Daud 2014

Accepted Manuscript
Title: Production of biodiesel and its wastewater treatment

technologies: A review
Author: Nurull Muna Daud Siti Rozaimah Sheikh Abdullah
Hassimi Abu Hasan Zahira Yaakob
PII:
DOI:
Reference:
S0957-5820(14)00171-2
http://dx.doi.org/doi:10.1016/j.psep.2014.10.009
PSEP 493
To appear in:
Process Safety and Environment Protection
Received date:
Revised date:
Accepted date:
23-6-2014
9-10-2014
19-10-2014
Please cite this article as: Daud, N.M., Abdullah, S.R.S., Hasan,
H.A., Yaakob, Z.,Production of biodiesel and its wastewater treatment
technologies: A review, Process Safety and Environment Protection (2014),
http://dx.doi.org/10.1016/j.psep.2014.10.009
This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Ac
ce
p
te
an
us
cr
ip
t
Highlights
Biodiesel is one of the promising alternative energy resources.
Biodiesel production generates highly polluted wastewater.
Biodiesel wastewater treatments developed so far have their own novelty and
weaknesses.
Coagulation-BAF processes seem feasible for biodiesel wastewater treatment.
1
Page 1 of 41
Title: Production of biodiesel and its wastewater treatment technologies: A review

Authors: Nurull Muna Daud, Siti Rozaimah Sheikh Abdullah, Hassimi Abu Hasan, ZahiraYaakob
Institute/University: Department of Chemical and Process Engineering, Faculty of Engineering and Built
ip
t
Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

Email addresses: nurullmuna.daud@gmail.com, rozaimah@eng.ukm.my. Phone: +603-89216407; Fax:
cr
+603-89216148
Acknowledgements: This work was supported by the Faculty of Engineering and Built Environment,
Ac
ce
p
te
an
us
Universiti Kebangsaan Malaysia under grant number INDUSTRI-2012-029.
2
Page 2 of 41
Production of biodiesel and its wastewater treatment technologies: A review

Nurull Muna Daud, Siti Rozaimah Sheikh Abdullah, Hassimi Abu Hasan, Zahira Yaakob
1.
ip
t
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
Corresponding author: Email addresses: nurullmuna.daud@gmail.com, rozaimah@eng.ukm.my
Phone: +603-89216407; Fax: +603-89216148
Abstract
an
us
cr
The development of technologies providing alternatives to petroleum fuel has led to the production of
biodiesel fuel. This paper reviews the methods used to produce biodiesel fuel from various types of
sources such as palm oil, jatropha oil, microalgae, and corn starch. It also includes a brief description of
the transesterification process and the point source of biodiesel wastewater, from which it is mainly
generated. Biodiesel wastewater is characterized by high contents of chemical oxygen demand (COD),
biological oxygen demand (BOD5), oil, methanol, soap and glycerol. The treatments developed so far for
biodiesel wastewater are also described. The authors also investigate the significance, ability and
possibility of biological aerated filter (BAF) to treat biodiesel wastewater discharged from a biodiesel fuel
production plant. The whole treatment; coagulation-biological aerated filter (CoBAF); involves the pretreatment of biodiesel wastewater using coagulation followed by the treatment using BAF.
2.
Introduction
Keywords: Biodiesel, transesterification, biodiesel wastewater, biodiesel wastewater treatment.
Ac
ce
p
te
Vegetable oil based biodiesel was introduced and investigated in the 1890s, when Rudolph Diesel
invented diesel engines to be used for machines in the agricultural sector (Orchad et al., 2007). In 1920,
the availability of low cost petroleum fuel had decreased the demand for biodiesel, leading to the
modification of diesel engines to match the properties of petroleum diesel fuel. Oil crises in the 1970s
renewed interest in vegetable oils and gave an advantage to their market (Talebian-Kiakalaieh et al.,
2013). However, the usage of traditional vegetable oils in modern diesel engines was not favourable. The
investigation of methods to produce low viscosity vegetable oils spread and a variety of methods were
introduced such as transesterification, pyrolysis, and blending of solvents. The first patent for an
industrial process for biodiesel production was filed in 1977 by a Brazilian scientist, Expedito Parente
(Lim & Teong, 2010). In 1979, South Africa initiated research into the production of biodiesel using
sunflower oil (Lin et al., 2011). Starting from 1980, the biodiesel revolution has been quite positive. A
small pilot plant was built in Austria in 1985, and in 1987 a biodiesel production plant based on
microalgae was operated in New Mexico. The commercialization of biodiesel using a variety of feedstock
such as rapeseed and used cooking oil was boosted in the 1990s and up until now. Biodiesel is not only
beneficial for transportation, it is also being used in manufacturing, construction machinery and
generators for firing boilers purpose as depicted in Figure 1 (Abdullah et al., 2009).
3
Page 3 of 41
Development of biodiesel production
ip
t
us
2.1
cr
Figure 1. Usage of biodiesel
te
an
The idea of using biodiesel fuel arose when the world started to find and develop alternative energy
resources, influenced by the depletion of non-renewable energy sources (Berchmans & Hirata, 2008).
High dependence on petroleum fuels or fossil fuels has led to uncertainty in price and supply (Raja et al.,
2011). Some alternative sources which are able to replace fossil fuels are water, solar, and wind energy
and biofuels (Abbaszaadeh et al., 2012). The increasing demand for biodiesel is also due to awareness of
the environmental impact of emissions from conventional fossil fuels combustion and the decline in
domestic oil production (Mondala et al., 2009). The production of biodiesel in several Asian countries is
shown in Table 1. The production capacity of each country is based on annual reports for the years 2011
and 2012. Among Asian countries, production of biodiesel is mainly dominated by Indonesia and
Thailand, which produce more than two billion litres every year and are also known as the main producers
of biodiesel in Southeast Asia.
Ac
ce
p
Table 1. Biodiesel production in several Asian countries (Source: www.thecropsite.com)

Production capacity
Country
Main feedstock
Production year
(billion litres/year)
Malaysia
Palm oil
0.147
2011
Indonesia
Palm oil
2.200
2012
Thailand
Palm oil
2.080
2011
Philippines
Coconut oil
0.138
2012
India
Jatropha
0.1400.300
2011
China
Waste cooking oil
0.568
2012
Commercially, biodiesel is produced through a transesterification process in the presence of

alcohol and catalyst. This process involves the conversion of triglycerides (oil) to methyl ester (biodiesel)
and by-product (glycerol) (Kolesrov et al., 2007; Chavalparit & Ongwandee, 2009; Low et al., 2011) as
described by Equation (1).
4
Page 4 of 41
3CH3OH
O
||
CH3-O-C-R2
O
||
CH3-O-C-R3
(Methanol)
(Mixture of fatty esters)
CH2-OH
|
CH-OH
|
CH2-OH
Equation (1)
(Glycerol)
Properties of biodiesel as transportation fuel
us
2.2
(Catalyst)
ip
t
(Triglycerides)
O
||
CH3-O-C-R1
cr
O
||
CH2-O-C-R1
|
|
O
|
||
CH-O-C-R2
|
|
O
|
||
CH2-O-C-R3
an
Biodiesel fuel is used as a substitute for petroleum, which traditionally has been used to produce
transportation fuel (Chavalparit & Ongwandee, 2009; El Diwani et al., 2009) and considered as the best
candidate compared to all other energy sources (Leung et al., 2010). For use as transportation fuel,
biodiesel is blended and named as B5, B10, B20, or B100, where 5, 10, 20, and 100 represent the
percentage of biodiesel in the petroleum diesel (Janaun & Ellis, 2010). Biodiesel is a methyl ester mixture
with long-chain fatty acids (Leung et al., 2010). It is made from a variety of sources of vegetables oil,
animal fats, and waste cooking oil (Kolesrov et al., 2011; Raja et al., 2011). Reportedly, Thailand has
claimed that biodiesel is one of the most promising alternative fuels to the diesel fuel used in that country
(Pleanjai et al., 2007). In Malaysia, the implementation of the B10 biofuel programme has had a positive
impact on Malaysias biodiesel market (Adnan, 2013).
Ac
ce
p
te
For biodiesel products to be used as transportation fuel, the fuel grade should fulfil the standard
requirements. Two of the international standards are tabulated in Table 2. There are many studies
conducted to produce biodiesel from various kind of feedstock. Each was analysed according to the
standard to ensure the compability of biodiesel to petroleum diesel to be used as transportation fuel. The
studies on biodiesel production are summarized in Table 3, while the methyl ester yields for each study
are illustrated in Figure 2.
The use of renewable feedstock as biodiesel production sources has made this fuel to be known as
a clean renewable fuel that is biodegradable and environmentally friendly (Leung et al., 2010; Kaercher et
al., 2013). These characteristics also provide this liquid fuel with advantage of lowering the production of
exhaust emissions from diesel engines (Hayyan et al., 2010) such as particulate matter (PM) (Kolesrov
et al., 2011), unburned hydrocarbons (HC) and carbon monoxide (CO) except for nitrogen oxides (NOx)
(Bouaid et al., 2012). The emission of nitrogen oxides usually increases due to the oxygen content in the
biodiesel (Sharma et al., 2008). Table 4 shows the emissions percentage from different studies regarding
this matter. The percentages were compared to 100% of exhaust emissions from petroleum diesel engines.
The variations in each study usually rely on the feedstock properties as well as oxygen content and
viscosity of the methyl esters.
5
Page 5 of 41
Table 2. Different standard specification for biodiesel fuel (Abdullah et al. 2009)
Limits
120 min
0.05 max
3.55.0
0.02 max
0.001 max
1a
51 min
0.3 max
0.50 max
0.02 max
0.25 max
10 max
130 min
0.05 max
1.96.0
0.020 max
0.0015 max
3a max
47 min
0.50 max
0.80 max
0.02 max
0.24 max
10 max
360 max
ip
t
C
mg/kg
mm2/s
% (m/m)
% (m/m)
Rating
% (m/m)
mg KOH/g
% (m/m)
% (m/m)
mg/kg
C
ASTM D6751
cr
Flash point, close cup

Water content
Kinematic viscosity, 40 C
Sulphated ash
Sulphur content
Copper corrosion strip (3h at 50C)
Cetane index
Carbon residue
Acid number
Free glycerol
Total glycerol
Phosphorus content
Distillation temperature (90% recovered)
EN14214
us
Units
an
Property
Pour
point
(C)
Palm oil
4.91
878
179
14
Transesterification
Castor oil
61.0
10.75
160
13
Transesterification
Jatropha
oil
Jatropha
oil
Sunflower
oil
Jatropha
oil
Waste
cooking
oil
76.0
5.25
166
te
Ac
ce
p
Transesterification
in supercritical
methanol
Transesterification
Table 3. Biodiesel properties from different feedstocks

Feedstock Yield Purity Viscosity Density Flash Cloud
(kg/m3) point
point
(%)
(%)
(mm2/s)
(C)
(C)
Soybean
97.8
oil
Process
Base catalysed
transesterification
Transesterification
Base catalysed
transesterification
Base-catalytic and
non-catalytic
supercritical
methanol
transesterification
Acidcatalysedtransester
ification
Transesterification
Municipal
sewage
sludge
Waste
sunflower
cooking
oil
4.82
128
4.72
860
183
5.20
162
98
References
Wei et al.
(2013)
Atadashi et
al. (2012)
Okullo et al.
(2012)
Okullo et al.
(2012)
Raja et al.
(2011)
Ahmad et
al. (2010)
El Diwani et
al. (2009)
Demirbas
(2009)
87
99.6
5.30
897
196
11
14.5
Mondala et
al. (2009)
99.5
9.50
Hossain and
Boyce
(2009)
6
Page 6 of 41
ip
t
cr
us
an
52
90
67
50
60
87
56
B100
B100
B100
B100
B100
B100
B100
Table 4. Percentage of exhaust emission from biodiesel engines

References
Hydrocarbon Nitric Sulfur
Particulate Polycyclic
oxide dioxide
matter
aromatic
hydrocarbons
33
110
53
Lotero et al. (2005)
90
115
67
Chincholkar et al. (2005)
23
75
0
33
Wirawan et al. (2008)
113
0
70
20
Khan et al. (2009)
50
105
0
35
Bouaid et al. (2012)
Tomi et al. (2013)
111
32
0
60
25
Talebian-Kiakalaieh et al.
(2013)
te
Carbon
monoxide
Ac
ce
p
Fuel
type
Figure 2. Methyl ester yields for different study
Other advantages from biodiesel usage are the use of agricultural surplus and reduce the
dependencies on crude oil (Abdullah et al., 2009). As stated by Mondala et al. (2009), the properties of
biodiesel with a flash point above 93.3C make it safer and easier to use, handle, and store. Another
reason that makes biodiesel comparable to petroleum diesel is the high-energy content or also known as
heating value. Referring to Table 5, the energy content of biodiesel produced in several studies have
similar or close value to the energy content of petroleum diesel which makes biodiesel comparable and
suitable to be used as transportation fuel. However, Yaakob et al. (2013) addressed that by using biodiesel
as transportation fuel, some may face few difficulties such as fuel pumping problems, cold start, poor low
temperature flow and high copper strip corrosion
7
Page 7 of 41
Table 5. Energy content of biodiesel fuel
Transesterification
Base-catalytic and supercritical
methanol transesterification
-
References
Talebian-Kiakalaieh et al. (2013)
Vivek and Gupta (2004)
Talebian-Kiakalaieh et al. (2013)
Demirbas (2009)
21.1
Demirbas and Demirbas (2011)
25.1
Demirbas and Demirbas (2011)
Transesterification
Transesterification
Transesterification
-
42.15
30.4
39.76
36.5
41
ip
t
Petroleum diesel
Karanja oil biodiesel
Tallow
WCO biodiesel
Okullo et al. (2012)

Okullo et al. (2012)
Raja et al.(2011)
Ramadhas et al. (2005)
Rawat et al. (2013)
an
Algae (Cladophora fracta)

biodiesel
Microalgae (Chorella
protothecoides) biodiesel
Jatropha oil biodiesel
Castor oil biodiesel
Jatropha oil biodiesel
Rubber seed oil biodiesel
Microalgal
Energy content
(MJ/kg)
45.00
39.66
40.05
42.65
cr
Production process
us
Type of fuel
Ac
ce
p
te
The positive impact in environmental aspect may be the main reason why biodiesel starts to gain
interest to be used as transportation fuel. However, the high price of biodiesel fuel compared to petroleum
fuel has limited the development of this renewable fuel development (Hayyan et al., 2010). The high
production cost due to the high feedstock cost limits the commercialization of biodiesel (Hasswa et al.,
2013). Another limitation to the development of biodiesel is the usage of edible vegetable oil. It arises the
problem of food supply competition, which can cause food crises, deforestation, and challenges in oil
supply management to ensure the oil supply is well managed for food consumption and consumer
products (Leung et al., 2010; Talebian-Kiakalaieh et al., 2013). Despite all these limitations, biodiesel
industry should find ways to overcome these challenges. In addition, since the increasing 53% of world
energy demand by the year 2030 (Talebian-Kiakalaieh et al., 2013) while the non-renewable energy;
fossil fuel depletes, government should really look forward to ensure that biodiesel can fulfil the energy
required by our society.
3.
Biodiesel production
3.1
Source of raw materials/feedstock
Traditionally, the main source of biodiesel is vegetable oil. The types of vegetable oils available depend
on the climate and soil conditions of the country (Siddiquee & Rohani, 2011). In Thailand, over 90% of
biodiesel production is from palm oil as raw material (Rattanapan et al., 2011). The most widely used
biodiesel feedstock in the United States is soybean oil (Mondala et al., 2009). Biodiesel feedstock can be
categorized into three types: edible oils, non-edible oils, and reusable sources or wastes, as summarized in
Table 6. Some researchers are interested in biodiesel production using oil from non-edible crops, due to
environmental issues. For instance, non-edible crops can be grown on waste lands (Leung et al. 2010).
Besides, the production of biodiesel using these types of feedstock helps governments to find suitable
ways to treat, recycle, and dispose of wastes (Suehara et al., 2005; Janaun & Ellis, 2010). Yaakob et al.
(2013) emphasized that waste cooking oil usage can reduce water pollution and also prevent blockages in
water drainage systems.
8
Page 8 of 41
us
cr
ip
t
Table 6. Different feedstocks for biodiesel production

Edible feedstocks Non-edible feedstocks Others
Soybean
Jatropha curcas
Waste cooking oil
Palm oil
Pongamia pinnata
Algal
Rapeseed
Sea mango
Municipal sewage sludge
Canola
Tallow
Sunflower
Poultry
Cottonseed
Nile tilapia
Peanut
Castor
Corn
Rubber seed
Olive
Coconut oil
Butter
Pumpkin
Linseed
Ac
ce
p
te
an
Free fatty acids (FFAs) and/or triglycerides are an important component of feedstock to be
converted to biodiesel (Janaun & Ellis, 2010). All fatty acids sources are favourable for use in biodiesel
production (Talebian-Kiakalaieh et al. 2013). Kinast (2003) classified biodiesel feedstock based on their
FFAs as illustrated in Figure 3. Types of refined oil feedstock which contain FFAs<1.5% are, for
example, soybean, canola, and palm oil. Used cooking oil, tallow, and poultry fat are types of feedstock
categorized as group II, having FFA contents below 4%. Waste grease usually falls into group III.
However, excess FFA content in feedstock might affect biodiesel production. For instance, Moser (2009)
stated that a content of FFA>3wt% will lead to soap formation due to the reaction between the FFA and
the catalyst. Consequently, stable emulsion will form, preventing the separation of biodiesel from
glycerine and consequently reducing the final yield (Canakci & Gerpen, 2001). For FFA>2.5wt%, a pretreatment process is usually required before further processing is carried out (Leung et al., 2010;
Talebian-Kiakalaieh et al., 2013). Based on these studies, biodiesel producers using any type of feedstock
with FFA content above 2.5wt% need to handle problems of those mentioned.
Group I
Refined oils
(FFA <1.5%)
Biodiesel feedstock
Group II
Low free fatty acid yellow
greases and animal fats
(FFA <4%)
Group III
High free fatty acid
greases and animal fats
(FFA 20%)
Figure 3. Classification of biodiesel feedstock
In Malaysia, a widely used biodiesel feedstock is palm oil (Siddiquee & Rohani, 2011). Palm oil
has dominated the biodiesel production industry because of its availability and versatile application and
because it is easily found (Janaun & Ellis, 2010). It is said to be one of the high-oil-yield sources. In
research done by Sanford et al. (2009) and Mata et al. (2010), analysis to determine the oil content was
9
Page 9 of 41
cr
ip
t
conducted for certain types of feedstock, and the oil content of each feedstock is illustrated in Figure 4.
Based on their studies, babassu oil is extracted from seeds of the babassu palm tree (Attalea speciosa),
which have high oil content; however only a few biodiesel studies using babassu oil have been reported
compared to common types of sources, that is, palm oil, jatropha oil, and so on. Meanwhile the coffee
seed has the lowest oil content. One of the reasons why there is an increment in the number of researches
on finding alternatives for biodiesel feedstock is the high cost of pure vegetables (edible crops) and seed
oils, which constitutes about 70 to 85% of the overall biodiesel production cost (Mondala et al., 2009;
Siddiquee & Rohani, 2011; Abbaszaadeh et al., 2012). Using reusable sources as biodiesel feedstock,
biodiesel production costs can be reduced by 60 to 90% since the price of waste edible oils is 2.5 to 3.0
times cheaper than that of vegetable oils (Talebian-Kiakalaieh et al., 2013).
Ac
ce
p
te
an
us
Choosing the right feedstock is very important to ensure it does not increase the production cost
(Leung et al., 2010). Even if the production cost can be reduced, the production of biodiesel using nonedible oils may sometimes require multiple chemical steps due to the high FFA contents (Leung et al.,
2010). For instance, Janaun and Ellis (2010) carried out methyl ester production, with a series of
processes: one-step alkaline-based catalysed transesterification and two-step acid-based catalysed
transesterification.
Figure 4. Seed oil yield depending on different feedstock
One of the promising non-edible sources for biodiesel feedstock is Jatropha curcas Linnaeus
seed oil. Usage of jatropha oil as the primary feedstock for producing biodiesel is one way of reducing the
production cost (Berchmans & Hirata, 2008). The high dependence on imports of petroleum and
abundance of this non-edible source in India led researchers to investigate the ability of jatropha oil to
produce biodiesel with similar properties or closer to those of diesel oil (Raja et al., 2011). It is also easy
to be found and grew, even on gravely, sandy and saline soils (Bouaid et al., 2012). The source of oil in
the Jatropha curcas plant is primarily its seeds, with an oil content of 2530%.
One of the interesting ideas for achieving low cost biodiesel production is the usage of low cost
feedstock such as waste cooking oil (WCO) (Demirbas, 2009). Usage of WCO is quite beneficial since it
can prevent the WCO from being discharged into the drainage system (Yaakob et al., 2013). In Kyoto, the
usage of biodiesel from WCO collected from restaurants, cafeterias, and households to be used as public
10
Page 10 of 41
ip
t
transport fuel has been implemented (Takashi, 2009). However, the quality of the biodiesel produced may
vary since the physical and chemical properties of WCO depend on the fresh cooking oil contents (Leung
et al., 2010). Siddiquee and Rohani (2011) said that broad WCO properties may affect the consistency of
biodiesel production. Undesired impurities and large amounts of FFAs in the feedstock may also reduce
the biodiesel quality (Demirbas, 2009). It is also lead to the need of pre-treatment of WCO before further
production process take place (Yaakob et al., 2013). Janaun and Ellis (2010) stated that some major
problems of using this type of feedstock are the infrastructure and logistics needed to collect the waste oil.
an
us
cr
The usage of algae as biodiesel feedstock is said to give a high yield of methyl ester (Janaun &
Ellis, 2010). In a review by Krishna et al. (2012), the production of biodiesel using microalgae with low
cost operation and easy handling was reported. The overall idea of their studies was to investigate the
extraction of biodiesel from the harvested algae collected from wastewater treatment ponds called High
Rate Algal Ponds (HRAPs), which were set up near the industrial areas. They claimed that the system of
HRAPs coupled with biodiesel production was efficient for wastewater management, simple and cost
effective in producing biodiesel. However, Janaun and Ellis (2010) stated that for commercialization of
algae-based biodiesel, it may result in a high production cost. For instance, this method requires effective
large scale bioreactors and an algae strain that can produce a high oil yield (Vasudevan & Briggs, 2008).
Ac
ce
p
te
A recent study done by Siddiquee and Rohani (2011) showed the ability of municipal sewage
sludge as biodiesel feedstock. The lipid was extracted from the sewage sludge before being subjected to
the process of biodiesel production and the process is known as a lipid extraction process. Study of
Mondala et al. (2009) showed that, the production of sludge biodiesel using in situ transesterification
managed to produce low cost biodiesel. The cost was compared to petroleum diesel (USD 4.80/gallon)
and soy biodiesel (USD 4.50/gallon) while the cost estimated for their sludge biodiesel only around
$4.00/gallon. However, commercialization of the usage of sewage sludge as biodiesel feedstock has some
large challenges, such as the pre-treatment process of raw sludge, the lipid extraction process, biodiesel
production methods from solid sludge, biodiesel quality, and process economics and safety.
In producing biodiesel, cost of overall production usually involves the cost of feedstock, cost of
processing the raw material; purification of raw material and oil pressing, cost of transesterification, cost
of electricity, transportation and working capital (Pimentel & Patzek, 2005; Sharma et al. 2008).
Siddiquee and Rohani (2011) classified the factors that affects the production cost into two major factors;
the cost of raw materials and the operating costs. However, Kapilakarn and Peugtong (2007) stated that
almost 80% of biodiesel production cost was contributed by the cost of feedstock. Their study on palm oil
biodiesel production at different reaction process conditions showed that for palm oil biodiesel
production, the cost was contributed by three major factors that were the cost of palm oil (80%), methanol
(15%) and energy (5%). Based on several studies done by Mondala et al. (2009), Demirbas (2009) and
Talebian-Kiakalaieh et al. (2013), the production cost of biodiesel depending on the feedstock used can be
classified as depicted in Figure 5 while Table 7 shows the cost of producing biodiesel from different
feedstock based on previous studies.
11
Page 11 of 41
ip
t
Moderate-cost
productions feedstock
Vegetable oil
High-cost productions
feedstock
unflower oil
oybean oil
us
cr
Low-cost productions
feedstock
unicipal sludge
Figure 5. Classification of biodiesel production cost based on different feedstock
Biodiesel production process
te
3.2
an
Table 7. Cost of producing biodiesel from different feedstock using transesterification process
Feedstock
Biodiesel production cost (USD per gallon)
References
Municipal sludge oil
USD 3.11 per gallon
Siddiquee and Rohani (2011)
Soybean oil
USD 4.00-4.50 per gallon
Siddiquee and Rohani (2011)
Animal fats
USD 1.59 per gallon*
Sivasamy et al. (2009)
Rapeseed oil
Sivasamy et al. (2009)
Palm oil
Ong et al. (2012)
Rapeseed oil
Ong et al. (2012)
Castor oil
Ong et al. (2012)
Soybean oil
Ong et al. (2012)
Waste cooking oil
Ong et al. (2012)
* Calculated production costs after unit conversion
3.2.1
Ac
ce
p
Biodiesel can be produced by four primary techniques: direct use and raw oils blending, micro-emulsions,
transesterification, and pyrolysis (Vyas et al., 2010). However, the common reaction being used
nowadays is transesterification (Janaun & Ellis, 2010; Siddiquee & Rohani, 2011; Abbaszaadeh et al.,
2012).
Direct use and raw oils blending
The direct use method is a method whereby crude vegetable oil is mixed or diluted with diesel fuel in
order to improve the viscosity (Abbaszaadeh et al., 2012). For ratios of 1:10 to 2:10, use of the diesel was
found to be successful. However, Ma and Hanna (1999) stated that blends of oils are not practical for
direct and indirect engines. Problems related to this situation are due to the high viscosity, acid
composition, FFA content, and gum formation.
3.2.2
Micro emulsions
It was stated by Abbaszaadeh et al.(2012) that the micro-emulsion process is developed and used to solve
the problem regarding high viscosity of vegetable oil. A micro-emulsion is made by blending the
vegetable oil with suitable solvents. Solvents that have been used and studied previously are methanol,
12
Page 12 of 41
ethanol, and 1-butanol. The disadvantages of this process are that it can result in heavy carbon deposits
and incomplete combustion.
3.2.3
Pyrolysis
3.2.4
an
us
cr
ip
t
Pyrolysis of oils involves the heating process with or without catalyst to convert one organic substance
into another (Mohan et al., 2006). It was previously reported that biodiesel fuel produced through a
pyrolysis process or known as bio-oil is suitable for diesel engines; however, low-value materials are
produced due to the elimination of oxygen during the process (Abbaszaadeh et al., 2012). Oxygen
elimination is done to upgrade the fuel produced so that it will be economically attractive and acceptable.
Undesirable properties that sometimes restrict the application of biodiesel produced through this process
are low heating value, incomplete volatility, and instability (French & Czernik, 2010). This process
requires expensive equipment and has several advantages such as lower processing cost, simplicity, less
waste, and no pollution (Singh & Singh, 2010). It was suggested by Ito et al. (2012) that the pyrolysis
method is suitable for WCO processing.
Transesterification
Ac
ce
p
te
Transesterification is said to be the most favourable reaction in producing biodiesel because it can reduce
the oil viscosity (Abbaszaadeh et al., 2012). The conventional process flow diagram for transesterification
is shown in Figure 6. The transesterification process involves the formation of glycerol and methyl esters
from the reaction of oil feedstock with alcohol in the presence of catalyst. The process continues with the
separation of biodiesel and glycerol followed by the alcohol recovery process. Recovered alcohol is
recycled back to the initial process while the methyl ester produced is sent for purification, also known as
the washing step. It will then undergo a drying process where refined/purified biodiesel is obtained.
Factors that might affect the transesterification yield are the catalyst type, the alcohol/vegetable oil molar
ratio, the content of water and FFAs, temperature, and reaction duration (Siddiquee & Rohani, 2011;
Abbaszaadeh et al., 2012).
There are three types of catalysts: alkalis, acids, and enzymes. Alkali-catalysed transesterification
is widely used in commercial production because this method produces a high conversion of oil in a short
time (Srirangsan et al., 2009) and is less corrosive to industrial equipment (Jayed et al., 2009). It is said to
have a very fast reaction compared to other catalysts (Siddiquee & Rohani, 2011; Berrios & Skelton,
2008). However, the reaction between FFA and alkali catalyst is undesirable because the soap formation
can inhibit the effectiveness of separation of glycerol from methyl ester and lower the biodiesel yield
(Atadashi et al., 2012). It also leads to the consumption of catalyst. Enzyme catalyst can help avoid the
formation of soap. Like acid catalysts, this catalyst has a longer reaction time and is costly. The catalyst
chosen is usually depends on the starter material and the conditions of its reaction (Kaercher et al., 2013).
Stated by Huang et al. (2010), commonly used alcohols are methanol, ethanol, propanol, butanol, and
amyl alcohol. Methanol is more favourable because has a lower cost (Berrios & Skelton, 2008), is easily
obtained (Atadashi et al., 2012), and can react with triglycerides quickly and dissolve the alkali catalyst
easily (Ma & Hanna, 1999). Process conditions of transesterification reaction with respect to different
kind of feedstock are tabulated in Table 8.
13
Page 13 of 41
Refined
biodiesel
Drying
Fat/oil
Transesterification
Washing
Water
+
acid
Glycerol
Acid
us
Alcohol
Wastewater
for treatment
cr
Alcohol
recovery
Biodiesel/glycerol
Separator
ip
t
Biodiesel
Figure 6. Process flow diagram of conventional transesterification process for biodiesel production
Generation of biodiesel wastewater
an
4.
Biodiesel washing process
4.1
As can be seen from Figure 6, biodiesel wastewater is mainly generated from the washing process. The
washing process is important to remove excess contaminants and impurities to ensure that only high
quality biodiesel that meets stringent international standard specifications is produced (Ngamlerdpokin et
al., 2011; Atadashi et al., 2012).
4.1.1
Ac
ce
p
te
In the washing process, the undesirable substances being removed include soap (Rattanapan et al., 2011),
catalyst, free glycerol, residual alcohol (Atadashi et al., 2011), water, and FFAs (Berrios & Skelton, 2008;
Leung et al., 2010). Non-removed contaminants will reduce the quality of biodiesel and affect engine
performance (Atadashi et al., 2011). The washing process is commonly done via two techniques: wet and
dry washing (Berrios & Skelton, 2008). Recently, another alternative washing method has been
investigated, which is membrane extraction (Leung et al., 2010).
Wet washing process
In the wet washing process, distilled warm water or softened water is used to remove glycerol, alcohol,
sodium salts, and soaps. Water mist is sprayed over the unpurified product and the mixture of water and
impurities will be settled and drained out as effluent. Colourless water obtained on repeating this process
indicates that complete removal of impurities is achieved (Atadashi et al., 2011). The solubility of
glycerol and methanol in water make this process favourable and effective in removing both contaminants
(Berrios & Skelton, 2008; Leung et al., 2010). However, Low et al. (2011) stated that some disadvantages
of this process are long separation time and loss of yield. The loss of fatty acid methyl ester yields in the
rinsing water contributes to the generation of highly polluted liquid effluent (Kumjadpai et al., 2011). The
large amount of biodiesel wastewater generated by the washing process creates a significant problem for
the industry and environment. In 2011, worldwide generation of biodiesel wastewater was approximately
28 million m3 (Veljkovi et al., 2013).
14
Page 14 of 41
ip
t
Process
Catalyst
Jatropha oil
Heterogeneous
catalysed
transesterification
Heterogeneous
catalysed
transesterification
Two-step
transesterification
Two-step
catalysed
transesterification
Base catalysed
transesterification
Transesterification
EFB
Table 8. Process conditions of transesterification reaction

Catalyst: oil
Methanol: oil
Reaction time
Reaction
weight ratio
ratio
(min)
temperature
(C)
20:1
15:1
90
65
KOH/EFB
15:1
H2SO4
NaOH
H2SO4
KCH3O
Jatropha oil
Jatropha oil
H2SO4
us
98.5
Yaakob et al.
(2012)
65
99.5
Yaakob et al.
(2012)
24:1
120
65
90.0
6:1
60
45
98.0
Berchmans and
Hirata (2008)
Bouaid et al.
(2012)
6:1
60
60
6:1
65
98.0
20:1
NaOH
KOH
NaOH
6:1
180
40
99.0
Sunflower oil
Two-step
transesterification
Transesterification
6:1
60
80.0
Karanja oil
Transesterification
KOH
8-10:1
68-70
30-40
88.0
WCO
Transesterification
29:1
169
115
79.7
WCO
Supercritical
methanol
transesterification
Alkaline
modified
zirconia
No catalyst
41:1
30
286
99.6
Ac
Sunflower oil
NaOH
M
an
Jatropha oil
References
45
ed
Jatropha oil
Yield (%)
15:1
ce
pt
Jatropha oil
cr
Feedstock
Raja et al.
(2011)
El Diwani et al.
(2001)
Hossain &
Boyce (2009)
Ahmad et al.
(2010)
Vivek and
Gupta (2004)
Wan Omar and
Saidina Amin
(2011)
Demirbas
(2009)
15
Page 15 of 41
4.1.2
Dry washing process
Membrane extraction
an
4.1.3
us
cr
ip
t
The dry washing process involves the use of an ion exchange resin (Atadashi et al., 2011) or magnesium
silicate powder (Low et al., 2011). These materials are used to replace the usage of water in order to
remove the impurities (Leung et al., 2010; Berrios & Skelton, 2008). The filtration process is usually
added in the final stage to enhance the process efficiency. The advantages of this treatment are that no
wastewater is produced and the total surface area coverage of the wash tank is minimized (Atadashi et al.,
2011). Magnesium silicate used in this process can be reused while synthetic magnesium silicate has
added value as it can be used as compost and animal feed additive (Dugan, 2007). Even though this
process offers the advantage of being waterless, it is reported that the products obtained from this process
never meet the limits of the international biodiesel standard (Leung et al., 2010). For instance, in research
done by Berrios and Skelton (2008), their dry washing process was able to produce or provide biodiesel
with a free glycerol level less than that specified by the EN14214 Standard but failed to meet the standard
level for methanol, triglycerides, and soap and water contents.
Ac
ce
p
te
The aim of reducing the quantity of water required for the washing process has led to the development of
the membrane extraction method. This method can reduce the environmental impact due to a reduction in
the amount of oil in the discharged water. The usage of membrane extraction is beneficial in minimizing
the volume of water used (Gomes et al., 2013), effectively avoiding the occurrence of emulsification
during the washing step and resulting in a decrement of the methyl ester loss during the refining process
(Leung et al., 2010), and it is said to be a promising method of biodiesel purification. Membrane studies
carried out by Low et al. (2011) involved the usage of two types of membrane: flat microfiltration mixed
cellulose acetate (MCA) polymeric membrane and flat ultrafiltration polytetrafluoroethylene (PTFE)
polymeric membrane. The experimental set-up of this study is shown in Figure 7. The crude biodiesel was
pumped from the recirculation tank to the membrane module, where the methyl ester permeate that passes
through the membrane was collected in a beaker, and the rejected fluid was sent back to the recirculation
tank. Their study found that the ultrafiltration PTFE polymeric membrane successfully filtered a higher
volume of methyl ester compared to the MCA polymeric membrane. Membrane technology was also used
and reported by Gomes et al. (2013). Tubular -Al2O3/TiO2 membranes with average pore diameters of
0.2, 0.1, and 0.05 m and 20 kDa were used. In the investigation using acidified water with a mass
concentration of 10%, glycerol was separated effectively, giving final free glycerol content below 0.02%
of the maximum value. Table 9 below summarizes the novelty of each treatment.
16
Page 16 of 41
ip
t
cr
us
Table 9. Advantages and disadvantages of each washing process

Advantages
Disadvantages
References
Treatment
an
Figure 7. Schematic diagram of membrane process experimental set-up (Low et al. 2011)
Very effective in removing

contaminants. Purified biodiesel
obtained direct from glycerol
separation fulfils EN14214
Standard requirements.
Increased cost and

production time; large
amount of water used,
emulsion formation
Veljkovi et al. (2013);

Berrios and Skelton
(2008); Atadashi et al.
(2011)
Dry washing
Decreases production time; lower

cost; less space required to
conduct dry washing process.
Waterless.
Exceeds the limit in the EN

Standard
Berrios and Skelton

(2008); Leung et al.
(2010)
Avoids the formation of

emulsions. Refining loss
Probably high cost. Low

throughput due to existing
contaminants.
Gomes et al. (2013);

Leung et al. (2010);
Atadashi et al. (2011)
Ac
ce
p
te
Wet washing
Membrane
extraction
decreases. Minimizes the volume

of water used. Provide cost benefit
4.2
Biodiesel wastewater and its characteristics
The large amount of wastewater generated by the commonly used wet-washing process is drawing the
attention of researchers. It was previously reported that the washing process is normally repeated two to
five times depending on the impurity level of methyl ester, with about 20120 L of wastewater being
generated per 100 L biodiesel produced (Srirangsan et al., 2009). In other literature, it was reported that
for every 100 L of biodiesel produced, more than 20 L of wastewater was generated (Suehara et al.,
2005). In Thailand, production of more than 350000 L/day biodiesel consequently produced more than
70000 L of wastewater per day (Ngamlerdpokin et al., 2011; Jaruwat et al., 2010). Siles et al. (2010)
17
Page 17 of 41
stated that wastewater disposal from this high growth rate industry may rise the environmental concerns.
The characteristics of biodiesel wastewater studied by previous researchers are summarized in Table 10.
It is normally found with high contents of COD, SS, oil and grease (O&G) with various pH level
depending on the type of process being used.
an
us
cr
ip
t
Biodiesel wastewater is a viscous liquid with an opaque white colour (Jaruwat et al., 2010). A
high pH, high level of hexane-extracted oil and low nitrogen and phosphorus concentrations make this
wastewater difficult to degrade naturally since these conditions make it unfavourable for the growth of
microorganisms (Srirangsan et al., 2009; Kolesrov et al., 2011). A study by Suehara et al. (2005) found
that the main component of biodiesel wastewater is residual remaining oil and this is also supported by
Rattanapan et al. (2011). Thus, discharges of biodiesel wastewater into public drainage might lead to
plugging of the drain due to the high content of oil and might also disturb the biological activity in
sewage treatment. Investigations by Ngamlerdpokin et al. (2011) and Chavalparit and Ongwandee (2009)
found that biodiesel wastewater contains water, glycerol, soap, methanol, FFAs, catalyst, and a portion of
methyl ester. These contaminants contribute to the high contents of COD and O&G (Srirangsan et al.,
2009).
8.9
30980
Table 10. Characteristics of biodiesel wastewater

SS
TSS
O&G
BOD5
(mg/L)
(mg/L)
(mg/L)
(mg/L)
2670
15100
8850
1500
700044300 105000
28790
300000
340
6020
9.2510.76
312588800
10.350.03
8.510.5
42800012000
60000150000
15005000
10.110.2
312000
588800
542400
11.11
11.21
9.2510.26
3681
40975
2959554362
4.346.56
1900037000
233405
670
690
4.3
Ac
ce
p
te
11.0
6.7
8.510.5
COD
(mg/L)
18362
60000545000
pH
18000
22000
700015000
168000
300000
3000060000
18000
22000
21048
168000
300000
224630
387
459
10401710
1600
15260
14922286
2601600
References
Suehara et al. (2005)
Berrios et al. (2008)
Ruengkong et al.
(2008)
Chavalparit and
Ongwandee (2009)
Jaruwat et al. (2010)
Siles et al. (2010)
Rattanapan et al.
(2011)
Ngamlerdpokin et al.
(2011)
Kumjadpai et al.
(2011)
Ramrez et al. (2012)
Ramrez et al. (2012)
Pitakpoolsil and
Hunsom (2013)
This study (2013)
Level of environmental pollution by biodiesel wastewater
In Malaysia, discharge of biodiesel wastewater into drains must comply with the Environmental Quality
Act and Regulations standard for industrial discharge. The parameters of biodiesel wastewater are
monitored according to the Environmental Quality (Industrial Effluent) Regulations 2009. The standard is
18
Page 18 of 41
governed by Malaysia's Environmental Law, the Environmental Quality Act, 1974. Table 11 shows the
industrial effluent standard limits of the Malaysian government compared with other countries. Compared
to Thailand, China, and the Philippines, the standard limits of temperature, pH, and COD are almost the
same. For BOD5, SS, and O&G content, Malaysias government requires lower limit values compared to
other countries.
Temperature
pH value
BOD5 at
20C
COD
SS
O&G
Colour
mg/L
40
6.09.0
20
40
5.59.0
50
mg/L
mg/L
mg/L
ADMI
80
50
1.0
100
200
100
10.0
200
Environmental
Quality Act and
Regulations 1974
40
5.59.0
20
Under
consideration
of PCC
40
5.59.0
60
<35
6.09.0
50
120
50
5
400
150
15
Enhancement and
Conservation of the
National Quality Act
Akta Kualiti Alam Thaveesri (2003)

Sekeliling 1974
*ADMI: American Dye Manufacturers Institute
*PCC: Pollution Control Committee
*OEI: Old/Existing Industry
*NPI: New/Proposed Industry
Coastal waters
OEI
NPI
OEI
NPI
40
69
150
40
69
120
40
59
120
40
59
100
200
50
10
250
200
150
PtCo
200
150
150
PtCo
250
200
15
300
PtCo
200
150
10
300
PtCo
Water
Pollution
Control Act
Philippine Regulations
on
Sanitation and Wastewater Systems
Tang (1993)
Magtibay (2006)
5.
Ac
ce
p
te
References
Inland waters
cr
Unit
Philippines
us
Parameter
Regulations
Taiwan,
China
Thailand
an
Malaysia
Country
ip
t
Table 11. Standards for industrial effluents in several countries
Treatment and management of biodiesel wastewater
Due to the large amount of biodiesel wastewater generated during the biodiesel production process, the
wastewater treatment should be solved effectively. In Thailand, some production plants are more likely to
deliver the wastewater to a treatment facility of a water agency due to their inability to treat this
wastewater with high organic matter content (Kumjadpai et al., 2011). They need to pay around USD
128.45 to 160 for 1 m3 of wastewater as reported by Ngamlerdpokin et al. 2011. Other alternative have
been tried previously was incinerated the wastewater in cement industry (Veljkovi et al. 2014).
However, no further investigation was reported. Incineration method is said having a cheaper cost rather
that the cost they need to pay to water treatment agency but still expensive when compared to other
industrial wastewater treatment. Srirangsan et al. (2009) stated that most previous studies usually focused
on the production of biodiesel without considering the environmental management and treatment aspect.
This has led some researchers to be eager to seek a better treatment in terms of simplicity and cost.
Certain industries generating oily wastewater employ dissolved air flotation to separate the oil and grease
before the wastewater is sent to the next process (Chavalparit & Ongwandee, 2009). Some studies have
proposed the application of pre-treatment before the wastewater flows to the treatment facility of the
wastewater agency and some have proposed full treatment of biodiesel wastewater.
19
Page 19 of 41
5.1
Current treatment technologies
5.1.1
ip
t
The individual treatments that have been reported include coagulation (Ngamlerdpokin et al., 2011;
Kumjadpai et al., 2011), electrocoagulation (Srirangsan et al., 2009; Chavalparit & Ongwandee, 2009),
biological processes (Suehara et al., 2005), adsorption (Pitakpoolsil & Hunsom, 2013), and microbial fuel
cell systems (Sukkasem et al., 2011).
Coagulation treatment
an
us
cr
In coagulation process, coagulant is added to separate the small particle content from a solution in a
reasonable time. These particles are destabilized and flocculate into larger, settleable flocs (Aygun &
Yilmaz, 2010). The formation of flocsis responsible for removing contaminants such as metals and toxic
wastes and reducing COD, BOD5, SS, turbidity, and colour (Saraswathi & Saseetharan, 2012). Two
stages of mixing are involved in the coagulation process: rapid and slow mixing. The rapid mixing helps
the coagulants to disperse uniformly in aqueous solution, while slow mixing helps the flocs size to grow
(Kim et al. 2009). Xie et al. (2011) stated that coagulation process offers some advantages such as simple
and economical, and proven in reducing COD, BOD5, TSS, colour and organic compounds levels
effectively. According to Butler et al. (2011), the coagulation process can be very expensive depending on
the treated wastewater volume. However, a comparative study of the coagulation and electrocoagulation
process in treating biodiesel wastewater showed that coagulation is more economical but produces treated
wastewater of slightly lower quality (Ngamlerdpokin et al., 2011).
Ac
ce
p
te
Factors that might affect the efficiency of the coagulation process include the type of coagulant
used or pre-hydrolyzed metal salt used (Xie et al. 2011), coagulant dosage, pH (Aygun & Yilmaz, 2010),
mixing rate (Zhou et al. 2008), and settling time (Rattanapan et al., 2011; Ngamlerdpokin et al., 2011).
Numerous types of coagulants are used, such as alum, polyamine (Xie et al. 2011), polyaluminium
chlorides, ferric chloride (Rattanapan et al., 2011), and titanium chloride (Kim et al., 2009). Organic and
natural coagulants were also used before, such as Moringa oleifera, Viciafaba, Pisumsativum, and
bentonitic clay (Saraswathi & Saseetharan, 2012). In a review by Rattanapan et al. (2011) it was stated
that ferric chloride, ferrous sulphate, and alum were highly effective coagulants in reducing COD.
However, the performance of each coagulant still depends on the overall process, and in choosing the type
of coagulant, the suitability of wastewater and economic reasons should be taken into consideration.
pH control is important in the coagulation mechanism for generation of flocs or generating
flocculation (Rattanapan et al., 2011) and affects the coagulation performance (Aygun & Yilmaz, 2010).
It is often efficient in the range of pH 5 to 7, but the nature of the water might lead to some differences in
finding a suitable pH (Parmar et al., 2011). Sometimes, it is also depends on the type of coagulant; for
example; alum is effective at reducing pollutants in wastewater over a relatively wide pH range of 68
(Ngamlerdpokin et al., 2011), PACl used pH in the range of 7 to 9 (Xie et al. 2011). Rattanapan et al.
(2011) study showed pH of wastewater did affect the dosage of coagulant used. Investigation they carried
out showed at pH 6-7, only 1.0 g/L PACl required to remove more than 90% O&G, however at pH 5, the
coagulation process used up to 2.0 g/L PACl to achieve the same removal efficiency.
20
Page 20 of 41
us
cr
ip
t
The effect of retention time on the coagulation process of biodiesel wastewater was also studied
by Rattanapan et al. (2011). The O&G removal increased from 81.65% at one day-retention time to
95.4% at five day-retention time showing that the demulsion effectiveness/O&G removal was affected by
the duration of the retention time. Their study also focused on the pH factor effect (5-7) and coagulants
effect with variable dosage (alum and ferric chloride; 0.5-1.5 g/L, PACl: 0.5-2.0 g/L). A study by
Ngamlerdpokin et al. (2011) showed that the COD and O&G were independent of the mixing rate, while
BOD5 was dependent on the mixing rate, which showed an increment in its removal from 73.5% at 100
rpm to 96.1% at 250 rpm. Zhou et al. (2008) stated that the increment of mixing rate affects the velocity
gradient as well as collision frequency and this will consequently increase the efficiency of coagulation
process. Another factor that gaining interest nowadays is the addition of coagulant aids in the coagulation
process. Aygun and Yilmaz (2010) investigated the effect of coagulant aids and they found that
coagulation treatment of detergent wastewater using FeCl3 and clay mineral as coagulant aid managed to
increase the COD removal from 71 to 84%, while the addition of polyelectrolyte aid gave up to 87%
COD removal.
Ac
ce
p
te
an
Treatment of biodiesel wastewater was done in many ways. For example, in the study done by
Ngamlerdpokin et al. (2008), it involved the acidifying process of the wastewater with three different
acids: H2SO4, HNO3, and HCl before coagulation process took place. The most effective acid was H2SO4.
The acidified wastewater was subjected to pH adjustment with the addition of calcium oxide (CaO). CaO
was used as a pH adjuster because it can work as coagulant coupling. Another factors being manipulated
were alum dosage (0-6 g/L) and mixing rate (100-300 rpm). Kumjadpai et al. (2011) carried out an
investigation of treatment of wastewater from waste used oil biodiesel production plant using a two-step
process involving chemical recovery using three types of acids (H2SO4, HNO3, and HCl) followed by a
coagulation process using either Al2(SO4)3 (pH 4.510) or PAC (pH 2.57.0) by the addition of CaO.
Optimally, through acidification using H2SO4 at pH 12.5, approximately 1530% fatty acid methyl
esters (FAMEs) were recovered. The removal efficiencies of pollutants parameter for each study are
listed in Table 12.
In another study, Xie et al. (2011) identified the performance of coagulation process in treating
raw waste glycerol produced from biodiesel production process. The pH of wastewater was first being
adjusted from 9 to 3 using HCl and NaOH prior to determine the appropriate pH for soap and oil
separation. Through this acidification process, the waste glycerol was pre-treated with appropriate pH
before coagulation process took places. In this study, PACl coagulant was used. The coagulants dosage
and pH were varied from 2 to 6 g/L and 6 to 9 respectively. Even coagulation process was proven in
treating various kind of wastewater successfully, some study underlined problems related to this process
such as the use of chemicals (Chavalparit & Ongwandee 2009) and generation of low-density sludge with
low-decomposition efficiency (Kumjadpai et al. 2011). Despite all this problems, reported that many still
choose to use chemical coagulation since it is one of the ways to enhance the wastewater treatment
(Butler et al. 2011).
21
Page 21 of 41
ip
t
Alum
Ferric
chloride
PACl
PACl
2 g/L
2 g/L
2 g/L
5 g/L
cr
6
4
us
2 g/L
1 g/L
M
an
Alum
PAC
Others
References
Ngamlerdpokin et
al. (2011)
Kumjadpai et al.
(2011)
Rattanapan et al.
(2011)
TSS: 98.1
Glycerol:
65.4
Methanol:
85.8
Xie et al. (2011)
Ac
ed
pH
Table 12. Process conditions of different coagulation treatments for biodiesel wastewater
Removal parameters (%)
Source of
Wastewater
Mixing Settling
wastewater
characteristics
COD
BOD5 O&G
rate
time
Wastewater from
pH: 2.5
97.5
97.2
98.2
washing unit
COD: 271000-341712
mg/L
BOD5: 6739-67389
mg/L
O&G: 210-421 mg/L
Wastewater from
pH: 10.1-10.2
98.8
98.6
99.5
washing unit
COD: 271200-341712
98.7
97.9
99.1
mg/L
BOD5: 6739-67389
mg/L
O&G: 210-421 mg/L
1 hr
O&G: 7120 mg/L
99.9
Wastewater from
1 hr
99.8
biodiesel
production
1 hr
99.7
96.2
93.3
35 rpm 15 min
Raw waste
pH: 9.7-10.4
glycerol
COD: 1.7-1.9 x 106
mg/L
BOD5: 0.9-1.2 x 106
mg/L
TSS: 21.3-38.7 x 105
mg/L
Glycerol: 413-477 g/L
Methanol: 112-203 g/L
ce
pt
Process conditions
Type of
Dosage of
coagulant coagulant
Alum
2 g/L
22
Page 22 of 41
5.1.2
Electrocoagulation treatment
cr
ip
t
One of the attractive treatments for biodiesel wastewater is the electrocoagulation process (Figure 8). It is
also known as an alternative method to chemical coagulation to reduce the usage of chemical coagulants
(Butler et al., 2011) This treatment has been successfully introduced in treating municipal wastewater,
dyeing wastewater (Aoudj et al., 2010), and wastewater containing organic species (phenol) (Chavalparit
& Ongwandee, 2009). This versatile treatment is said to have several advantages such as requiring only
simple equipment, ease of operation, less treatment time, and use of less or no chemicals (Tezcan et al.,
2009). It also produces a smaller amount of sludge and leads to rapid sedimentation of the flocs
generated. Electrocoagulation uses electrochemistry principles, treating the wastewater better by
oxidizing the cathode while the water is reduced (Butler et al., 2011).
an
us
The electrocoagulation process consists of three main mechanisms: electrode oxidation, gas
bubble generation, and flotation or sedimentation of formed flocs (Emamjomeh & Sivakumar, 2009).
Example of electrochemical reactions using alum as anode is described as in equation (2) (Chavalparit &
Ongwandee 2009). Listed by Butler et al. (2011) several considerations that might affect the treatment
efficiency; wastewater type, pH, current density, type of metal electrodes, number and size of electrodes
as well as metals configuration. However, there is other factor, which was investigated before such as
reaction/retention times.
Equation (2)
Ac
ce
p
te
Anodic reactions: Al(s) Al3+ + 3e

Cathodic reaction: H2O +2e H2(g) + 2OH
In the solution: Al3+(aq) + 3H2O Al(OH)3 + 3H
Figure 8. Schematic diagram of electrocoagulation set-up (Maha Lakshmi & Sivashanmugam, 2013)
(1. DC power supply, 2. Anode, 3. Cathode, 4. Electrocoagulation cell, 5. Effluent, 6. Magnetic bead, 7. Magnetic
stirrer)
The efficiency of the electrocoagulation process for biodiesel wastewater treatment has been
investigated by Chavalparit and Ongwandee (2009). The electrodes used were aluminium and graphite,
and the effect of several factors like initial pH, applied voltage, and reaction time were observed. Each
factor were varied from 4 to 9, 10 to 30 V and 10 to 40 minutes respectively. Chavalparit and Ongwandee
23
Page 23 of 41
ip
t
(2009) also optimized the process using a Box-Behnken design and found that pollutants were efficiently
removed at pH 47, while an increment of pH up to 9 resulted in a decrement of removal because there
was less formation of reactive flocs of aluminium hydroxide. The increment of voltage led to an
increment in final pH greater than 7.5 and resulted in ineffective removal. Reported that, any additional
time more than 25 minutes does not have any significant impact on the removal efficiency. Their study
showed under the optimum conditions, electrocoagulation consumed about 5.57 kWh power for the
treatment of 1 m3 biodiesel wastewater.
5.1.3
an
us
cr
A study done by Srirangsan et al. (2009) determined the ability of the electrocoagulation process
to perform biodiesel treatment using different operational conditions in terms of the types of electrode,
current density level, retention time periods, and initial pH levels. Types of electrode pairs were Fe-Fe,
Fe-C, Al-Al, Al-C and C-C. Range of current density level, retention times and initial pH were 3.5 to 11
mA/cm2, 10 to 40 minutes and 4 to 9 respectively. The process was efficient at pH 6 with 25 minutes
retention time and a current density level of 8.32 mA/cm2 using aluminium and carbon (Al-C) electrodes.
The overall removal efficiency was found to be 55.4, 96.9, and 97.8% for COD, SS, and O&G
respectively. The electrocoagulation process has also been used by Ngamlerdpokin et al. (2011) for
treating the same wastewater source, biodiesel wastewater. With a current density of 12.42 mA/cm2,
COD and BOD5 removals of 99.6 and 91.5%, were achieved respectively. Table 13 shows the process
conditions for different electrocoagulation treatments for biodiesel wastewater.
Biological treatment
Ac
ce
p
te
Various researchers have developed biological technologies for the treatment of biodiesel wastewater
(Siles et al., 2010; Sukkasem et al., 2011; Ramirez et al., 2012; De Gisi et al. 2013). However, the study
of this treatment is quite limited. Since the content of solid presents in biodiesel wastewater is quite high,
it inhibits the growth of microorganism and reduces the removal efficiencies of biological treatment. Few
studies reporting on this matter were discussed. Some factors that play an important role and influence the
effectiveness of biological process are nutrients and oxygen supply, pH value, chemical and physical
characteristics of the wastewater (Margesin & Schinner, 2001), and hydraulic retention time (HRT)
(Rajasimman & Karthikeyan, 2007). Sufficient nutrients are usually needed to ensure the sustainability of
bacterial growth and to allow treatment to proceed optimally. For oxygen level in biological treatment, it
depends on the process type either aerobic or anaerobic. For aerobic process, sufficient oxygen is needed
to create the proper environment for bacterial inoculation to become dominant. Insufficient oxygen
content in aerobic treatment may become a limiting factor for bacterial growth. However, excess oxygen
supply might lead to high energy consumption and reduce the process efficiency (Holenda et al., 2008).
pH should be taken into consideration because an unsuitable pH might lead to washout of the
biomass in the reactor (Patel & Madamwar, 2002). A study of HRT effect was investigated by Patel and
Madamwar (2002). Their study showed that petrochemical wastewater are likely to be treated by aerobic
process with a shorter HRT compared to anaerobic digestion, which requires a longer time and has a slow
reaction. In another study by Bassin et al. (2011), a longer HRT may be beneficial to treatment process
since it may result in a higher capacity of biomass and avoid washout of slow-growing bacteria.
According to Rajasimman and Karthikeyan (2007), at shorter HRTs, there is insufficient time for the
24
Page 24 of 41
biomass to degrade the substrate. This condition may lead to a lower removal percentage (Mohamad et al.
2008). However, it still depends on the suitability of the overall process, bacteria, and type of wastewater.
an
us
cr
ip
t
Study of biodiesel wastewater treatment was also done by Suehara et al. (2005). Their aim was to
achieve rapid biodegradation of the remaining oil contained in the three types of biodiesel wastewaters,
that is, artificial wastewater, raw biodiesel wastewater, and diluted biodiesel wastewater. Nutrients added
to make the process conditions favourable for the growth of bacteria were urea, yeast extract, potassium
phosphate and magnesium sulphate. This was also done to avoid eutrophication. The result showed that
the microorganism used, Rhodotorula mucilaginosa HCU-1,was able to degrade about 98% of the oil
content in the diluted biodiesel wastewater. However it gave almost zero degradation efficiency in the raw
biodiesel wastewater, which may be due to the inhibition of microorganisms present in the solids of the
raw wastewater. In another study, Chavan and Mukherji (2008) showed that they were able to treat dieselrich wastewater using Bacillus cepacia and the treatment was carried out in a rotating biological contactor
(RBC). Various N:P range were varied in order to observe the performance of RBC at constant HRT of
21 hours. At N:P ratio of 19:1, 28.5:1, 38:1 and 47.4:1, they managed to remove 98.6, 99.4, 99.4 and
99.3% of TPH respectively and they also removed 84.6, 97.8, 97.0 and 95.6% of TCOD respectively.
Their investigation concluded that the use of algal-bacterial biofilm in RBC may suitable for
petrochemical industries and petroleum refineries wastewater.
te
Ramrez et al. (2012) conducted a study of an activated sludge biological treatment applied prior
to treating biodiesel wastewater. In this case, 1.5 L of sludge from a biological treatment plant for textile
wastewater was used as the inoculums in a reactor with an operating volume of 4.5 L; 2.5 mL of nutrients
(38.5 g/L of urea, 33.4 g/L of NaH2PO4, 8.5 g/L of KH2PO4, 21.75 g/L of K2HPO4, and 5 g/L of
CaCl2.2H2O) and 2 to 4 mg/L of dissolved oxygen were supplied to the tank. The treatment succeeded in
reducing COD by 90% after 13 days of operation but gave only 21% TOC removal in 15 days.
Ac
ce
p
The potential of biological process to be used in biodiesel wastewater treatment also being
reviewed by Khan and Yamsaengsung (2011). They stated that the biological process using submerged
membrane bioreactor (MBR) could be a popular advanced process for biodiesel wastewater treatment.
MBR has successfully treated various type of wastewaters such as refinery wastewater (Rahman & AlMalack, 2006), oily wastewater (Tri, 2002), petrochemical wastewater (Llop et al., 2009), and oilcontaminated wastewater (Scholz & Fuchs, 2000). Some main parameters involved in the MBR system
are the configuration of the membrane, membrane material, membrane pore size, and HRT. Based on
their study on previous research showed that MBR was efficiently proven for treating oily wastewater,
and the authors concluded that MBR can be used in biodiesel wastewater treatment. Unfortunately, the
cost of the treatment can be higher than that of conventional treatment due to the membrane fouling. This
includes the cost of maintenance and cleaning, membrane replacement cost, and membrane module cost.
Table 14 summarized the removal efficiencies of biodiesel wastewater using biological treatments.
25
Page 25 of 41
ip
t
cr
6.00
Iron plate
Current
density:
12.42
mA/cm2
7.40
ce
pt
Current
density:
8.32
mA/cm2
us
6.06
References
Others
M
an
pH
Anode:
Aluminium
Cathode:
Graphite
Type of
treatment
Table 13. Process conditions of electrocoagulation treatments for biodiesel wastewater

Removal parameters (%)
Source of
Wastewater
Reaction
wastewater
characteristics
COD
BOD5 O&G
time
25 min
Oily wastewater
pH: 8.9
55.4
98.4
from biodiesel
COD: 30980 mg/L
production
O&G: 6020 mg/L
TSS: 340 mg/L
Glycerol: 1360 mg/L
Methanol: 10667 mg/L
25 min
Wastewater from
pH: 8.9
55.7
97.8
washing unit
COD: 30980 mg/L
O&G: 6020 mg/L
TSS: 340 mg/L
Glycerol: 1360 mg/L
Methanol: 10667 mg/L
4 hours
Wastewater from
pH: 2.5
99.6
91.5
biodiesel
COD: 271000-341712
production
mg/L
BOD5: 6739-67389 mg/L
O&G: 210-421 mg/L
ed
Process conditions
Anode &
Applied
Cathode
voltage
Anode:
18.2 V
Aluminium
Cathode:
Graphite
TSS: 96.6
Chavalparit and
Ongwandee (2009)
SS: 97.5
Kumjadpai et al.
(2011)
Ngamlerdpokin et
al. (2011)
Table 14. Removal efficiencies of biodiesel wastewater using biological treatments

Type of wastewater
Wastewater characteristics
Type of microorganism
Removal parameters
Rhodotorula mucilaginosa
Rotating
biological
contactor
Bacillus cepacia
Diesel-rich wastewater
Batch reactor
Textile wastewater
treatment inoculums
Wastewater from palm

oil biodiesel
production plant
Ac
Agar plate
Raw biodiesel
wastewater;
artificial wastewater
Raw BDF wastewater:

pH: 11
Oil concentration: 15.1 g/L
Solid content: 2.67 g/L
pH: 7.5
TCOD: 4512 mg/L
TPH: 4961 mg/L
pH 11,1
COD: 3681 mg/L
TOC: 1700 mg/L
O&G: 387 mg/L
References
COD
-
BOD5
-
O&G
-
Others
Oil:
98.0%
97.0%
TPH:
98.4%
90.0%
TOC:
21%
Suehara et al.
(2005)
Chavan and
Mukherji
(2008)
Ramirez et al.
(2012)
26
Page 26 of 41
5.1.4
Adsorption
5.1.5
an
us
cr
ip
t
Adsorption process is reported as versatile, easily operated, and effective method of separating a wide
range of chemical compounds (Zhang et al. 2010). They offer several advantages; for example, no
additional sludge is produced, no pH adjustment is required, and the pH of the discharged wastewater is
unaffected. There are various type of adsorbents, including peat, bentonite clay, activated carbon,
agricultural waste, and chitosan. The treatment of biodiesel wastewater using adsorption has been
conducted by Pitakpoolsil and Hunsom (2013). In their investigation, commercial chitosan flakes were
used as adsorbent and several operating parameters were varied, including adsorption time (0.5 to 5
hours), initial wastewater pH (2 to 8), adsorbent dosage (1.5 to 5.5 g/L), and mixing rate (120-350 rpm).
Pre-treatment of biodiesel wastewater was carried out first by an acidification process using H2SO4 to
reduce the pH to 2.0 before subjecting it to the adsorption process prior to separate the oil-rich phase. By
adding NaOH, pH of wastewater was adjusted according to the preferred range. Under optimum
conditions (adsorption time of 3 hours, initial wastewater pH of 4.0, chitosan at 3.5 g/L, and mixing rate
of 300 rpm), their investigation succeeded in reducing BOD5, COD, and O&G by 76, 90, and 67%
respectively. However, these pollutant levels were still not in the acceptable range for wastewater to be
discharged to the environment. They emphasized that further treatment is needed either repetition of
adsoption using fresh chitosan or other methods. It is also might facing difficulties in disposing the usable
chitosan flakes.
Microbial fuel cell
Ac
ce
p
te
Another treatment that has been investigated is the use of microbial fuel cells (MFCs). In a study
by Sukkasem et al. (2011), they reinvented and used a kind of biocatalytic MFC, an upflow bio-filter
circuit (UBFC). This treatment offers high COD removal but is costly due to the expensive materials used
such as platinum or gold metal catalysts, proton exchange membranes, mediators, and graphite electrodes.
In the study, biodiesel wastewater characterized by 218 000 30 000 mg/L COD was successfully treated
with up to 60% removal. Existing treatments of biodiesel wastewater and their removal efficiency are
summarized in Table 15. Each treatment has advantages and disadvantages, as listed in Table 16.
Table 15. Summary of other individual process for biodiesel wastewater treatment
SS
O&G
References
Treatment process
COD
BOD5
removal
removal
removal
removal
(%)
(%)
(%)
(%)
Adsorption
90
76
67
Pitakpoolsil and Hunsom (2013)
Microbial fuel cell
60
Sukkasem et al. (2011)
27
Page 27 of 41
Table 16. Advantages and disadvantages of different individual treatments

Advantages
Disadvantages/Problems
References
Simple and economical,
Require handling chemical,
Xie et al. (2011); Butler
proven enhance wastewater
operation relatively
et al. (2011); Chavalparit
treatment
complicated, generates lowand Ongwandee (2009);
density sludge with lowKumjadpai et al. (2011)
decomposition efficiency.
Less treatment time, no
chemical required simple
equipment, ease of operation
Higher cost compared to

coagulation, less effective for
methanol and glycerol
removal
Biological processes
Economical, versatile
arrangements for small areas,
simple and suitable for small
scale plant
Generates large amounts of

low-density sludge with low
decomposition efficiency,
time consuming, need to
manage the optimum
condition first
Adsorption
No additional sludge is
produced, pH of discharged
wastewater is unaffected
Offers high COD removal
Need further treatment, facing

difficulties in disposing the
adsorbents
Costly
5.2
Pitakpoolsil and Hunsom

(2013); Ramrez et al.
(2012); Suehara et al.
(2007)
us
an
Pitakpoolsil and Hunsom

(2013)
Sukkasem et al. (2011)
Microbial fuel cell
Ngamlerdpokin et al.
(2011); Chavalparit and
Ongwandee (2009);
Srirangsan et al. (2009)
cr
Electrocoagulation
ip
t
Treatment
Coagulation
Integrated system
5.2.1
Ac
ce
p
te
Most of the treatments used on biodiesel wastewater were able to decrease the contaminants found in it. A
specialty of each type of treatment lies in its suitability in terms of environmental and economic factors.
Many researchers suggested an additional treatment for every pre-treatment investigated in order to
achieve the highest efficiency. Several integrated systems being investigated for biodiesel wastewater
treatment are dissolved air flotationcoagulation (Rattanapan et al., 2011), the photo-Fentonaerobic
sequential batch reactor (Ramrez et al., 2012), acidificationelectrocoagulation and biomethanization
(Siles et al., 2011), and electroflotation and electrooxidation (Romero et al., 2013). Integrated systems and
the proposed integrated coagulationbiological aerated filter (CoBAF) system are further discussed in the
following section. The authors are aiming to propose a system that applies green technology that requires
the use of fewer chemicals and is economical and safe for the environment and human beings.
Dissolved air flotation-coagulation
A typical treatment of oily wastewater, dissolved air flotation, was studied by Rattanapan et al. (2011).
However, the authors suggested additional methods and pre-treatment of the systems by acidification and
a coagulation process. About 1 N of pure HCl and H2SO4 was used for acidification, and the coagulation
process was done using a Jar test unit under conditions of 100 rpm for 1 minute followed by 30 rpm for
20 minutes. A decrement in wastewater pH from 7 to 5 made the oil droplets flocculate with each other
and rise to the surface. In the acidification process, the authors found that the COD removal was efficient
at pH 3. Oil recovered in the acidification process was intended to be used in biodiesel production.
Moreover, H2SO4 was found to be a more suitable acid, since the operating cost is cheaper than with HCl.
The performance of the coagulation process was determined for different types of coagulants: alum,
polyaluminium chloride, and ferric chloride. The authors found that the usage of these three coagulants
28
Page 28 of 41
5.2.2
ip
t
provides almost similar trends of COD and O&G removal, namely more than 30 and 90% removal,
respectively. But in terms of cost, alum was found to be the more suitable coagulant. In the final process
of this research, the dissolved air flotation method was used with acidification and coagulation. The pH
was maintained at 3 with three days-retention time and alum as the coagulant. With alum dose 150 mg/L
and 40% recycle rate, this system was able to give 98100% SS removal, 8595% O&G removal, and
4050% COD removal.
Photo-Fenton-aerobic sequential batch reactor
an
us
cr
Ramrez et al. (2012) investigated the efficiency of an integrated process which combined the photoFenton advanced oxidation technique with an aerobic sequential batch reactor (SBR). Photo-Fenton
reaction was said potentially successful in removing large amount of COD content. It involved the
oxidation of Fe (II) to Fe (III) to decompose hydrogen peroxide. The oxidation rate was then increased via
the photo-reduction of Fe (III) back to Fe (II) through the exposure to radiation of UV-VIS. The
production of hydroxyl radical from this cycle is used for the oxidation of organic compounds.
Equation (3)
Fe2+ + H2O2 Fe3+ +OH + OH

Fe3++ H2O + hv Fe2+ +OH+ H+
RH + OH photo-products + H2O
5.2.3
Ac
ce
p
te
This system was applied to the treatment of wastewater from a biodiesel production plant. In this
experiment, wastewater with its pH adjusted to 2.3 was treated in a 7 L Mighty Pure MP-36 commercial
UV reactor. Hydrogen peroxide (H2O2) and ferrous ions were added to the wastewater and a sample was
taken after 2 hours. MnO2 was added to each sample in order to destroy the H2O2, avoid subsequent
reactions, prevent interference with the COD readings, and prevent inhibition of the bioreactor. The final
sample was then sent to a 4.5 L operating SBR with a dissolved oxygen level between 2 and 4 mg/L.
Seven days of treatment were applied for the degradation of organic matter. Palm oil and castor oil
biodiesel wastewaters were used, and during this experiment more than 90% of COD and BOD5 and 72%
of TOC were removed from the palm oil biodiesel wastewater. Meanwhile, the removal efficiencies for
castor oil biodiesel wastewater were 76.1, 69, and 67.7% for COD, BOD5, and TOC respectively. They
stated that through this combined system, wastewater with high biodegradability rate can be obtained and
the treatment time can be reduced. However, some problems have been pointed such as the cost for UV
radiation which is quite high and the difficulties to decompose the formed sludge in SBR.
Acicidification-electrocoagulation and anaerobic co-digestion
This treatment was carried out by Siles et al. (2010). This study was initially done to convert biodiesel-by
product which is glycerol into more valuable products. It is said that the pollution can be controlled and
the energy can be recovered through this treatment. Due to the existence of inhibitors of anaerobic codigestion which is long-chain fatty acids contained in biodiesel wastewater, they decided to add pretreatment steps; acidification and electrocoagulation process prior to reduce the effect of the inhibitors. It
is said that long chain fatty acids results in toxicity to the anaerobic consortium. Through acidification
using sulphuric acid and electrocoagulation with 5 L stirred tank containing eight aluminium electrodes,
the COD content was reduced by 45%. The treatment was then continued with anaerobic co-digestion
29
Page 29 of 41
5.2.4
Acidification-electrocoagulation and biomethanization
ip
t
using three 1-L stirred reactor. The reactors were inoculated with granular biomass obtained from
brewery wastewater treatment anaerobic tank. The organic load of biodiesel wastewater was varied from
1.0 g to 2.0 and 3.0 g COD in the range of 18-45 h retention time. The whole treatment managed to
remove 80-90% of COD with methane production as an added value to the process (310 mL methane/g
COD removed).
5.2.5
an
us
cr
Integrated acidificationelectrocoagulation and biomethanization treatment was applied by Siles et al.

(2011). Wastewater derived from biodiesel manufacturing with 428 000 mg/L of COD was used and
treated by the system. In this study, another integrated system, acidificationcoagulationflocculation and
biomethanization, was also used prior to comparing the two systems efficiencies. The pre-treatment
processes of acidificationelectrocoagulation and acidificationcoagulationflocculation gave COD
removal rates of 45 and 63% respectively. However, during the whole treatment, 99% COD removal was
recorded using acidificationelectrocoagulation and biomethanization compared to only 94% using
acidificationcoagulationflocculation and biomethanization.
Electroflotation and electrooxidation
5.2.6
Ac
ce
p
te
The utilization of electroflotation and electrooxidation in treating biodiesel wastewater treatment was
investigated by Romero et al. (2013). A bench scale reactor was used and the optimum conditions of this
combined process were achieved by varying several parameters such as current density, conductivity, and
reaction time. By using aluminium electrodes with current density of 8.0 mA cm-2 for a reaction time of
60 minutes, the electroflotation process managed to remove 92, 98, 100, 57, and 23% of turbidity, total
solids, O&G, COD, and methanol respectively. The effluent was then subjected to an electrooxidation
process using Ti/RuO2 anodes. With an applied current density of 40.0 mA cm-2 for a reaction time of 240
minutes, the methanol and COD were effectively reduced by 68 and 95% respectively.
Chemical recovery and electrochemical
Jaruwat et al. (2010) studied the ability of a combined chemical recovery and electrochemical process.
Chemical recovery by acid protonation was used to recover the biodiesel while the second stage treatment
was named electrooxidation. This treatment managed to recover 67% (w/w) biodiesel from the raw
biodiesel wastewater through the protonation reaction and decreased the BOD5, COD, and O&G levels by
1324, 4074, and 8798% respectively. More than 95 and 100% of COD was removed through
electrooxidation.
5.2.7
Coagulation-biological aerated filter (CoBAF) system
The biological aerated filter (BAF) is one of the biological treatment methods which have been proven in
treating various types of wastewater such as textiles (Chang et al., 2002; He et al., 2013), oily wastewater
(Zhao et al., 2006; Su et al., 2007), leachate (Wu et al., 2011; Wang et al,. 2012), and pulp and paper mill
wastewater (Adachi & Fuchu, 1991). BAF has also been investigated and used as a system for removing
ammonium (NH4+-N) and manganese (Mn2+) from drinking water (Abu Hasan et al., 2013). Our study
30
Page 30 of 41
ip
t
aims to use this system in the proposed integrated process, which combines coagulation treatment and the
BAF system (CoBAF), as depicted in Figure 9. The simple and economical operation of the coagulation
process make this treatment favourable to be added as an initial stage prior to reducing and removing the
high solid content and COD before biological treatment takes place. High solid and COD contents might
inhibit the microorganisms growth (Kumjadpai et al., 2011). It was stated by Suehara et al. (2007) that
the biological process alone is not suitable to treat biodiesel wastewater.
an
us
cr
Table 17. Summary of integrated system performance for biodiesel wastewater treatment
Treatment process
COD
BOD
SS
O&G
References
removal (%) removal (%) removal (%) removal (%)
Dissolved air flotation
4050
98100
8595
Rattanapan et al.
coagulation
(2011)
Membrane bioreactorbiological 89.999.9
97.699.9
Tri (2002)
activated carbon
Acidification-electrocoagulation
80-90
Siles et al. (2010)
and anaerobic co-digestion

Acidificationelectrocoagulation 99
Siles et al. (2011)

and biomethanization
Acidificationcoagulation
94
Siles et al. (2011)

flocculation and
biomethanization
Photo-Fenton-aerobic sequential
76.1
69
Ramrez et al.
batch reactor
(2012)
Electroflotation and
57
98
100
Romero (2013)
electrooxidation
Ac
ce
p
te
Biological treatment seems suitable for use because of its economic value (Jou & Huang, 2003;
Gasim et al., 2000) and are proven for its ability to give lower levels of contaminants (Malakahmad et al.,
2011). As shown by previous studies, biological treatment is suitable for treating biodiesel wastewater
because it can reduce the content of methanol and glycerol since they are easily biodegradable
(Srirangsan et al., 2009). Biological treatments such as the activated sludge process have been used
widely in treating wastewater from the petrochemical industry (Shokrollahzadeh et al., 2008; Khaing et
al., 2010; Sponza & Gk, 2010). Pramanik et al. (2012) stated that BAF usage can provide a secondary
treatment in industrial treatments and is proven to be more reliable than conventional biological
treatment. The normal operation of the BAF process with aeration involves the attachment of a
microorganism growth process on media which are stationary (Zhou et al., 2006). Some advantages that
make this system favourable for use are its flexibility, where solids separation or aerobic biological
treatment can be carried out, ease of operation, and relative compactness (Pramanik et al., 2012); it
requires a small working space and provides a small footprint with a large surface area (Abu Hasan et al.,
2009). Several important criteria in biological aerated systems are the microorganism growth, flow
configuration, aeration system, filter media, media types, size, and BAF design (Abu Hasan et al., 2009).
31
Page 31 of 41
ip
t
Figure 9. Schematic of proposed integrated process of CoBAF system in our study
an
us
cr
The BAF system has been studied before by Zhao et al. (2006). The system was used to
successfully pre-treat oil field wastewater from Renerlian Factory drainage outlet. With the usage of
group B350M immobilized microorganisms, the overall system was able to degrade about 78% of total
organic carbon (TOC) and remove 94% of oil content. It also successfully removed up to 90% of the
PAHs content. The authors also emphasized that the BAF system was suitable for use as an alternative to
the conventional activated sludge system. Su et al. (2007) also investigated the ability of down-flow BAF
in treating oil-field produced water. The anaerobic baffled reactor (ABR) was combined with the BAF
system and the hydraulic loading rates were varied from 0.6 to 1.4 m.h-1. The treatment effectively
removed 76.380.3, 31.657.9, 86.396.3, and 76.482.7% of oil, COD, BOD, and SS respectively.
Chang et al. (2002) used BAF to treat textile wastewater. They found that the BAF system could remove
about 88 and 97% of COD and suspended solids, respectively.
Ac
ce
p
te
The main reason why authors are interested in investigating CoBAF integrated system is that we
are trying to find simpler and greener processes, which could treat biodiesel wastewater. So far, none of
the discussed treatment process could treat biodiesel wastewater alone. For example, dissolved air
flotation, as currently and widely used treatment in biodiesel production plant could not treat biodiesel
wastewater alone. Additional process/processes is/are needed to ensure that the effluent of biodiesel
wastewater meet the effluent standard requirement. Based on previous study, researchers came out with
different type of treatment system in order to study their performance, capabilities and each having their
own advantages and disadvantages. We aim to use biological process while simultaneously the process
required to remove the microorganisms inhibitor through coagulation is considered. Study of Xie et al.
(2011) showed that coagulation process was proven in releasing wastewater that was easily treated by
biodegradation. For this reason, the biological aerated filter combined with the pre-treatment process of
coagulation might have a successful potential in treating biodiesel wastewater. For the time being, we are
working on this integrated system in the lab scale and hoping that it will give a positive outcome on
biodiesel wastewater treatment.
6.
Conclusions
Biodiesel is mainly produced from vegetable oils through the transesterification process. Several issues
such as economic and environmental factors have led to the development of biodiesel production
technologies from various types of feedstock using various types of processes. The development of
biodiesel, due to the scarcity of fossil fuel sources, has led to the emergence of another issue that needs to
be solved. The process results in the production of a high amount of wastewater. Soap, glycerol,
methanol, and O&G contents in the wastewater make it impossible to treat efficiently with a single
32
Page 32 of 41
treatment. This wastewater, which has a milky colour and bad odour, needs to be treated efficiently.
Numerous treatments are being studied and proven for treating or pre-treating biodiesel wastewater and
each has its own benefits and disadvantages. The ability and performance of integrated treatment using a
coagulationbiological aerated filter (CoBAF) system will be investigated.
Acknowledgements
ip
t
7.
8.
cr
This research was financially supported by the Faculty of Engineering and Built Environment, Universiti
Kebangsaan Malaysia, through grant number INDUSTRI-2012-029.
References
us
Abbaszaadeh, A., Ghobadian, B., Omidkhah, M.R. & Najafi, G. (2012). Current biodiesel production technologies:
A comparative review. Energy Convers. Manag.,63, 138148. doi:10.1016/j.enconman.2012.02.027
an
Abdullah, A.Z.., Salamatinia, B., Mootabadi, H. & Bhatia, S. (2009). Current status and policies on biodiesel
industry in Malaysia as the worlds leading producer of palm oil. Energy Policy, 37(12), 54405448.
doi:10.1016/j.enpol.2009.08.012
Abu Hasan, H., Sheikh Abdullah, S.R., Kamarudin, S.K. & Tan Kofli, N. (2009). A review on the design criteria of
biological aerated filter for COD, ammonia and manganese. Journal-The Institution of Engineers,
Malaysia,70(4), 2533.
te
Abu Hasan H., Sheikh Abdullah S.R., Kamarudin S.K., Tan Kofli N. & Anuar N. (2013). Simultaneous NH4+-N and
Mn2+ removal from drinking water using abiological aerated lter system: Effects of different aeration rates.
Sep. Purif. Technol.,118, 547556.
Adachi, S. & Fuchu, Y. (1991). Reclamation and reuse of wastewater by biological aerated filter process. Water Sci.
& Technol., 24(9), 195204.
Ac
ce
p
Adnan, H. The Star Online. (2013). Malaysias B10 biodiesel programme and its benefit. Retrieved from:
http://biz.thestar.com.my/news/story.asp?file=/2013/2/12/business/12699472&sec=business
Ahmad, M., Ahmed, S., Fayyaz-Ul-Hassan, A.M., Khan, M.A., Zafar, M. & Sultana, S. (2010). Base catalyzed
transesterification of sunflower oil biodiesel. Afr. J. Biotechnol., 9(50), 86308635.
Akta Kualiti Alam Sekeliling 1974 (Environmental Quality Act 1974). (2009). International Law Book Services.
Direct Art Company, Kuala Lumpur, Malaysia.
Aoudj, S., Khelifa, A., Drouiche, N., Hecini, M. & Hamitouche, H. (2010). Electrocoagulation process applied to
wastewater containing dyes from textile industry. Chem. Eng. and Process.: Process Intensif., 49(11), 1176
1182. doi:10.1016/j.cep.2010.08.019
Atadashi, I.M., Aroua, M.K., Abdul Aziz, A.R & Sulaiman, N.M.N. (2011). Refining technologies for the
purification of crude biodiesel. Appl. Energy, 88(12), 42394251. doi:10.1016/j.apenergy.2011.05.029
Atadashi, I.M., Aroua, M.K., Abdul Aziz, A.R. & Sulaiman, N.M.N. (2012). High quality biodiesel obtained
through membrane technology. J. Memb. Sci., 421-422, 154164. doi:10.1016/j.memsci.2012.07.006
33
Page 33 of 41
Aygun, A. & Yilmaz, T. (2010). Improvement of Coagulation-Flocculation Process for Treatment of Detergent
Wastewaters Using Coagulant Aids. Int. J. Chem. Environ. Eng., 1(2), 97101.
Bassin, J.P., Dezotti, M. & Geraldo L.S.J. (2011). Nitrification of industrial and domestic saline wastewaters in
moving bed biofilm reactor and sequencing batch reactor. J. Hazard. Mat., 185(1), 2428.
doi:10.1016/j.jhazmat.2010.09.024
ip
t
Berchmans, H.J. & Hirata, S. (2008). Biodiesel production from crude Jatropha curcas L. seed oil with a high
content of free fatty acids. Bioresour. Technol., 99(6), 171621. doi:10.1016/j.biortech.2007.03.051
us
Biodiesel market reports. Retrieved from: http://www.thecropsite.com/reports/
cr
Berrios, M. & Skelton, R.L. (2008). Comparison of purification methods for biodiesel. Chem. Eng. J., 144, 459465.
doi:10.1016/j.cej.2008.07.019
an
Bouaid, A., El Boulifi, N., Martinez, M. & Aracil, J. (2012). Optimization of a two-step process for biodiesel
production from Jatropha curcas crude oil. International Journal of Low-Carbon Technologies, 331337.
doi:10.1093/ijlct/ctr047
Butler, E., Hung, Y.T., Yeh, R.Y.L. & Al Ahmad, M.S. (2011). Electrocoagulation in Wastewater Treatment. Water,
3(4), 495525. doi:10.3390/w3020495
Canakci, M. & Gerpen, J.V. (2001). Biodiesel production from oils and fats with high free fatty acids. J. Agric.Saf.
Health., 44(6), 14291436.
Chang, W.S., Hong, S. & Park, J. (2002). Effect of zeolite media for the treatment of textile wastewater in a
biological aerated filter. Process Biochem., 37, 693698.
te
Chavalparit, O. & Ongwandee, M. (2009). Optimizing electrocoagulation process for the treatment of biodiesel
wastewater using response surface methodology. J. Environ. Sci., 21(11), 14911496. doi:10.1016/S10010742(08)62445-6
Ac
ce
p
Chavan, A. & Mukherji, S. (2008). Treatment of hydrocarbon-rich wastewater using oil degrading bacteria and
phototrophic microorganisms in rotating biological contactor: effect of N:P ratio. J. Hazard. Mater., 154(1-3),
6372. doi:10.1016/j.jhazmat.2007.09.106
Chincholkar S.P., Srivastava S., Rehman, A., Dixit, S. & Lanjewar, A. (2005). Biodiesel as an alternative fuel for
pollution control in diesel engine. Asian J. Exp. Sci., 19(2), 13-22.
De Gisi, S., Galasso M. & De Feo G. (2013). Full-scale treatment of wastewater from a biodiesel fuel production
plant with alkali-catalyzedtransesterification. Environ. Technol.34(7), 861-870.
Demirbas, A. (2009). Biodiesel from waste cooking oil via base-catalytic and supercritical methanol
transesterification. Energy Convers. Manag., 50(4), 923927. doi:10.1016/j.enconman.2008.12.023
Demirbas, A. & Demirbas, M.F. (2011). Importance of algae oil as a source of biodiesel. Energy Convers. Manag.,
52(1), 163170. doi:10.1016/j.enconman.2010.06.055
Dugan, J. Biodiesel Magazine. (2007). A dry wash approach to biodiesel purification. Retrieved from:
http://biodieselmagazine.com/articles/1918/a-dry-wash-approach-to-biodiesel-purification/
34
Page 34 of 41
El Diwani, G., Attia, N.K., & Hawash, S.I. (2009). Development and evaluation of biodiesel fuel and by-products
from jatropha oil. Int. J. Environ. Sci. Technol., 6(2), 219224.
Emamjomeh, M.M. & Sivakumar, M. (2009). Review of pollutants removed by electrocoagulation and
electrocoagulation/flotation
processes.
J.
Environ.
Manage.,
90(5),
16631679.
doi:10.1016/j.jenvman.2008.12.011
ip
t
Enhancement and Conservation of the National Quality Act 1992. Water Quality Standards. Retrieved from:
http://www.pcd.go.th/info_serv/en_reg_std_water04.html#s1
cr
French, R. & Czernik, S. (2010). Catalytic pyrolysis of biomass for biofuels production. Fuel Processing Technol.,
91(1), 2532. doi:10.1016/j.fuproc.2009.08.011
us
Gasim, H., Kutty, S.R.M., & Isa, M.H. (2000). Biodegradability of Petroleum Refinery Wastewater in Batch
Reactor, PhD thesis, UTP.
an
Gomes, M.C.S., Arroyo, P.A. & Pereira, N.C. (2013). Influence of acidified water addition on the biodiesel and
glycerol
separation
through
membrane
technology.
J.
Memb.
Sci.,
431,
2836.
doi:10.1016/j.memsci.2012.12.036
Hasswa, R., Dub, M.A. & Tremblay, A.Y. (2013). Distribution of soap in a membrane reactor in the production of
fame from waste cooking oil. Can. J. Chem. Eng., 91(3), 459465. doi:10.1002/cjce.21686
Hayyan, A., Alam, Z., Mirghani, M.E.S., Kabbashi, N. A., Irma, N., Mohd, N. & Mohd, Y. (2010). Sludge palm oil
as a renewable raw material for biodiesel production by two-step processes. Bioresour. Technol., 101(20),
78047811. doi:10.1016/j.biortech.2010.05.045
te
He, Y., Wang, X., Xu, J., Yan, J., Ge, Q., Gu, X. & Jian, L. (2013). Application of integrated ozone biological
aerated filters and membrane filtration in water reuse of textile effluents. Bioresour. Technol., 133, 150157.
doi:10.1016/j.biortech.2013.01.074
Ac
ce
p
Holenda B., Domokos E., Rdey A. & Fazakas J. (2008). Dissolved oxygen control of the activated sludge
wastewater treatment process using model predictive control, Comput. Chem. Eng., 32, 12701278.
Hossain, A.B.M. & Boyce, A.N. (2009). Biodiesel production from waste sunflower cooking oil as an
environmental recycling process and renewable energy. Bulg. J. Agricultural Sci., 15(4), 312317.
Huang, G.H., Chen, F., Wei, D., Zhang, X.W., & Chen, G. (2010). Biodiesel production by microalgal
biotechnology. Appl. Energy, 87(1), 38-46.
Ito, T., Sakurai, Y., Kakuta, Y., Sugano, M. & Hirano, K. (2012). Biodiesel production from waste animal fats using
pyrolysis method. Fuel Process. Technol., 94(1), 4752. doi:10.1016/j.fuproc.2011.10.004
Janaun, J. & Ellis, N. (2010). Perspectives on biodiesel as a sustainable fuel. Renew. Sustain. Energy Rev., 14(4),
13121320. doi:10.1016/j.rser.2009.12.011
Jaruwat, P., Kongjao, S. & Hunsom, M. (2010). Management of biodiesel wastewater by the combined processes of
chemical recovery and electrochemical treatment. Energy Convers. Manag., 51(3), 531537.
doi:10.1016/j.enconman.2009.10.018
Jayed, M.H., Masjuki, H.H., Saidur, R., Kalam, M.A. & Jahirul, M.I. (2009). Environmental aspects and challenges
of oilseed produced biodiesel in Southeast Asia. Renew. Sustain. Energy Rev., 13, 24522462.
doi:10.1016/j.rser.2009.06.023
35
Page 35 of 41
Jou C.G. & Huang G.C. (2003). A pilot study for oil refinery wastewater treatment using a fixed film bioreactor.
Adv. Environ. Res. 7, 463469.
Kaercher, J.A., Cassia, R.De, Schneider, D.S., Klamt, R.A., Leonardo, W., Schmatz, W.L. & Szarblewski, S. (2013).
Optimization of biodiesel production for self-consumption: considering its environmental impacts. J. Clean.
Prod., 46, 7482. doi:10.1016/j.jclepro.2012.09.016
ip
t
Kapilakarn, K. & Peugtong, A. (2007). A comparison of costs of biodiesel production from transesterication.
International Energy Journal, 8: 16.
cr
Khaing, T.-H., Li, J., Li, Y., Wai, N. & Wong, F. (2010). Feasibility study on petrochemical wastewater treatment
and reuse using a novel submerged membrane distillation bioreactor. Sep. Purif. Technol., 74(1), 138143.
doi:10.1016/j.seppur.2010.05.016
us
Khan, S.A., Hussain, M.Z., Prasad, S. & Banerjee, U.C. (2009). Prospects of biodiesel production from microalgae
in India. Renewable and Sustainable Energy Reviews, 13, 23612372. doi:10.1016/j.rser.2009.04.005
an
Khan Y.A., & Yamsaengsung R. (2011). Review of Wastewater Treatment Methods and MBR Technology for
Application in Biodiesel Plants. Conference topic: Environmental and Safety Technology. TIChE International
Conference, 1011 November 2011 at Hatyai, Songkhla, Thailand.
Kim, S., Yoon, J. & Lee, S. (2009). Utilization of floc characteristics for the evaluation of seawater coagulation
process. Desalin. Water Treat., 10, 95100.
Kinast, J.A. National Renewable Energy Laboratory 2003. (2003).Subcontractor report: Production of biodiesel
from multiple feedstocks and properties of biodiesels and biodiesel/diesel blends.
te
Kolesrov, N., Hutan, M., Bodk, I., & Spalkov, V. (2011). Utilization of biodiesel by-products for biogas
production. J. Biomed. Biotechnol., 2011, 115. doi:10.1155/2011/126798
Ac
ce
p
Krishna, A.R., Dev, L. & Thankamani, V. (2012). An integrated process for Industrial effluent treatment and
Biodiesel production using Microalgae. Res. Biotechnol., 3(1), 4760.
Kumjadpai, S., Ngamlerdpokin, K., Chatanon, P., Lertsathitphongs, P.,& Hunsom, M. (2011). Management of fatty
acid methyl ester (fame) wastewater by a combined two stage chemical recovery and coagulation process.
Can. J. Chem. Eng., 89(2), 369376. doi:10.1002/cjce.20429
Leung, D.Y.C., Wu, X. & Leung, M.K.H. (2010). A review on biodiesel production using catalyzed
transesterification. Appl. Energy, 87(4), 10831095. doi:10.1016/j.apenergy.2009.10.006
Lim, S. & Teong, L.K. (2010). Recent trends, opportunities and challenges of biodiesel in Malaysia: An overview.
Renew. Sustain. Energy Rev., 14, 938954. doi:10.1016/j.rser.2009.10.027
Lin, L., Cunshan Z,, Vittayapadung, S., Xiangqian, S. & Mingdong, D. (2011). Opportunities and challenges for
biodiesel fuel. Applied Energy 88 (4), 10201031
Llop, A., Pocurull, E. & Borrull, F. (2009). Evaluation of the removal of pollutants from petrochemical wastewater
using a membrane bireactor treatment plant. Water Air Soil Pollut., 197, 349359.
Lotero, E., Liu, Y., Lopez, D.E., Suwannakarn, K., Bruce, D.A. & Goodwin, J.G. (2005). Synthesis of biodiesel via
acid catalysis. Industrial & Engineering Chemistry Research, 44(14), 53535363. doi:10.1021/ie049157g
36
Page 36 of 41
Low, S.C., Gan, G.K., & Cheong, K.T. (2011). Separation of Methyl Ester from Water in a Wet Neutralization
Process. J. Sustain. Energy Environ., 2, 1519.
Ma, F. & Hanna, M.A. (1999). Biodiesel production: a review. Bioresour. Technol., 70, 115.
ip
t
Magtibay, B.B. (2006). Philippines regulations on sanitation and wastewater system. Biosphere Environment and
Health System Series. B.B. Magtibays Publishing House, Philippines.
cr
Maha Lakshmi, P. & Sivashanmugam, P. (2013). Treatment of oil tanning effluent by electrocoagulation: Influence
of ultrasound and hybrid electrode on COD removal. Sep. Purif. Technol., 116, 378384.
doi:10.1016/j.seppur.2013.05.026
us
Malakahmad, A., Hasani, A., Eisakhani, M., & Isa, M.H. (2011). Sequencing Batch Reactor (SBR) for the removal
of Hg2+ and Cd2+ from synthetic petrochemical factory wastewater. J. Hazard. Mater., 191(1-3), 11825.
doi:10.1016/j.jhazmat.2011.04.045
an
Margesin, R. & Schinner, F. (2001). Biodegradation and bioremediation of hydrocarbons in extreme environments.
Appl. Microbiol. Biotechnol., 56(5-6), 650663. doi:10.1007/s002530100701
Mata, T.M., Martins, A.A. & Caetano, N.S. (2010). Microalgae for biodiesel production and other applications: A
review. Renew. Sustain. Energy Rev., 14(1), 217232. doi:10.1016/j.rser.2009.07.020
Mohamad, A.B., Abd Rahman, R., Hassan Kadhum, A.A., Sheikh Abdullah, S.R, Wan Sudin, Z. & Shaari, S.
(2008). Removal of adsorbable organic halides (AOX) from recycled pulp and paper (P&P) mill effluent using
granular activated carbon-sequencing batch biofilm reactor (GAC-SBBR). Modern Applied Science 2(5), 37
45.
te
Mohan, D., Pittman Jr, C.U., & Steele P.H. (2006). Pyrolysis of wood/ biomass for bi-oil: a critical review. Energy
Fuel, 20, 848889.
Ac
ce
p
Mondala, A., Liang, K., Toghiani, H., Hernandez, R. & French, T. (2009). Biodiesel production by in situ
transesterification of municipal primary and secondary sludges. Bioresour. Technol., 100(3), 120310.
doi:10.1016/j.biortech.2008.08.020
Moser, B.R. (2009). Biodiesel production, properties and feedstocks. In Vitro Cell. Dev. Biol.-Plant, 45, 229266.
Ngamlerdpokin, K., Kumjadpai, S., Chatanon, P., Tungmanee, U., Chuenchuanchom, S., Jaruwat, P.,
Lertsathitphongs P. & Hunsom, M. (2011). Remediation of biodiesel wastewater by chemical- and electrocoagulation: a comparative study. J. Environ. Manage., 92(10), 245460. doi:10.1016/j.jenvman.2011.05.006
Orchard, B, Denis J. & Cousins J. (2007). Developments in biofuel processing technologies. World Pumps,
2007(487), 2428.
Okullo, A., Temu, A.K., Ogwok, P. & Ntalikwa, J.W. (2012). Physico-chemical properties of biodiesel from
jatropha and castor oil. International Journal of Renewable Energy Research 2(1):4752.
Ong, H.C., Mahlia, T.M.I., Masjuki, H.H. & Honnery, D. (2012). Life cycle cost and sensitivity analysis of palm
biodiesel production. Fuel, 98: 131-139.
37
Page 37 of 41
Parmar, K.A., Prajapati, S., Patel, R. & Dabhi, Y. (2011). Effective use of ferrous sulfate and alum as a coagulant in
treatment of dairy industry wastewater. Journal of Engineering and Applied Sciences, 6(9), 4245.
Patel, H. & Madamwar, D. (2002). Effects of temperatures and organic loading rates on biomethanation of acidic
petrochemical wastewater using an anaerobic upflow fixed-film reactor. Bioresour. Technol., 82(1), 6571.
doi:10.1016/S0960-8524(01)00142-0
ip
t
Pitakpoolsil, W. & Hunsom, M. (2013). Adsorption of pollutants from biodiesel wastewater using chitosan flakes. J.
Taiwan Ins. Chem. Eng., in press. doi:10.1016/j.jtice.2013.02.009
cr
Pimentel, D. & Patzek, T.W. (2005). Ethanol production using corn , switchgrass, and wood; biodiesel production
using soybean and sunflower. Natural Resources Research, 14(1), 65-76. doi:10.1007/s11053-005-4679-8
us
Pleanjai, S., Gheewala, S.H. & Garivait, S. (2007). Environmental evaluation of biodiesel production from palm oil
in a life cycle perspective. Asian J. Energy Environ., 8(1), 1532.
an
Pramanik, B.K., Suja, F., Shahrom, Z. & Ahmed, E. (2012). Biological aerated filters (BAFs) for carbon and
nitrogen removal: A review. Journal of Engineering Science and Technology 7(4), 428446.
Rahman, M., & Al-Malack, M. (2006). Performance of a cross-flow membrane bioreactor (CF-MBR) when treating
refinery. Desalination 191, 1626
Raja, S.A., Robinson, D.S. & Lee, C.L.R. (2011). Biodiesel production from jatropha oil and its characterization.
Res. J. Chem. Sci., 1(1), 8187.
te
Rajasimman, M. & Karthikeyan, C. (2007). Aerobic digestion of starch wastewater in a fluidized bed bioreactor
with low density biomass support. J. Hazard. Mater., 143, 82-86.
Ac
ce
p
Ramadhas, A., Jayaraj, S. & Muraleedharan, C. (2005). Biodiesel production from high FFA rubber seed oil. Fuel,
84(4), 335340. doi:10.1016/j.fuel.2004.09.016
Ramrez, X.M.V., Meja, G.M.H., Lpez, K.V.P., Vsquez, G.R. & Seplveda, J.M.M. (2012). Wastewater
treatment from biodiesel production via a coupled photo-Fenton aerobic sequential batch reactor (SBR)
system. Water Sci. Technol., 66(4), 824830. doi:10.2166/wst.2012.250
Rattanapan, C., Sawain, A., Suksaroj, T. & Suksaroj, C. (2011). Enhanced efficiency of dissolved air flotation for
biodiesel wastewater treatment by acidification and coagulation processes. Desalination, 280(1-3), 370377.
doi:10.1016/j.desal.2011.07.018
Rawat, I., Ranjith Kumar, R., Mutanda, T. & Bux, F. (2013). Biodiesel from microalgae: A critical evaluation from
laboratory to large scale production. Appl. Energy, 103: 444467. doi:10.1016/j.apenergy.2012.10.004
Romero, J.A.P., Cardoso Junior, F.S.S., Figueiredoa, R.T, Silvaa, D.P. & Cavalcantia, E.B. (2013). Treatment of
biodiesel wastewater by combined electroflotation and electrooxidation processes. Separ. Sci. Technol., 48,
2073-2079.
Ruengkong, J., Krimpikun, S., Toonguri, C. & Boonsawang, P. (2008). Biogas production from wastewater of
biodiesel process, 7th National Environmental Conference, Bangkok, Thailand.
38
Page 38 of 41
Sanford, S.D., White, J.M., Shah, P.S., Wee, C., Valverde, M.A. & Meier, G.R. Renewable Energy Group, Inc.
(2009). Feedstock and biodiesel characteristics report. Retrieved from: www.regfuel.com
ip
t
Saraswathi, R. & Saseetharan, M. K. (2012). Simultaneous optimization of multiple performance characteristics in

coagulation-flocculation process for Indian paper industry wastewater. Water Sci. Technol., 66(6), 12311238.
doi:10.2166/wst.2012.304
cr
Scholz, W. & Fuchs, W.(2000).Treatment of oil contaminated wastewater in a membrane bioreactor. Wat. Res., 34,
3621-3629.
us
Sharma, Y.C., Singh, B. & Upadhyay, S.N. (2008). Advancements in development and characterization of biodiesel:
A review. Fuel, 87: 2355-2373.
an
Shokrollahzadeh, S., Azizmohseni, F., Golmohammad, F., Shokouhi, H. & Khademhaghighat, F. (2008).
Biodegradation potential and bacterial diversity of a petrochemical wastewater treatment plant in Iran.
Bioresour. Technol., 99(14), 61276133. doi:10.1016/j.biortech.2007.12.034
Siddiquee, M.N. & Rohani, S. (2011). Lipid extraction and biodiesel production from municipal sewage sludges: A
review. Renew. Sustain. Energy Rev., 15(2), 10671072. doi:10.1016/j.rser.2010.11.029
Siles, J.A., Martn, M.A., Chica, A.F. & Martn, A. (2010). Anaerobic co-digestion of glycerol and wastewater
derived
from
biodiesel
manufacturing.
Bioresour.
Technol.,
101(16),
63156321.
doi:10.1016/j.biortech.2010.03.042
te
Siles, J.A., Gutirrez, M.C., Martn, M.A. & Martn, A. (2011). Physical-chemical and biomethanization treatments
of wastewater from biodiesel manufacturing. Bioresour. Technol., 102(10), 63486351.
doi:10.1016/j.biortech.2011.02.106
Ac
ce
p
Singh, S.P. & Singh, D. (2010). Biodiesel production through the use of different sources and characterization of
oils and their esters as the substitute of diesel: A review. Renew. Sustain. Energy Rev., 14(1), 200216.
doi:10.1016/j.rser.2009.07.017
Sivasamy, A., Cheah, K.Y., Fornasiero, P., Kemausuor, F., Zinoviev, S. & Miertus, S. (2009). Catalytic applications
in the production of biodiesel from vegetable oils. ChemSusChem, 2(4), 278300.
doi:10.1002/cssc.200800253
Sponza, D.T. & Gk, O. (2010). Effect of rhamnolipid on the aerobic removal of polyaromatic hydrocarbons
(PAHs) and COD components from petrochemical wastewater. Bioresour. Technol., 101(3), 91424.
doi:10.1016/j.biortech.2009.09.022
Srirangsan A., Ongwandee M. & Chavalparit O. (2009). Treatment of biodiesel wastewater by electrocoagulation
process. Environment Asia, 2, 15-19.
Su, D., Wang, J., Liu, K. & Zhou, D. (2007). Kinetic performance of oil-field produced water treatment by
biological aerated filter. Chinese J. Chem. Eng., 15(4), 591594.
Suehara, K., Kawamoto, Y., Fujii, E., Kohda, J., Nakano, Y. & Yano, T. (2005). Biological treatment of wastewater
discharged from biodiesel fuel production plant with alkali-catalyzed transesterification. J. Biosci. Bioeng.,
100(4), 43742. doi:10.1263/jbb.100.437
39
Page 39 of 41
Suehara, K., Owari, K., Kohda, J., Nakano, Y. & Yano, T. (2007). Rapid and simple determination of oil and urea
concentrations and solids content to monitor biodegradation conditions of wastewater discharged from a
biodiesel fuel production plant. J. Near Infrared Spectrosc., 15(2), 89. doi:10.1255/jnirs.721
ip
t
Sukkasem, C., Laehlah, S., Hniman, A., Sompong, O. & Boonsawang, P. (2011). Upflow bio-filter circuit (UBFC):
Biocatalyst microbial fuel cell (MFC) configuration and application to biodiesel wastewater treatment.
Bioresour. Technol., 102(22), 1036310370. doi:10.1016/j.biortech.2011.09.007
Takashi O. (2009). Challenge of climate protection and BDF from used cooking oil in the City of Kyoto, Japan.
Retrieved from: http://www.iclei.org/documents/Japan/O.Takashi.pdf
cr
Talebian-Kiakalaieh, A., Amin, N.A.S. & Mazaheri, H. (2013). A review on novel processes of biodiesel production
from waste cooking oil. Appl. Energy, 104, 683710. doi:10.1016/j.apenergy.2012.11.061
us
Tang, D.T.C. (1993). Water Pollution Control Act. (1993). The Environmental Laws and Policies of Taiwan: A
comparative Law Perspective. Pacicfic Rim Law & Policy Association.
an
Tezcan Un, U., Koparal, A.S. & Bakir Ogutveren, U. (2009). Electrocoagulation of vegetable oil refinery
wastewater
using
aluminum
electrodes.
J.
Environ.
Manage.,
90(1),
42833.
doi:10.1016/j.jenvman.2007.11.007
Thaveesri, J. (2003). Expert Meeting on Definitions and Dimensions of Environmental Goods and Services in Trade
and Development. Geneva, 9-11 July 2003.
Tomi, M.D., Savin, L.Dj., Mii, R.D., Simiki M.Dj. & Furman, T.F. (2013). Effects of fossil diesel and biodiesel
blends on the performances and emissions of agricultural tractor engines. Thermal Science, 17(1), 263-278.
te
Tri, P. (2002). Oily wastewater treatment by membrane bioreactor process coupled with biological activated carbon
process. Thesis: AIT. Bangkok, Thailand.
Ac
ce
p
Vasudevan, P.T. & Briggs, M. (2008). Biodiesel production-current state of the art and challenges. J. Ind. Microbiol.
Biotechnol., 35(5), 421430.
Vivek & Gupta, A. (2004). Biodiesel production from Karanja oil. Journal of Scientific & Industrial Research, 63:
39-47.
Veljkovi, V.B., Stamenkovi, O.S. & Tasi, M.B. (2012). Wastewater management in biodiesel production.
Reporting for sustainability , 471475.
Vyas A.P., Verma J.L. & Surahmanyam N. (2010). A review on FAME production processes. Fuel, 89, 1-9.
Wan Omar, W.N.N., & Amin, N.A.S. (2011). Biodiesel production from waste cooking oil over alkaline modified
zirconia catalyst. Fuel Process. Technol., 92(12), 23972405. doi:10.1016/j.fuproc.2011.08.009
Wang, X., Han, J., Chen, Z., Jian, L., Gu, X. & Lin, C. (2012). Combined processes of two-stage Fenton-biological
anaerobic filter biological aerated filter for advanced treatment of landfill leachate. Waste Manag., 32(12),
24012405. doi:10.1016/j.wasman.2012.06.022
Wei, C.Y., Huang, T.C. & Chen, H.H. (2013). Biodiesel production using supercritical methanol with carbon
dioxide and acetic acid. Journal of Chemistry 2013, 16.doi:10.1155/2013/789594
40
Page 40 of 41
Wirawan, S.S., Tambunan, A.H., Djamin, M. & Nabetani, H. (2008). The effect of palm biodiesel fuel on the
performance and emission of the automotive diesel engine.Agricultural Engineering International: the CIGR
Ejournal. Manuscript EE 07 005.
ip
t
Wu Y., Zhou S., Ye X., Chen D., Zheng K. & Qin F. (2011). Transformation of pollutants in landfill leachate
treated by a combined sequence batch reactor, coagulation, Fenton oxidation and biological aerated filter
technology. Process Saf. Environ. Prot., 89, 112-120.
cr
Xie, Q., Taweepreda, W., Musikavong, C. & Suksaroj, C. (2011). Separation of oily sludge and glycerol from
biodiesel processing waste by coagulation. Songklanakarin Journal of Science and Technology, 33(6), 699
703.
us
Yaakob, Z., Sukarman, I.S., Narayanan, B., Sheikh Abdullah, S.R. (2012). Utilization of palm empty fruit bunch for
the production of biodiesel from Jatropha curcas oil. Bioresour. Technol., 104, 695700.
doi:10.1016/j.biortech.2011.10.058
an
Yaakob, Z., Mohammad, M., Alherbawi, M., Alam, Z. & Sopian, K. (2013). Overview of the production of
biodiesel from Waste cooking oil. Renew. Sustain. Energy Rev., 18, 184193. doi:10.1016/j.rser.2012.10.016
Zhang M.H., Zhao Q.L., Bai X. & Ye Z.F. (2010). Adsorption of organic pollutants from coking wastewater by
activated coke. Physico. Chem. Eng. Asp., 62, 140-146.
Zhou Y., Liang Z. & Wang Y. (2008). Decolorization and COD removal of secondary yeast wastewater effluents by
coagulation using aluminium sulfate. Desalination, 225, 301311.
Ac
ce
p
te
Zhao X., Wang Y., Ye Z., Borthwick A.G.L. & Ni J. (2006). Oil field wastewater treatment in biological aerated
filter by immobilized microorganisms. Process Biochem., 41, 1475-1483.
41
Page 41 of 41

Daud 2014

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Daud 2014

Uploaded by

Copyright:

Available Formats

Accepted Manuscript

Title: Production of biodiesel and its wastewater treatment

Process Safety and Environment Protection

Title: Production of biodiesel and its wastewater treatment technologies: A review

Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

Universiti Kebangsaan Malaysia under grant number INDUSTRI-2012-029.

Production of biodiesel and its wastewater treatment technologies: A review

Keywords: Biodiesel, transesterification, biodiesel wastewater, biodiesel wastewater treatment.

Development of biodiesel production

Figure 1. Usage of biodiesel

Table 1. Biodiesel production in several Asian countries (Source: www.thecropsite.com)

Commercially, biodiesel is produced through a transesterification process in the presence of

(Mixture of fatty esters)

Properties of biodiesel as transportation fuel

Flash point, close cup

Table 3. Biodiesel properties from different feedstocks

Table 4. Percentage of exhaust emission from biodiesel engines

Figure 2. Methyl ester yields for different study

Table 5. Energy content of biodiesel fuel

Demirbas and Demirbas (2011)

Demirbas and Demirbas (2011)

Okullo et al. (2012)

Algae (Cladophora fracta)

Source of raw materials/feedstock

Table 6. Different feedstocks for biodiesel production

Figure 3. Classification of biodiesel feedstock

Figure 4. Seed oil yield depending on different feedstock

Figure 5. Classification of biodiesel production cost based on different feedstock

Biodiesel production process

Generation of biodiesel wastewater

Biodiesel washing process

Table 8. Process conditions of transesterification reaction

Dry washing process

Table 9. Advantages and disadvantages of each washing process

Very effective in removing

Increased cost and

Veljkovi et al. (2013);

Decreases production time; lower

Exceeds the limit in the EN

Berrios and Skelton

Avoids the formation of

Probably high cost. Low

Gomes et al. (2013);

decreases. Minimizes the volume

Biodiesel wastewater and its characteristics

Table 10. Characteristics of biodiesel wastewater

Level of environmental pollution by biodiesel wastewater

Akta Kualiti Alam Thaveesri (2003)

Table 11. Standards for industrial effluents in several countries

Treatment and management of biodiesel wastewater

Current treatment technologies

Xie et al. (2011)

Anodic reactions: Al(s) Al3+ + 3e

Table 13. Process conditions of electrocoagulation treatments for biodiesel wastewater

Table 14. Removal efficiencies of biodiesel wastewater using biological treatments

Wastewater from palm

Raw BDF wastewater:

Sukkasem et al. (2011)

Table 16. Advantages and disadvantages of different individual treatments

Higher cost compared to

Generates large amounts of

Need further treatment, facing

Pitakpoolsil and Hunsom

Pitakpoolsil and Hunsom