Applied Energy 88 (2011) 42394251

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Rening technologies for the purication of crude biodiesel

I.M. Atadashi, M.K. Aroua , A.R. Abdul Aziz, N.M.N. Sulaiman
Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603 Kuala Lumpur, Malaysia

a r t i c l e

i n f o

Article history:
Received 14 February 2011
Received in revised form 13 May 2011
Accepted 18 May 2011
Available online 1 July 2011
Keywords:
Biodiesel rening
Wet washing
Dry washing
Membrane rening and biodiesel quality

a b s t r a c t
In biodiesel production, downstream purication is an important step in the overall process. This article
is a critical review of the most recent research ndings pertaining to biodiesel rening technologies. Both
conventional rening technologies and the most recent biodiesel membrane rening technology are
reviewed. The results obtained through membrane purication showed some promise in term of biodiesel yield and quality. Also, membranes presented low water consumption and less wastewater discharges. Therefore, exploration and exploitation of membrane technology to purify crude biodiesel is
necessary. Furthermore, the success of membrane technology in the purication of crude biodiesel could
serve as a boost to both researchers and industries in an effort to achieve high purity and quality biodiesel
fuel capable of replacing non-renewable fossil fuel, for wide range of applications.
2011 Elsevier Ltd. All rights reserved.

Contents
1.
2.
3.

4.

5.

6.
7.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodiesel separation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodiesel wet washing technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Dionized water washing technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Acids and dionized water washing technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Organic solvents washing technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dry washing technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Magnesol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Washing with ion exchange resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Washing with other dry washing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodiesel membrane refining technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Organic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Ceramic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Prospects of biodiesel membranes refining technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Advantages and disadvantages of biodiesel refining technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions and recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Today, continuous increase in World energy consumption, fuel
price hike, depletion of non-renewable fossil fuels and global
warming effects are among the greatest challenges facing the globe
[1]. Also environmental concerns have drastically increased globally over the past decade, particularly after the Earth Summit 92
Corresponding author. Tel.: +60 3 79674615; fax: +60 3 79675319.
E-mail address: mk_aroua@um.edu.my (M.K. Aroua).
0306-2619/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2011.05.029

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[2]. Thus, the most viable approach to meet this rising demand, decrease greenhouse gas emissions and minimize the effects of fossil
fuels depletion is by exploring alternative renewable energy
sources [35]. Biofuels, particularly biodiesel is such a fuel that
shows great potential to replace petro-diesel [68]. Biofuels are
commonly known to offer several advantages over fossil fuel such
as sustainability, biodegradability, lower greenhouse gas emissions, regional development, social structure and agriculture
development, and fuel security supply [9,10]. Further, replacing
petro-diesel with biodiesel fuel could reduce the accumulation of

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Table 1
Negative effects of contaminants on biodiesel and engines.
Contaminants

Negative effect

Methanol

Deterioration of natural rubber seals and gaskets, lower ash points (problems in storage, transport, and utilization, etc.), Lower viscosity and
density values, Corrosion of pieces of Aluminum (Al) and Zinc (Zn)
Reduces heat of combustion, corrosion of system components (such as fuel tubes and injector pumps) failure of fuel pump, hydrolysis (FFAs
formation), formation of ice crystals resulting to gelling of residual fuel, Bacteriological growth causing blockage of lters, and Pitting in the
pistons
Damage injectors, pose corrosion problems in engines, plugging of lters and weakening of engines
Less oxidation stability, corrosion of vital engine components

Water

Catalyst/soap
Free fatty acids
(FFAs)
Glycerides
Glycerol

Crystallization, turbidity, higher viscosities, and deposits formation at pistons, valves and injection Nozzles
Decantation, storage problem, fuel tank bottom deposits Injector fouling, settling problems, higher aldehydes and acrolein emissions, and severity
of engine durability problems

green house gases such as CO2 in the atmosphere [11,12]. Also biodiesel fuel has been commonly found to offer similar engine performance to that of petro-diesel fuel, whilst reducing engine
emissions of particulates, hydrocarbons and carbon monoxide [13].
Biodiesel fuel is usually produced from virgin and used vegetable oils and animal fats [10,14]. Presently several efforts are made
to produce biodiesel from microalgae. Microalgae clearly offers a
few advantages among others include: much higher biomass productivities than land plants (doubling times may be as short as
3.5 h), some species can accumulate up to 2050% triacylglycerols,
while no high-quality agricultural land is necessary to grow the
biomass, and even no land at all, offshore microalgae farming could
be a reasonable alternative [15]. Conventionally, the triglycerides
of fats and oils are transesteried using short-chain alcohol such
as methanol and ethanol in the presence of alkali catalysts. Also,
acid catalysts are used for the transesterication reaction [16,17].
Transesterication reaction is the most adopted process for biodiesel production [18,19].
At the end of transesterication, biodiesel is mostly separated
via gravitational settling or centrifugation. The crude biodiesel is
then puried and dried to meet the stringent international standard specication provided by EN14214 [20]. Otherwise the contaminants could reduce biodiesel quality and affects engine
performance as shown in Table 1. The production of biodiesel using
alkaline catalysts such as sodium and potassium hydroxides
(NaOH and KOH), and sodium and potassium methoxides (CH3ONa
and CH3OK), could provide higher biodiesel yield (>98%), but the
process of biodiesel rening is complicated [21,22]. This is due to
soaps formation associated with alkaline catalyst [23]. Further,
the formation of soap decreases biodiesel yield obtained after the
clarication and separation stages. As well, the dissolved soaps increase the biodiesel solubility in glycerol, an additional cause of
yield loss [3]. However to mitigate the problems faced with the
use of homogeneous alkaline and acid catalysts, heterogeneous
catalysts such as solid and enzymes catalysts are developed and
used during biodiesel production process [24,25].
The purication of crude biodiesel is usually achieved via two
notable techniques; wet and dry washings. Conventionally wet
washing is the most employed technique to remove impurities
such as soap, catalyst, glycerol and residual alcohol from biodiesel.
However, the major disadvantage in the use of water to purify biodiesel is increase in cost and production time [26]. Besides, separation of biodiesel phase from water phase is difcult and produces
large amount of wastewater. Thus for each litre of biodiesel, close
to 10 L of wastewater is produced [27]. Rening of crude biodiesel
alone accounts for 6080% of the total processing cost [28].
Furthermore, dry washing technique (ion exchange resins and
magnesol powder) was introduced to substitute water washing
to remove biodiesel contaminants. This technique is also employed
in commercial plants to purify biodiesel [29]. However, the understanding of the chemistry of dry washing substances is still skeletal
[30].

The difculties regarding operation of wet and dry washing processes for the purication of crude biodiesel have derived the discussion on the use of membrane technology to purify crude
biodiesel. Biodiesel purication via membrane has so far shown
to provide promising results, in addition to less water utilization
[31]. In view of the above, more efforts need to be made to explore
and exploit better purication processes such as membranes to
effectively replace conventional biodiesel separation and washing
techniques. Thus, this study critically examines and reports on
the rening technologies employed to purify crude biodiesel.

2. Biodiesel separation technologies

The rst step usually employed to recover biodiesel after
transesterication reaction is separation of crude biodiesel from
by-product, glycerol. The fast separation of biodiesel and glycerol
is as a result of differences in their polarities and also signicant
difference in their densities. The density of biodiesel and glycerol
are 0.88 gm/cc and 1.05 gm/cc or more respectively. The density
of glycerol is dependent on the amount of water, catalyst and
methanol present in it. This density difference is sufcient to employ simple gravity separation technique to separate biodiesel
phase from glycerol phase [23]. However, the separation process
between biodiesel and glycerol can be difcult in the presence of
soaps formation, which mostly solidies and form a semi solid substance [32]. This problem is usually circumvented using heterogeneous catalysts [33,34]. Chew and Bhatia [24] stated that
separation cost of homogeneous catalyst and high consumption
of energy and has pinched the need for the growth and development of heterogeneous catalysts for the production of biodiesel.
Heterogeneous catalysts are simply estranged from the crude biodiesel product and recyclable. Sharma et al. [22] stated that several
researchers have tried heterogeneous catalysts to circumvent the
problem of time and water consumption encountered during alkali-biodiesel rening process. Table 2 presents reduced biodiesel
water washing process using heterogeneous catalysts in biodiesel
production [35]. Zabeti et al. [36] reviewed biodiesel production
via heterogeneous catalysts (solid catalysts). The authors noted
that heterogeneous catalysts are not dissolved or consumed during
transesterication, therefore they are easily separated. This characteristic limits impurities and reduces cost of nal biodiesel product
separation. Additionally, the catalysts can be regenerated and reused and as added advantage, the catalysts are environmentally
friendly since the need to use acids, solvents and water during separation stage is minimized. Also, Shimada et al. [33] reviewed
enzymatic alcoholysis for biodiesel fuel production. Production of
biodiesel via enzymes could alleviate separation difculties commonly encountered with alkaline catalyst. The authors noted that
application of enzymes also minimizes large quantity of wastewater generated via use of homogeneous catalyst. As well increase in
purity of biodiesel above 90% is achievable.

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Table 2
Comparison between alkaline catalysts and heterogeneous catalysts on the purication of biodiesel (modied from Ref. [35]).
Variable

Alkaline catalysis

Enzyme catalysis

Solid catalyst

Reaction temperature, C
Free fatty acids in raw materials
Water in raw materials
Yield of methyl esters
Recovery of glycerol
Purication of methyl esters
Production cost of catalyst

6070
Saponied products
Inhibit transesterication reaction
Normal
Difcult
Repeated washings
Not exorbitant

3040
Alkyl esters
Insignicant
Higher
Straightforward
None
Relatively exorbitant

453493
Very low
Insignicant
Normal
Straightforward
Straightforward
Potentially cheap

Further, application of higher alcohols to oil ratios during

transesterication could enhance the rate of biodiesel production.
However, this process complicates removal of alcohol and increase
the cost of biodiesel purication [37]. Agarwal [2] reported that
conversion of vegetable oils to biodiesel is effected by alcohol to
oil molar ratio ranging from 1:1 to 6:1 and noted conversion of
9398% at a 6:1 M ratio. The author stated that alcohol to oil molar
ratios greater than 6:1 do not improve the yield of biodiesel above
9899%, but could hinder the separation of glycerol from the product mixture.
Also, to simplify biodiesel separation, production of biodiesel
through non-catalytic transesterication of vegetable oil with
supercritical methanol was proposed by Kusdiana and Saka [38]
and Demirbas [39]. Kusdiana and Saka [38] observed post treatment of crude biodiesel produced via conventional methods to
cause severe separation difculties, since several steps are required
to remove the catalyst, glycerol, alcohol, soap, and glycerides, etc.
They adopted supercritical methanol method under the following
conditions; temperature of 350 and 400 C, pressure of 45
60 MPa, and molar ratio of 1:42 of the rapeseed oil to methanol
with the aim of circumventing problems associated with the common method. They noted that supercritical methanol method for
biodiesel production consumed less energy, and present less separation difculties. Furthermore, Han et al. [40] investigated supercritical methanol technique using methanol to oil ratio of 24,
temperature of 280 C, CO2 to methanol ratio of 0.1, and pressure
of 14.3 MPa and achieved biodiesel yield of 98% within in 10 min.
The authors noted that the process is practically viable in the
industry, safer, and less costly. However the process requires higher temperatures and pressures ranging from 252402 C and 35
60 MPa respectively [41].
The separation between biodiesel and the by-product, glycerol
is primary achieved through different techniques as presented in
Table 3. Gomes et al. [45] remarked that separation of biodiesel
from glycerol via decantation is cost effective. However, the process requires a long period of time ranging from 1 to 8 h to achieve
good separation [23]. Therefore to hasten products separation process, centrifugation technique is mostly employed. The process of
centrifugation is fast, but the cost involve is considerably high [50].
In recent times, membranes are applied to separate and purify
crude biodiesel. The process seems to be promising providing
high-quality biodiesel [51], besides being energy efcient [52].
Dube et al. [53] investigated the application of membrane reactor
to produce biodiesel fuel. The authors employed membrane reactor
Table 3
Techniques for the separation of biodiesel from transesteried product mixture.
Technique

Reference

Gravitational settling
Centrifugation
Filtration
Decantation
Sedimentation

[8,12,42]
[3,25,43,44]
[27,45,46]
[23,45]
[4749]

with membrane pore size of 0.05 lm, tube length of 1200 mm, surface area of 0.022 m2, internal and external diameters of 6 and
8 mm respectively. The membrane reactor performed well for its
ability to retain the unreacted triglyceride, and provide high purity
and quality biodiesel fuel. The authors noted that one of the advantages of triglyceride free fatty alkyl esters is the simplication of
the often onerous downstream purication of crude biodiesel. Also,
Gomes et al. [45] stated that to produce biodiesel fuel, separation
of free glycerol is ranked among the most critical factors to consider. The authors studied the effectiveness of microltration with
ceramic membranes to separate biodiesel and glycerol. They
experimented tubular Al2O3/TiO2 ceramic membranes with ltration area of 0.005 m2 and average pore size of 0.2, 0.4, and
0.8 lm and the crude biodiesel was microltered at transmembrane pressures of 1.0, 2.0, and 3.0 bar and temperature of 60 C.
The lowest ux decline rate and the highest glycerol retention
(99.6%) were achieved for the feed solution with 5% ethanol. Recently, Saleh et al. [54] reported that use of water to wash biodiesel
can be avoided using membrane rening technique. The authors
noted that membranes could facilitate recovery of valuable products and treatment of efuents, thereby minimizing their harm
to the atmosphere and providing solutions for many environmental problems encountered during biodiesel production. They employed polyacrylonitrile (PAN) membrane at a temperature of
25 C to remove soap, methanol, water and glycerol. The authors
added small amounts of water to improve glycerol separation from
biodiesel, and achieved a glycerol content as low as 0.013 mass%,
which is below the ASTM D6751 standard of 0.020 mass%.
3. Biodiesel wet washing technologies
Production of biodiesel is usually followed with soaps formation and water production especially when low quality feedstock
and alkaline catalysts are used as shown in Fig. 1. Van Gerpen
[55] stated that water content, free fatty acid level, and saturation
level are the main differences between feedstocks. The author revealed that feedstocks should be dried to control water content
which causes hydrolysis of fats and oils to FFAs. The presence of
FFAs leads to soap formation, thus interfering in the products purication process. Demirbas [41] noted that in alkali-catalyzed
transesterication, the yields of fatty acid methyl esters and purication process are negatively affected by presence of water. Wang
and Yang [56] stated that the difculties involve in the removal of
homogeneous catalyst lead to additional cost of biodiesel product.
Further, Ma and Hanna [18] remarked that during transesterication reaction, water content is a more critical variable than FFAs.

Fig. 1. Formation of soap and water.

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Consequently, feedstocks with high amount of water and FFAs

molecules could easily interfere with the transesterication reaction resulting in soaps formation, thereby affecting the purication
of crude biodiesel and lowering the yield of alkyl esters as shown
in Figs. 2 and 3 [38]. Therefore to meet international standard specication of high purity requirements for biodiesel fuel as provided
by European standard (EN 14214) and the American standard for
testing materials (ASTM D6751) as shown in Table 4 [41], it is necessary to extensively purify crude biodiesel. Traditionally until recently the commonest effective technique to remove glycerol and
methanol from biodiesel product mixture is by water washing,
since both glycerol and methanol are highly soluble in water
[26]. Sandra and Dejan [57] reported that use of hot water washing
can provide ester yield of 86% and high purity of 99%. The authors
stated that to meet either EN 14214 or ASTM D6751-07, biodiesel
should contain 96.5 wt.% Fatty acid methyl esters (FAME).
Biodiesel wet washing technique involves addition of certain
amount of water to crude biodiesel and agitating it gently to avoid
formation of emulsion. The process is repeated until colorless wash
water is obtained, indicating complete removal of impurities. Wet
washing processes usually requires a lot of water [27,58], approximately water wash solution at the rate of 28% by volume of oil and
1 g of tannic acid per liter of water [59]. The use of large quantity of
water generates huge amount of wastewater and incur high energy
cost [6062]. Jaruwat et al. [63] reported that Thailand is producing about 350,000 L/day of fatty acid esters (biodiesel), resulting

120

Methyl esters (%)

100
80
60
40
20

Alkaline catalyst
Acid catalyst

10

15

20

25

30

35

Water content (%)

Fig. 2. Graph of yield of methyl esters against water content in transesterication.

120

Methyl esters (%)

100
80
60
40

Alkaline catakyst
Acid catalyst

20
0

FFA (%)
Fig. 3. Graph of yield of methyl esters against FFAs in transesterication.

to no less than 70,000 L/day of contaminated wastewater. The

authors noted that the wastewater disposed is at a high pH due
to signicant levels of residual KOH and hexane-extracted oil, high
solid content and low nitrogen concentration, besides higher concentration values of BOD, COD, oil and grease, etc. as shown in Table 5. These components were found to inhibit the growth of
microorganisms, making it difcult for the wastewater to naturally
degrade [63].
Wet washing is mostly conducted through washing with dionized water, washing with acid (5% phosphoric acid) and water and
washing with organic solvent and water as discussed below:
3.1. Dionized water washing technology
Water washing has been traditionally used to purify crude biodiesel after its separation from glycerol [50]. Demirbas [59] reported that air was cautiously introduced into the aqueous layer,
while gently stirring the mixture of crude biodiesel and water. This
process was continued until the ester layer became cleared. In
addition, after settling the aqueous solution was drained and water
alone was added at 28% by volume of oil for the nal washing process [59]. Van Gerpen [55] noted water washing to be the most
problematic step in biodiesel production. The author reported that
although water washing involves heated, softened water, wastewater treatment and water/methanol separation. But the process
of water application provides an avenue for the addition of acid
to neutralize the remaining catalyst and remove the salts formed.
Further, excess alcohol sometimes needs to be removed before
the washing step. This usually prevents the addition of alcohol to
the wastewater efuent. In some cases the alcohols is removed
with the wastewater and then later remove from wastewater.
The application of distilled water (120140 F) couple with gentle
water washing eliminates precipitation of saturated biodiesel and
prevents the formation of emulsions [55]. Balat and Balat [21] remarked that after transeterication, crude biodiesel and glycerol
can be phase separated within the rst 10 min and a complete separation could be achieved in 2 h after stirring is stopped. Also alcohol can be removed through distillation and evaporation and that
care must be taken to ensure zero water accumulation in the
recovered alcohol stream. The authors reported that after phase
separation dionized water is added to crude biodiesel at the rate
of 5.5% by volume of the feedstock and the mixture stirred for a
period of 5 min and allowed to settle for glycerol removal. The removal of complete glycerol is an indication of high-quality biodiesel production. Also, Fangrui et al. [64] noted that washing two
times is enough to get rid of impurities from the methyl esters.
The crude methyl esters produced was washed and distilled under
vacuum at 3080 C and 133 pa. The product was then dried at
80 C for 10 min to remove traces of moisture and the methyl ester
yield was found to be 9799%. Chongkhong et al. [42] stated that
after transesterication, 10.24 wt.% of 3 M NaOHH2O solution
was used to neutralize crude biodiesel product containing residual
FFAs of about 1.4 wt.%. The crude biodiesel and the solution of
NaOHH2O were mixed and stirred at a temperature of 80 C for
20 min. The biodiesel phase was removed from the top of the separator whilst soap was taken from the bottom. The nal biodiesel
product was then heated in an evaporator to remove the residual
water in the product.
Furthermore, Saifuddin and Chua [65] washed esters phase separated from the mixture by placing the esters on a glass cylinder
and spraying water on top of the cylinder at low velocity. Both catalyst and alcohol were separated through the cylinder via percolation process. They used microwave heating power (750 W) for 3
4 min to speed up the separation process and the cylinder was then
left to stand for 10 min after irradiation. Consequently a clear esters
phase at the top was obtained and the residual alcohol and catalyst

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Table 4
International biodiesel standard specications [41].
Properties

Units

ASTM Method

EN14214

Ester content
Flash point
Water and sediment
Kinematic viscosity, 40 C
Sulfated ash
Sulfur
S 15 grade
S 500 grade
Copper strip corrosion
Cetane
Cloud point
Carbon residue 100% sample
Acid number
Triglyceride
Free glycerin
Total glycerin
Phosphorus content
Methanol content
Distillation temperature, atmospheric equivalent temperature,
90% recovered
Sodium/potassium

% (m/m)
C
vol.%
mm2/s
% (m/m)
mg/kg
ppm

rating

C
% (m/m)
mg KOH/gm
% (m/m)
% (m/m)
% (m/m)
mass%
% (m/m)
C

130 min.
0.050 max.
1.96.0
0.020 max.

15 max.
500 max.
No.3 max.
47 min.
Report
0.050 max,
0.50 max.
0.20 max.
0.020 max.
0.240 max.
0.001 max.
360 max.

96.5
>101
0.05
3.55
0.02
610

class1
P51

0.50 max.
0.20 max.
0.02 max.
0.25 max.
0.001 max.
0.20 max.

ppm

5 max. combined

5 max.

Max: Maximum.
Min: Minimum.

Table 5
Chemical and physical properties of raw biodiesel wastewater.
Parameters

Thailand standard [63]

Values of raw biodiesel wastewater [63]

Biodiesel waste water [26]

pH
COD (mg/L)
BOD (mg/L)
Oil and grease (mg/L)
TKN (mg/L)
Conductivity (Scm 1)
TSSa (mg/L)
VSSb (mg/L)
MSSc (mg/L)

5.59
6400
660
65
6100

9.2510.76
312,000588,800
168,000300,000
18,00022,000
439464

6.7
18,362

1119
8850
8750
100

TKN: Total Kjeldahl Nitrogen.

a
Total suspended solids.
b
Volatile suspended solids.
c
Mineral suspended solids.

were collected from the bottom. The nal ester product was dried
using anhydrous sodium sulfate (Na2SO4). The authors remarked
that agitation during water washing could lead to high ester losses
as much as 18% due to formation of an emulsion. They stated that
the amount of water needed in the purication of biodiesel could
be minimized, if rened raw materials, moderate catalyst amount
and lower alcohol ratios are employed. In another study, Suprihastuti and Aswati [66] reported that to achieve low glycerol content in
biodiesel as stipulated by ASTM D6751 and EN14214, the washing
should be done in multistage process. The authors noted that water
washing could signicantly affect the extraction of glycerol. They
added that during water washing process, higher temperatures
gives more glycerol extraction. The authors experimented different
washing times and remarked that for washing time more than
20 min and at room temperature and by using esters to water volume ratio of 1:3, the glycerol content in esters was reduced from
0.9331% to 0.0423% and the pH was down to 7.3. Although, the glycerol value obtained was higher than the allowable value for international standards.
3.2. Acids and dionized water washing technology
Acids such as phosphoric acid, sulfuric acid and hydrochloric
acid are mostly used in the purication of crude biodiesel. This

process is followed with use of distilled water to completely remove biodiesel impurities. For the purpose of immediate use on
diesel engines and long term storage, puried biodiesel is properly
dried. Cayli and Kusefoglu [67] noted that after one-step transesterication reaction, the crude methyl esters produced was puried
with hot water at 70 C, and 5% H3PO4 (aq) at 50 C. The authors
dried the methyl ester layer in a vacuum and checked with ceric
ammonium nitrate reagent for glycerol removal. Hass et al. [13]
stated that water have to be reduced to a limit of 0.050% (v/v) to
meet the ASTM D6751 standard specication. The authors washed
biodiesel with water of pH 4.5. The process helped in neutralizing
the catalyst and converting the soap formed to FFAs, thus reducing
its emulsifying tendencies. Further, vacuum dryer was used to reduce the residual water from the initial value of 2.4% to nal value
of 0.045%. The water removed via drying was recycled into washing operation. As well, to reduce the cost of production, the glycerol produced was also rened to a concentration level suitable
to the market value (80w/w%). Karaosmanoglu et al. [68] investigated rening of crude biodiesel via neutralization with Sulfuric
acid (1:1). Two processes were explored: use of catalyst in solid
form and use of catalyst dissolved in methanol. In the case of rening technique for catalyst in solid form, decantation was used to remove the catalyst and the product was transferred into a
separatory funnel to separate biodiesel from glycerol. Sulfuric

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I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

(1:1) was then applied to reduce the pH from the initial 11.92 to a
pH of 7.0. The biodiesel phase was then separated via centrifugation and the water content of biodiesel fuel was removed overnight
by leaving the product over heated Na2SO4 (25% of the quantity of
biodiesel). For the case of catalyst dissolved in methanol containing
pH of 13.07, the pH was reduced to neutral pH value of 7.0 with
similar rening approach as that of catalyst in solid form being
adopted. In addition, Faccini et al. [69] thoroughly washed crude
biodiesel using 10% acid water at 55 C. The acid water was prepared by adding 2% (v/v) H3PO4 to distilled water. This washing
step was conducted in the same transesterication reactor with
constant stirring over 5 min, maintaining the temperature at
55 C. Subsequently, the mixture of wastewater and biodiesel
was separated using separatory funnel. The wastewater (bottom
layer) was removed and the biodiesel was washed three times with
portions of 10% (v/v) hot water (55 C). The upper layer, containing
the puried biodiesel, was dried and stored for further analysis.
Furthermore, Srivastava and Verma [70] stated that separation
of glycerol was achieved after the product mixture was allowed
to stay for 8 h. The upper layer of crude biodiesel was puried
via bubble washed technique using 10% H3PO4. The product was
puried by passing air by aquarium stone for at least a day. The
product was nally washed with distilled water to remove the dissolved impurities such as catalyst, soap and alcohol. The product
was then transferred into a separatory funnel and allowed to stay
for half an hour. The nal biodiesel with much lighter color was obtained and stored in container for use. This method of biodiesel
purication is efcient for a small biodiesel installation [71]. However, this technique is not employed by any large biodiesel purication facility. In another study, He et al. [51] used HCl (pH = 1) to
treat crude biodiesel at room temperature (20 C). The product was
then washed twice with deionized water at a volume ratio of 1:1.
The nal biodiesel product was placed over heated Na2SO4 (10% of
the amount of biodiesel) for a period of 12 h to remove biodiesel
water content and the product was ltered. Similarly, Atapour
and Kariminia [72] employed 35 mL of hot distilled water to wash
the biodiesel produced. In order to neutralize the residual catalyst
and decompose the soaps formed, the product was treated with
35 mL of HCl (0.5%). Further the product was washed three times
with 35 mL of hot distilled water. They observed that successive
rinses successfully removed contaminants such as methanol, residual catalyst, soaps and glycerol. Finally the biodiesel obtained was
then dried using manganese sulfate and ltered under vacuum
conditions to eliminate manganese sulfate crystals. Also, Qiu
et al. [10] reported that the upper layer containing biodiesel, traces
of the catalyst, n-hexane and residual methanol was thoroughly
cleaned by washing with deionized water to eliminate the contaminants such as catalyst, n-hexane and residual methanol. They used
rotary evaporation at 70 C to remove n-hexane and the residual
methanol from the product. The nal biodiesel product was then
washed twice with HCl solution (0.5 mol/L) until a clear phase
(biodiesel) was achieved. In another investigation, Tint and Mya
[73] used stainless steel tank having 45 gallons capacities to separate biodiesel and glycerol. The crude biodiesel was washed using
phosphoric acid followed by multiple water washings to achieve
pH of 7. The authors stated that repeated water washing is necessary to achieve clear biodiesel layer free from methanol, residual
catalyst and soap. Thus, after water washing the nal biodiesel
product was sent to the sand stainless steel ltration tank. The tank
was open at the top containing 100 mesh size stainless steel screen
supported by steel frame. The sand consisting the size of
( 20 + 60) mesh was put over the 100 mesh size screen. After ltration, a clear amber-yellow liquid biodiesel with a viscosity comparable to that of petro-diesel was obtained.
In additional, Van Gerpen [55] noted that to eliminate magnesium and calcium contamination and neutralize the remaining

base catalysts, softened water (slightly acidic) is usually applied.

Similarly, copper and iron ions removal eradicates the sources of
catalysts that decreases the fuel stability and minimize the tendency for the fuel to be out of specication. Finally, the rened biodiesel is dried using vacuum ash technique, sent to storage unit
and made available for diesel engine consumption [55].
3.3. Organic solvents washing technology
Organic solvents such as petroleum ether have been used to
purify crude biodiesel. This process is usually followed with the
use of large amount of demineralized water to remove residual
soap and catalyst. Wang et al. [74] distilled fatty acid methyl ester
(FAME) under vacuum (40 5 mmHg) at 180 C. When the temperature reached 240 C (40 5 mmHg), the distillation was assumed
to be completed. The crude FAME was separated after acidic
transesterication and then puried with petroleum ether and
washed with hot water (50 C) until the washing reached a neutral
pH. n-Hexane was also used for the extraction of crude biodiesel at
a 1:1 ratio at room temperature. The mixture was washed three
times using distilled water and the nal yield obtained was
93.0 wt.%. Soriano et al. [75] reported that after transesterication,
the residual alcohol and the tetrahydrofuran (THF) were removed
via vacuum distillation followed by extraction with petroleum
ether. The residual catalyst was then removed by ltration process.
The nal biodiesel product was achieved by using vacuum
distillation.
Furthermore, Fangrui et al. [64] reported that methyl esters
were washed with petroleum ether, and glacial acetic acid was
added to adjust the pH to 7. The authors revealed that the products
obtained were further puried by washing three times with water.
The products were then dried over anhydrous magnesium sulfate,
ltered and the solvent removed by evaporation. Karaosmanoglu
et al. [68] used petroleum ether to rene crude biodiesel. The process was employed after biodiesel and glycerol were separated via
decantation. The catalyst was removed in solid form from the
reacting vessel while rotary evaporator under vacuum was used
to remove the methanol. The crude biodiesel was then poured into
a separatory funnel and then petroleum ether and distilled water
were added, the pH of the mixture was adjusted by adding acetic
acid. To further purify the product, water washing was repeated
three times and the nal biodiesel was heated via Na2SO4 overnight and separated. The separation of petroleum ether was
achieved via rotary evaporator under vacuum.
4. Dry washing technologies
The dry washing technique commonly employed to purify
crude biodiesel is usually achieved through the use of silicates
(Magnesol or Trisyl), ion exchange resins (Amberlite or purolite),
cellulosics, activated clay, activated carbon, and activated ber,
etc. These Adsorbents consist of acidic and basic adsorption (binding) sites and have strong afnity for polar compounds such as
methanol, glycerin, glycerides, metals and soap [76]. This technique is followed with the use of a lter to enable the process to
be more effective and efcient as shown in Fig. 4. Dry washing is
usually carried out at a temperature of 65 C and the process is
mostly completed within 2030 min [77]. Therefore during washing process, the amount of glycerides and total glycerol in crude
biodiesel are lowered to a reasonable level. Besides, the process
has the advantage of being waterless, strong afnity to polar compounds, easy to integrate into existing plant, signicantly lower
purication time, no wastewater, total surface area coverage of
wash tank is minimized, solid waste has alternate uses, saves
space, and improves fuel quality [76]. Dugan [78] have discussed

I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

Crude
biodiesel

4245

Excess
alcohol
Removal

Mixer
(65oC for
20-30min)

Fig. 4. Schematic diagram of biodiesel dry washing process.

the process of dry washing technique to purify biodiesel, and noted

the process to decreases production time, and lower cost of production. The author stated that dry washing provides high-quality
fuel and since water is not added, it is possible to achieve less than
500 ppm water content as stipulated by ASTM D6751. However in
wet washing, the water content of the fuel is usually above
1000 ppm, which makes its removal difcult, time-consuming
and costly [78].
The use of magnesol, ion exchange resin, and other adsorbents
such as activated clay, activated carbon, and activated ber are discussed as follows.

crude biodiesel. Samples were also taken at 10 and 20 min,

although the standard washing time is 30 min. A vacuum ltration
using a Bchner funnel and water ejector was employed to separate the nal product. Also, a centrifuge was used to remove the
intermediate product. The authors noted that since magnesol is
hygroscopic the bag was opened with care and re-sealed as tightly
as possible. They suggested use of mask before handling magnesol,
since the powder is very ne. At the end of the purication process,
biodiesel containing methanol content of 0.51%, and free glycerol
content of 0.03% were obtained. However the major limitation
about use of magnesol is that little is known about the process,
its catalytic efciency and performance intricacies [76].

4.1. Magnesol
Cooke et al. [79] remarked that water washing is been substituted by dry washing (magnesol powder or an ion exchange resin)
to neutralize impurities. The authors reported the adoption of both
dry washing techniques in industrial plants. The treatment of
crude biodiesel with magnesol, a synthetic magnesium silicate, requires 1.53 wt.% of biodiesel and need to be thoroughly mixed.
The mixture is ltered using cloth lter of size 5 lm and 1 lm
nominal lter is used to conduct nal ltration process. The nal
product is polished through a lter with sizes 0.45 lm or
0.55 lm before being used as fuel. The process of magnesol biodiesel purication was experimented and the results obtained were
comparable to those provided by ASTM D6751 and EN14214
[30]. Also, Bryan [80] have experimented use of magnesol on both
soybean and grease biodiesels and the physicochemical properties
met both EN 14214 and ASTM D6751. The author stated that
megnesol has a strong afnity for polar compounds, thereby actively ltering out metal contaminants, mono and di-glycerides,
free glycerin, and excess methanol as well as free fatty acids and
soap.
Furthermore, Faccini et al. [69] studied different types of dry
washing techniques. The adsorbent experimented showed good
performance, the results from the two best adsorbents (Magnesol
1% and silica 2%) are 0.17 mgKOHg 1 for acid number, 61 ppm of
soap, 500 mg kg 1 of water, 0.22% of methanol and 0.03% of free
glycerol. Although the value of the free glycerol obtained exceeded
the minimum glycerol requirement as stipulated by ASTM6751
standard. Similarly, Berrios and Skelton [26] experimented use of
magnesol of varying concentrations: 0.25, 0.50, 0.75 and 1.00% at
60 C, using a batch reactor with sample size of 200 mL tted with
a variable speed agitator and immersed in a water batch to purify

4.2. Washing with ion exchange resins

Ion exchange resin is an insoluble matrix (or support structure)
normally in the form of small (12 mm diameter) beads, usually
white or yellowish, fabricated from an organic polymer substrate
[81]. The application of ion exchange resins as a dry washing agent
is being promoted by the resins manufacturers; Purolite (PD206)
and Rohm and Haas (BD10 Dry). Purolite (PD206) is a dry polishing
media specically formulated to remove by-products remaining
after production of biodiesel [82]. Although being sold as ion exchange materials, but none of the suppliers advocates its regeneration because of being acting as adsorbents. Berrios and Skelton
[26] studied the effects of ion exchange resins on the purication
of crude biodiesel. The authors reported that the feed were passed
through a column of resin supported in a glass tube and metered
pump was used to control the ow, and restricted outlets were employed to ensure a liquid head above the resins. They noted that
initial loading and ows of the resins were based on the recommendation of R&H trade literature. The authors analyzed the samples at interval of 2 h for methanol and glycerol and demonstrated
that ion exchange resin has the capability to reduce glycerol to a
value of 0.01 wt and considerably remove soap, but could not successfully remove methanol. They obtained methanol content of
1.14%, which is far above EN14214 standard specication. More
so, the adsorption of little soap indicates a constraint for feed containing high soap content [76]. Additionally, ion exchange resins
offers good performance and provide cost benets in the removal
of glycerin and water, removal of salts, soap, and catalyst and also
eradicate water washing [83]. However, it has less effect on the removal of methanol [8].

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I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

4.3. Washing with other dry washing agents

Dry washing agent such as activated carbon is commonly used
to remove biodiesel excess color. Thus for effective dry washing of
crude biodiesel, the adsorbent is channeled into a paddle type mixing tank and thoroughly agitated. Hayafuji et al. [84] experimented
use of activated bers, activated carbon, activated clay and acid
clay to purify biodiesel. Further, glycerin was also used as a solvent
to wash impurities. The authors noted that clay; especially acid
clay treated with sulfuric acid is a preferable, which is superior
in the aspects of dealkaline effect, deodorant effect and decoloring
effect. Also clay grain size ranging from 0.1 mm to 1.5 mm is more
suitable for effective biodiesel purication. They stated that clay
with smaller grain size provides superior purication process,
but separation after the purication treatment is more difcult.
However, when the clay grain size is larger, separation after the
treatment becomes easier, but purication process is inferior.
5. Biodiesel membrane rening technology
Basically, membranes are semi-permeable barriers that separate different species of solution by allowing restricted passage
of some component of mixture in a selective manner [85]. A membrane can be homogenous or heterogeneous, symmetric or asymmetric in structure, solid or liquid, and can carry a positive or
negative charge or be neutral or bipolar. Transport through a membrane can be affected by convection or by diffusion of individual
molecules, induced by an electric eld or concentration, pressure
or temperature gradient [86]. Membrane based separations are
well-established technologies in water purication, protein separations and gas separations. However, commercial applications of
membrane technologies are limited to separations involving aqueous solutions and relatively inert gases. Thus the use of membranes
to treat non aqueous uids is an emerging area in membrane technologies [53]. Lin et al. [52] reported that membrane separation is
primarily a size exclusion-based pressure-driven process. Therefore, different components are separated according to their particle
sizes and shapes of individual components or molecular weights.
The mode of components operation is somewhat dependent on
their interactions with the membrane surface and other components of the mixture. Also, performance of membrane separation
is affected by membrane composition, pressure, temperature,
velocity of ow and interactions between components of the feed
with membrane surface [52].
5.1. Organic membranes
The membranes used for the pressure driven separation processes, are microltration (MF), ultraltration (UF) and reverse
osmosis (RO). Initially most of such membranes were cellulosic
in nature. These are now being replaced by polyamide, polysulphone, polycarbonate and several other advanced polymers. These
synthetic polymers have improved chemical stability and better
resistance to microbial degradation [87]. Additionally, Salahi
et al. [88] remarked that polyacrylonitrile (PAN) is porous and
asymmetric membrane which combines high selectivity with high
permeation rate. However in organic solvents, polymeric membranes may swell, resulting to instant and/or long-term pore-size
changes. Consequently, polymeric membranes in solvent applications have shorter operating lifetimes [89].
5.2. Ceramic membranes
Ceramic membranes have great potentials and represent a
distinct class of inorganic membranes. Much attention has been

focused on inorganic membranes for their superiority than organic

ones in thermal, chemical and mechanical stability, high porosity,
high ux, long life time, resistance to microbial degradation, increased resistance to fouling, and a narrower pore size distribution.
Thus, porous inorganic membranes (e.g. Al2O3, TiO2, ZrO2, SiC) possess some practical advantages over the polymeric ones such as
higher mechanical strength, thermal and corrosive resistance
among others [90]. In addition to membrane material, pore size
inuences membranes and small pore sizes give more stable membranes [91]. Porous ceramic membranes are normally prepared by
solgel or hydrothermal methods, and have high stability and
durability in high temperature, harsh impurity and hydrothermal
environments [92]. Saffaj et al. [93] reported that using asymmetric multilayer conguration, ceramic membranes with high performance parameters such as permeation ow and mechanical
resistance can be achieved. The development of such a multilayer
conguration includes: shaping of a suitable support material, formation of a microltration interlayer and synthesis of an ultraltration (UF) top layer. Multilayer asymmetric membranes usually
consist of permselective material as a thin lm on one or a series
of porous supports, which provide the required mechanical stability without dramatically reducing the total transmembrane ux
[94]. Tsuru et al. [95] state that one indicator of molecular size is
molecular weight, i.e. a molecular sieving effect. Therefore, the
interaction between solutes and membrane appears to be important. The effect of interaction between solutes and membrane surface would be more pronounced in nanoltration membranes
having pores approximately 1 nm than for ultraltration and
microtration membranes having much larger pores.
5.3. Prospects of biodiesel membranes rening technology
The criteria for selecting membranes are complex and this depends on the application. Important considerations on productivity
and separation selectivity, as well as the membranes durability
and mechanical integrity at the operating conditions must be balanced against cost issues in all cases. The relative importance of
each of these requirements varies with the application. However,
selectivity and permeation rate (permeances) are clearly the most
basic properties of a membrane. The higher the selectivity, the
more efcient the process, the lower the driving force required to
achieve a given separation. The higher the ux, the smaller the
membrane area is required [93]. Further the driving force is often
pressure or concentration gradient across the membrane. Additionally, an authoritative outline of basic concepts and denitions
for membranes is obtained in a report of International Union of
Pure and Applied Chemistry [92]. Usually, membranes are applied
for different purposes. Thus, Table 6 compares polymeric and inorganic membranes features. Thus, inorganic membranes favor
applications under higher temperature and chemical conditions,
whereas polymeric ones have the advantages of being economical.
The successful application of membrane technology to purify crude
biodiesel has re-ignited the interest in the struggle to develop commercial biodiesel production. Table 7 shows that membrane biodiesel purication could provide high purity and quality biodiesel
comparable to those obtained via conventional wet and dry washing techniques. Contrary to both wet and dry washing techniques,
membrane biodiesel purication process does not require both
water and absorbent [62]. Membrane processes are usually based
on the theory that higher permeates uxes are followed by lower
selectivity and higher selectivity is followed with lower permeates
uxes. Fig. 5 shows ceramic membrane biodiesel purication
process.
Cao et al. [61] stated that maintaining a separate lipid phase is a
key factor to assure high-quality biodiesel production with the
membrane reactor system. The membrane used had a 300 kDa

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I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

Table 6
Comparison of polymeric and inorganic membranes [92].
Membrane

Advantages

Inorganic









Polymeric

Long term durability

High thermal stability (>200 C)
Chemical stability in wide pH
High structural integrity
Cheap
Mass production (larger scale)
Good quality control

Disadvantages

Current status

 Brittle (Pd)
 Expensive
 Some have low hydrothermal stability

 Small scale applications

 Surface modications to improve hydrothermal stability

 Structurally weak, not stable, temp. limited

 Prone to denature & be contaminated separation
 (short life)

 Wide applications in aqueous phase, and some gas

Table 7
Comparison of biodiesel purication of different types of rening techniques.
Rening
techniques

Methanol
(wt.%)

Glycerol
(wt.%)

Triolein
(wt.%)

FAME
(wt.%)

NaOH
(wt.%)

Water/
sediment
(wt.%)

Ester
loss
(wt.%)

Cloud
point
(C)

Cetane
number

Density @
15(C) (kg/
m3)

Viscosity @
40C (mm2/
s)

Flash
point (C)

Ref.

Wet
washing

0.5

4.02

95.34

0.14

0.6

0.0

[57]

<0.001
1.40

0.201
0.196
0.11

0.43

99.6
97.1

95.3

0.03
<0.01
0.0

1.0 0.1

55.9

879
887

4.87
4.90 0.20
4.207

180
170.0 3.0
163

[42]
[47]
[79]
[26]

0.11
0.011

0.20 max

0.45
0.191

0.25
max

0.2

0.20
max

98.5

99.0
96.5

0.18
0.04
0.042 0.004
0.05

8.1 0.2

55.2
51.3

P51

881.2

876 7

4.91
4.097
3.906 0.006
3.55

132
200

>101

[30]
[79]
[51]
[41]

Dry
washing

Membranes
EN14214

MWCO. This property provided an exceptional means of retaining

emulsions formed. Table 8 compares glycerin purication results
obtained from membrane and conventional rening technologies.
In the case of batch reaction, the total glycerin and free glycerin
were approximately twice that obtained from the membrane system. Wang et al. [62] have experimented use of inorganic (ceramic)
membrane to purify biodiesel from impurities such as; glycerol,
soap and catalyst. The authors explored micro-ltration technique
using different membrane pore sizes (0.6, 0.2 and 0.1 lm) at temperature of 60 C and pressure of 0.15 Mpa. The removal of glycerol
was less difcult due its formation of reverse micelle with soap
forming molecule size of 2.21 lm which was analyzed by zeta
potential analyzer and showed to be bigger than that of biodiesel
molecule, and therefore was easily removed by membrane. However, great caution is required during membrane rening process
to achieve biodiesel with glycerol content of 0.02 wt.%. They also
showed that ceramic membranes can considerably reduce biodiesel metal contents as depicted in Table 9. The removal of biodiesel
metal contents automatically limits the presence of soap [62]. Also,
Cheng et al. [96] have puried crude biodiesel using a membrane
separator integrated with liquidliquid extraction for the oil
FAMEMeOH system. They used porous ceramic disk membranes
(47 mm in diameter) with an effective membrane area of 13.1
cm2, the pore size of 0.14 lm, and the molecular weights cut off
(MWCO) of 300 kDa. The membrane active layer consisted of zirconia oxide supported on carbon. The authors noted that the tested
modied UNIFAC models are not adequate for simulating the phase
behavior of the oilFAMEMeOH system and envisage exploration
of different models using the results of liquidliquid extraction
(LLE) obtained.
Furthermore, He et al. [51] conducted experimental studies on
membrane extraction using hollow polysulfone and polyacrylonitrile ber membranes and the conventional extraction techniques
to purify crude biodiesel. The biodiesel obtained from polysulfone
ber membrane gave purity of 99%, besides properties such as
kinematic viscosity (3.906 mm/s2) density (0.876 g/cm) and water
content (0.042 wt.%) met the ASTM D6751 standard specication.

The authors remarked that, these results were possible due to

the absence of emulsion formation, zero density difference between uids for hollow ber membranes, and high interfacial area
[51]. The membrane purication provided better results in terms of
low water requirement, zero emulsion and less wastewater discharges than the conventional methods such as water washing,
which produce signicant amounts of wastewater containing
impurities. This results in an economic gain and the avoidance of
a serious environmental disposal problem [97]. In another study,
Low and Cheong [31] used polymeric membrane system to purify
crude biodiesel and reported improved biodiesel yield and less
water consumption. They have experimented different types of
membranes such as: PAN membrane, hydrophobic polypropylene
0.2 lm, 0.2 lm polyethersulfone membrane, at PVDF 0.2 lm
membrane, 0.2 lm ceramic tube membrane, 0.45 lm polysulfone
membrane, and 0.2 lm at mixed cellulose acetate membrane.
The water discharged from the membranes was slightly basic
and only contained trace of oil content. This effectively reduced
the environmental impact, and the cost of wastewater treatment.
The authors demonstrated that rening of methyl esters by membrane method may reduce water consumption by 75% in volume,
save oil losses up to 44%, achieve high yield and low effect of environmental pollution. In addition, Saleh et al. [27] used modied
polyacrylonitrile (PAN) membrane, with 100 kD molecular weight
cut-off to remove glycerol from fatty acid methyl esters (FAME or
biodiesel). The experiments were conducted at a temperature of
25 C and operating pressure of 552 kPa. Using gas chromatography according to ASTM D6584, the free glycerol content in permeate, retentate and feed, of the membrane system was analyzed. The
experimental results revealed low concentrations of water had a
considerable effect in removing glycerol from the biodiesel even
at approximate value of 0.08 mass%. The authors noted that conventional water washing requires 10 L of water per litre of treated
biodiesel, whereas membranes need only 2.0 g of water per litre of
treated biodiesel. They achieved 0.02 wt.% glycerol content in biodiesel at FAME + 0.1 wt.% water, and FAME + 0.2 wt.% water
respectively.

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I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

Crude fatty
acid alkyl
esters
(Biodiesel)

Inorganic
Membrne

Purified
Biodiesel

Removal of
glycerol/
alcohol/other
contaminants

Alcohol for
storage/recycling

Consumption/
storage

Purified
glycerol for
sale to other
industries

Recovered
catalyst

Fig. 5. Schematic diagram for biodiesel purication process.

Table 8
Comparison between different rening techniques for the removal of glycerin from biodiesel.
Lipid feedstock

Canola
Yellow grease
Brown grease
Palm oil
Canola oil
Soybean oil

a
b
c

Biodiesel from membrane reactor (w%)

Biodiesel from batch reaction (w%)

Total glycerin

Free glycerin

Total glycerin

Free glycerin

0.0712
0.0989
0.104

0.00654
0.00735
0.0138
0.0152 0.0074
0.013a
0.04 0.004a

0.131
0.685a
0.797a

0.0124
0.0234a
0.0171
0.0179 0.0067

0.03a,b
0.03a,c

Ref.

[61]
[61]
[61]
[62]
[54]
[45]
[26]
[26]

Does not meet the ASTM standard for glycerin in biodiesel (0.02 wt.%).
Ion exchange resin.
Magnesol.

Table 9
Contents of metals in the permeates and the retentate by membrane [62].
Component

Feed biodiesel
The permeate (0.6 lm):
The permeate (0.2 lm):
The permeate (0.1 lm):
Biodiesel by water washing:
a

Metals content (mg/kg)a

Potassium

Sodium

Calcium

Magnesium

160 19
4.25 0.37
2.20 0.42
1.70 0.31
2.46 0.41

8.98 1.52
0.68 0.15
0.88 0.23
1.36 0.34
1.41 0.35

1.45 0.36
0.70 0.24
0.55 0.25
0.95 0.38
0.64 0.29

0.33 0.12
0.25 0.11
0.26 0.16
0.15 0.07
0.18 0.08

Results are means SD (n = 5).

Demirbas [98] reported that alcohols such as ethanol forms

azeotropes with water during transesterication reaction and most
often cannot be completely recovered during purication process.
However, it was noted that pervaporation, a membrane process is
a promising technique in removing ethanol from alkyl esters [99].

6. Advantages and disadvantages of biodiesel rening

technologies
The rening of crude biodiesel is primarily done to achieve high
purity and quality biodiesel products that can be used in compressionignition (diesel) engines [100]. Furthermore, rening of crude

biodiesel is a key factor to its commercial production and application. Thus continuous development of these rening technologies
to purify biodiesel has raised hope for biodiesel industrial production and practical usability. Furthermore, achievement of highquality biodiesel fuel could provide the following benets: reduction in elastomeric seal failures, decrease in fuel injector blockages
and corrosion due absence of glycerol, catalysts and soaps, reduces
degradation of engine oil thereby providing high engine performance, better lubricant properties and better quality exhaust emissions. In addition, generation of high-quality biodiesel could also
lead to elimination of fuel tanks corrosion effects, eradication of
bacterial growths and congestion of fuel lines and lters, and annihilation of pump seizures emanating owing to higher viscosity at

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I.M. Atadashi et al. / Applied Energy 88 (2011) 42394251

Table 10
Advantages and disadvantages of different rening techniques.
Technique

Advantages

Disadvantages

Ref.

Wet washing

Excellent methanol removal

Emulsion formation, wastewater treatment, no effects on

glycerides, and drying of nal product
Consumption of water and Na2SO4, high biodiesel products
drying cost long time for water washing and the process is less
ecologically viable
Considerable loss in product due to formation of soap and
emulsion, and treatment could incur high energy cost

[26]

Information regarding the chemical composition of the resin

is difcult and little effects on methanol

[26,80]

Can reduce methanol, soap and free glycerol levels below

the amount needed by EN14214, with biodiesel purity of
99%

Dry washing

Membrane
purication

Magnesol can remove free and bonded glycerol, soap and

potassium.
Magnesol is efcient and has the Ability to replace water
washing
Can effectively remove residual methanol, catalyst traces
Can augments the stability of bio-diesel in the oxidation
process, besides it ability to remove sulfur
Can save time, lower energy, save capital cost, and lead
signicant disposal cost reduction

Provided good yield, high purity and quality nished

products that are comparable to the conventional diesel
fuels, simple, with less energy consumption, provide
enormous environmental benets and energy savings
Reduction in separation and purication costs, improved
fuel quality, and high recovery of valuable products
Zero waster washing with no waste discharges, and provide
biodiesel with less glycerol content

low temperatures [26]. Table 10 summarizes the advantages and

disadvantages of rening techniques used to purify crude biodiesel.
7. Conclusions and recommendations
Based on the foregoing the following conclusions and recommendations were made:
1. Wet rening technologies were reported to meet EN14214 in
terms of methanol and free glycerol level required in biodiesel
fuel, but the process is associated with wastewater discharges,
which leads to environmental pollution, thus raising environmental concerns.
2. It was reported that separation of glycerol is critical to achieved
high-quality biodiesel fuel.
3. It was found that dry washing process (using magnesol and ion
exchange resins) does not meet EN14214 in terms of methanol
required in biodiesel fuel.
4. It was also discovered that with little addition of water, membrane process could provide biodiesel with 0.013 wt.% glycerol,
a value below the level stipulated by both ASTM D6751 and
EN14214.
5. Membrane biodiesel rening proved to be less energy consuming and generate almost zero wastewater. These advantages
makes membrane rening technology to be more environmentally friendly compared to wet water washing technology.
6. The signicant effects of membrane on the removal of triglycerides and residual glycerol placed it at an advantage compared to
some dry washing processes.
7. Development of membrane technology is necessary to exploit
its inherent characteristic of operating under moderate
conditions.
8. Application of adsorbents to overcome problems of wet rening
was noticed to result in spent adsorbents that are not regenerated and cannot be re-used.
9. Wet biodiesel rening need to be completely discouraged for its
high energy and water consumption and considerable wastewater discharges.

Involve highly consumable incurring expensive, require

signicant resources, larger size of powder grains making
them exceedingly difcult to remove, and this caused an
abrasive contaminated fuel

Organic membranes are less stable and easily get swollen in

organic solvent
No large-scale industrial applications

[77,81,100]

[101,102]
[69]

[103]
[104]
[79,81]

[31,51,52]

[27,31,53,54,105]
[61,62,106]

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