Renewable and Sustainable Energy Reviews 49 (2015) 500–516

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/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

art ic l e i nf o a b s t r a c t

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
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 type
Dry washing
of raw materials used in biodiesel production. Furthermore, advantages and disadvantages of the crude
Ion-exchange
biodiesel purification methods are emphasized. Finally, environmental aspects of crude biodiesel
Membrane extraction
Precipitation 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 16 242 859. Biodiesel has gained world-wide attention in recent years as an
E-mail address: veljkovicvb@yahoo.com (V.B. Veljković). alternative fuel that has a number of favorable properties such as

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) 500–516
Table 1
Comparison of homogeneous and heterogeneous catalysis for biodiesel production.a
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
501
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
502 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
surprising that the majority of publications deals with the pur-
ification of crude biodiesel obtained in homogeneous catalytic
processes. Surveys on the methods for purification of crude
biodiesel produced by alkali-transesterification of various feed-
stocks can be found in the recent reviews [8,14,15].
The main objective of this review paper is to present the
purification methods that have been used to date in heteroge-
neous biodiesel production processes. At first, a typical biodiesel
production process using solid catalysts is shortly described,
paying attention to the main processing steps. Then, possible
impurities and their effects on the biodiesel quality are pointed
out. The main part of this review paper deals with the traditional
(wet and dry washing) and novel (membrane extraction, precipi-
tation, complexation, simultaneous ion-exchange and precipita-
tion as well as simultaneous biodiesel synthesis and purification)
purification methods. In addition, these purification methods are
compared with respect of their refining efficiency. A special
attention is paid to their comparison regarding the type of raw
materials used in biodiesel production. Furthermore, the advan-
tages and disadvantages of the crude biodiesel purification meth-
ods are summarized. Finally, the environmental aspects of crude
biodiesel purification are highlighted.
2. Biodiesel production process using heterogeneous catalysts
Heterogeneous catalysts for transesterification/esterification
can be either chemicals or enzymes, the former catalysts being
acidic or basic types. Selection of a heterogeneous catalyst
depends on its catalytic activity, cost and availability as well as
on the type of feedstock and operating conditions [16]. Mainly,
inorganic catalysts are employed because of their cheapness,
availability, stability, durability and easiness of regeneration [6].
Recent researches have been focused towards the heterogeneous
base inorganic catalysts that are low cost, eco-friendly and highly
effective. Among them, the CaO-based catalysts that can be
obtained from natural sources or wastes appear to be promising
for catalyzing transesterification of various feedstocks. For
instance, quick lime [17], calcium-containing shells [18,19] and
lime mud, a solid waste from the paper mill [20] have been shown
to own excellent catalytic properties that make them suitable for
biodiesel production. The use of these catalysts not only makes the
transesterification process economic and environmentally friendly
but also eliminates the wastes from the environment. It is also
worth mentioned that solid acids favoring esterification and
transesterification reactions simultaneously are of special impor-
tance for biodiesel production from low-cost feedstocks having
high FFA content. Development of new, more effective and cheaper
heterogeneous catalysts will lead to a lower total biodiesel
production cost from different oily resources. For instance,
improved catalyst performance can be achieved by utilization
macro- and meso-porous solids support that enhances TAG and
FFA diffusion to active acid/basic groups and has beneficial effects
on the reaction rates [21]. Also, the application of eco-friendly
technologies such as microwaves, ultrasound and membrane
reactors can be used for solving the operation problems including
high energy consumption, long reaction and low productivity that
increase the production cost [22].
2.1. Description of typical biodiesel production processes using solid
catalysts
A typical biodiesel production process based on esterification
and transesterification reactions of oily feedstocks with an alcohol
in the presence of a solid catalyst comprises the following main
process stages (Fig. 1): (1) esterification reaction of FFAs,
(2) separation of the reaction mixture from the solid catalyst,
(3) transesterification of TAGs, (4) separation of the ester phase
(crude biodiesel) from the methanol/glycerol phase and (5) pur-
ification of crude biodiesel. Also, the overall process includes the
crude glycerol processing through acidification and separation of
glycerol from alcohol. The purification of crude biodiesel and the
recovery of alcohol and glycerol improve the biodiesel product
quality and reduce the overall process costs, respectively. The
biodiesel production process is further briefly described.
Biodiesel production process using solid catalyst can be con-
ducted as a one-step or two-step process, depending on the type
of oily feedstock. When the oily feedstock, such as refined
vegetable oils, contains less than 1% FFAs and no impurities, an
base-catalyzed transesterification process is applied. However,
when the oily feedstock, such as non-edible vegetable and waste
cooking oils, contains high FFA, water and impurities, a special
attention in the process design and selection of catalysts is
required. Because of the high FFA content and water, the acid-
catalyzed transesterification process is preferable for biodiesel
production. However, this process requires relatively high tem-
peratures, long reaction times and the equipment made from
corrosion-resistant materials. To overcome these problems, the
two-step process is applied, which includes an acid-catalyzed pre-
esterification followed by the base-catalyzed transesterification to
convert FFAs and TGAs into esters, respectively. Since both reac-
tions are reversible, an excess of alcohol is usually employed to
force the reaction towards the methyl ester formation. By using
bifunctional catalyst that catalyzes both esterification of FFAs and
transesterification of TAGs simultaneously, the biodiesel produc-
tion can be 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.
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
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 corroding, injector damaging, filter plugging and engine
weakening. FFAs reduce the oxidation stability of biodiesel and
503
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 þH 2 O
which then can be subjected to the hydrolysis:
CaðC3 H7 O3 Þ2 þ 2H2 O⇄Ca2 þ þ 2OH þ 2C3 H8 O3
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
504 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516

Table 2
Survey on purification methods of crude biodiesel produced by transesterification catalyzed by calcium-based catalysts.

Production Purification Product propertiesa 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:oil¼ 1:10) calcium; biodiesel
methanol yield: 69.5%
(1:9) Complexation: Decalcification
EDTA (agent:Ca¼ 1:1) efficiency: 83.9%;
biodiesel yield: 92.3%
Precipitation: ν (20 1C): 7.32 mm2/s, ρ Decalcification
Oxalic and citric acid (agent: (20 1C): 878.4 kg/m3, FP: efficiency :492%;
Ca¼ 1:1) 4170 1C, CV: o0.05%, citric acid is the
SA: o 0.005%, SC: better agent (96.2%)
0.0036%, CN: 56.1 ensuring the
biodiesel yield of
95.5%

Sunflower oil, CaO (0.2) 60 1C, Wet washing:
methanol 1000 rpm,
(1:14) 5h
Distilled water (10 wt%)
washing
Twice distilled water (10 wt%)
washing
Twice distilled water (10 wt%)
washing followed by aq. HCl
(0.1 M; 10 wt%) washing
Distilled water (10 wt%)
washing followed by aq. HCl
(0.1 M; 10 wt%) washing
Dry washing:
Sulfonic resin (DOWEX DR
2030; 50 wt% to the
biodiesel mass)
Ion-exchange/precipitation:
Solid Na2CO3 suspended in
methanol:
1 wt% (of biodiesel mass)
5 wt%
10 wt%
Sunflower oil, Simultaneous reaction and
methanol ion-exchange/precipitation
(1:30) with Na2CO3 (5 wt%)
Washing (RT,b 500 rpm, 1 h) was Ca-soaps cannot be [10]
followed by decanting, separating removed below 5 ppm
and outgassing (100 mbar, 70 1C and
1 h) FP: 174 1C, WC:
200 ppm, AV:
0.06 mg KOH/g, MEC:
98%, ν (40 1C):
4.41 mm2/s, ρ (20 1C):
883 kg/m3, Ca2 þ :
362 ppm
MEC: 98%, Ca2 þ :
320 ppm
MEC: 97.3%, Ca2 þ :
209 ppm
MEC: 96.5%, Ca2 þ :
312 ppm
Stirring with resin (2 h) was MEC: 97.4%, Ca2 þ : Ca-soaps can be
followed by filtering, decanting, o1 ppm, AV: removed below
distilled water washing (10 wt%, RT, 3.8 mg KOH/g 5 ppm. Ca-soaps are
500 rpm, 1 h), decanting, separating transformed to FFAs
and outgassing (100 mbar, 70 1C and
1 h)
Precipitating (biodiesel:methanol
mass ratio¼ 2, 60 1C, 1000 rpm, 4 h)
was followed by distilled water
washing (RT, 500 rpm, 1 h), MEC: 92.8%, Ca2 þ : Optimal amount of
decanting, separating and 390 ppm, Na þ : 140 ppm Na2CO3 for Ca
outgassing (100 mbar, 343 K, 1 h) MEC: 96.7%, Ca2 þ : removal: 5 wt%
o5 ppm, Na þ : 0 ppm
MEC: 98.3%, Ca2 þ :
o5 ppm, Na þ : 12 ppm
Distilled water washing (10 wt%, RT, MEC: 96.9%, Ca2 þ :
500 rpm, 1 h) was followed by o3 ppm, Na þ : o1 ppm
decanting, separating and
outgassing (100 mbar, 70 1C and 1 h)

Waste CaO BTb, 2 h Dry washing: RT, LHSVc: 2 h  1 15DRY and IRC76 are [12]
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
Amberlyst-15DRY with FGC: 0.12% 100% removal of CaO
methanol (20 vol% to
biodiesel)

Soybean oil, CaO (0.8 g/ BTb, 2 h Dry washing: RT, LHSVc: 0.5 h  1 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) 499% (sulfonated resin) 139 ppm)
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516 505

Table 2 (continued )

Production Purification Product propertiesa 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
Membrane extraction: 2.11 mL/min, RT, flux 26.4 L/(m2h) 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 ratio¼2, 60 1C, 1200 rpm, 5 h):
membrane extraction or precipitating with methanol-Na2CO3
water washing: (5 wt% to biodiesel mass), filtering
Dry washing using resin (6 wt 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
506 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.

Biodiesel production Biodiesel purification Biodiesel product Concluding remarks Ref.

propertiesa
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), and good compliance with the content, while it increases
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 mL/mL) water specification ( o 500 ppm)

Jatropha curcas oil, Na/SiO2 (3 wt%) Batch ultrasonic- Wet Washing and drying ρ (15 1C): 887.3 kg/m3, The product fulfills the [41]
methanol (1:9) assisted reactor washing: over Na2SO4 WC: 236 ppm, AV: standard biodiesel
(200 W, 24 kHz), hot water 0.22 mg KOH/g, CN: 53, specifications
15 min FP: 134, TS: 100 ppm

Crude palm kernel SO24/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) ρ (15 1C): 894 kg/m3, ν the next standard
fat (AF-1), waste SBA-15, reactor, 209 1C, distilled (40 1C): 5.9 mm2/s, FP: specifications: MEC, ρ, FP,
cooking oil, pork agglomerated 70 bar, residence water, twice 160 1C, CN: 64, AV: CN, IV, Naþ K, Caþ 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]
methanol (1:1, PK208LH, 1.2 kg) followed by washing: 0.04–0299 L/h; best 879 kg/m3, 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) exchange three packed-bed resin evaporation under IV: 95.9 g I2/100 g
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
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
by heterogeneous reaction systems. However, the purification
efficiency of wet washing depends on the type of heterogeneous
catalyst applied to catalyze the transesterification reaction. On the
one hand, water washing processes are not suitable for purifying
the crude biodiesel from heterogeneous processes using calcium-
based catalysts such as calcium oxide [10,13]. This can be attrib-
uted to the formation of very stable calcium soaps dissolved into
crude biodiesel [10]. On the other hand, water washing methods
are suitable for purifying the crude biodiesel after heterogeneous
processes using other catalysts [39–43]. Residual glycerol and
methanol are very effectively eliminated from crude biodiesel by
water washing because of high solubility in water. This method is
also successful in removing residual sodium soaps resulting from
the cation-ion exchange in the novel washing methods [10,11].
Wet washing is performed by distilled water or acidulated water
(aqueous mineral acid solution). Water is used either at room
temperature or as hot [39–43]. Before the wet washing step, the
excess of alcohol is sometimes separated from the ester by distilla-
tion or evaporation. Since crude biodiesel and water are immiscible,
the mixture is vigorously stirred to promote the contact between the
phases. After water washing, the washed biodiesel is dehydrated by
convective heat drying, vacuum flash evaporation, hot air bubbling,
anhydrous salts (sodium sulfate) or other water absorbents. The main
drawback of water washing is the generation of wastewater that
should be adequately treated, thus increasing the overall costs of the
biodiesel production process. Also, water washing appears inefficient
in removing of the leached calcium oxide [10,13]. Furthermore, the
operability of water washing is poor. At too high agitation speed
emulsification occurs, reducing the biodiesel yield. Contrary, at too
low agitation speed the purification efficiency is not obvious.
Zhu et al. [13] observed that warm water (45 1C, mass ratio of
water to jatropha oil ¼1:10) removed only 58.3% of the calcium
present in the biodiesel containing 1.200 mg/mL of calcium ions.
The remaining calcium concentration of 0.50 mg/mL (correspond-
ing approximately to 560 mg/kg of biodiesel) indicated that the
quality of the purified product did not meet the biodiesel standard
specification (max 5 mg/kg). In addition, a large amount of the
purified biodiesel was lost (about 30%), affecting the overall
process economics negatively.
According to Alba-Rubio et al. [10], simple water washing of crude
biodiesel at room temperature under stirring (1 h) did not result in
the purified biodiesel satisfying the calcium content specification as
its level (362 ppm) was significantly higher than the specified limit.
All other analyzed properties can be easily satisfied with a water
rinsing step. For comparison, the biodiesel obtained by the homo-
geneously alkali-catalyzed transesterification of sunflower oil met all
standard specifications after simple water washing. With respect to
decalcification of crude biodiesel, doubled water washing, as well as
simple and double water washing, as well as double water washing
followed by acid washing were also useless because the calcium
concentration in the purified biodiesels (320, 209 and 312 ppm,
respectively) was similar to that achieved by simple water rinsing
(362 ppm). The ester content was not reduced by double water
washing. However, the ester content decreased from 98.0% to 96.5%
with the additional acid washing because of the ester hydrolysis
catalyzed by the acid. Therefore, very stable calcium soaps formed
during the CaO-catalyzed transesterification of sunflower oil cannot
be removed by water washing or by exchange of the calcium soaps
with aqueous protons.
Contrary to crude biodiesels from CaO-catalyzed processes, the
biodiesel obtained from transesterification using other heteroge-
neous catalyst is in good compliance with the standard specifications
after water-based washing. According to Salamatinia et al. [39] and
Kim et al. [40], water washing of crude biodiesel obtained from palm
oil and brown grease using strontium oxide and ZnO/ZrO2, respec-
tively resulted in the purified product satisfying the standard
507
specifications. Water washing of biodiesel slightly reduced its den-
sity, total acid value, as well as moisture and sulfated ash contents,
while it increased viscosity, flash point, iodine and saponification
values [39]. The residual catalyst (leached strontium oxide) was also
removed from the crude biodiesel successfully. After water washing,
the products from jatropha oil [41], animal fats [43] and yellow
grease [45] fulfilled the standard specifications. In addition, the
washed biodiesel obtained from brown grease met the ASTM diesel
fuel sulfur specification [40].
3.1.2. Dry washing
Dry washing is developed with the aim of replacing water
washing by environmentally friendly water-free purification
methods. It removes the impurities from crude biodiesel using
waterless washing agents: adsorbents and acid resins. These
agents are used either as suspended in crude biodiesel in a stirred
vessel or as a fixed bed in the column through which crude
biodiesel flows. When used as suspended, the waterless washing
agent is collected after treatment by filtration. The basic mechan-
isms of removing impurities from crude biodiesel by dry washing
are filtration, adsorption, ion exchange and glycerol/soap interac-
tion [52]. One or more mechanisms can be dominant in removing
impurities, depending on the process conditions and the proper-
ties of the waterless washing agent.
The waterless washing agents cannot remove all the methanol
and glycerol, which should be removed as much as possible during
the gravitational separation stage [53]. In order to increase the
removal efficiency, the purified biodiesel is sometimes washed
with distilled water in a stirred tank [10]. The ester phase is then
separated from the aqueous phase by decantation and outgassed.
3.1.2.1. Dry washing by adsorption. Only the commercial adsorbent
Magnesol (magnesium silicate) has been used to date for refining
of crude biodiesel obtained from soybean oil and beef tallow using
ethanol and a sulfonic resin as the catalyst [44]. The crude
biodiesel was treated with 2 wt% Magnesol at 65 1C. After
stirring for 20 min, the 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 the homogeneously alkali-
catalyzed transesterification but more effective than the Magnesol
treatment [53]. However, a higher biodiesel yield was achieved by
water washing (96%) than by adsorption using a cation exchange
resin (92%) because a part of biodiesel remained in the column after
purification [62]. Strong acid resins have also been used in purifying
crude biodiesels produced by CaO-catalyzed transesterification
aimed at dissolved calcium removal [10,12]. In this process of
decalcification, protons of the functional groups on the resin are
exchanged by calcium ions of calcium soaps, glyceroxide, methoxide
and hydroxide that are believed to compose the leached catalyst.
Thus, the removal of leached calcium is by absorption into cation-
exchange resin with the help of its basicity. According to Kouzu and
Hidaka [12], the major driving force for the calcium removal from
508 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
crude biodiesel is the ion-exchange ability. Also, the strong acid
resins are effective in free glycerol removal [12,53]. However,
contents of acylglycerols in crude biodiesel are hardly reduced by
treating with the strong acid resin [12].
The use of strong acid resins can generate a new problem,
arising from the formation of FFAs through the exchange of
calcium ions of calcium soaps by protons of the acid sites of the
resin. This reaction increases the acid value of the treated biodiesel
produced from sunflower oil above the standard limit [10].
However, it is possible that the protons liberated by the resin in
the cation exchange react with the anionic species generated from
the leached catalyst, without affecting the acid value [12]. For
instance, calcium diglyceroxide reacts with the liberated protons
from the cation exchange forming glycerol as a by-product:
CaðC3 H7 O3 Þ2 þ2H  SO3 -2C3 H5 ðOHÞ3 þ Ca  2SO3
The same type of reaction is possible with calcium methoxide and
hydroxide composed of the leached catalyst. Indeed, the increased
free glycerol content was observed in the purified biodiesel,
compared to the treated one [12].
Calcium removal by a fixed-bed column depends on the polymer
matrix of the cation-exchange resin, the operating temperature and
the methanol addition [12]. All these factors affect the absorption of
the leached calcium into the resin by influencing the rate of internal
mass transfer. The macro-reticular resin with large pores leads to the
fast internal mass transfer, compared to the gelular resin, which
enhances accessibility of the leached calcium to the inner active sites.
With increasing operating temperature, viscosity of crude biodiesel
decreases, leading to the accelerated internal mass transfer. Calcium
removal is also improved by adding methanol to the crude biodiesel.
Methanol reduces viscosity of the crude biodiesel and enhances
swelling of the polymer matrix, both accelerating the internal mass
transfer. Moreover, methanol dissolves a part of the leached calcium
and intensifies ion-exchanging ability of the resin by its proton-
donating activity.
Alba-Rubio et al. [10] used a sulfonic resin (50% to the biodiesel
mass) to refine the crude biodiesel in a stirred tank. The suspen-
sion was stirred for 2 h at room temperature and then filtered to
separate the ester phase from the resin. Then, the ester phase was
washed with distilled water (10 wt%) in a stirred tank for an hour
at room temperature. The ester and aqueous phases were dec-
anted, and the former was outgassed. The calcium content was
reduced from 748 ppm in the crude biodiesel to less than 1 ppm in
the purified biodiesel. However, the acid value increased to
3.8 mg KOH/g, which was above the limit value. FFAs were not
removed by water washing. Also, the ester content in the purified
biodiesel was 97.4%, which was compatible with the presence of
FFAs. Thus, rinsing with a strong acid resin reduces the calcium
level satisfactory but it generates another problem by increasing
the acid value above the specified limit.
Kouzu et al. [31] removed about 50% and more than 99% of the
dissolved calcium from the crude soybean oil biodiesel using
carboxylated and sulfonated resins, respectively in a fixed-bed resin
column operating at liquid hourly space velocity (LHSV) of 0.5 h  1. In
a later study, the same research group [12] used four resins
(Amberlyst-15DRY, Amberlite-200CTNA, Amberlite-IRC76 and
Amberlyst-31WET) differing in the polymer matrix, the acidic func-
tional group and the counter-cation to reduce the calcium content in
the crude biodiesel obtained from waste cooking oil. The polymeric
beads ranging between 0.5 mm and 0.9 mm were used in the
original shape after swelling with methanol. The crude biodiesel
passed through a 15 mm i.d. column packed with the swelled resin.
In order to eliminate water from the resin, methanol flowed through
the column (50 mL/h) for 2 h. The crude biodiesel was then pumped
into the column with the LHSV of 2 h  1. The purification tests were
conducted at room temperature and 50 1C. All tested resins were
useful in refining crude biodiesel with respect to the calcium content
and their removal efficiency was better at the higher operating
temperature because of accelerating the internal mass transfer.
Calcium removal efficiencies of the tested resins were in the
following order: Amberlyst-15DRY¼ Amberlite-IRC764Amberlyst-
31WET4Amberlite-200CTNA. The higher removal efficiency of the
Amberlyst-15DRY resin compared to that of the Amberlite-200CTNA
resin was attributed to the protonated form of the former resin.
Beside the 100% calcium removal, the free glycerol content was
reduced below 0.01 wt%. The acid value of the purified biodiesel was
0.2 mg KOH/g, i.e. bellow the standard limit. The calcium removal by
cation-exchange resin was significantly promoted by adding metha-
nol (20 vol%) to the crude biodiesel. However, the free glycerol
content was not reduced in the presence of methanol. The
Amberlyste-15DRY resin was successfully regenerated by rinsing
with methanol and 1 M hydrochloric acid flowed through the
cation-exchange column. About 90% of the absorbed calcium was
washed off the resin, which then allowed the 100% calcium removal.
Ferrero et al. [11] have recently purified the methanol-free
crude biodiesels produced using the calcium glyceroxide catalyst
by dry washing with a strong acid resin with sulfonic groups
(Purolites PD206). The resin has cation-exchange and dehydrat-
ing (desiccant) abilities. When using the cation-exchange resin,
crude biodiesel was washed with 6 wt% or 50 wt% of resin (based
on the biodiesel mass) under magnetic stirring (500 rpm) within
2 h at room temperature. Both resin dosages were ineffective
regarding calcium removal which was about 2 wt%.
3.1.3. Membrane extraction
Because of their thermal, chemical and physical stability,
ceramic membranes have high potential in the separation of soaps
and alcohols [63,64]. They are also considered effective for crude
biodiesel purification by removing glycerol [65] or by retaining the
unreacted TAGs [63] or soaps [64].
Ferrero et al. [11] used two monochannel ceramic membranes
with a pore diameter of 0.05 and 0.1 μm, respectively to purify
crude biodiesel by forcing it to recirculate through the membrane
tube (2.11 mL/min) at room temperature. The crude biodiesel was
cross-filtered by the ceramic membrane tube with the flux
through the membrane of 26.4 L/m2/h. When the volumetric
concentrated factor reached 3, the recirculation was stopped.
Calcium removal efficiency of the two membranes was very poor
although the membrane with higher porosity presented better
result (30%) than that with lower porosity (22%). The result agreed
with those of Wang et al. [64], who reported inefficient removal of
the calcium soap by the ceramic membrane.
3.1.4. Precipitation
This purification method is based on the use of precipitating
agents to remove calcium ions from crude biodiesel. When the
precipitating agent, such as oxalic acid or citric acid, is added to
crude biodiesel containing calcium ions, an insoluble compound is
formed in the reaction between the agent and calcium ions while
stirring the reaction mixture. The reactions of calcium ions with
oxalic and citric acid are presented by the following stoichiometric
equations, respectively:
Ca2 þ þ H2 C2 O4 þH2 O-CaC2 O4  H2 O↓ þ 2H þ
3CaO þ 2H3 C6 H5 O7 -Ca3 ðC6 H5 O7 Þ2 ↓ þ 6H þ
The precipitate can be separated from the purified biodiesel by
filtration or centrifugation. It can be expected that successful
precipitation will depend on calcium concentration, temperature,
pH and rate of precipitating agent addition.
Zhu et al. [13] tested two precipitating agents, namely oxalic
acid and citric acid, at different agent-to-calcium molar ratios for
 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
509
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:
Ca2 þ þ ½H2 Y2  ⇄½CaY2  þ 2H þ
where ½H2 Y2  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-
ing species is ½Y4  , 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
510 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 ( o5 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,
Table 4
Comparison of precipitation and complexation with water washing.a
Purification method Ester yield (wt Calcium Decalcification efficiency
%) (μg/mL)b (%)
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
(o5 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.
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516 511

Table 5
Comparison of efficiency of various purification methods.a,b

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,
dry washing and membrane extraction.a,b

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 recently produced biodiesel from
soybean oil or waste frying oil and methanol in the reaction
catalyzed by calcium diglyceroxide. After the reaction was com-
pleted, the catalyst was collected by filtration and the ester phase
was separated from the alcoholic phase by gravitational settling.
The remaining methanol was removed from the ester phase by
vacuum evaporation. Then, various purification methods were
employed: (a) dry washing using a cation-exchange resin,
(b) membrane extraction and (c) the treatment with sodium
carbonate suspended in boiling methanol according to the method
of Alba-Rubio et al. [10] followed by the resin, the ceramic
membrane or the simple water washing. The purification efficien-
cies of these methods are compared in Table 6. Their results
showed that the dry washing using resin and the membrane
extraction alone were not efficient in purifying the crude biodie-
sels as required by the quality standard specification. Contrary, the
pretreatment with sodium carbonate suspended in boiling metha-
nol and additional water or water-free washing were effective in
removing calcium and sodium, respectively. However, the decalci-
fication efficiency appears to be dependent on the type of oily
feedstock since the calcium content of the purified waste frying oil
biodiesel was higher than that of the soybean oil. The purified
biodiesels fulfilled all the quality standard specifications since the
ester content (somewhat lower than the limit value) agreed with
an acceptable margin of error.
Bearing in the mind the difficulty of simultaneous removal of
free glycerol and calcium, Kouzu and Hidaka [12] suggest a two-step
process for purifying the crude biodiesel obtained by the CaO-
catalyzed transesterification with intermediate methanol distilla-
tion. The first step is decalcification of the crude biodiesel in the
presence of methanol and the second step is absorption of free
glycerol from decalcified, methanol-free biodiesel into the resin.
This water-free process seems to be promising for practical use of
the CaO-catalyzed transesterification producing biodiesel matching
the quality standard specifications.
3.3. Comparison of crude biodiesel purification methods regarding
oily feedstocks
A few studies can be utilized for comparing the final biodiesel
product purification methods regarding oily feedstocks employed
in heterogeneously catalyzed biodiesel production processes, as it
can easily be concluded from Tables 2 and 3. Crude biodiesels
employed in purification studies originate from vegetable oils
(soybean, sunflower, palm, coconut and jatropha oils), animal fats
(pork lard and category-1 animal fat) and waste frying oil.
However, no systematic study on the combined effect of the
purification method and the type of feedstock on the fuel proper-
ties of the final product has been carried out to date. Only a study
compares the purification efficiency of crude biodiesels obtained
from sunflower and waste cooking oils by dry washing, membrane
extraction and ion exchange-based precipitation with sodium
carbonate followed by simple water washing, dry washing or
membrane extraction [11]. While dry washing and membrane
512 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516

Table 7
Advantages and disadvantages of purification methods employed for refining crude biodiesel produced by heterogeneously catalyzed transesterification processes.

Purification Advantage Disadvantage

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
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

Dry washing Simpler and less hard than wet washing All methanol and glycerol residues cannot be removed
Require less space Possibility of increasing the acid value of the purified biodiesel when
strong acid resins are used
Low energy consumption Use of strong acid resin hardly reduces acylglycerols contents in crude
biodiesel
Generate less waste/wastewater Effective removal of calcium ions
Possibility for continuous process application Increase of free glycerol content if calcium diglyceroxide, methoxide
or hydroxide are present in crude biodiesel
Reduce overall biodiesel production time Disposal of spent ion-exchange resins
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 Inefficient removal of calcium soap
extraction Use of reduced amount of water used, so little wastewater is generated Membrane must be cleaned
Environmentally friendly Decrease of throughput by possible contamination
Operational simplicity and flexibility Increase of biodiesel production cost
Relatively high selectivity and permeability
Low energy requirements
Easy control and scale-up

Precipitation Calcium ions are removed as a precipitate Slightly higher viscosity of the purified biodiesel than the standard
limit
High decalcification efficiency of citric acid ( 496%) Successful precipitation depends on operating conditions
High yield of purified biodiesel Further studies are needed to optimize the precipitation conditions
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 High initial methanol-to-oil molar ration
and Low-cost washing agent (sodium carbonate) Additional water or water-free washing step is needed to remove
precipitation sodium soaps formed by ion exchange
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 Further studies are needed to optimize the operating conditions
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 Preparation of aqueous EDTA solution with difficulty
Calcium remains in solution without ionic reactions Medium decalcification efficiency
Calcium–EDTA complex can easily be separated by decanting Further studies are needed to optimize the reaction conditions
EDTA is a hazardous substance

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
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) 500–516 513

Table 8
Physico-chemical properties of biodiesels arising from different purification methods.

Feedstock 0% AF- 10% AF- 30% AF- Jatropha Pork lard Waste frying Mixture of PL (22%) Sunflower Jatropha Jatropha EN14214
1a 1b 1b 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
stepc
Property, unit
Methyl esters (%) 97.1 95.2 96.2 92.5 94.3 92.1 98.0 99.3 96.5 min
Density at 15 1C (kg/ 894 891 886 887.3 883 878.4d 879 860/900
m3)
Viscosity at 40 1C 5.9 5.7 5.2 4.59 4.70 4.74 4.41 7.32d 4.357 3.50/5.00
(mm2/s)
Flash point (1C) 160 167 172 134 174 4170 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 o0.005 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
(NaþK) (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 (%) o0.05 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 ( o0.2 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 (Naþ K).
514 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
3.4. Environmental aspects of crude biodiesel purification methods
Compared to homogeneous catalysis, heterogeneous biodiesel
production processes are considered as environmentally friendly
since the problems related to biodiesel purification are reduced.
Heterogeneous catalysts can easily be separated from the reaction
mixture by filtration, and thus the purification of the products is
much simplified and does not require a large amount of water:
hence, the need for wastewater treatment alleviates in hetero-
geneous biodiesel production processes [68]. However, different
types of wastes are generated during biodiesel production via
heterogeneously catalyzed processes, which can generally be
classified into two groups:
– wastes originated from biodiesel product separation and pur-
ification such as used catalyst, wastewater, spent dry washing
agents (adsorptive materials, cation-exchange resins), ceramic
membranes, insoluble compounds formed by precipitation or
ion exchange and the aqueous phase obtained by complexation
of calcium ions with EDTA and
– wastes originated during catalyst reactivation in their repeated
use (organic solvents, alcohols, water).
Previous researches of heterogeneously catalyzed alcoholysis
have been aimed at developing a catalyst with a high catalytic
activity and optimizing the reaction conditions in order to obtain
the high ester yield in economically suitable process. However,
there is no reported study on handling of used catalysts. Some
researchers have made attempts to improve catalytic stability of
the used catalyst in order to reduce its leaching and consequently
facilitate biodiesel purification, to allow long-term use of catalyst
and development of continuous process. Tang et al. [69] modified
calcium oxide by dipping in bromooctane/hexane solution that
bound bromooctane to the catalyst particles. The modified catalyst
maintained activity even for 15 cycles. The leached calcium
concentrations into the reaction medium were 26 ppm and
10 ppm after first and second cycles, respectively [69], which were
significantly lower than those reported for unmodified calcium
oxide [10,31].
According to the best of authors' knowledge there is no data
about wastewater treatment generated during water washing of
crude biodiesels obtained in heterogeneously catalyzed processes.
The comprehensive review of wastewater treatment in the bio-
diesel production by homogeneously alkali-catalyzed alcoholysis
has recently been reported by our group [23]. Almost the same
methods, modified depending on the type of ions that are leached
from the catalyst into the biodiesel and alcohol phases, can be
used for treating the wastewater generated by heterogeneous
biodiesel production processes. When the solid catalyst is used
as suspended in the stirred reactor, the additional separation stage
is the removal of solid particles from the reaction mixture. More-
over, if leaching of solid catalyst occurs, the ions generated must
be removed from the crude biodiesel.
Dry washing agents are used either as a fixed bed or as
suspended in the crude biodiesel. In the latter case, suspended
particles of the dry washing agent are separated from the treated
biodiesel by filtration. To date, there are only limited data about
the spent dry washing agent treatment. The spent adsorbent can
be disposed of to landfill or other uses might be invented [53]. The
suppliers of ion-exchange resins Purolites PD206 and Thermax T-
45 BD [70] notify that their ability to absorb glycerol can be
regenerated by methanol washing, which cannot recover the ionic
capacity. If the resin exhausts ionically, after several methanol
washes, the resin should be returned to manufacturer for tradi-
tional ionic regeneration to restore the ability of removing catalyst
traces and soaps. Once resins are ready for disposal, it should be
disposed of as a non-hazardous material according to local
regulations. Incineration and land filling are two options that are
often adopted.
Shibasaki-Kitakawa et al. [46] proposed method for the regen-
eration of anion-exchange resin (Diaion PA306S) activity used in
the bench-scale process for simultaneous biodiesel synthesis and
purification. The regeneration of the Diaion PA306S resin includes
washing with methanol to remove glycerol and water from the
resins, treatment with acetic acid solution in methanol to displace
the fatty acid ion in the resin with the acetic acid ion, which
further was displaced with the hydroxyl ion by using NaOH
aqueous solution, washing with deionized water and finally the
resin was swelled by feeding the column with methanol. The
proposed regeneration method completely recovered the resin
activity and it was successfully used more than 50 times.
Ren et al. [67] suggested regenerating the D261 anion exchange
resin in-situ by a three steep process including flushing by
methanol for removing glycerol, ester and less triglycerides,
washing with a solution of KOH in methanol to activate the resin
and finally washing with methanol to pH  7. After regeneration,
the ion exchange capacity value was equal to the fresh
activate resin.
The ceramic membranes are increasingly used in the biodiesel
separation and purification processes [71] because of their numer-
ous advantages over polymeric membranes, such as high perme-
ability rate and high chemical, mechanical and thermal stability
[72]. They can be used for almost one year when the alkali solid
base catalysts are used for biodiesel production [73]. According to
Cao et al. [74], the ceramic carbon membrane can be cleaned more
proficiently even unrefined oily feedstocks are used for biodiesel
production. However, there are no available data about the
membrane cleaning methods. It can be expected that it will
include washing with appropriate solvent to remove unreacted
TAGs, catalyst, glycerol, soap and even methanol collected by the
membrane [71].
The use of precipitating agents, such as citric acid, or by ion-
exchanging compounds, such as Na2CO3 for biodiesel purification
leads to the formation of insoluble 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.
4. Conclusion
The ester product of heterogeneously-catalyzed transesterifica-
tion of oily feedstocks should be purified after collecting the solid
 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
catalyst and the precipitate of possibly formed insoluble com-
pounds by filtration and separating the glycerol/methanol phase
by settling in order to fulfill the biodiesel standard specifications.
Sometimes, methanol removal by evaporation of vacuum flash
vaporization is also required. Further purification of this crude
biodiesel may include various traditional or novel methods. The
former are wet and dry washing, and the latter are membrane
extraction, precipitation, complexation and simultaneous ion-
exchange and precipitation. A possible improvement might be
achieved by simultaneous conduction of biodiesel synthesis and
purification using appropriate ion-exchange resins. Since each of
these methods has its advantages and drawbacks, a careful
analysis should be conducted when selecting the proper one for
purifying crude biodiesel. Also, further improvement of purifica-
tion methods is required to increase their purification efficiency.
The efficiency of a purification method depends on the type of
solid catalyst employed in the transesterification of raw materials.
In the case of some solid catalysts, simple water washing results in
the product satisfying the biodiesel quality standard specifications.
Contrary, this is not valid for crude biodiesel obtained by calcium-
based catalysis of oily feedstocks. Therefore, special attention
should be paid to eliminating the leached calcium from the crude
biodiesel when calcium compounds (most frequently, calcium
oxide) are used as catalysts. It seems that two-step processes
might be important for practical use of the CaO-catalyzed trans-
esterification in commercial biodiesel production. The first two-
step process is consisted of simultaneous transesterification, ion-
exchange and precipitation followed by simple water washing, and
the second water-free two-step process includes decalcification of
the crude biodiesel in the presence of methanol and absorption of
free glycerol from decalcified biodiesel into the resin as well as
intermediate methanol distillation. Both processes result with the
purified biodiesel satisfying the quality standard limits. However,
further research is needed to optimize both purification processes.
Although heterogeneous catalysts are considered as a promis-
ing the possibility for the improvements of biodiesel production
process, further investigation and development is needed with
respect to catalytic activity, leaching and reusability. These
improvements will contribute not only to the optimization of
biodiesel synthesis and purification but also to the further reduc-
tion of overall process environmental impact.
Acknowledgments
This work has been funded by the Ministry of Education,
Science and Technological Development of the Republic of Serbia
(Project III 45001).
References
[1] Canakci M, Sanli H. Biodiesel production from various feedstocks and their
effects on the fuel properties. J Ind Microbiol Biotechnol 2008;35:431–41.
[2] Di Serio M, Tesser R, Pengmei L, Santacesaria E. Heterogeneous catalysts for
biodiesel production. Energy Fuel 2008;22:207–17.
[3] Dossin TF, Reyniers MF, Berger RJ, Marin GB. Simulation of heterogeneously
MgO-catalyzed transesterification for fine-chemical and biodiesel industrial
production. Appl Catal B—Environ 2006;67:136–48.
[4] Romero R, Martineź SL, Natividad R. Biodiesel production by using heterogeneous
catalysts. Available from:. In: Manzanera M, editor. Alternative fuel. InTech; 2011.
〈http://www.intechopen.com/books/alternative-fuel/
biodiesel-production-by-usingheterogeneous-catalysts〉.
[5] Banavalil R, Hanlon RT, Jerabek K, Schultz AK. Heterogeneous catalyst and
process for the production of biodiesel from high free-fatty acid-containing
feedstocks. In: Prunier ML, editor. Catalysis of Organic Reactions. Boca Raton:
CRC Press; 2009. p. 279–89.
[6] Endalew AK, Kiros Y, Zanzi R. Inorganic heterogeneous catalysts for biodiesel
production from vegetable oils. Biomass Bioenergy 2011;35:3787–809.
515
[7] Bournay L, Casanave D, Delfort B, Hillion G, Chodorge JA. New heterogeneous
process for biodiesel production: a way to improve the quality and the value of
the crude glycerin produced by biodiesel plants. Catal Today 2005;106:190–2.
[8] Stojković IJ, Stamenković OS, Povrenović DS, Veljković VB. Purification tech-
nologies for crude biodiesel obtained by alkali-catalyzed transesterification.
Renew Sustain Energy Rev 2014;32:1–15.
[9] Yang R, Su M, Li M, Zhang J, Hao X, Zhang H. One-pot process combining
transesterification and selective hydrogenation for biodiesel production from
starting material of high degree of unsaturation. Bioresour Technol
2010;101:5903–9.
[10] Alba-Rubio AC, Alonso Castillo ML, Albuquerque MCG, Mariscal R, Cavalcante
Jr. CL, Granados ML. A new and efficient procedure for removing calcium soaps
in biodiesel obtained using CaO as a heterogeneous catalyst. Fuel
2012;95:464–70.
[11] Ferrero GO, Almeida MF, Alvim-Ferraz MCM, Dias JM. Water-free process for
eco-friendly purification of biodiesel obtained using a heterogeneous Ca-based
catalyst. Fuel Process Technol 2014;121:114–8.
[12] Kouzu M, Hidaka J. Purification to remove leached CaO catalyst from biodiesel
with the help of cation-exchange resin. Fuel 2013;105:318–24.
[13] Zhu H, Wu Z, Chen Y, Zhang P, Duan S, Liu X, et al. Preparation of biodiesel
catalyzed by solid super base of calcium oxide and its refining process. Chin J
Catal 2006;27:391–6.
[14] Atadashi IM, Aroua MK, Abdul Aziz A. Biodiesel separation and purification: a
review. Renew Energy 2011;36:437–43.
[15] Atadashi IM, Aroua MK, Abdul Aziz AR, Sulaiman NMN. Refining technologies
for the purification of crude biodiesel. Appl Energy 2011;88:4239–51.
[16] Helwani Z, Othman MR, Aziz N, Kim J, Fernando WJN. Solid catalysis for
transesterification of triglycerides with methanol. Appl Catal A—Gen
2009;363:1–10.
[17] Miladinović MR, Krstić JB, Tasić MB, Stamenković OS, Veljković VB. A kinetic
study of quicklime-catalyzed sunflower oil methanolysis. Chem Eng Res Des
2014;92:1740–52.
[18] Viriya-empikul N, Krasae P, Puttasawat B, Yoosuk B, Chollacoop N, Faungna-
wakij K. Waste shells of mollusk and egg as biodiesel production catalysts.
Bioresource Technol 2010;101:3765–7.
[19] Wei Z, Xu C, Li B. Application of waste eggshel aslow-cost solid catalyst for
biodiesel production. BioresourceTechnol 2009;100:2883–5.
[20] Li H, Niu SL, Lu CM, Liu MQ, Huo MJ. Use of lime mud from paper mill as a
heterogeneous catalyst for transesterification. Sci China Technol Sci
2014;57:438–44.
[21] Lee AF, Wilson K. Recent developments in heterogeneous catalysis for the
sustainableproduction of biodiesel. Catal Today 2014.
[22] Teixeira CB, Madeira Junior JV, Macedo GA. Biocatalysis combined with
physical technologies for development of a green biodiesel process. Renew
Sustain Energy Rev 2014;33:333–43.
[23] Veljković VB, Stamenković OS, Tasić MB. The wastewater treatment in the
biodiesel production with alkali-catalyzed transesterification. Renew Sustain
Energy Rev 2014;32:40–60.
[24] Banga S, Varshney PK. Effect of impurities on performance of biodiesel: a
review. J Sci Ind Res 2010;69:575–9.
[25] Alba-Rubio AC, Santamaría-González J, Mérida-Robles JM, Moreno-Tost R,
Martín-Alonso D, Jiménez-López A, et al. Heterogeneous transesterification
processes by using CaO supported on zinc oxide as basic catalysts. Catal Today
2010;149:281–7.
[26] Albuquerque MCG, Jiménez-Urbistondo I, Santamaría-González J, Mérida-
Robles JM, Moreno-Tost R, Rodríguez-Castellón E, et al. CaO supported on
mesoporous silicas as basic catalysts for transesterification reactions. Appl
Catal A—Gen 2008;334:35–43.
[27] Alonso DM, Vila F, Mariscal R, Ojeda M, Granados ML, Santamaría-González J.
Relevance of the physicochemical properties of CaO catalysts for the metha-
nolysis of triglycerides to obtain biodiesel. Catal Today 2010;158:114–20.
[28] Kawashima A, Matsubara K, Honda K. Acceleration of catalytic activity of
calcium oxide for biodiesel production. Bioresour Technol 2009;100:696–700.
[29] Kouzu M, Umemoto M, Kasuno T, Tajika M, Aihara Y, Sugimoto, et al. Biodiesel
production from soybean oil using calcium oxide as a heterogeneous catalyst. J
Jpn Inst Energy 2006;85:135–41.
[30] Kouzu M, Kasuno T, Tajika M, Sugimoto Y, Yamanaka S, Hidaka J. Calcium
oxide as a solid base catalyst for transesterification of soybean oil and its
application to biodiesel production. Fuel 2008;87:2798–806.
[31] Kouzu M, Yamanaka S, Hidaka J, Tsunomori M. Heterogeneous catalysis of
calcium oxide used for transesterification of soybean oil with refluxing
methanol. Appl Catal A—Gen 2009;355:94–9.
[32] Lopez Granados M, Poves MDZ, Alonso DM, Mariscal R, Galisteo FC, Moreno-
Tost R, et al. Biodiesel from sunflower oil by using activated calcium oxide.
Appl Catal B—Environ 2007;73:317–26.
[33] Lopez Granados M, Alonso DM, Sádaba I, Mariscal R, Ocón P. Leaching and
homogeneous contribution in liquid phase reaction catalysed by solids: the
case of triglycerides methanolysis using CaO. Appl Catal B—Environ
2009;89:265–72.
[34] Lopez Granados M, Alba-Rubio AC, Vila F, Alonso DM, Mariscal R. Surface
chemical promotion of Ca oxide catalysts in biodiesel production reaction by
the addition of monoglycerides, diglycerides and glycerol. J Catal
2010;276:229–36.
[35] Meher LC, Kulkarni MG, Dalai AK, Naik SN. Transesterification of karanja
(Pongamia pinnata) oil by solid basic catalysts. Eur J Lipid Sci Technol
2006;108:389–97.
516 V.B. Veljković et al. / Renewable and Sustainable Energy Reviews 49 (2015) 500–516
[36] Reddy CRV, Oshel R, Verkade JG. Room-temperature conversion of soybean oil
and poultry fat to biodiesel catalyzed by nanocrystalline calcium oxide. Energy
Fuel 2006;20:1310–4.
[37] Yan S, Lu H, Liang B. Supported CaO catalysts used in the transesterification of
rapeseed oil for purpose of biodiesel production. Energy Fuel 2008;22:646–51.
[38] Dias JM, Alvim-Ferraz MCM, Almeida MF, Díaz JDM, Polo MS, Utrilla JR.
Biodiesel production using calcium manganese oxide as catalyst and different
raw materials. Energy Convers Manag 2013;65:647–53.
[39] Salamatinia B, Abdullah AZ, Bhatia S. Quality evaluation of biodiesel produced
through ultrasound-assisted heterogeneous catalytic system. Fuel Process
Technol 2012;97:1–8.
[40] Kim M, Di Maggio C, Yan S, Wang H, Salley SO, Ng KYS. Performance of
heterogeneous ZrO2 supported metaloxide catalysts for brown grease ester-
ification and sulfur removal. Bioresour Technol 2011;102:2380–6.
[41] Kumar D, Kumar G, Singh PCP. Ultrasonic-assisted transesterification of
Jatropha curcus oil using solid catalyst Na/SiO2. Ultrason Sonochem
2010;17:839–44.
[42] Jitputti J, Kitiyanan B, Rangsunvigit P, Bunyakiat K, Attanatho L, Jenvanitpan-
jakul P. Transesterification of crude palm kernel oil and crude coconut oil by
different solid catalysts. Chem Eng J 2006;116:61–6.
[43] Iglesias J, Melero JA, Bautista LF, Morales G, Sánchez-Vázquez R. Continuous
production of biodiesel from low grade feedstock in presence of Zr-SBA-15:
catalyst performance and resistance against deactivation. Catal Today
2014174–81.
[44] Soldi RA, Oliveira ARS, Ramos LP, Cesar-Oliveira MAF. Soybean oil and beef
tallow alcoholysis by acid heterogeneous catalysis. Appl Catal A—Gen
2009;361:42–8.
[45] Gombotz K, Parette R, Austic G, Kannan D, Matson JV. MnO and TiO solid
catalysts with low-grade feedstocks for biodiesel production. Fuel
2012;92:9–15.
[46] Shibasaki-Kitakawa N, Kanagawa K, Nakashima K, Yonemoto T. Simultaneous
production of high quality biodiesel and glycerin from Jatropha oil using ion-
exchange resins as catalysts and adsorbent. Bioresour Technol
2013;142:732–6.
[47] Kwiecien J, Hájek M, Skopal F. The effect of the acidity of rapeseed oil on its
transesterification. Bioresour Technol 2009;100:5555–9.
[48] Vicente G, Martínez M, Aracil J. Integrated biodiesel production: a comparison
of different homogeneous catalysts systems. Bioresour Technol
2004;92:297–305.
[49] Kouzu M, Hidaka J, Wakabayashi K, Tsunomori M. Solid base catalysis of
calcium glyceroxide for a reaction to convert vegetable oil into its methyl
esters. Appl Catal A—Gen 2010;390:11–8.
[50] Knothe G, Gerpen JV, Krahl J. The biodiesel handbook. Urbana: AOCS Press;
2005.
[51] Huerga IR, Zanuttini MS, Gross MS, Querini CA. Biodiesel production from
Jatropha curcas: integrated process optimization. Energy Convers Manag
2014;80:1–9.
[52] Wall J, Van Gerpen J, Thompson J. Soap and glycerin removal from biodiesel
using waterless processes. Trans ASABE 2011;54:535–41.
[53] Berrios M, Skelton RL. Comparison of purification methods for biodiesel. Chem
Eng J 2008;144:459–65.
[54] Dmytryshyn SL, Dalai AK, Chaudhari ST, Mishra HK, Reaney MJ. Synthesis and
characterization of vegetable oil derived esters: evaluation for their diesel
additive properties. Bioresour Technol 2004;92:55–64.
[55] Fadhil AB, Dheyab MM, Abdul-Qader A-QY. Purification of biodiesel using
activated carbons produced from spent tea waste. J. Assoc Arab Univ Basic
Appl Sci 2012;11:45–9.
[56] Leeruang U, Pengprecha S. Purification of biodiesel by adsorption with
activated low silica bentonite. In: International conference on chemical
processes and environmental issues (ICCEEI02012). Singapore; July 15–16,
2012.
[57] Sohling U, Ruf F, Schurz K, Emmerich K, Steudel A, Schuhmann R, et al.
Natural mixture of silica and smectite as a new clayey material for industrial
applications. Clay Miner 2009;44:525–37.
[58] Solval KM, Sathivel S. Use of an adsorption process for purification of
pollockoil-based biodiesel comprises methyl esters. J Am Oil Chem Soc
2012;89:1713–21.
[59] Yori JC, D’Ippolito SA, Pieck CL, Vera CR. Deglycerolization of biodiesel streams
by adsorption over silica beds. Energy Fuel 2007;21:347–53.
[60] Suppalakpanya K, Ratanawilai SB, Tongurai C. Production of ethyl ester from
esterified crude palm oil by microwave with dry washing by bleaching earth.
Appl Energy 2010;87:2356–9.
[61] Özgül-Yücel S, Türkay S. Purification of FAME by rice hull ash adsorption. J Am
Oil Chem Soc 2003;80:373–6.
[62] Farrell S, Cavanagh E. Biodiesel production, characterization, and perfor-
mance: a hands-on project for first-year students. Educ Chem Eng 2014;9:
e21–e31.
[63] Dubé MA, Tremblay AY, Liu J. Biodiesel production using a membrane reactor.
Bioresour Technol 2007;98:639–47.
[64] Wang Y, Wang X, Liu Y, Ou S, Tan Y, Tang S. Refining of biodiesel by ceramic
membrane separation. Fuel Process Technol 2009;90:422–7.
[65] Gomes MCS, Pereira NC, De Barros STD. Separation of biodiesel and glycerol
using ceramic membranes. J Membr Sci 2010;352:271–6.
[66] Ellingboe JL, Runnels JH. Solubilities of sodium carbonate and sodium
bicarbonate in acetone–water and methanol–water mixtures. J Chem Eng
Data 1966;11:323–4.
[67] Ren Y, He B, Yan F, Wang H, Cheng Y, Lin L, et al. Continuous biodiesel
production in a fixed bed reactor packed with anion-exchange resin as
heterogeneous catalyst. Bioresour Technol 2012;113:19–22.
[68] Yan S, Di Maggio C, Mohan S, Kim M, Salley SO, Ng KYS. Advancements in
heterogeneous catalysis for biodiesel synthesis. Top Catal 2010;53(11):721–36.
[69] Tang Y, Xu J, Zhang J, Lu Y. Biodiesel production from vegetable oil by using
modified CaO as solid basic catalysts. J Clean Prod 2013;42:198–203.
[70] 〈http://utahbiodieselsupply.com/purolite.php〉 [assessed 25.03.14].
[71] Atadashi IM, Aroua MK, Abdul Aziz AR, Sulaiman NMN. Membrane biodiesel
production and refining technology: a critical review. Renew Sustain Energy
Rev 2011;15:5051–62.
[72] Barredo-Damas S, Alcaina-Miranda MI, Bes-Piá A, Iborra-Clar MI, Iborra-Clar A,
Mendoza-Roca JA. Ceramic membrane behavior in textile wastewater ultra-
filtration. Desalination 2010;250:623–8.
[73] Baroutian S, Aroua MK, Raman AAA, Sulaiman NMN. A packed bed membrane
reactor for production of biodiesel using activated carbon supported catalyst.
Bioresour Technol 2010;102:1095–102.
[74] Cao P, Dubé MA, Tremblay AY. High-purity fatty acid methyl ester production
from canola, soybean, palm, and yellow grease lipids by means of a membrane
reactor. Biomass Bioenergy 2008;32:1028–36.
[75] García A, Egüés I, Sánchez C, Barta Z, Labidi J. Study of different bio-processing
pathways in a lignocellulosic biorefinery by process simulation. Chem Eng
Trans 2013;35:505–10.
[76] Chouhan APS, Sarma AK. Biodiesel production from Jatropha curcas L. oil using
Lemna perpusilla Torrey ash as heterogeneous catalyst. Biomass Bioenergy
2013;55:386–9.
[77] Madhuvilakku R, Mariappan R, Jeyapal S, Sundar S, Piraman S. Transesterifica-
tion of palm oil catalyzed by fresh water bivalve mollusk (Margaritifera falcata)
shell as heterogeneous catalyst. Ind Eng Chem Res 2013;52:17407–13.
[78] Balakrishnan K, Olutoye MA, Hameed BH. Synthesis of methyl esters from
waste cooking oil using construction waste material as solid base catalyst.
Bioresour Technol 2013;128:788–91.
[79] Song X-l, Fu X-b, Zhang C-w, Huang W-y, Zhu Y, Yang J, et al. Preparation of a
novel carbon based solid acid catalyst for biodiesel production via a sustain-
able route. Catal Lett 2012;142:869–74.