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CHAPTER 2

LITERATURE REVIEW

2.1 Overview

Most of the biodiesel production company has mainly focused on their technical
process of the production, while the environmental management part has been obliterate
(Chavalparit and Ongwandee 2009). Discharging of the biodiesel wastewater to the
environment such as river and public drainage will cause the water pollution in the
environment and decreases biological activity in sewage treatment. The wastewater must
be treated before discharging to the environment.

A previous study shows the composition of biodiesel is not appropriate for

microbial growth, hence, the biological treatment of biodiesel wastewater is difficult
(Suehara et al. 2005). The most frequently applied methods is coagulation (Daud et al.
2015). Coagulation is the treatment process where metals salts are added to the wastewater
to destabilize the colloid material (Daud et al. 2015). While the method for flocculation,
it can be done through agitation or by adding flocculating agents. Colloidal solution is a
heterogeneous mixture in which the colloidal particles can't be seen by the eye and can
pass through a filter paper (Ryan 2006).
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In the flocculation process, the polymers are used as flocculating agent for the formation
of bridges between the flocs (Ryan 2006). In this study, the level removal of turbidity and
SS by using coagulation and flocculation will be investigated. Optimum pH and flocculant
dosage for the flocculation process will also be determined.

2.2 Introduction to Biodiesel

Biodiesel is a clean-burning, alternative and renewable diesel fuel which is similar to

conventional diesel found in the petrol station. The first practical of biodiesel production
from vegetable oil was running the heavy duty vehicles in South Africa before World War
II (Demirbaş 2003). Therefore, the biodiesel has been given the terms to describe its
function, which act as diesel fuel. Biodiesel has particular uses as an alternative fuel in
compression-ignition engines (Demirbaş 2003; Knothe, Dunn, and Bagby 1997).
Biodiesel fuel also has some significant potential replacement for petroleum based diesel
oil (Chavan et al. 2014). This is because biodiesel is considered as the greater option of
renewable petroleum fuel due to its environmental friendly characteristics as well as
giving nearly the same functional properties as the fossil fuels (Semwal et al. 2011).
Biodiesel is also an organic derived product, it consists of oxygen in its molecule, resulting
the biodiesel produced cleaner burning than the petrol and diesel (Sastry et al. 2006).

A number of methods have been studied and they are currently available for the
biodiesel fuel production (Daud et al. 2015). Biodiesel is produced based on 4 primary
ways which are blending of raw oils, micro-emulsions, thermal cracking, and
transesterification (Ma and Hanna 1999). The Table 2.1 shows the primary ways to
produce the biodiesel.
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Table 2.1: Primary ways to produce biodiesel (Leung et al. 2010).

Methods Definition Advantages Disadvantage

Direct use and blending Direct use as diesel fuel or blend with diesel fuel. Liquid nature-portability. Higher viscosity
Lower volatility
Reactivity of unsaturated
hydrocarbon chanins.

Micro emulsions A colloidal equilibrium dispersion of optically isotropic Better spray pattern during Lower cetane number
fluid microstructures with dimension in the 1-150nm range combustion Lower energy content.
formed spontaneously from two immiscible liquids and Lower fuel viscosities.
one or more ionic or non-ionic amphiphiles.

Thermal cracking The conversion of long-chain and saturated substance to Chemically similar to petroleum- Energy intensive and hen higher
(pyrolysis) biodiesel by means of heat. derived gasoline and diesel fuel. cost.

Transesterification The reaction of a fat or oil with an alcohol in the presence Renewable, higher cetane Disposal of harmful by-product.
of catalyst to form esters and glycerol. number, lower emissions and
higher combustion.

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Biodiesel which burns with low sulfur and carbon monoxide has several
advantages such as nontoxic, reduce harmful gas emissions and greenhouse effect.
Biodiesel is also useable for sensitive environments and more environmentally friendly
compared to the conventional diesel (Ivana, Kesic, and Skala 2016). Biodiesel also
consists of lower sulfur and aromatic contents, higher combustion efficiency, and also
higher cetane number compared to the conventional diesel fuel (Harrington 1986).
Furthermore, biodiesel is also a biodegradable substance, nearly 90% of the biodiesel can
be biodegraded within 21days (Mudge and Pereira 1999). It also minimize the produce of
the unburned hydrocarbons, exhaust emissions except monoxide, and particulate matter
(Knothe et al. 1997).

Generally, the tranesterification reaction is the most commonly used method to

convert the organic crude oils to the biodiesel fuel. A usual biodiesel production process
which undergoes the transesterification reaction is shown in Figure 2.1.

Figure 2.1: Equation of transesterification reaction of triglycerides (Mohadesi, Hojabri,

and Moradi 2014).

2.2.1 Feed Stocks of Biodiesel Production

In chemically, biodiesel is a combination of the methyl esters with long chain fatty acids.
Biodiesel is usually made from organic resources such as vegetable oils and plant oils.
Vegetable oils also includes edible and non-edible oils, while in excess of 95% of
biodiesel production feed stocks comes from edible oils since they are mainly produced
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in many regions, the properties of biodiesel made by the edible oils are much appropriate
to be used as diesel fuel substitute(Gui et al. 2008). The species of edible and non-edible
oils are shown in the Table 2.2.

However, the edible oils also bring disadvantage, production of biodiesel by using
edible oil may cause several problems such as the competition with the edible oil market,
which rises the cost of edible oils and biodiesel(Qin et al. 2010). Furthermore, it will also
cause deforestation in some countries because there are many jungles have been felled for
plantation purposes.

In order to overcome these disadvantages, many researchers have developed the

non-edible oils which are not suitable for human consumption because of the presence of
some toxic components in the oils. Furthermore, non-edible oil harvest can be grown in
leftover lands which are not suitable for food harvest and the cost of cultivation is much
lesser because these harvest can still withstand reasonably high yield without concerted
caring (Gui et al. 2008). However, most of the non-edible oils consists high level of fatty
acid, therefore multiple chemical steps is required to produce biodiesel (Leung et al.
2010).
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Table 2.2: Physicochemical properties of biodiesel feed stock (Leung et al. 2010).

Type of Oil Species Density (g/cm3) Flash Point (OC) Kinematic

Viscosity (cst, at
40OC)
Edible Oil Soybean 0.91 254 32.9
Rapeseed 0.91 246 35.1
Sunflower 0.92 274 32.6
Palm 0.92 267 39.6a
Peanut 0.90 271 22.72
Corn 0.91 277 34.9a
Camelina 0.94 - -
Canola - - 38.2
Cotton 0.91 234 18.2
Pumpkin 0.92 >230 35.6
Non-edible Oil Jatropha 0.92 225 29.4
Pongamina 0.91 205 27.8
Sea mango 0.92 - 29.6
Palanga 0.9 221 72.0
Tallow 0.92 - -
Nile talipia 0.91 - 32.1b
Poultry 0.90 - -
Others Used cooking oil 0.9 - 44.7
a. Kinematic viscosity at 38°C, mm²/s
b. Kinematic viscosity at 37°C, mm²/s

Animal fats consists of high soaked fatty acids and normally be in the solid state at
room temperature which may cause problems during the production process. It also has a
higher cost than vegetable oils (Singh and Singh 2010). Despite cooking oil is not suitable
for human consumption, but it is also a feedstock to produce biodiesel (Leung et al. 2010).
However, the quality of cooking oil may cause concern because it may consist of
undesired impurity such as water and free fatty acids (Gui et al. 2008; Leung et al. 2010;
Singh and Singh 2010).

Various feed stocks have also been applied for the production of biodiesel from plant
oils such as soybeans, peanuts, rapeseed, palm, corn, sunflower, sorghum, canola, cotton
and so on (Mohadesi et al. 2014). This is because florae produce oils from sunlight and
air, and can do so year after year on cropland, these oils are considered renewable and
sustainable. Selecting a proper feedstock is very important because the raw material is
charged up to 60-80% of the total cost of biodiesel production. Besides, the properties and
yield of biodiesel products would be dissimilar from each other if the biodiesel is produced
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from different feed stocks. Physicochemical properties of biodiesel fuel produced from
the different oil source under different production conditions is shown in Table 2.3.

Table 2.3: Physicochemical properties of biodiesel produced from the different oil
source under different production condition (Leung et al. 2010).

Feedstock Density (g/cm3) Saponification Iodine Value Yield (%)

Number
Soybean 0.885 201 138.7 >95
Rapeseed 0.88-0.888 - - 96
Sunflower 0.88 200 142.7 97.1
Palm 0.86-0.9 207 60.07 89.23
Peanut 0.883 200 67.45 89
Corn 0.88-0.89 202 120.3 85-96
Carmelina 0.882-0.888 - 152-157 97.9
Canola 0.88-0.9 182 103.8 80-95
Cotton 0.875 204 104.7 96.9
Pumpkin 0.8837 202 115 97.5
Jaropha Curcas 0.8636 202 108.4 98
Pongamina 0.883 - - 97
Tallow 0.856 244.5 126 98.28
Poultry 0.867 251.23 130 99.72

2.3 Biodiesel Wastewater

In the final process of the biodiesel production, water is usually used for wet washing to
purify the crude biodiesel (Daud et al. 2015). This wet washing process produces the
wastewater. The washing step is repeated for around 2 to 5 times until the colorless spent
washing water is obtained, which is depending on the impurity quantity that in the methyl
ester. Therefore, a huge amount of wastewater is produced by the washing step. According
to the previous studies, approximately 20-120L of wastewater is produced from the 100L
of the biodiesel fuel produced, depending on the washing process. Besides, the biodiesel
production plant also generates the additional wastewater streams from other area
including the steam condensate, the wastewater from the process water softening, the
water used for washing the equipment and floors and sanitary wastewater (Veljković et
al. 2014).
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The biodiesel manufacturing process results in about 0.2-3 liters of the biodiesel
wastewater per liter of the produced biodiesel, the world generation of the biodiesel
wastewater in 2011 is estimated to be 13000 to 193000 m3/d (Veljković et al. 2014).
Therefore, the environmental and economic importance of treating biodiesel wastewater
is extremely high because of their high pollution levels and volume. Biodiesel wastewater
is a milky white color viscous liquid. This is because the biodiesel wastewater are highly
stable mixtures containing soap, oil and grease and cause the appearance of white cloudy
particles in the wastewater. The wastewater produced from the biodiesel production is
alkaline that consists of residual oil, soluble salts, continued catalysts, soap and organic
scums such as fatty acids, methyl esters, methanol and glycerin, as well as the low
concentration of phosphorus and nitrogen(Chavalparit and Ongwandee 2009). The
wastewater produced by the process of biodiesel production also consists high level of
turbidity, suspended solid, pH, color, oil and greases. Table 2.4 shows the characteristics
of the biodiesel wastewater that have been reported from several researchers.

Table 2.4: Characteristics of the biodiesel wastewater (Suehara et al. 2005).

Parameter Value
pH 8.5-10.5
Suspended solid (mg/L) 1500-28790
Chemical oxygen demands (g/L) 60000-545000
Biological oxygen demands (g/L) 105000-300000
Oil and grease (g/L) 70000-44300
Color (Hazen unit) >500
Methanol (g/L) 0.315
Carbon (g/L) 1.7

2.3.1 Turbidity

Turbidity is the muddiness or mistiness of a liquid affected by large number of invisible

particles. Turbidity is also known as a common test for quality of water. High level of
turbidity in water can upsurge the water treatment cost for human being consumption. It
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can also harm the aquatic life by plummeting the food supplies, humiliating laying beds,
and affecting gill function.

Turbidity is caused by some factors in water such as occurrence of suspended and

dissolved solid, size and form of elements and arrangement of the particles. While
sediment is often tops the list of substances or pollutants causing the turbidity. While any
watershed has numerous sources of the impurities or physical characteristic that can affect
clearness of water. These turbidity sources could be separated into natural or background,
and occurred by human. Natural sources can contain corrosion from highland, riparian,
stream bank and stream network zones (Miller, 2008).

Water quality measurements that can help in the classification of turbidity include
suspended solids, total dissolved solid, absorption of suspended sediment and elements
size analysis (Miller, 2008). Other influences such as sediment source and composition,
flows, sediment transport and algal species features can also provide important
information in classifying the turbidity that existing in the water. Table 2.5 shows the
Minnesota’s water quality standards according to the turbidity numbers.

Table 2.5: Minnesota’s water quality standards according to the turbidity numbers
(Miller, 2008).

Classes Turbidity (NTU)

1B (drinking water) 10
2A (cold water fishery, all recreation) 10
2B (warm water fishery, all recreation) 25
2C (indigenous fish, most recreation) 25

2.3.2 Suspended Solid

The settlement of particulate substances is stated as sediment, and the particulate

substance that suspends in water is named as suspended solid. Suspended solid can be
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referred as the small solid substances which remained in suspension of water as a colloid
or because of the gesture of the water. It can also be used to indicate the water quality
undergoes standard suspended solid test.

Removal of suspended solids is usually achieved by conducting the water filtration

and sedimentation treatment. By removing most of the suspended solids in a water supply,
the significant water is usually rendered close to human consumption quality. This process
is then followed by fumigation to ensure that any pathogens associated with the small
amount of suspended solids remained and the free floating pathogens. Removal of the
suspended solid in wastewater is mostly conducted by using coagulation, flocculation and
sedimentation process.

2.3.3 The pH Value

The pH is a parameter used to identify the acidity or basicity of an aqueous solution.

Solutions which pH less than 7 are known as acidic solution. In contrast, solution with a
pH greater than 7 are considered as basic or alkaline solution. Furthermore, solution with
pH value less than 0 are considered as a very strong acid while pH value greater than 14
are very strong bases (Lim 2006).

The pH value is commonly determined by using pH indicator paper. When a

sample is examined, indicator paper shows the color and it is compared to the standard
color diagram which provides the nearest whole number to show the accuracy of the pH
value measured in the wastewater. Colorimeter of spectrophotometer is used sometimes
for more precise measurements. The pH indicator paper is made by absorbent paper that
has been soaked with universal indicator. Today, the pH measurements are widely used
in many applications such as medicine, biology, chemistry, environmental science,
engineering, oceanography, nutrition and so on.

2.4 Biodiesel Wastewater Treatment

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Wastewater treatment is a process to convert the water that is no longer suitable to use
into the water that brings minimal issues to the environment. Treatment aims to reduce
the impurities of the wastewater to make the water safe for discharge back into the
environment.

Today, wastewater from the biodiesel production has become a general issue, most
of the research and developments are focused on the biodiesel production and fuel
properties while the environmental management has mostly been neglected. Biodiesel
wastewaters that have been discharged to the environment can cause serious problems
such as degradation of microbial action and plugging of the system reported (Veljković et
al. 2014). Besides, biodiesel wastewater that consists of high level of suspended solids
and turbidity will also cause the diseases, death of aquatic species, disruptions of food
chain and destruction of ecosystems. Therefore, an effective treatments is needed to
reduce to the level of pollutants (Veljković et al. 2014).

Several wastewater treatments have been developed such as physical, chemical-

physical, chemical, electrochemical, biological and integrated treatment. These processes
have been implemented since 2005 when the first treatment on biodiesel wastewater were
testified (Veljković et al. 2014). Table 2.6 shows the type of the wastewater treatment and
their removal efficiency (Leung et al. 2010).

The biological treatment of biodiesel wastewater is difficult because the

composition of such wastewater is not suitable for microbial growth. A growth inhibitor
was also present in the biodiesel wastewater, this growth inhibitor could be detected by
measuring the solid content in an aqueous solution. The microorganisms could not grow
in condition of solid contents higher than 2.14g/L (Suehara et al. 2005). The biological
treatment method is ineffective in reducing color. Therefore, the physic-chemical
treatment method is recommended instead of biological treatment. Some researcher
(Delcolle et al. 2017) has studied the treatment of biodiesel wastewater by using the
chemical techniques.
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The physic-chemical treatment of the biodiesel wastewater involves chemical

treatments such as adsorption, acidification, coagulation and flocculation processes, and
also the physical treatment such as sedimentation, filtration or floatation (Veljković et al.
2014). By conducting the chemical wastewater treatment, most of the total suspended
solid will be reduced rapidly during the process, therefore, it can lead to make it efficiently
before the secondary treatment (Irfan et al. 2017). Besides, physic-chemical treatment
works effective to reduce the suspended, colloidal. dissolved and non- settable solid as
well as the color (Ariffin et al., 2009).

In this treatment, flocculants is added to destabilize the oil in water suspension to

form flocs (Stephenson and Duff 1996). In the coagulation and flocculation method,
addition of suitable coagulants is assumed to adjust the pH value, and level of suspended
solid thus cause the coagulation and flocculation.
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Table 2.6: Type of the wastewater treatment and their removal efficiency (Leung et al. 2010).

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2.5 Coagulation and Flocculation

In the wastewater treatment practice, the term coagulation is defined as the initial process that
destabilizes the colloidal particles and causing the particles to suspend in the water.
Flocculation describes the later process whereby the decomposed particles into micron and
sub-microns size range undergo aggregation and particle growth to become bigger flocs
(‘Complimentary Contributor Copy’, 2018). Coagulation has also been practiced to remove
colloidal particles and pollutants of the wastewater (Jadhav and Mahajan 2014). Coagulation
and flocculation results from different mechanisms to decomposed suspended particles and
colloids including electrostatic attraction, sorption and bridging (Lee, Robinson, and Chong
2014).

Formation of colloid particle destabilization are conducted in a rapid-mixing stage

when coagulants are added and dispersed throughout the water to be treated (Jiang & Graham,
1998). The emulsification of wastewater can also be done by using the coagulation and
flocculation (Veljković et al. 2014).

Coagulation or flocculation process is also implemented for the treatment of wastewater

to achieve the maximum removal of suspended solid (Ariffin et al.,). The optimum condition
in a coagulation and flocculation process can be determined by the least dosage of coagulant
used and the pH value in the condition which produce the clean water (Jadhav and Mahajan
2014).

2.5.1 Flocculants

Charge-neutralized solids can be further agglomerated by using flocculants. Flocculants can be

thought of a sort of a “high-tech rope” tying particles together, thereby increasing particle size.
Flocculants come in various charges, charge densities, molecular weights, and forms (Ziyad
2005).

2.5.1.1 Cationic Flocculants

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Mostly based on copolymers of AETAC (N,N-Dimethylaminoethyl Acrylate Methyl Chloride

Quaternary) or METAC (N,N-Dimethylaminoethyl Methacrylate Methyl Chloride Quaternary)
and acrylamide. These products can perform a dual function by both coagulating with their
positive ionic charge and flocculating with their high molecular weight (Ziyad 2005).

2.5.1.2 Anionic Flocculants

Mostly based on copolymers of acrylamide and acrylic acid, anionic flocculants possess a
negative ionic charge and work by binding with residual cationic charges on coagulants
adsorbed to coagulated colloids (Ziyad 2005).

2.6 Malaysia Sewage and Industrial Effluent Discharge Standards

The biodiesel wastewater consists high level of suspended solid, turbidity and other impurities,
so direct releasing the wastewater to the environment can cause a serious pollution. Therefore,
the sewage and industrial effluent discharge standard is carried out according to Malaysia’s
Environmental Law. The parameter limits of effluent of standards is shown in Table 2.7.

Table 2.7: Parameter limits of effluent of standards (Ministery of Science &

Environment, 1979).

Parameter Unit Standard A Standard B

Temperature °C 40 40
pH value - 6-9 5.5-9
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BOD at 20°C mg/L 20 50

COD mg/L 50 100
Suspended solid mg/L 50 100
Mercury mg/L 0.005 0.05
Cadmium mg/L 0.01 0.02
Hexavalent Chromium mg/L 0.05 0.05
Arsenic mg/L 0.05 0.1
Cyanide mg/L 0.05 0.1
Lead mg/L 0.1 0.5
Manganese mg/L 0.2 1.0
Nickel mg/L 0.2 1.0
Tin mg/L 0.2 1.0
Zinc mg/L 1.0 1.0
Boron mg/L 1.0 4.0
Iron mg/L 1.0 5.0
Phenol mg/L 0.001 1.0
Free chlorine mg/L 1.0 2.0
Sulphide mg/L 0.5 0.5
Oil and Grease mg/L None detectable 10
Trivalent Chromium mg/L 0.2 1.0
Copper mg/L 0.2 1.0
Table 2.7: (continued)