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Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Contents lists available at ScienceDirect

Process Safety and Environmental Protection


journal homepage: www.elsevier.com/locate/psep

Review

Production of biodiesel and its wastewater


treatment technologies: A review
Nurull Muna Daud , Siti Rozaimah Sheikh Abdullah ,
Hassimi Abu Hasan, Zahira Yaakob
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

a b s t r a c t
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 transesterication 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 signicance, ability and possibility of biological aerated lter (BAF) to treat biodiesel wastewater discharged from
a biodiesel fuel production plant. The whole treatment; coagulation-biological aerated lter (CoBAF); involves the
pre-treatment of biodiesel wastewater using coagulation followed by the treatment using BAF.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Biodiesel; Biodiesel production; Transesterication; Biodiesel wastewater; Biodiesel wastewater treatment;
Biodiesel wastewater management

Contents
1.

2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Development of biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2. Properties of biodiesel as transportation fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Source of raw materials/feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Biodiesel production process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1. Direct use and raw oils blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2. Micro emulsions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4. Transesterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Generation of biodiesel wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Biodiesel washing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1. Wet washing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding authors. Tel.: +60 3 89216407; fax: +60 3 89216148.


E-mail addresses: nurullmuna.daud@gmail.com (N.M. Daud), rozaimah@eng.ukm.my (S.R. Sheikh Abdullah).
Received 23 June 2014; Received in revised form 9 October 2014; Accepted 19 October 2014
Available online 27 October 2014
http://dx.doi.org/10.1016/j.psep.2014.10.009
0957-5820/ 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

488
488
489
490
490
493
493
493
493
494
494
494
495

488

4.

5.

1.

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

3.1.2. Dry washing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .


3.1.3. Membrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Biodiesel wastewater and its characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. Level of environmental pollution by biodiesel wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Treatment and management of biodiesel wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Current treatment technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1. Coagulation treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.2. Electrocoagulation treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.3. Biological treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.4. Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.5. Microbial fuel cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Integrated system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.1. Dissolved air otationcoagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.2. Photo-Fenton-aerobic sequential batch reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.3. Acidicationelectrocoagulation and anaerobic co-digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.4. Acidicationelectrocoagulation and biomethanization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.5. Electrootation and electrooxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.6. Chemical recovery and electrochemical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.7. Coagulation-biological aerated lter (CoBAF) system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Introduction

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 (Orchard
et al., 2007). In 1920, the availability of low cost petroleum
fuel had decreased the demand for biodiesel, leading to the
modication 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 transesterication, pyrolysis, and blending of solvents. The rst patent for an industrial process for
biodiesel production was led in 1977 by a Brazilian scientist,
Expedito Parente (Lim and Teong, 2010). In 1979, South Africa
initiated research into the production of biodiesel using sunower 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 benecial for transportation, it
is also being used in manufacturing, construction machinery
and generators for ring boilers purpose as depicted in Fig. 1
(Abdullah et al., 2009).

1.1.

495
495
496
496
496
498
498
498
500
501
501
501
502
502
503
503
503
503
504
505
505
505

Development of biodiesel production

The idea of using biodiesel fuel arose when the world started to
nd and develop alternative energy resources, inuenced by
the depletion of non-renewable energy sources (Berchmans
and 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

Transportation

Generators

Manufacturing

Construction

Fig. 1 Usage of biodiesel.

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.
Commercially, biodiesel is produced through a transesterication process in the presence of alcohol and catalyst.
This process involves the conversion of triglycerides (oil) to
methyl ester (biodiesel) and by-product (glycerol) (Chavalparit
and Ongwandee, 2009; Low et al., 2011) as described by Eq.
(1).

489

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Table 1 Biodiesel production in several Asian countries.


Country

Main feedstock

Production capacity
(billion litres/year)

Malaysia
Indonesia
Thailand
Philippines
India
China

Palm oil
Palm oil
Palm oil
Coconut oil
Jatropha
Waste cooking oil

0.147
2.200
2.080
0.138
0.1400.300
0.568

Production year
2011
2012
2011
2012
2011
2012

Source: Biodiesel market reports.

O
||
CH2-O-C-R1
|
|
O
|
||
CH-O-C-R2
|
|
O
|
||
CH2-O-C-R3
(Triglycerides)

3CH3OH

(Catalyst)

O
||
CH3-O-C-R2

CH2-OH
|
CH-OH
|
CH2-OH

O
||
CH3-O-C-R3
(Methanol)

(Mixture of fatty esters)

Equation (1)

(Glycerol)

(1)

Properties of biodiesel as transportation fuel

Biodiesel fuel is used as a substitute for petroleum, which


traditionally has been used to produce transportation fuel
(Chavalparit and 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 and 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).
For biodiesel products to be used as transportation fuel,
the fuel grade should full 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 analyzed according to the
standard to ensure the compatibility 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 Fig. 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.
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 ash point above 93.3 C make it
safer and easier to use, handle, and store. Another reason that
makes biodiesel comparable to petroleum diesel is the highenergy 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 difculties such as fuel pumping problems,
cold start, poor low temperature ow and high copper strip
corrosion.

Yield percentage (%)

1.2.

O
||
CH3-O-C-R1

100
90
80
70
60
50
40
30
20
10
0

Fig. 2 Methyl ester yields for different study.

490

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Table 2 Different standard specication for biodiesel fuel (Abdullah et al., 2009).
Property

Units

Limits

C
mg/kg
mm2 /s
% (m/m)
% (m/m)
Rating

% (m/m)
mg KOH/g
% (m/m)
% (m/m)
mg/kg

2.

Biodiesel production

2.1.

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 and 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

ASTM D6751

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

70
60
50
40
30
20
10
0
Soybean
Canola
Algae
Jatropha
Palm oil
Rapeseed
Sunower
Castor
Corn
Babassu oil
Camelina
Coee
Blue waxweed
Hemp
Karanja
Linseed

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
nd 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 full the energy required by
our society.

% oil by wt in biomass

Flash point, close cup


Water content
Kinematic viscosity, 40 C
Sulphated ash
Sulphur content
Copper corrosion strip (3 h at 50 C)
Cetane index
Carbon residue
Acid number
Free glycerol
Total glycerol
Phosphorus content
Distillation temperature (90% recovered)

EN14214

Fig. 4 Seed oil yield depending on different feedstock.

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 nd suitable
ways to treat, recycle, and dispose of wastes (Suehara et al.,
2005; Janaun and Ellis, 2010). Yaakob et al. (2013) emphasized
that waste cooking oil usage can reduce water pollution and
also prevent blockages in water drainage systems.
Free fatty acids (FFAs) and/or triglycerides are an important
component of feedstock to be converted to biodiesel (Janaun
and Ellis, 2010). All fatty acids sources are favourable for use in
biodiesel production (Talebian-Kiakalaieh et al., 2013). Kinast
(2003) classied biodiesel feedstock based on their FFAs as
illustrated in Fig. 3. Types of rened 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 >3 wt%
will lead to soap formation due to the reaction between the
FFA and the catalyst. Consequently, stable emulsion will form,

Biodiesel feedstock

Group I
Refined oils
(FFA <1.5%)

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%)

Fig. 3 Classication of biodiesel feedstock.

Table 3 Biodiesel properties from different feedstocks.


Process

Feedstock

Purity (%)

Soybean oil

97.8

Palm oil
Castor oil
Jatropha oil
Jatropha oil

61.0
76.0

Sunower oil
Jatropha oil

98

Waste cooking oil

87

Municipal sewage sludge

14.5

Waste sunower cooking oil

99.5

Viscosity
(mm2 /s)

Density
(kg/m3 )

Flash point
( C)

Cloud point
( C)

Pour point
( C)

References

4.91
10.75
5.25
4.82

878

179
160
166
128

14
13
6
8

Atadashi et al. (2012)


Okullo et al. (2012)
Okullo et al. (2012)
Raja et al. (2011)

4.72
5.20

860

183
162

4
0

5
6

Ahmad et al. (2010)


El Diwani et al. (2009)

99.6

5.30

897

196

11

Mondala et al. (2009)

9.50

Hossain and Boyce (2009)

Wei et al. (2013)

Demirbas (2009)

Table 4 Percentage of exhaust emission from biodiesel engines.


Fuel type
B100
B100
B100
B100
B100
B100
B100

Carbon monoxide

Hydrocarbon

52
90
67
50
60
87
56

33
90
23

50

32

Nitric oxide
110
115
75
113
105
111

Sulfur dioxide

Particulate matter

0
0
0

53
67
33
70
35

60

Polycyclic aromatic hydrocarbons

20

25

References
Lotero et al. (2005)
Chincholkar et al. (2005)
Wirawan et al. (2008)
Khan et al. (2009)
Bouaid et al. (2012)
Tomic et al. (2013)
Talebian-Kiakalaieh et al. (2013)

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Transesterication
in supercritical
methanol
Transesterication
Transesterication
Transesterication
Base catalyzed
transesterication
Transesterication
Base catalyzed
transesterication
Base-catalytic and
non-catalytic
supercritical
methanol
transesterication
Acid-catalysed
transesterication
Transesterication

Yield (%)

491

492

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Table 5 Energy content of biodiesel fuel.


Type of fuel

Production process

Energy content (MJ/kg)

References

Petroleum diesel

45.00

Karanja oil biodiesel


Tallow

Transesterication

39.66
40.05

WCO biodiesel

Base-catalytic and
supercritical methanol
transesterication

42.65

25.1

Transesterication
Transesterication
Transesterication

42.15
30.4
39.76
36.5

Okullo et al. (2012)


Okullo et al. (2012)
Raja et al. (2011)
Ramadhas et al. (2005)

41

Rawat et al. (2013)

Algae (Cladophora
fracta) biodiesel
Microalgae (Chorella
protothecoides)
biodiesel
Jatropha oil biodiesel
Castor oil biodiesel
Jatropha oil biodiesel
Rubber seed oil
biodiesel
Microalgal

preventing the separation of biodiesel from glycerine and


consequently reducing the nal yield (Canakci and Gerpen,
2001). For FFA >2.5 wt%, a pre-treatment 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 2.5 wt% need to handle problems of those mentioned.
In Malaysia, a widely used biodiesel feedstock is palm oil
(Siddiquee and Rohani, 2011). Palm oil has dominated the
biodiesel production industry because of its availability and
versatile application and because it is easily found (Janaun and
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 conducted
for certain types of feedstock, and the oil content of each feedstock is illustrated in Fig. 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 nding alternatives for biodiesel

Table 6 Different feedstocks for biodiesel production.


Edible
feedstocks

Non-edible
feedstocks

Soybean
Palm oil
Rapeseed

Jatropha curcas
Pongamia pinnata
Sea mango

Canola
Sunower
Cottonseed
Peanut
Corn
Olive
Coconut oil
Butter
Pumpkin
Linseed

Tallow
Poultry
Nile tilapia
Castor
Rubber seed

Others
Waste cooking oil
Algal
Municipal
sewage sludge

21.1

Talebian-Kiakalaieh et al.
(2013)
Vivek and Gupta (2004)
Talebian-Kiakalaieh et al.
(2013)
Demirbas (2009)

Demirbas and Demirbas


(2011)
Demirbas and Demirbas
(2011)

feedstock is the high cost of pure vegetables (edible crops)


and seed oils, which constitutes about 7085% of the overall biodiesel production cost (Mondala et al., 2009; Siddiquee
and Rohani, 2011; Abbaszaadeh et al., 2012). Using reusable
sources as biodiesel feedstock, biodiesel production costs can
be reduced by 6090% since the price of waste edible oils is
2.53.0 times cheaper than that of vegetable oils (TalebianKiakalaieh et al., 2013).
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 non-edible 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 alkalinebased catalyzed transesterication and two-step acid-based
catalyzed transesterication.
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 and 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 J. 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
benecial 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 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

493

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

(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.
The usage of algae as biodiesel feedstock is said to give a
high yield of methyl ester (Janaun and 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 efcient 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 and
Briggs, 2008).
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 transesterication 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 pretreatment 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; purication of raw material and oil pressing, cost
of transesterication, cost of electricity, transportation and
working capital (Pimentel and Patzek, 2005; Sharma et al.,
2008). Siddiquee and Rohani (2011) classied 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 classied as depicted in Fig. 5 while Table 7 shows the cost
of producing biodiesel from different feedstock based on previous studies.

2.2.

Biodiesel production process

Biodiesel can be produced by four primary techniques: direct


use and raw oils blending, micro-emulsions, transesterication, and pyrolysis (Vyas et al., 2010). However, the common
reaction being used nowadays is transesterication (Janaun

Low-cost productions
feedstock
Municipal sludge
Waste cooking oil

Moderate-cost
productions feedstock
Vegetable oil

High-cost productions
feedstock
Sunflower oil
Soybean oil
Rapeseed oil
Cotton oil
Jatropha oil

Fig. 5 Classication of biodiesel production cost based on


different feedstock.
Table 7 Cost of producing biodiesel from different
feedstock using transesterication process.
Feedstock

Municipal sludge oil

USD 3.11 per gallon

Soybean oil
Animal fats

USD 4.004.50 per


gallon
USD 1.59 per gallona

Rapeseed oil

USD 6.51 per gallona

Palm oil
Rapeseed oil

USD 1.26 per gallona


USD 10.64 per
gallona
USD 4.04 per gallona
USD 1.70 per gallona
USD 1.56 per gallona

Castor oil
Soybean oil
Waste cooking oil
a

References

Biodiesel
production cost
(USD per gallon)

Siddiquee and
Rohani (2011)
Siddiquee and
Rohani (2011)
Sivasamy et al.
(2009)
Sivasamy et al.
(2009)
Ong et al. (2012)
Ong et al. (2012)
Ong et al. (2012)
Ong et al. (2012)
Ong et al. (2012)

Calculated production costs after unit conversion.

and Ellis, 2010; Siddiquee and Rohani, 2011; Abbaszaadeh


et al., 2012).

2.2.1.

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 1:102:10,
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.

2.2.2.

Micro emulsions

It was stated by Abbaszaadeh et al. (2012) that the microemulsion 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, ethanol, and 1-butanol. The disadvantages of this
process are that it can result in heavy carbon deposits and
incomplete combustion.

2.2.3.

Pyrolysis

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 biooil 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

494

Demirbas (2009)
99.6
286
30
41:1

Ahmad et al. (2010)


Vivek and Gupta (2004)
Wan Omar and Amin (2011)
80.0
88.0
79.7
60
3040
115

6870
169
6:1
810:1
29:1

El Diwani et al. (2009)


Hossain and Boyce (2009)
98.0
99.0
65
40

180
6:1
6:1

Transesterication
Transesterication
Transesterication

Supercritical methanol
transesterication

Jatropha oil
Sunower oil

Sunower oil
Karanja oil
WCO

WCO

Jatropha oil

Two-step catalyzed
transesterication
Base catalyzed
transesterication
Transesterication
Two-step transesterication

H2 SO4
NaOH
KOH
NaOH
KOH
Alkaline modied
zirconia
No catalyst

Raja et al. (2011)

60
60
6:1

Bouaid et al. (2012)


98.0
45
60
6:1
20:1

Berchmans and Hirata (2008)


90.0
65
120
24:1

Yaakob et al. (2012)


99.5
65
45
15:1
15:1

Jatropha oil

EFB

KOH/EFB

98.5
65
90
15:1
20:1

Reaction
temperature ( C)
Reaction
time (min)
Methanol:oil
ratio
Catalyst:oil
weight ratio
Catalyst

H2 SO4
NaOH
H2 SO4
KCH3 O
NaOH
Jatropha oil

In the washing process, the undesirable substances being


removed include soap (Rattanapan et al., 2011), catalyst,

Jatropha oil

Biodiesel washing process

Heterogeneous catalyzed
transesterication
Heterogeneous catalyzed
transesterication
Two-step transesterication

3.1.

Jatropha oil

As can be seen from Fig. 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 specications is produced
(Ngamlerdpokin et al., 2011; Atadashi et al., 2012).

Process

Generation of biodiesel wastewater

Feedstock

3.

Yield (%)

Transesterication

Transesterication 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 ow
diagram for transesterication is shown in Fig. 6. The transesterication 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 purication, also known as the washing step. It will then
undergo a drying process where rened/puried biodiesel is
obtained. Factors that might affect the transesterication yield
are the catalyst type, the alcohol/vegetable oil molar ratio, the
content of water and FFAs, temperature, and reaction duration
(Siddiquee and Rohani, 2011; Abbaszaadeh et al., 2012).
There are three types of catalysts: alkalis, acids, and
enzymes. Alkali-catalyzed transesterication 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 and Rohani, 2011; Berrios and 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 and Skelton,
2008), is easily obtained (Atadashi et al., 2012), and can react
with triglycerides quickly and dissolve the alkali catalyst easily
(Ma and Hanna, 1999). Process conditions of transesterication reaction with respect to different kind of feedstock are
tabulated in Table 8.

Table 8 Process conditions of transesterication reaction.

2.2.4.

References

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 and Czernik, 2010). This process requires
expensive equipment and has several advantages such as
lower processing cost, simplicity, less waste, and no pollution
(Singh and Singh, 2010). It was suggested by Ito et al. (2012)
that the pyrolysis method is suitable for WCO processing.

Yaakob et al. (2012)

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

495

Fig. 6 Process ow diagram of conventional transesterication process for biodiesel production.


free glycerol, residual alcohol (Atadashi et al., 2011), water,
and FFAs (Berrios and 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 and Skelton, 2008). Recently,
another alternative washing method has been investigated,
which is membrane extraction (Leung et al., 2010).

3.1.1.

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 unpuried product
and the mixture of water and impurities will be settled and
drained out as efuent. 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 and 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 efuent (Kumjadpai et al., 2011). The large amount of
biodiesel wastewater generated by the washing process creates a signicant problem for the industry and environment.
In 2011, worldwide generation of biodiesel wastewater was
approximately 28 million m3 (Veljkovic et al., 2012).

3.1.2.

but failed to meet the standard level for methanol, triglycerides, and soap and water contents.

3.1.3.

Membrane extraction

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 benecial in minimizing the volume of water used (Gomes et al.,
2013), effectively avoiding the occurrence of emulsication
during the washing step and resulting in a decrement of the
methyl ester loss during the rening process (Leung et al.,
2010), and it is said to be a promising method of biodiesel
purication. Membrane studies carried out by Low et al. (2011)
involved the usage of two types of membrane: at microltration mixed cellulose acetate (MCA) polymeric membrane and
at ultraltration polytetrauoroethylene (PTFE) polymeric
membrane. The experimental set-up of this study is shown
in Fig. 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 uid was sent back to the recirculation tank. Their study found that the ultraltration PTFE
polymeric membrane successfully ltered a higher volume

Dry washing process

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 and Skelton, 2008). The ltration process is usually
added in the nal stage to enhance the process efciency. 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 specied by the EN14214 Standard

Fig. 7 Schematic diagram of membrane process


experimental set-up (Low et al., 2011).

496

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Table 9 Advantages and disadvantages of each washing process.


Treatment

Advantages

Wet washing

Very effective in removing


contaminants. Puried
biodiesel obtained direct
from glycerol separation
fulls EN14214 Standard
requirements.
Decreases production time;
lower cost; less space
required to conduct dry
washing process. Waterless.
Avoids the formation of
emulsions. Rening loss
decreases. Minimizes the
volume of water used.
Provide cost benet.

Dry washing

Membrane
extraction

of methyl ester compared to the MCA polymeric membrane.


Membrane technology was also used and reported by Gomes
et al. (2013). Tubular -Al2 O3 /TiO2 membranes with average
pore diameters of 0.2, 0.1, and 0.05 m and 20 kDa were used.
In the investigation using acidied water with a mass concentration of 10%, glycerol was separated effectively, giving
nal free glycerol content below 0.02% of the maximum value.
Table 9 below summarizes the novelty of each treatment.

3.2.

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 ve 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 350,000 L/day biodiesel
consequently produced more than 70,000 L of wastewater per
day (Ngamlerdpokin et al., 2011; Jaruwat et al., 2010). Siles
et al. (2010) 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.
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 difcult 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

Disadvantages

References

Increased cost and


production time; large
amount of water used,
emulsion formation.

Veljkovic et al. (2012),


Berrios and Skelton (2008)
and Atadashi et al. (2011)

Exceeds the limit in the EN


Standard.

Berrios and Skelton (2008)


and Leung et al. (2010)

Probably high cost. Low


throughput due to existing
contaminants.

Gomes et al. (2013), Leung


et al. (2010), and Atadashi
et al. (2011)

contaminants contribute to the high contents of COD and O&G


(Srirangsan et al., 2009).

3.3.
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 Efuent) Regulations 2009. The
standard is governed by Malaysias Environmental Law, the
Environmental Quality Act, 1974. Table 11 shows the industrial
efuent 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.

4.
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 128.45160 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 (Veljkovic 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 otation to separate the oil and grease
before the wastewater is sent to the next process (Chavalparit
and Ongwandee, 2009). Some studies have proposed the

Table 10 Characteristics of biodiesel wastewater.


pH

SS (mg/L)

18,362
60,000545,000
30,980
312,000588,800
428,000 12,000
60,000150,000
312,000588,800
542,400
3681
40,975
29,59554,362
19,00037,000

2670

150028,790
340

15005000

233405

TSS (mg/L)

8850

670690

O&G (mg/L)
15,100

700044,300
6020
18,00022,000

700015,000
18,00022,000
21,048
387
459
10401710

BOD5 (mg/L)

References

105,000300,000

168,000300,000

30,00060,000
168,000300,000
224,630
1600
15,260
14922286
2601600

Suehara et al. (2005)


Berrios and Skelton (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)

Table 11 Standards for industrial efuents in several countries.


Country

Malaysia

Parameter

Unit

Temperature
pH value
BOD5 at 20 C
COD
SS
O&G
Colour
Regulations

Thailand
B

Taiwan, China

Under
consideration
of PCC*

Philippines
Inland waters

OEI*

References

mg/L
mg/L
mg/L
mg/L
ADMI*

40
6.09.0
20
80
50
1.0
100
Environmental
Quality Act and
Regulations 1974
Akta Kualiti Alam
Sekeliling 1974

40
5.59.0
50
200
100
10.0
200

40
5.59.0
20
120
50
5

Enhancement and
Conservation of the
National Quality Act
Thaveesri (2003)

40
5.59.0
60
400
150
15

NPI*

Coastal waters

OEI

<35
6.09.0
50
200
50
10

Water Pollution
Control Act

40
40
40
69
69
59
150
120
120
250
200
250
200
150
200

15
150 PtCo
150 PtCo
300 PtCo
Philippine Regulations on Sanitation and
Wastewater Systems

Tang (1993)

Magtibay (2006)

40
59
100
200
150
10
300 PtCo

497

*ADMI: American Dye Manufacturers Institute; PCC: Pollution Control Committee; OEI: Old/Existing Industry; NPI: New/Proposed Industry.

NPI

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

11.0
6.7
8.510.5
8.9
9.2510.76
10.35 0.03
8.510.5

10.110.2
11.11
11.21
9.2510.26
4.346.56

COD (mg/L)

498

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

application of pre-treatment before the wastewater ows to


the treatment facility of the wastewater agency and some have
proposed full treatment of biodiesel wastewater.

4.1.

Current treatment technologies

The individual treatments that have been reported include


coagulation (Ngamlerdpokin et al., 2011; Kumjadpai et al.,
2011), electrocoagulation (Srirangsan et al., 2009; Chavalparit
and Ongwandee, 2009), biological processes (Suehara et al.,
2005), adsorption (Pitakpoolsil and Hunsom, 2013), and microbial fuel cell systems (Sukkasem et al., 2011).

4.1.1.

Coagulation treatment

In coagulation process, coagulant is added to separate the


small particle content from a solution in a reasonable time.
These particles are destabilized and occulate into larger, settleable ocs (Aygun and Yilmaz, 2010). The formation of ocsis
responsible for removing contaminants such as metals and
toxic wastes and reducing COD, BOD5 , SS, turbidity, and colour
(Saraswathi and 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 ocs 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).
Factors that might affect the efciency of the coagulation
process include the type of coagulant used or pre-hydrolyzed
metal salt used (Xie et al., 2011), coagulant dosage, pH (Aygun
and 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 and 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 ocs or generating occulation (Rattanapan
et al., 2011) and affects the coagulation performance (Aygun
and Yilmaz, 2010). It is often efcient in the range of pH 57,
but the nature of the water might lead to some differences
in nding 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 79 (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
67, 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 efciency.
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 dayretention time to 95.4% at ve 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 (57) and coagulants effect with variable
dosage (alum and ferric chloride; 0.51.5 g/L, PACl: 0.52.0 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 efciency 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.
Treatment of biodiesel wastewater was done in many ways.
For example, in the study done by Ngamlerdpokin et al. (2011),
it involved the acidifying process of the wastewater with
three different acids: H2 SO4 , HNO3 , and HCl before coagulation
process took place. The most effective acid was H2 SO4 . The
acidied 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 (06 g/L) and mixing rate
(100300 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 (H2 SO4 , 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 acidication using H2 SO4 at pH 12.5, approximately
1530% fatty acid methyl esters (FAMEs) were recovered. The
removal efciencies of pollutants parameter for each study
are listed in Table 12.
In another study, Xie et al. (2011) identied the performance
of coagulation process in treating raw waste glycerol produced
from biodiesel production process. The pH of wastewater was
rst being adjusted from 9 to 3 using HCl and NaOH prior
to determine the appropriate pH for soap and oil separation.
Through this acidication process, the waste glycerol was pretreated 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 and Ongwandee, 2009) and generation of lowdensity sludge with low-decomposition efciency (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).

4.1.2.

Electrocoagulation treatment

One of the attractive treatments for biodiesel wastewater is


the electrocoagulation process (Fig. 8). It is also known as

Xie et al. (2011)

Rattanapan et al.
(2011)

Raw waste glycerol

pH: 9.710.4
COD: 1.71.9 106 mg/L
BOD5 : 0.91.2 106 mg/L
TSS: 21.338.7 105 mg/L
Glycerol: 413477 g/L
Methanol: 112203 g/L

99.9
99.8
99.7

93.3

96.2
Wastewater from
biodiesel production

35 rpm

2 g/L
2 g/L
2 g/L
5 g/L

1h
1h
1h
15 min

Wastewater from
washing unit

6
4
2 g/L
1 g/L

Fig. 8 Schematic diagram of electrocoagulation set-up


(Maha Lakshmi and Sivashanmugam, 2013). (1) DC power
supply, (2) anode, (3) cathode, (4) electrocoagulation cell, (5)
efuent, (6) magnetic bead, (7) magnetic stirrer.
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 and
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 ocs generated. Electrocoagulation uses electrochemistry principles,
treating the wastewater better by oxidizing the cathode while
the water is reduced (Butler et al., 2011).
The electrocoagulation process consists of three main
mechanisms: electrode oxidation, gas bubble generation,
and otation or sedimentation of formed ocs (Emamjomeh
and Sivakumar, 2009). Example of electrochemical reactions
using alum as anode is described as in Eq. (2) (Chavalparit
and Ongwandee, 2009). Listed by Butler et al. (2011) several considerations that might affect the treatment efciency;
wastewater type, pH, current density, type of metal electrodes,
number and size of electrodes as well as metals conguration.
However, there is other factor, which was investigated before
such as reaction/retention times.
Anodic reactions : Al(s) Al3+ + 3e
Cathodic reaction : H2 O + 2e H2 (g) + 2OH

Alum
Ferric chloride
PACl
PACl

Alum
PAC

Alum

3+

Type of
coagulant

499

TSS: 98.1
Glycerol:
65.4
Methanol:
85.8

Kumjadpai et al.
(2011)
99.5
99.1
98.6
97.9
98.8
98.7

98.2
97.2

pH: 2.5
COD: 271000341712 mg/L
BOD5 : 673967389 mg/L
O&G: 210421 mg/L
pH: 10.110.2
COD: 271200341712 mg/L
BOD5 : 673967389 mg/L
O&G: 210421 mg/L
O&G:
7120 mg/L

6
2 g/L

Settling
time
Mixing rate
pH
Dosage of
coagulant

Wastewater from
washing unit

Wastewater
characteristics
Source of
wastewater
Process conditions

Table 12 Process conditions of different coagulation treatments for biodiesel wastewater.

97.5

Others
O&G
BOD5
COD

Removal parameters (%)

References

Ngamlerdpokin et al.
(2011)

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

In the solution : Al

(2)

(aq) + 3H2 O Al(OH)3 + 3H

The efciency 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

500

Ngamlerdpokin
et al.
(2011)

91
.5
99
.6

Kumjadpai
et al.
(2011)
SS:
97.5
97
.8

55
.7

Chavalparit
and
Ongwandee
(2009)
TSS:
96.6
98
.4

Wastewater from
biodiesel production
4h
Current density:
12.42 mA/cm2
Iron plate

7.40

6.00
Current density:
8.32 mA/cm2
Anode: Aluminium
Cathode: Graphite

25 min

Oily wastewater
from biodiesel
production
25 min
6.06
18.2 V
Anode: Aluminium
Cathode: Graphite

Reaction time
pH
Applied voltage
Anode & Cathode

Wastewater from
washing unit

pH: 8.9
COD: 30,980 mg/L
O&G: 6020 mg/L
TSS: 340 mg/L
Glycerol: 1360 mg/L
Methanol: 10,667 mg/L
pH: 8.9
COD: 30,980 mg/L
O&G: 6020 mg/L
TSS: 340 mg/L
Glycerol: 1360 mg/L
Methanol: 10,667 mg/L
pH: 2.5
COD: 271000341712 mg/L
BOD5 : 673967389 mg/L
O&G: 210421 mg/L

55
.4

Others
O&G
BOD5
COD

Removal parameters (%)


Wastewater
characteristics
Source of
wastewater

Biological treatment

Various researchers have developed biological technologies


for the treatment of biodiesel wastewater (Siles et al., 2010;
Sukkasem et al., 2011; Ramrez 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 efciencies of biological treatment. Few
studies reporting on this matter were discussed. Some factors
that play an important role and inuence the effectiveness
of biological process are nutrients and oxygen supply, pH
value, chemical and physical characteristics of the wastewater (Margesin and Schinner, 2001), and hydraulic retention
time (HRT) (Rajasimman and Karthikeyan, 2007). Sufcient
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,
sufcient oxygen is needed to create the proper environment
for bacterial inoculation to become dominant. Insufcient
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 efciency (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 and 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

Process conditions

4.1.3.

Table 13 Process conditions of electrocoagulation treatments for biodiesel wastewater.

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 min respectively. Chavalparit and Ongwandee (2009) also
optimized the process using a BoxBehnken design and found
that pollutants were efciently 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 ocs
of aluminium hydroxide. The increment of voltage led to an
increment in nal pH greater than 7.5 and resulted in ineffective removal. Reported that, any additional time more than
25 min does not have any signicant impact on the removal
efciency. Their study showed under the optimum conditions,
electrocoagulation consumed about 5.57 kW h power for the
treatment of 1 m3 biodiesel wastewater.
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 FeFe, FeC, AlAl, AlC and CC. Range of
current density level, retention times and initial pH were
3.511 mA/cm2 , 1040 min and 49 respectively. The process
was efcient at pH 6 with 25 min retention time and a current density level of 8.32 mA/cm2 using aluminium and carbon
(AlC) electrodes. The overall removal efciency 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.

References

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

digestion, which requires a longer time and has a slow reaction. In another study by Bassin et al. (2011), a longer HRT
may be benecial 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 insufcient time for the 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.
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, articial 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 efciency 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 diesel-rich 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 h. 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 biolm in RBC may suitable for
petrochemical industries and petroleum reneries wastewater.
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 NaH2 PO4 , 8.5 g/L of
KH2 PO4 , 21.75 g/L of K2 HPO4 , and 5 g/L of CaCl2 2H2 O) and
24 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.
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 renery wastewater (Rahman and Al-Malack, 2006), oily
wastewater (Tri, 2002), petrochemical wastewater (Llop et al.,
2009), and oil-contaminated wastewater (Scholz and Fuchs,
2000). Some main parameters involved in the MBR system
are the conguration of the membrane, membrane material,
membrane pore size, and HRT. Based on their study on previous research showed that MBR was efciently 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

501

the cost of maintenance and cleaning, membrane replacement cost, and membrane module cost. Table 14 summarized
the removal efciencies of biodiesel wastewater using biological treatments.

4.1.4.

Adsorption

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
akes were used as adsorbent and several operating parameters were varied, including adsorption time (0.55 h), initial
wastewater pH (28), adsorbent dosage (1.55.5 g/L), and mixing rate (120350 rpm). Pre-treatment of biodiesel wastewater
was carried out rst by an acidication process using H2 SO4
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 h, 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 adsorption using fresh chitosan or other methods. It is
also might facing difculties in disposing the usable chitosan
akes.

4.1.5.

Microbial fuel cell

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 upow bio-lter 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
efciency are summarized in Table 15. Each treatment has
advantages and disadvantages, as listed in Table 16.

4.2.

Integrated system

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 efciency. Several integrated
systems being investigated for biodiesel wastewater treatment are dissolved air otationcoagulation (Rattanapan
et al., 2011), the photo-Fentonaerobic sequential batch reactor (Ramrez et al., 2012), acidicationelectrocoagulation and
biomethanization (Siles et al., 2011), and electrootation and
electrooxidation (Romero et al., 2013). Integrated systems and
the proposed integrated coagulationbiological aerated lter

502

Ramrez et al. (2012)


TOC:
21%

90
.0%

Chavan and Mukherji (2008)


TPH:
98.4%

97
.0%

Suehara et al. (2005)


Oil:
98.0%

Others
O&G
BOD5

Wastewater from
palm oil biodiesel
production plant

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
Raw biodiesel
wastewater; articial
wastewater

Diesel-rich
wastewater

Wastewater
characteristics
Type of
wastewater

(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.

4.2.1.

Dissolved air otationcoagulation

A typical treatment of oily wastewater, dissolved air otation,


was studied by Rattanapan et al. (2011). However, the authors
suggested additional methods and pre-treatment of the systems by acidication and a coagulation process. About 1 N of
pure HCl and H2 SO4 was used for acidication, and the coagulation process was done using a Jar test unit under conditions
of 100 rpm for 1 min followed by 30 rpm for 20 min. A decrement in wastewater pH from 7 to 5 made the oil droplets
occulate with each other and rise to the surface. In the acidication process, the authors found that the COD removal was
efcient at pH 3. Oil recovered in the acidication process
was intended to be used in biodiesel production. Moreover,
H2 SO4 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
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 nal process of this research, the dissolved air
otation method was used with acidication 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.

4.2.2.

Photo-Fenton-aerobic sequential batch reactor

Ramrez et al. (2012) investigated the efciency of an integrated process which combined the photo-Fenton 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
UVvis. The production of hydroxyl radical from this cycle is
used for the oxidation of organic compounds.
Fe2+ + H2 O2 Fe3+ + OH + OH
Fe3+ + H2 O + hv Fe2+ + OH + H+

(3)

Type of
microorganism

Rhodotorula
mucilaginosa

Bacillus cepacia

Textile wastewater
treatment
inoculums

Agar plate

Rotating biological
contactor

Batch reactor

RH + OH photo-products + H2 O

Type of treatment

Table 14 Removal efciencies of biodiesel wastewater using biological treatments.

COD

Removal parameters

References

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

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 (H2 O2 )
and ferrous ions were added to the wastewater and a sample was taken after 2 h. MnO2 was added to each sample in
order to destroy the H2 O2 , avoid subsequent reactions, prevent
interference with the COD readings, and prevent inhibition
of the bioreactor. The nal 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

503

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Table 15 Summary of other individual process for biodiesel wastewater treatment.


Treatment process
Adsorption
Microbial fuel cell

COD removal (%)

BOD5 removal (%)

90
60

76

SS removal (%) O&G removal (%)

67

References
Pitakpoolsil and Hunsom (2013)
Sukkasem et al. (2011)

Table 16 Advantages and disadvantages of different individual treatments.


Treatment

Advantages

Coagulation

Simple and economical,


proven enhance
wastewater treatment

Electrocoagulation

Less treatment time, no


chemical required simple
equipment, ease of
operation
Economical, versatile
arrangements for small
areas, simple and suitable
for small scale plant

Biological processes

Adsorption

Microbial fuel cell

No additional sludge is
produced, pH of discharged
wastewater is unaffected
Offers high COD removal

the palm oil biodiesel wastewater. Meanwhile, the removal


efciencies 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 difculties to decompose the formed sludge in
SBR.

4.2.3. Acidicationelectrocoagulation 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 co-digestion which is long-chain fatty acids
contained in biodiesel wastewater, they decided to add pretreatment steps; acidication 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 acidication 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
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 1845 h retention time. The whole treatment managed to remove 8090% of COD with methane production
as an added value to the process (310 mL methane/g COD
removed).
. The simple and economical operation of the coagulation

Disadvantages/problems
Require handling chemical,
operation relatively
complicated, generates
low-density sludge with
low-decomposition
efciency.
Higher cost compared to
coagulation, less effective
for methanol and glycerol
removal
Generates large amounts of
low-density sludge with
low decomposition
efciency, time consuming,
need to manage the
optimum condition rst
Need further treatment,
facing difculties in
disposing the adsorbents
Costly

References
Xie et al. (2011), Butler et al.
(2011), Chavalparit and
Ongwandee (2009) and
Kumjadpai et al. (2011)

Ngamlerdpokin et al. (2011),


Chavalparit and
Ongwandee (2009) and
Srirangsan et al. (2009)
Pitakpoolsil and Hunsom
(2013), Ramrez et al. (2012)
and Suehara et al. (2007)

Pitakpoolsil and Hunsom


(2013)
Sukkasem et al. (2011)

4.2.4. Acidication
electrocoagulation and biomethanization
Integrated acidicationelectrocoagulation 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, acidication
coagulationocculation and biomethanization, was also used
prior to comparing the two systems efciencies. The
pre-treatment processes of acidicationelectrocoagulation
and acidicationcoagulationocculation gave COD removal
rates of 45 and 63% respectively. However, during the
whole treatment, 99% COD removal was recorded using
acidicationelectrocoagulation and biomethanization compared to only 94% using acidicationcoagulationocculation
and biomethanization.

4.2.5.

Electrootation and electrooxidation

The utilization of electrootation 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 cm2 for a reaction time of
60 min, the electrootation process managed to remove 92,
98, 100, 57, and 23% of turbidity, total solids, O&G, COD, and
methanol respectively. The efuent was then subjected to
an electrooxidation process using Ti/RuO2 anodes. With an
applied current density of 40.0 mA cm2 for a reaction time
of 240 min, the methanol and COD were effectively reduced
by 68 and 95% respectively.

4.2.6.

Chemical recovery and electrochemical

Jaruwat et al. (2010) studied the ability of a combined chemical recovery and electrochemical process. Chemical recovery

504

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

Fig. 9 Schematic of proposed integrated process of CoBAF system in our study.


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.

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 and 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 (Zhao et al., 2006). Some advantages that make this
system favourable for use are its exibility, 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, ow conguration, aeration system,
lter media, media types, size, and BAF design (Abu Hasan
et al., 2009).
The BAF system has been studied before by Zhao et al.
(2006). The system was used to successfully pre-treat oil eld
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-ow BAF in
treating oil-eld produced water. The anaerobic bafed reactor (ABR) was combined with the BAF system and the hydraulic
loading rates were varied from 0.6 to 1.4 m h1 . 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.

4.2.7. Coagulation-biological aerated lter (CoBAF)


system
The biological aerated lter (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 and 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 aims to use this system
in the proposed integrated process, which combines coagulation treatment and the BAF system (CoBAF), as depicted in
Fig. 9 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. Table 17 shows the summary
of integrated system performance for biodiesel wastewater
treatment.
Biological treatment seems suitable for use because of its
economic value (Jou and 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.,

Table 17 Summary of integrated system performance for biodiesel wastewater treatment.


Treatment process
Dissolved air otationcoagulation
Membrane bioreactorbiological activated
carbon
Acidicationelectrocoagulation and
anaerobic co-digestion
Acidicationelectrocoagulation and
biomethanization
Acidicationcoagulationocculation
and biomethanization
Photo-Fenton-aerobic sequential batch
reactor
Electrootation and electrooxidation

COD
removal (%)

BOD
removal (%)

4050
89.999.9

98100

8595
97.699.9

Rattanapan et al. (2011)


Tri (2002)

8090

Siles et al. (2010)

99

Siles et al. (2011)

94

Siles et al. (2011)

69

Ramrez et al. (2012)

98

100

Romero et al. (2013)

76.1
57

SS removal
(%)

O&G
removal (%)

References

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

The main reason why authors are interested in investigating CoBAF integrated system is that we are trying to nd
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 otation, 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 efuent of biodiesel wastewater meet
the efuent 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 lter 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.

5.

Conclusions

Biodiesel is mainly produced from vegetable oils through the


transesterication 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 efciently with a
single treatment. This wastewater, which has a milky colour
and bad odour, needs to be treated efciently. Numerous treatments are being studied and proven for treating or pre-treating
biodiesel wastewater and each has its own benets and disadvantages. The ability and performance of integrated treatment
using a coagulationbiological aerated lter (CoBAF) system
will be investigated.

Acknowledgements
This research was nancially supported by the Faculty of
Engineering and Built Environment, Universiti Kebangsaan
Malaysia, through grant number INDUSTRI-2012-029.

References
Abbaszaadeh, A., Ghobadian, B., Omidkhah, M.R., Naja, G., 2012.
Current biodiesel production technologies: a comparative
review. Energy Convers. Manage. 63, 138148,
http://dx.doi.org/10.1016/j.enconman.2012.02.027.
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, http://dx.doi.org/10.1016/j.enpol.2009.08.012.
Abu Hasan, H., Sheikh Abdullah, S.R., Kamarudin, S.K., Tan Koi,
N., 2009. A review on the design criteria of biological aerated
lter for COD, ammonia and manganese. J. Inst. Eng., Malays.
70 (4), 2533.

505

Abu Hasan, H., Sheikh Abdullah, S.R., Kamarudin, S.K., Tan Koi,
N., Anuar, N., 2013. Simultaneous NH4 + N and Mn2+ removal
from drinking water using a biological 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 lter process. Water Sci. Technol. 24 (9),
195204.
Adnan, H., 2013. The Star Online. Malaysias B10 Biodiesel
Programme and its Benet, Retrieved from: http://biz.
thestar.com.my/news/story.asp?le=/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 transesterication
of sunower 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. Process.:
Process Intensif. 49 (11), 11761182,
http://dx.doi.org/10.1016/j.cep.2010.08.019.
Atadashi, I.M., Aroua, M.K., Abdul Aziz, A.R., Sulaiman, N.M.N.,
2011. Rening technologies for the purication of crude
biodiesel. Appl. Energy 88 (12), 42394251,
http://dx.doi.org/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. Membr. Sci. 421422, 154164,
http://dx.doi.org/10.1016/j.memsci.2012.07.006.
Aygun, A., Yilmaz, T., 2010. Improvement of
coagulationocculation 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. Nitrication of
industrial and domestic saline wastewaters in moving bed
biolm reactor and sequencing batch reactor. J. Hazard. Mater.
185 (1), 242248,
http://dx.doi.org/10.1016/j.jhazmat.2010.09.024.
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), 17161721,
http://dx.doi.org/10.1016/j.biortech.2007.03.051.
Berrios, M., Skelton, R.L., 2008. Comparison of purication
methods for biodiesel. Chem. Eng. J. 144, 459465,
http://dx.doi.org/10.1016/j.cej.2008.07.019.
Biodiesel market reports. Retrieved from:
http://www.thecropsite.com/reports/
Bouaid, A., El Bouli, N., Martinez, M., Aracil, J., 2012.
Optimization of a two-step process for biodiesel production
from Jatropha curcas crude oil. Int. J. Low Carbon Technol.,
331337, http://dx.doi.org/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, http://dx.doi.org/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 lter.
Process Biochem. 37, 693698.
Chavalparit, O., Ongwandee, M., 2009. Optimizing
electrocoagulation process for the treatment of biodiesel
wastewater using response surface methodology. J. Environ.
Sci. 21 (11), 14911496,
http://dx.doi.org/10.1016/S1001-0742(08)62445-6.
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 (13), 6372,
http://dx.doi.org/10.1016/j.jhazmat.2007.09.106.

506

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

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),
1322.
De Gisi, S., Galasso, M., De Feo, G., 2013. Full-scale treatment of
wastewater from a biodiesel fuel production plant with
alkali-catalyzed transesterication. Environ. Technol. 34 (7),
861870.
Demirbas, A., 2009. Biodiesel from waste cooking oil via
base-catalytic and supercritical methanol transesterication.
Energy Convers. Manage. 50 (4), 923927,
http://dx.doi.org/10.1016/j.enconman.2008.12.023.
Demirbas, A., Demirbas, M.F., 2011. Importance of algae oil as a
source of biodiesel. Energy Convers. Manage. 52 (1), 163170,
http://dx.doi.org/10.1016/j.enconman.2010.06.055.
Dugan, J., Biodiesel Magazine, 2007. A Dry Wash Approach to
Biodiesel Purication, Retrieved from: http://
biodieselmagazine.com/articles/1918/a-dry-wash-approachto-biodiesel-purication/
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/otation processes. J. Environ. Manage. 90
(5), 16631679,
http://dx.doi.org/10.1016/j.jenvman.2008.12.011.
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
French, R., Czernik, S., 2010. Catalytic pyrolysis of biomass for
biofuels production. Fuel Process. Technol. 91 (1), 2532,
http://dx.doi.org/10.1016/j.fuproc.2009.08.011.
Gasim, H., Kutty, S.R.M., Isa, M.H., 2000. Biodegradability of
Petroleum Renery Wastewater in Batch Reactor, PhD thesis,
UTP.
Gomes, M.C.S., Arroyo, P.A., Pereira, N.C., 2013. Inuence of
acidied water addition on the biodiesel and glycerol
separation through membrane technology. J. Membr. Sci. 431,
2836, http://dx.doi.org/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,
http://dx.doi.org/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,
http://dx.doi.org/10.1016/j.biortech.2010.05.045.
He, Y., Wang, X., Xu, J., Yan, J., Ge, Q., Gu, X., Jian, L., 2013.
Application of integrated ozone biological aerated lters and
membrane ltration in water reuse of textile efuents.
Bioresour. Technol. 133, 150157,
http://dx.doi.org/10.1016/j.biortech.2013.01.074.
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 sunower cooking oil as an environmental recycling
process and renewable energy. Bulg. J. Agric. 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), 3846.
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,
http://dx.doi.org/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,
http://dx.doi.org/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.
Manage. 51 (3), 531537,
http://dx.doi.org/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, http://dx.doi.org/10.1016/j.rser.2009.06.023.
Jou, C.G., Huang, G.C., 2003. A pilot study for oil renery
wastewater treatment using a xed lm bioreactor. Adv.
Environ. Res. 7, 463469.
Kaercher, J.A., DeCassia, R., 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, http://dx.doi.org/10.1016/j.jclepro.2012.09.016.
Kapilakarn, K., Peugtong, A., 2007. A comparison of costs of
biodiesel production from transesterication. Int. Energy J. 8,
16.
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,
http://dx.doi.org/10.1016/j.seppur.2010.05.016.
Khan, S.A., Hussain, M.Z., Prasad, S., Banerjee, U.C., 2009.
Prospects of biodiesel production from microalgae in India.
Renew. Sustain. Energy Rev. 13, 23612372,
http://dx.doi.org/10.1016/j.rser.2009.04.005.
Khan, Y.A., Yamsaengsung, R., 2011. Review of wastewater
treatment methods and MBR technology for application in
biodiesel plants. In: 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 oc characteristics for
the evaluation of seawater coagulation process. Desalin.
Water Treat. 10, 95100.
Kinast, J.A., 2003. National Renewable Energy Laboratory 2003.
Subcontractor Report: Production of Biodiesel from Multiple
Feedstocks and Properties of Biodiesels and Biodiesel/Diesel
Blends.

Kolesrov, N., Hutnan,


M., Bodk, I., Spalkov, V., 2011.
Utilization of biodiesel by-products for biogas production. J.
Biomed. Biotechnol. 2011, 115,
http://dx.doi.org/10.1155/2011/126798.
Krishna, A.R., Dev, L., Thankamani, V., 2012. An integrated
process for industrial efuent 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, http://dx.doi.org/10.1002/cjce.20429.
Leung, D.Y.C., Wu, X., Leung, M.K.H., 2010. A review on biodiesel
production using catalyzed transesterication. Appl. Energy
87 (4), 10831095,
http://dx.doi.org/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,
http://dx.doi.org/10.1016/j.rser.2009.10.027.
Lin, L., Cunshan, Z., Vittayapadung, S., Xiangqian, S., Mingdong,
D., 2011. Opportunities and challenges for biodiesel fuel. Appl.
Energy 88 (4), 10201031.
Llop, A., Pocurull, E., Borrull, F., 2009. Evaluation of the removal of
pollutants from petrochemical wastewater using a membrane
bioreactor 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.
Ind. Eng. Chem. Res. 44 (14), 53535363,
http://dx.doi.org/10.1021/ie049157g.

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

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.
Magtibay, B.B., 2006. Philippines Regulations on Sanitation and
Wastewater System. Biosphere Environment and Health
System Series. B.B. Magtibays Publishing House, Philippines.
Maha Lakshmi, P., Sivashanmugam, P., 2013. Treatment of oil
tanning efuent by electrocoagulation: inuence of
ultrasound and hybrid electrode on COD removal. Sep. Purif.
Technol. 116, 378384,
http://dx.doi.org/10.1016/j.seppur.2013.05.026.
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 (13), 118125,
http://dx.doi.org/10.1016/j.jhazmat.2011.04.045.
Margesin, R., Schinner, F., 2001. Biodegradation and
bioremediation of hydrocarbons in extreme environments.
Appl. Microbiol. Biotechnol. 56 (56), 650663,
http://dx.doi.org/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,
http://dx.doi.org/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 efuent using granular activated
carbon-sequencing batch biolm reactor (GAC-SBBR). Mod.
Appl. Sci. 2 (5), 3745.
Mohan, D., Pittman Jr., C.U., Steele, P.H., 2006. Pyrolysis of
wood/biomass for bi-oil: a critical review. Energy Fuel 20,
848889.
Mondala, A., Liang, K., Toghiani, H., Hernandez, R., French, T.,
2009. Biodiesel production by in situ transesterication of
municipal primary and secondary sludges. Bioresour.
Technol. 100 (3), 12031210,
http://dx.doi.org/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 electro-coagulation: a comparative study. J.
Environ. Manage. 92 (10), 24542460,
http://dx.doi.org/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. Int. J. Renew. Energy Res. 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, 131139.
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. J. Eng. Appl. Sci. 6 (9), 4245.
Patel, H., Madamwar, D., 2002. Effects of temperatures and
organic loading rates on biomethanation of acidic
petrochemical wastewater using an anaerobic upow
xed-lm reactor. Bioresour. Technol. 82 (1), 6571,
http://dx.doi.org/10.1016/S0960-8524(01)00142-0.
Pitakpoolsil, W., Hunsom, M., 2013. Adsorption of pollutants from
biodiesel wastewater using chitosan akes. J. Taiwan Inst.
Chem. Eng. 44 (6), 963971,
http://dx.doi.org/10.1016/j.jtice.2013.02.009.
Pimentel, D., Patzek, T.W., 2005. Ethanol production using corn,
switchgrass, and wood; biodiesel production using soybean
and sunower. Nat. Resour. Res. 14 (1), 6576,
http://dx.doi.org/10.1007/s11053-005-4679-8.

507

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.
Pramanik, B.K., Suja, F., Shahrom, Z., Ahmed, E., 2012. Biological
aerated lters (BAFs) for carbon and nitrogen removal: a
review. J. Eng. Sci. Technol. 7 (4), 428446.
Rahman, M., Al-Malack, M., 2006. Performance of a cross-ow
membrane bioreactor (CF-MBR) when treating renery.
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.
Rajasimman, M., Karthikeyan, C., 2007. Aerobic digestion of
starch wastewater in a uidized bed bioreactor with low
density biomass support. J. Hazard. Mater. 143, 8286.
Ramadhas, A., Jayaraj, S., Muraleedharan, C., 2005. Biodiesel
production from high FFA rubber seed oil. Fuel 84 (4), 335340,
http://dx.doi.org/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,
http://dx.doi.org/10.2166/wst.2012.250.
Rattanapan, C., Sawain, A., Suksaroj, T., Suksaroj, C., 2011.
Enhanced efciency of dissolved air otation for biodiesel
wastewater treatment by acidication and coagulation
processes. Desalination 280 (13), 370377,
http://dx.doi.org/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,
http://dx.doi.org/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 electrootation and electrooxidation processes.
Sep. Sci. Technol. 48, 20732079.
Ruengkong, J., Krimpikun, S., Toonguri, C., Boonsawang, P., 2008.
Biogas production from wastewater of biodiesel process. In:
7th National Environmental Conference, Bangkok, Thailand.
Sanford, S.D., White, J.M., Shah, P.S., Wee, C., Valverde, M.A.,
Meier, G.R., 2009. Feedstock and Biodiesel Characteristics
Report. Renewable Energy Group, Inc, Retrieved from:
www.regfuel.com
Saraswathi, R., Saseetharan, M.K., 2012. Simultaneous
optimization of multiple performance characteristics in
coagulationocculation process for Indian paper industry
wastewater. Water Sci. Technol. 66 (6), 12311238,
http://dx.doi.org/10.2166/wst.2012.304.
Scholz, W., Fuchs, W., 2000. Treatment of oil contaminated
wastewater in a membrane bioreactor. Water Res. 34,
36213629.
Sharma, Y.C., Singh, B., Upadhyay, S.N., 2008. Advancements in
development and characterization of biodiesel: a review. Fuel
87, 23552373.
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,
http://dx.doi.org/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,
http://dx.doi.org/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, http://dx.doi.org/10.1016/j.biortech.2010.03.042.
Siles, J.A., Gutirrez, M.C., Martn, M.A., Martn, A., 2011.
Physicalchemical and biomethanization treatments of
wastewater from biodiesel manufacturing. Bioresour. Technol.
102 (10), 63486351,
http://dx.doi.org/10.1016/j.biortech.2011.02.106.

508

Process Safety and Environmental Protection 9 4 ( 2 0 1 5 ) 487508

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,
http://dx.doi.org/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,
http://dx.doi.org/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), 914924,
http://dx.doi.org/10.1016/j.biortech.2009.09.022.
Srirangsan, A., Ongwandee, M., Chavalparit, O., 2009. Treatment
of biodiesel wastewater by electrocoagulation process.
Environ. Asia 2, 1519.
Su, D., Wang, J., Liu, K., Zhou, D., 2007. Kinetic performance of
oil-eld produced water treatment by biological aerated lter.
Chin. 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
transesterication. J. Biosci. Bioeng. 100 (4), 437442,
http://dx.doi.org/10.1263/jbb.100.437.
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,
http://dx.doi.org/10.1255/jnirs.721.
Sukkasem, C., Laehlah, S., Hniman, A., Sompong, O.,
Boonsawang, P., 2011. Upow bio-lter circuit (UBFC):
biocatalyst microbial fuel cell (MFC) conguration and
application to biodiesel wastewater treatment. Bioresour.
Technol. 102 (22), 1036310370,
http://dx.doi.org/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
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,
http://dx.doi.org/10.1016/j.apenergy.2012.11.061.
Tang, D.T.C., 1993. Water Pollution Control Act. (1993). The
Environmental Laws and Policies of Taiwan: A Comparative
Law Perspective. Pacic Rim Law & Policy Association.
Tezcan, U.U., Koparal, A.S., Bakir Ogutveren, U., 2009.
Electrocoagulation of vegetable oil renery wastewater using
aluminum electrodes. J. Environ. Manage. 90 (1), 428433,
http://dx.doi.org/10.1016/j.jenvman.2007.11.007.
Thaveesri, J., 2003. Expert Meeting on Denitions and
Dimensions of Environmental Goods and Services in Trade
and Development. Geneva, 911 July 2003.
M.D., Savin, L.Dj., Mici
c,
R.D., Simikic,
M.Dj., Furman, T.F.,
Tomic,
2013. Effects of fossil diesel and biodiesel blends on the
performances and emissions of agricultural tractor engines.
Therm. Sci. 17 (1), 263278.
Tri, P., (thesis) 2002. Oily Wastewater Treatment by Membrane
Bioreactor Process Coupled with Biological Activated Carbon
Process. AIT, Bangkok, Thailand.

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. J.
Sci. Ind. Res. 63, 3947.
V.B., Stamenkovic,
O.S., Tasic,
M.B., 2012. Wastewater
Veljkovic,
Management in Biodiesel Production. Reporting for
Sustainability., pp. 471475.
V.B., Stamenkovic,
O.S., Tasic,
M.B., 2014. The
Veljkovic,
wastewater treatment in the biodiesel production with
alkali-catalyzed transesterication. Renew. Sustain. Energy
Rev. 32, 4060, http://dx.doi.org/10.1016/j.rser.2014.01.007.
Vyas, A.P., Verma, J.L., Surahmanyam, N., 2010. A review on FAME
production processes. Fuel 89, 19.
Wan Omar, W.N.N., Amin, N.A.S., 2011. Biodiesel production from
waste cooking oil over alkaline modied zirconia catalyst.
Fuel Process. Technol. 92 (12), 23972405,
http://dx.doi.org/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 lter
biological aerated lter for advanced treatment of landll
leachate. Waste Manage. 32 (12), 24012405,
http://dx.doi.org/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. J. Chem. 2013, 16, http://dx.doi.org/10.1155/2013/789594.
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. Agric. Eng. Int.:
CIGR Ejournal, Manuscript EE 07 005.
Wu, Y., Zhou, S., Ye, X., Chen, D., Zheng, K., Qin, F., 2011.
Transformation of pollutants in landll leachate treated by a
combined sequence batch reactor, coagulation, Fenton
oxidation and biological aerated lter technology. Process Saf.
Environ. Prot. 89, 112120.
Xie, Q., Taweepreda, W., Musikavong, C., Suksaroj, C., 2011.
Separation of oily sludge and glycerol from biodiesel
processing waste by coagulation. Songklanakarin J. Sci.
Technol. 33 (6), 699703.
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, http://dx.doi.org/10.1016/j.biortech.2011.10.058.
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,
http://dx.doi.org/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, 140146.
Zhou, Y., Liang, Z., Wang, Y., 2008. Decolorization and COD
removal of secondary yeast wastewater efuents by
coagulation using aluminium sulfate. Desalination 225,
301311.
Zhao, X., Wang, Y., Ye, Z., Borthwick, A.G.L., Ni, J., 2006. Oil eld
wastewater treatment in biological aerated lter by
immobilized microorganisms. Process Biochem. 41,
14751483.

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