel occurs by the extraction through
complexation. The complexing agent showed the decalcification
efficiency of 83.9%, while the purified biodiesel yield was 92.3%.
3.1.7. Simultaneous biodiesel synthesis and purification
A possible improvement of the overall biodiesel production
process is to conduct both biodiesel synthesis and purification
simultaneously. So far, two such combined processes have been
investigated. They include either adsorption onto anion-exchange
resin or ion-exchange followed by precipitation during the ester
synthesis.
Shibasaki-Kitakawa et al. [46] have developed simultaneous
bench-scale production and purification of biodiesel from jatropha
oil, having high acid value, in reactors packed with cation- and
anion-exchange resins at 50 1C. The commercial cation-exchange
resin (Diaion PK208LH) was loaded in the first reactor and used to
catalyze the FFA esterification, while the anion-exchange resin
(Diaion PA306S) in the second and third columns was used as a
catalyst for TAG transesterification and as an adsorbent for
biodiesel purification. The time period with the unchanged ester
concentration and with no TAG detected in the effluent from the
third column decreased with the increase of the flow rate in the
range from 0.04 L/h to 0.233 L/h. The biodiesel produced at the
flow rate of 0.233 L/h contained TAGs below the standard limit.
Passing through the anion-exchange resin, the glycerol, water,
methanol and fatty acid residue were adsorbed on it. The biodiesel
254 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
254 516

Table 4
a
Comparison of precipitation and complexation with water washing.
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516
Fig. 2. Structures of the disodium salt of EDTA (a) and the calcium–EDTA
complex (b).
product contained residual methanol (about 1%) above the stan-
dard limit, but it was evaporated under reduced pressure. The
obtained biodiesel fulfilled the limits of EN 14214 and ASTM
D6751 biodiesel quality standards.
Alba-Rubio et al. [10] have recently demonstrated that the
synthesis of biodiesel and the removal of calcium and sodium to
levels below the standard limits (5 ppm) can simultaneously be
achieved if sodium carbonate is initially added to the CaO–
methanol–sunflower oil mixture employed in the CaO-catalyzed
methanolysis of sunflower oil. The process was conducted at the
methanol-to-oil molar ratio of 30:1 and the temperature of 60 1C
in a stirred reactor for 5 h. The amount of sodium carbonate was
5 wt% (based to the oil mass). The large initial amount of methanol
was used to ensure methanol for both reaction and washing. After
cooling to room temperature, the final reaction mixture was
filtered to separate the solids (calcium oxide, sodium carbonate
and calcium carbonate) from the liquid phases (ester and alcoholic
phases), which were subsequently separated. The ester phase was
washed with distilled water (10 wt%) in a stirred vessel (500
rpm) at 25 1C for an hour. After decantation, the ester phase
was outgassed. The biodiesel product contained both calcium
and sodium below the specified levels ( o 5 ppm) and esters
(96.9 wt%) above the standard limit.
Ren et al. [67] used a continuous reactor packed with the D261
anion exchange resin as a heterogeneous catalyst for the biodiesel
synthesis. Under the optimum reaction conditions (temperature
50 1C; residence time 56 min; n-hexane/soybean oil weight rate of
0.5; methanol/soybean oil molar ratio of 9:1 and feed flow rate of
1.2 ml/min), the conversion of 95.2% was achieved. Moreover, the
authors demonstrated the complete separation of glycerol from
biodiesel due to its adsorption on the resin.
3.2. Comparison of various crude biodiesel purification methods
The methods for the purification of crude biodiesel from
heterogeneously catalyzed processes have been compared only
in a few studies [10,11,13]. The main results of the comparison
are presented in Tables 4–6. These studies compared dry
washing, membrane extraction, complexation, precipitation,
ion-exchan- ging precipitation and simultaneously reaction and
ion-exchan- ging-caused precipitation with water washing.
Since calcium- based catalysts (calcium oxide and calcium
diglyceroxide) are used in the transesterification reactions, the
researchers focus their attention to the calcification of crude
biodiesel. The unified conclusion is that the wet washing
methods are unsuitable for decalcifying crude biodiesel.
However, better results in refining of crude biodiesel are obtained
by including water washing after the pre-purification step
consisting of dry washing with a resin,
255
255
Purification method Ester yield (wt Calcium Decalcification efficiency
b
%) (μg/mL) (%)
Simple water washing 69.45 500.00 58.33
Precipitation
Oxalic acid 90.65 93.83 92.18
Citric acid 95.45 45.20 96.23
Complexation with 92.31 193.75 83.85
EDTA
a
Based on Zhu et al. [13].
b
Calcium content in crude biodiesel: 1.2 mg/mL.
membrane extraction or ion-exchange-based precipitation.
Table 7 presents major advantages and disadvantages of the
purification methods employed for refining crude biodiesel pro-
duced by heterogeneously catalyzed transesterification processes.
Zhu et al. [13] compared warm water washing, complexation
with EDTA and precipitation with citric or oxalic acid in decalcify-
ing the crude biodiesel obtained from jatropha oil in the CaO-
catalyzed methanolysis (Table 4). Of the three methods tested,
the precipitation with citric acid was the best one, ensuring
the highest decalcification efficiency and the lowest biodiesel
loss. The purified biodiesel met most of the biodiesel standard
speci- fication, except for the slightly higher viscosity. The second
precipitating agent, oxalic acid, was also more efficient in decalci-
fying the crude biodiesel than the complexing agent (EDTA) and
warm water. The water washing method is considered not to be
suitable for decalcifying the crude biodiesel. Contrary, the pre-
cipitation with citric acid is simple, repeatable and promising for
potential use for the decalcification of crude biodiesel [13].
Alba-Rubio et al. [10] tested several procedures for removing
calcium from crude biodiesel prepared using calcium oxide as a
heterogeneous catalyst: wet washing (water or acidulated water),
dry washing (sulfonic resin) followed by water washing, treatment
with a boiling methanol–sodium carbonate mixture followed by a
water washing step and in situ treatment with sodium carbonate
during the methanolysis. The efficiencies of these methods are
compared in Table 5. Washing with water or water acidulated
with hydrochloric acid did not remove calcium ions below the
level specified by the biodiesel standard. The combination of
dry washing with sulfonic acid and water washing reduced
the calcium content efficiently, but the acid value of the
purified biodiesel did not meet the biodiesel standard
specification. Wash- ing of crude biodiesel with the boiling
methanol–sodium carbo- nate mixture and water resulted in the
effective calcium removal below the level specified by
biodiesel quality regulations ( o 5 ppm). The optimum amount
of sodium carbonate needed to achieve good removal of calcium
from the crude biodiesel was found to be 5 wt% (to the biodiesel
mass). Furthermore, when the biodiesel synthesis and the
calcium removal took part simulta- neously in the presence
of sodium carbonate, the biodiesel product met the standard
specifications for ester, calcium and sodium contents. The
drawback of the new procedure is the consumption of sodium
carbonate through exchange and dissolu- tion in the alcoholic
mixture, totally about 0.21 g per batch [10]. However, it offers
several advantages over the use of homoge- neous catalysts.
The combination of calcium oxide and sodium carbonate can be
recovered by filtration or centrifugation and reused for several
batches. Moreover, the dissolution of sodium carbonate does not
produce corrosive species. However, further investigations are
needed to optimize initial amounts of methanol and sodium
carbonate required for the simultaneous removal of calcium from
the ester phase.
Table 5
a,b
Comparison of efficiency of various purification methods.

Method Ester content Calcium Acid value (mg KOH/ Sodium

(wt%) (ppm) g) (ppm)

Simple water washing 98.0 362 0.06 –

Double water washing 98.0 320 – –
Double water washing followed by acid washing 97.3 209 – –
Water washing followed by acid washing 96.5 312 – –
Dry washing followed by water washing 97.4 o1 3.8 –
Washing with sodium carbonate suspended in methanol followed by water washing:
1 wt% 92.8 390 – 140
5 wt% 96.7 o5 – 0
10 wt% 98.3 o5 – 12
Simultaneous transesterification and washing with sodium carbonate followed by additional water 96.9 o3 o1
washing
Limit of EN 14214 Min. 96.5 Max. 5 Max. 0.5 Max. 5

a
Based on Alba-Rubio et al. [10].
b
Calcium content of the crude biodiesel: 748 ppm.

Table 6
Contribution of pretreatment with sodium carbonate suspended in boiling methanol (simultaneous ion-exchange and precipitation) to purification by simple water washing,
a,b
dry washing and membrane extraction.

Feedstock Method Ester content (wt%) Calcium Sodium Water

(ppm) (ppm) (ppm)

Soybean oil Dry washing using resin (6 wt.%) 384 – –

Membrane extraction
0.05 mm pore size 305 – –
0.1 mm pore size 270 – –
Pretreatment with sodium carbonate suspended in boiling methanol followed by
Simple water washing 98.0 2.8 ND 125
Dry washing using resin 95.7 2.3 ND 367
Membrane extraction 94.5 1.9 ND 458

Waste frying oil Pretreatment with sodium carbonate suspended in boiling methanol followed by
Simple water washing 95.4 4.7 ND 213
Dry washing using resin 95.8 3.4 ND 319
Membrane extraction 95.7 3.2 ND 331
Limit of EN 14214 Min. 96.5 Max. 5 Max. 5 Max. 500

a
Based on Ferrero et al. [11].
b
Soybean oil crude biodiesel: ester content 91.2% and calcium content 393 ppm; waste frying oil crude biodiesel: ester content 90.2% and calcium content 372 ppm.
 Ferrero et al. [11] have process for purifying the
recently produced biodiesel crude biodiesel obtained by
from soybean oil or waste the CaO- catalyzed
frying oil and methanol in transesterification with
the reaction catalyzed by intermediate methanol
calcium diglyceroxide. After distilla- tion. The first step is
the reaction was com- pleted, decalcification of the crude
the catalyst was collected by biodiesel in the presence of
filtration and the ester phase methanol and the second
was separated from the step is absorption of free
alcoholic phase by glycerol from decalcified,
gravitational settling. The methanol-free biodiesel into
remaining methanol was the resin. This water-free
removed from the ester process seems to be
phase by vacuum promising for practical use of
evaporation. Then, various the CaO-catalyzed
purification methods were transesterification producing
employed: (a) dry biodiesel matching the
washing using a cation- quality standard
exchange resin, (b) specifications.
membrane extraction and
(c) the treatment with 3.3. Comparison of crude
sodium carbonate suspended biodiesel purification methods
in boiling methanol according regarding oily feedstocks
to the method of Alba-Rubio
et al. [10] followed by the A few studies can be
resin, the ceramic utilized for comparing the
membrane or the simple final biodiesel product
water washing. The purification methods
purification efficien- cies of regarding oily feedstocks
these methods are employed in heterogeneously
compared in Table 6. Their catalyzed biodiesel production
results showed that the dry processes, as it can easily be
washing using resin and the concluded from Tables 2
membrane extraction alone and 3. Crude biodiesels
were not efficient in employed in purification
purifying the crude biodie- studies originate from
sels as required by the quality vegetable oils (soybean,
standard specification. sunflower, palm, coconut and
Contrary, the pretreatment jatropha oils), animal fats
with sodium carbonate (pork lard and category-1
suspended in boiling metha- animal fat) and waste
nol and additional water or frying oil. However, no
water-free washing were systematic study on the
effective in removing calcium combined effect of the
and sodium, respectively. purification method and the
However, the decalci- fication type of feedstock on the fuel
efficiency appears to be proper- ties of the final
dependent on the type of product has been carried out
oily feedstock since the to date. Only a study
calcium content of the compares the purification
purified waste frying oil efficiency of crude biodiesels
biodiesel was higher than obtained from sunflower and
that of the soybean oil. The waste cooking oils by dry
purified biodiesels fulfilled all washing, membrane
the quality standard extraction and ion exchange-
specifications since the ester based precipitation with
content (somewhat lower sodium carbonate followed
than the limit value) agreed by simple water washing,
with an acceptable margin of dry washing or membrane
error. extraction [11]. While dry
Bearing in the mind the washing and membrane
difficulty of simultaneous
removal of free glycerol and
calcium, Kouzu and Hidaka
[12] suggest a two-step
Table 7
Advantages and disadvantages of purification methods employed for refining crude biodiesel produced by heterogeneously catalyzed transesterification processes.
 Purification Advantage
method
Wet washing Simplicity and low cost
Effective removal of residual glycerol and methanol
Effective removal of sodium soaps formed by cation-ion exchange
Suitable for purifying the crude biodiesel obtained by using some
heterogeneous catalysts, such as SrO, ZnO/ZrO2, Zr-SBA-15 and
Na/SiO2
Dry washing Simpler and less hard than wet washing
Require less space
Low energy consumption
Generate less waste/wastewater
Possibility for continuous process application
Reduce overall biodiesel production time
No problems with moisture presence in the product
Can be conducted during transesterification reaction
Some resins can be regenerated
Membrane High potential in separating sodium soaps and alcohols
extraction Use of reduced amount of water used, so little wastewater is generated
Environmentally friendly
Operational simplicity and flexibility
Relatively high selectivity and permeability
Low energy requirements
Easy control and scale-up
Precipitation Calcium ions are removed as a precipitate
High decalcification efficiency of citric acid ( 4 96%)
High yield of purified biodiesel
Reduced amount of water used in the process
Simple removal of precipitate by filtration
Precipitate of calcium citrate may be converted back to citric acid for reusing
and to calcium sulfate
Ion exchange Efficient calcium removal
and Low-cost washing agent (sodium carbonate)
precipitation
Simple removal of the unreacted washing agent and the formed precipitate by Appropriate treatment of wastewater and precipitate is needed
filtration
Sodium soaps are easily removed using wet and dry washing
Can occur during transesterification reaction
After water washing, the biodiesel product may satisfy the quality standard
specifications
Complexation Calcium forms a complex with EDTA soluble in water
Calcium remains in solution without ionic reactions
Calcium–EDTA complex can easily be separated by decanting
extraction were ineffective in calcium removal, all two-step
processes removed the leached calcium effectively from both
crude biodiesels (Tables 2 and 6). Somewhat better results regard-
ing the calcium removal were achieved with the soybean oil
biodiesel than with the waste cooking oil biodiesel.
The quality of biodiesel purified by simple water washing
seems to depend on the quality of raw material used in the
biodiesel production. Iglesias et al. [43] purified the crude
biodie- sels obtained from low-grade feedstocks, such as
category-1 animal fat (AF-1) and the mixtures of AF-1 and
waste frying oil (10 and 30 wt% ), using washing with ultra-pure
water (Table 3). The AF-1 biodiesel met more quality EN 14214
standard specifica- tions than the purified biodiesels obtained
from the mixtures of
Disadvantage
Use of relatively large amount of water
Time consuming process
High energy consumption due to subsequent biodiesel drying
Generation of wastewater that requires appropriate treatment
Not suitable for purifying the crude biodiesel obtained by
methanolysis catalyzed by calcium oxide due to formation of stable
emulsion of calcium soaps
Reduction of biodiesel yield when aqueous acid solutions are used
because of the ester hydrolysis
Purified biodiesels may not fulfill the biodiesel quality standards
All methanol and glycerol residues cannot be removed
Possibility of increasing the acid value of the purified biodiesel when
strong acid resins are used
Use of strong acid resin hardly reduces acylglycerols contents in crude
biodiesel
Effective removal of calcium ions
Increase of free glycerol content if calcium diglyceroxide, methoxide
or hydroxide are present in crude biodiesel
Disposal of spent ion-exchange resins
Inefficient removal of calcium soap
Membrane must be cleaned
Decrease of throughput by possible contamination
Increase of biodiesel production cost
Slightly higher viscosity of the purified biodiesel than the standard
limit
Successful precipitation depends on operating conditions
Further studies are needed to optimize the precipitation conditions
High initial methanol-to-oil molar ration
Additional water or water-free washing step is needed to remove
sodium soaps formed by ion exchange
Further studies are needed to optimize the operating conditions
Preparation of aqueous EDTA solution with difficulty
Medium decalcification efficiency
Further studies are needed to optimize the reaction conditions
EDTA is a hazardous substance
AF-1 and waste frying oil. The former biodiesel had lower density,
viscosity, acid value, as well as diacylglycerol and TAG contents
than the latter one. However, methyl ester content, flash point,
iodine value, monoacylglycerols content and free glycerol content
increased with increasing the fraction of waste frying oil in the
mixture with AF-1. Jitputti et al. [42] applied the water washing
method for the purification of crude biodiesels obtained from
crude palm kernel and coconut oil with methanol. The higher
methyl ester content (95.8 wt%) was achieved in the case of crude
palm oil.
Table 8 presents the physico-chemical properties of biodiesels
obtained from various raw materials together with the European
standard specification limits. These properties are of decisive
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 11
516

Table 8
Physico-chemical properties of biodiesels arising from different purification methods.
22 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–
516

Feedstock 0% AF- 10% AF- 30% AF- Jatropha Pork lard Waste frying Mixture of PL (22%) Sunflower Jatropha Jatropha EN14214
1
a
1
b
1
b curcas oil (PL) oil (WFO) and WFO (78%) oil curcas oil curcas oil limits min/
max

Catalyst Zirconium functionalized Na/SiO2 CaMnOx CaO CaO Ion-

SBA-15 (agglomerated) exchange
resins
Method of purification Water Water No Water Precipitation Dry washing
washing washing washing washing
c
step
Property, unit
Methyl esters (%) 97.1 95.2 96.2 92.5 94.3 92.1 98.0 99.3 96.5 min
d
Density at 15 1C (kg/ 894 891 886 887.3 883 878.4 879 860/900
m3)
d
Viscosity at 40 1C 5.9 5.7 5.2 4.59 4.70 4.74 4.41 7.32 4.357 3.50/5.00
(mm2/s)
Flash point (1C) 160 167 172 134 174 4 170 139.3 101 min
Sulfur (mg/kg) 36 o5 10 max
Cetane number 54 - - 53 56.1 53.2 51 min
Sulfated ash (%) 0.005 o 0.005 o 0.005 0.02 max
Water (mg/kg) 236 400 400 400 200 280 500 max
Copper strip 1 1 1 1 Class 1 min
corrosion (3 h at
50 1C), rating
Oxidation stability at 5 1.48 6.0 min
110 1C (h)
Acid value (mg KOH/ 2.4 1.8 1.0 0.22 0.25 0.28 0.17 0.06 0.005 0.5
g)
Iodine value (g I2/ 100.8 86 91 68 129 117 95.9 120
100 g)
Methanol (%) 0.02 0.02 0.01 0.09 0.20 max
Monoacylglycerols (%) 0.55 0.84 0.96 o 0.08 0.03 0.80 max
Diacylglycerols (%) 2.11 2.39 1.75 o 0.06 0.015 0.20 max
Triacylglycerols (%) 0.21 1.58 1.08 o 0.06 0.13 0.20 max
Free glycerol (%) 0.02 0.01 0.02 0.005 0.02 max
Total glycerol (%) 0.39 0.49 0.40 0.03 0.25 max
Group I metals 1.8 1.5 2.1 o2 5.0 max
(Na þ K) (mg/kg)
Group II metals 0.4 1.0 1.0 362 o2 5.0 max
(Ca þ Mg) (mg/kg)
Phosphorus (mg/kg) 1.7 0.2 0.3 o1 4.0 max
CFPP (1C) 0 7 13 5 1.25 Not
specified
Coking value (%) o 0.05 Not
specified
Reference [43] [41] [38] [10] [13] [46]

a
Category-1 animal fat.
b
AF-1/waste cooking oil mixtures (10 i.e 30 wt% in AF-1).
c
Filtration followed by gravitational separation.
d
At 20 1C

importance for using the purified product from heterogeneous
reaction processes as an alternative diesel fuel in the engines with
internal combustion. It is evident that there are not many data of
this type in the literature, especially regarding the method of
product purification. The biodiesel purification methods used in
the mentioned studies are only water washing, dry washing and
precipitation.
Several significant conclusions can be drawn from the limited
number of studies related to the characterization of biodiesels
produced by heterogeneously-catalyzed transesterification reac-
tions. First of all, the biodiesels obtained from pork lard, waste
frying oil or their mixture that are not purified further after
separation of the solid catalyst (CaMnOx) and the glycerol phase
fulfill the limited number of the analyzed biodiesel quality
criteria, except the methyl ester content which was somewhat
lower than the limit value [38]. In addition, biodiesels
refined by water washing and precipitation meet most of the
quality standard specifications. The sunflower oil biodiesel does
not satisfy only
the prescribed calcium content, which is attributed to the use of
calcium oxide as catalyst, while the jatropha oil biodiesel fulfills all
standard regulations, except oxidation stability [41]. Furthermore,
density values of all biodiesels purified by water washing and
precipitation are between 860 and 900 kg/m3, complying the
EN14214 standard limits. However, the precipitation results in
the viscosity higher than that achieved by water washing and the
standard limit. Flash points of biodiesels were significantly higher
than that of standard limit, independently of purification methods.
Iglesias et al. [43] reported biodiesel flash points above 160 1C,
discarding the presence of residual alcohol, also confirmed by the
direct measurement of methanol content ( o 0.2 wt%). Biodiesels
presented in Table 8 have the acid value below the maximum
standard limit, except the one that is obtained from animal fats or
the mixtures of animal fats and waste cooking oil. Independent of
the purification method applied, the purified biodiesels have the
iodine value lower than the standard limit. Water washing is also
effective in removing the group I metals (Na þ K).
3.4. Environmental aspects of purification, to allow long- resins Purolites PD206 and disposed of as a non-
crude biodiesel purification term use of catalyst and Thermax T- hazardous material according
methods development of continuous 45 BD [70] notify that their to local regulations.
process. Tang et al. [69] ability to absorb glycerol Incineration and land filling
Compared to modified calcium oxide by can be regenerated by are two options that are
homogeneous catalysis, dipping in methanol washing, which often adopted.
heterogeneous biodiesel bromooctane/hexane solution cannot recover the ionic Shibasaki-Kitakawa et al.
production processes are that bound bromooctane to capacity. If the resin [46] proposed method for the
considered as the catalyst particles. The exhausts ionically, after regen- eration of anion-
environmentally friendly modified catalyst maintained several methanol washes, the exchange resin (Diaion
since the problems related to activity even for 15 cycles. resin should be returned to PA306S) activity used in the
biodiesel purification are The leached calcium manufacturer for tradi- tional bench-scale process for
reduced. Heterogeneous concentrations into the ionic regeneration to restore simultaneous biodiesel
catalysts can easily be reaction medium were 26 the ability of removing synthesis and purification. The
separated from the reaction ppm and catalyst traces and soaps. regeneration of the Diaion
mixture by filtration, and 10 ppm after first and second Once resins are ready for PA306S resin includes
thus the purification of the cycles, respectively [69], disposal, it should be washing with methanol to
products is much simplified which were significantly remove glycerol and water
and does not require a large lower than those reported from the resins, treatment
amount of water: hence, the for unmodified calcium oxide with acetic acid solution in
need for wastewater [10,31]. methanol to displace the
treatment alleviates in According to the best of fatty acid ion in the resin
hetero- geneous biodiesel authors' knowledge there is with the acetic acid ion,
production processes [68]. no data about wastewater which further was displaced
However, different types of treatment generated during with the hydroxyl ion by
wastes are generated during water washing of crude using NaOH aqueous
biodiesel production via biodiesels obtained in solution, washing with
heterogeneously catalyzed heterogeneously catalyzed deionized water and finally
processes, which can processes. The comprehensive the resin was swelled by
generally be classified into review of wastewater feeding the column with
two groups: treatment in the bio- diesel methanol. The proposed
production by regeneration method
– wastes originated from homogeneously alkali- completely recovered the
biodiesel product catalyzed alcoholysis has resin activity and it was
separation and pur- recently been reported by successfully used more than
ification such as used our group [23]. Almost the 50 times.
catalyst, wastewater, spent same methods, modified Ren et al. [67] suggested
dry washing agents depending on the type of ions regenerating the D261 anion
(adsorptive materials, that are leached from the exchange resin in-situ by a
cation-exchange resins), catalyst into the biodiesel three steep process
ceramic membranes, and alcohol phases, can be including flushing by
insoluble compounds used for treating the methanol for removing
formed by precipitation or wastewater generated by glycerol, ester and less
ion exchange and the heterogeneous biodiesel triglycerides, washing with a
aqueous phase obtained by production processes. When solution of KOH in methanol
complexation of calcium the solid catalyst is used as to activate the resin and
ions with EDTA and suspended in the stirred finally washing with
– wastes originated during reactor, the additional methanol to pH 7. After
catalyst reactivation in separation stage is the regeneration, the ion
their repeated use (organic removal of solid particles exchange capacity value
solvents, alcohols, water). from the reaction mixture. was equal to the fresh
More- over, if leaching of activate resin.
Previous researches of solid catalyst occurs, the ions The ceramic membranes
heterogeneously catalyzed generated must be removed are increasingly used in the
alcoholysis have been aimed from the crude biodiesel. biodiesel separation and
at developing a catalyst with Dry washing agents are purification processes [71]
a high catalytic activity and used either as a fixed bed because of their numer- ous
optimizing the reaction or as suspended in the advantages over polymeric
conditions in order to obtain crude biodiesel. In the latter membranes, such as high
the high ester yield in case, suspended particles of perme- ability rate and high
economically suitable the dry washing agent are chemical, mechanical and
process. However, there is no separated from the treated thermal stability [72]. They
reported study on handling biodiesel by filtration. To can be used for almost one
of used catalysts. Some date, there are only limited year when the alkali solid
researchers have made data about the spent dry base catalysts are used for
attempts to improve catalytic washing agent treatment. The biodiesel production [73].
stability of the used catalyst spent adsorbent can be According to Cao et al. [74],
in order to reduce its disposed of to landfill or other the ceramic carbon
leaching and consequently uses might be invented [53]. membrane can be cleaned
facilitate biodiesel The suppliers of ion-exchange more proficiently even
unrefined oily feedstocks are 4
used for biodiesel production. .
However, there are no
available data about the C
membrane cleaning o
methods. It can be n
expected that it will include c
washing with appropriate l
u
solvent to remove unreacted
s
TAGs, catalyst, glycerol, soap i
and even methanol collected o
by the membrane [71]. n
The use of precipitating
agents, such as citric acid, or The ester product of
by ion- exchanging heterogeneously-catalyzed
compounds, such as Na2CO3 transesterifica- tion of oily
for biodiesel purification leads feedstocks should be purified
to the formation of insoluble after collecting the solid
compounds which are simply
removed by filtration. There
is no reported investigation
on the treatment and uses of
obtained calcium salts.
Calcium citrate may be
converted to citric acid and
calcium sulfate using dilute
sulfuric acid [75], while
calcium carbonate can be
utilized in the construc- tion
industry either as a building
material, limestone aggregate
for road building or an
ingredient of cement.
The decalcification of
crude biodiesel with
chelating agent EDTA leads
to the formation of
aqueous phase containing
the calcium–EDTA complex,
which requires appropriate
treatment because of its
toxicological effects on human
health upon exposure to the
substance. A relevant
identified use of calcium–
EDTA complex is as fertilizer.
The repeated use of
catalyst can be performed
without or after its treatment
that commonly involves
washing by organic sol-
vents, such as hexane [69],
petroleum ether [76],
methanol [77], mixture of
methanol and hexane [78] or
a mixture of hot water and
acetone [79]. The mentioned
methods for regeneration of
catalyst activity generate the
hazardous waste filtrate after
catalyst separation. The
filtrate could be subjected to
evaporation or distillation in
order to recover the washing
agent, which allows its use in
the next cycle of the catalyst
treatment and minimizes the
waste.
V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500– 515
516
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