KKEK4283 Research Project

Research Proposal

P15: Removal of Glycerol from Biodiesel using Deep

Eutectic Solvents (DESs) in Bulk Liquid Membrane (BLM)
system

Semester 1, 2016/2017

Name: Wan Muhammad Faiz bin W Yusoff

Matric Number: KEK130059

Supervisors:

1) Associate Prof. Dr. Jayakumar Natesan Subramanian Nayagar

2) Prof. Dr. Mohd Ali bin Hashim

Date of Submission: 2nd December 2016

Contents

1.0 Introduction 1
1.1 Background of Study 1
1.2 Problem Statement 3
1.3 Objectives of Study 3
1.4 Scope and Limitation of the Study 4
1.5 Importance of the Study 5
2.0 Literature Review 6
2.1 Overview 6
2.2 Production of Biodiesel 7
2.3 Methods of Purification of Biodiesel 9
2.3.1 Wet washing 9
2.3.2 Dry washing 9
2.3.3 Novel techniques in biodiesel purification 11
2.4 Applications of DESs in Purification of Biodiesel 12
2.5 Applications of Bulk Liquid Membranes (BLM) in Purification Systems 15
2.6 Summary 16
3.0 Methodology 17
3.1 Experimental Flowchart 17
3.2 Materials 18
3.3 Equipment 18
3.4 Experimental Procedure 19
3.4.1 Preparation of Biodiesel 19
3.4.2 Preparation of DESs 19
3.4.3 Bulk Liquid Membrane (BLM) Experiment 20
3.5 Data Analysis 21
3.6 Sample Data Collection 21
3.7 Job Safety Analysis 22
4.0 Working Schedule 24
5.0 References 26

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List of Figures

1.1 Biodiesel demand by region with numbers in terms of percentage 1

1.2 Transesterification of oils or fats with alcohol using catalyst 2
1.3 Different types of liquid membranes 4
3.1 Experimental flowchart for the removal of glycerol from biodiesel using BLM system 17
3.2 Experimental setup for BLM experiment 20

List of Tables

2.1 Usages of DESs in biodiesel purification 13

3.1 Different DESs of different molar ratios 19
3.2 Job safety analysis for purification of biodiesel using BLM experiment 22

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1.0 Introduction

1.1 Background of Study

Usually produced via transesterification of vegetable oils with an alcohol in the presence of
catalyst, biodiesel is an emerging class of renewable fuel known as biofuels [1]. Alongside
bioethanol and biogas, biodiesel is expected to flourish in the near future as a replacement for the
conventional fossil fuels derived diesel to provide power for diesel engines [2]. The production
of biodiesel has been increasing almost sevenfold since 2005 with major producers being USA,
Brazil, Germany, Indonesia and Argentina [3]. The demand of biodiesel can be broken down
according to regions, given by the chart below:

Figure 1.1: Biodiesel demand by region with numbers in terms of percentage [3].

As compared to the conventional diesel fuel, biodiesel offers several advantages including
sustainability, due to the fact that it is produced from biomass. In addition, it is biodegradable
and has higher flash point. Other than that, biodiesel is often associated with reducing the
greenhouse effect, due to the lesser emission of CO2 during its combustion. This in turn
decreases the accumulation of CO2 in the atmosphere [4-6]. Transesterification of oil and alcohol
produces biodiesel and glycerol. Due to its insolubility in biodiesel, glycerol is easily removed
from the produced biodiesel by settling or centrifugation. However, after the phase separation,
there are still traces of glycerol in the biodiesel.

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These traces of glycerol need to be removed from the biodiesel as it can cause detrimental effects
on the engine including higher aldehyde and acrolein production, fuel settling problems,
deposition, decantation, fouling of injector and reduces durability of the engine [7]. Thus,
stringent international codes, ASTM D 6751 and EN 14214 have been released as to ensure all
produced biodiesel have less than 0.02 wt% of glycerol. Usually, this is accomplished via
conventional wet washing method, using water to wash the biodiesel [8]. However, this is
usually associated with generation of large amount of wastewater. The table of standards is
attached in Appendix A1.

Figure 1.2: Transesterification of oils or fats with alcohol using catalyst.

Thus, dry washing methods have been developed to overcome this problem. Dry washing
methods are usually associated with adsorption process, based on trial-and-error methods, using
adsorbents [8]. Commercial adsorbents usually have high prices. Thus, novel adsorbents such
activated carbon produced from palm shell wastes [9], sugarcane bagasse [8] and cellulose [10]
have been developed. However, problems such as disposal of spent adsorbents need to be
rectified [11]. Therefore, novel techniques including usage of membrane separation have been
developed.

Several studies have been done using ultrafiltration and microfiltration membranes, which is
proven to be effective in glycerol removal, but, these membranes need regeneration and might be
plugged after filtration process due to fouling [7]. Other studies using liquid-liquid extraction
(solvent extraction) using ionic liquids and deep eutectic solvents (DESs) have also been
conducted. However, little information about recovery of solvents used have been developed.

2
Therefore, liquid membrane, which is a development of the conventional solvent extraction is
seen as a good alternative for the purification of biodiesel as it combines the extraction and
stripping process in a single operation. Other advantages of liquid membrane include simple
operation, high selectivity and high efficiency and as such, liquid membranes are being looked
into for its applicability in the industry [12]. There are several types of liquid membranes namely
emulsion liquid membrane (ELM), supported liquid membrane (SLM) and bulk liquid membrane
(BLM). Due to its simplicity in design, simple operation and low cost [13], BLM system has
been chosen for this study.

1.2 Problem Statement

Due to the fact that biodiesel is used to fuel diesel engines, impurities such as excess alcohol,
catalysts and glycerol need to be removed. Even after phase separation by centrifugation or
settling, there are still traces of glycerol present in the biodiesel phase. If not treated, the excess
glycerol can lead to higher aldehyde and acrolein production, fuel settling problems, deposition,
decantation, fouling of injector and finally, reduces durability of the engine.

Several methods can be used to remove these traces of glycerol to below than 0.02 wt%
according to the ASTM standards. With the problems associated with wet and dry washing
techniques, novel techniques such as membrane separation and extraction using ionic liquids and
deep eutectic solvents (DESs) have been developed. Extraction using DESs have been effective
in reducing the glycerol content. However, the solvent recovery methods have not been widely
discussed. Therefore, these problems need to be addressed.

1.3 Objectives of the Study

From the problem statement, several objectives have been developed for this research.
Essentially, these objectives are associated to overcome the solvent recovery which are DESs
after performing the extraction of glycerol from biodiesel. The objectives are:

1) To synthesize different DESs for the extraction of glycerol and study its physical
properties.
2) To screen different DESs for the extraction of glycerol.
3) To reduce the glycerol content using bulk liquid membrane system which employ deep
eutectic solvents (DESs) as the membrane phase.

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 4) To determine the optimized condition for glycerol extraction in BLM system.

1.4 Scope and Limitation of the Study

A bulk liquid membrane system (BLM) is one of the liquid membrane system consisting of three
phases. Namely, these are feed phase, containing the substances to extracted, membrane phase,
which is the transport media and strip phase, whereby the solute extracted will be stripped into,
thus allowing the membrane phase to be recovered and used for the next extraction process [14].
The system can be represented by the diagram below, which shows as well the comparison of (c)
BLM with other liquid membrane system which are (a) supported liquid membrane (SLM) and
(b) emulsion liquid membrane (ELM).

Figure 1.3: Different types of liquid membranes [15].

BLM system offers simple extraction and stripping operation at ambient pressure and
temperature. The process can be enhanced by increasing the kinetic energy of the molecules by
increasing the temperature by an external heater. Mass transfer can be improved by adjusting the
stirring speed of all the three phases. Other parameters that can be varied to improve the mass
transfer process include pH of feed and strip phase, ratio of different phases viz. feed to
membrane ratio, membrane to strip phase ratio or feed to strip phase ratio. Also, different strip
phase might be used as according to liquid-liquid extraction experiment performed before
carrying out the BLM experiment.

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However, since the system is non-flexible once constructed, the interfacial area between the
phases for example areas between the biodiesel to membrane phase and membrane phase to strip
phase is not adjustable. Thus, the mass transfer might be limited by the interfacial areas between
the phases. Also, when too much stirring is affected, emulsions might be formed which will
hinder the mass transfer process and thus decreases both the extraction and stripping efficiencies.

1.5 Importance of the Study

The usage of bulk liquid membrane (BLM) system in the purification of biodiesel using deep
eutectic solvents (DESs) serves several important purposes. These are stated below:

1) Explore the possibility of application of the BLM system in purification of biodiesel due
to its simple design, operation and relatively cheap cost.
2) Combining the usage of BLM system with the usage of environmentally benign solvents
which are deep eutectic solvents (DESs) as the membrane phase as a low-cost solvent for
the purification of biodiesel.
3) Mitigate the need to conduct separate DESs recovery as an extension of the liquid-liquid
extraction experiments that have been conducted to remove glycerol from biodiesel using
DESs before.
4) Provide a possible alternative for the purification of biodiesel as a system that generate
less wastes due to high selectivity nature of the DESs towards the solute to be extracted
as compared to the conventional wet and dry washing methods.

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2.0 Literature Review

2.1 Overview

Rising alongside other renewable energy sources such as solar, wind, geothermal and water
energy, biofuels such bioethanol and biodiesel is an attractive alternative for the conventional
non-renewable fossil fuels. It is predicted that the global energy demand will increase by 48%
from 2012 to 2040 and in 2040, 78% of total energy consumption will be based on fossil fuel
with most consumptions coming from the industrial and transportation sectors [16]. However,
problems associated with conventional fossil fuels viz. declining reserves, environmental
pollution and global warming have catalyzed the development of cleaner fuels [7].

Presently, biofuels particularly biodiesel, is seen as the best alternative towards replacing the
conventional petroleum-based fuels since it is derived from biomass. It holds numerous
advantages over the conventional fossil fuels including renewability and sustainability,
biodegradability, and higher flash point. Other than that, it contains less sulfur and aromatic
content. Also, biodiesel results in less emission of CO2 which subsequently reduces the global
warming effects due to decreasing accumulation of CO2 in the atmosphere. Also, biodiesel
possesses higher combustion efficiency due to its high cetane number as well as its high-energy
content [4-6].

Biodiesel is a renewable energy source derived from animal fats, plant oils and wastes such as
cooked vegetable oils. However, these materials usually have high viscosities and thus leading to
poor atomization of the fuel, incomplete combustion and coking of the fuel injectors. Currently,
there are four known methods which are being used to produce biodiesel with the intention to
reduce the viscosities of these materials making it suitable as a fuel. The four methods are
namely microemulsion [17], thermal cracking [18], direct blending of oils [19], and
transesterification [1].

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2.2 Production of Biodiesel

The most common method in producing biodiesel is by transesterification of triglyceride from oil
such as vegetable oil or whole stillage-extracted corn oil [20] with alcohol, usually methanol and
ethanol. Although, usage of longer chain alcohols such as propanol and butanol have also been
reported by Homan et al. [21], to produce fatty acid alkyl esters (FAAE) which is the biodiesel
and glycerol. The transesterification reaction can be catalyzed via acid, base or enzyme catalysts.
Hui Min et al. have studied the difference between these three different catalysts to produce
biodiesel [6].

Lotero and his team reviewed the production of biodiesel using acid catalysis, through both
homogeneous and heterogeneous catalysis [22]. According to their finding, usage of liquid acid
catalysts such as H2SO4, HCl, BF3 and H3PO4 allows for usage of low cost feedstocks such as
waste greases from used cooking oils and animal fats, usually containing higher amount of free
fatty acids (FFAs) up to or greater than 15%. Thus, this lowers production costs as well as
helping to overcome the problem of recycling of the waste oils which unless can only be used for
animal feedstock additives. However, when using these low-grade feedstocks, some pretreatment
such as filtration, water removal, steam distillation and bleaching adds to the production costs
[23]. Other disadvantages associated with homogeneous acid catalysts include slower reaction
time of up to 4000 times slower than the base catalyzed transesterification which consumes a lot
more time, higher reaction temperature and causes equipment corrosion.

Problems associated with homogeneous acid catalyst such as difficult separation and serious
contamination, can be overcome by using heterogeneous acid catalyst [22]. The solid acid
catalysts can be incorporated in a continuous flow packed bed reactor which simplifies product
separation and minimizing waste generation. To further investigate the possibility of using acid
catalysts in the production of biodiesel, Canakci and Gerpen investigated the effect of different
parameters in the production of biodiesel via transesterification of soybean oil with methanol
using sulphuric acid catalyst [24].

Canakci and Gerpen varied several different parameters such as molar ratio of methanol to oil,
reaction temperature, catalyst amount, reaction time, amount of water and the amount of FFAs.

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They found that the transesterification reactions are largely affected by the amount of catalyst
used, water content and also the amount of FFAs present in the feedstock. It was found that by
increasing the amount of catalyst from 1-5%, fatty acid methyl esters (FAME) formation reached
95.0% from 72.7%. Also, concentration of water of 1 g/kg of feedstock reduced the formation of
biodiesel. When water concentration reached 50 g/kg, the reaction is totally inhibited.

Base catalyzed transesterifications can be carried out using either homogeneous or

heterogeneous base catalysts. The base catalyzed reaction between oils and alcohol is usually
catalyzed with sodium or potassium hydroxide (NaOH and KOH) or alkoxide (mixture of
alcohol with the catalyst prior to reaction) [1]. By using base catalysts, higher conversions of oils
can be achieved, with lower reaction time and temperature [6]. Although it holds several
advantages over the acid catalyzed reactions, it also suffers from several drawbacks including the
requirement of high-grade feedstock with low amount of FFAs to prevent excessive formation of
soap, feedstocks with low water content as well as the generation of alkaline wastewater since
water is largely used to wash the biodiesel to remove the alkaline catalyst used.

Many researches have been done to develop heterogeneous base catalyst system as to simplify
separation process and minimize waste generation. As reported by Kouzu and Hidaka [25],
several different solid base catalysts have been identified for the production of biodiesel
including alkali metal exchanged zeolite, alkaline earth metal oxide and anion-exchange resin. In
their study, Kouzu and Hidaka produced biodiesel from transesterification of waste cooking oil
with methanol in the presence of calcium oxide (CaO) catalyst in their study to remove leached
calcium from the biodiesel using cation-exchange resin.

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2.3 Methods of Purification of Biodiesel

The production of biodiesel is accompanied by several different impurities including excess

alcohol, soap, glycerol and the catalyst [26]. Since biodiesel is used to fuel diesel engines,
purification of biodiesel is a must to meet the stringent international standards which are ASTM
D 6751 and EN 14214 specifications.

2.3.1 Wet washing

Stojkovic et al. have reviewed different purification methods of biodiesel refining viz. wet
washing methods, dry washing methods and novel techniques of purification using membranes
and extraction using ionic liquids etc [11]. In conventional purification methods, Atadashi et al.
stated that water is used to remove impurities from biodiesel [27]. In the purification stage, water
is added to the biodiesel and gently agitated as to avoid emulsion formation. The washing is
stopped until a colorless wash water is obtained. Despite being an effective method of
purification, this method is usually associated with generation of large amount of wastewater and
also energy intensive. Other disadvantages associated with wet washing are increase in cost and
production time as well as loss in biodiesel. Thus, to overcome this, dry washing methods have
been developed.

2.3.2 Dry washing

Dry washing methods involve mostly trial-and-error process [7]. Usual dry washing methods use
adsorption with different adsorbents developed. Adsorbents used ranged from usual adsorbents
such as activated carbon and newly developed adsorbents such as cellulose and activated fibre.
For example, Kouzu and Hidaka studied the application of cation-exchange resin to remove
leached CaO catalyst from biodiesel produced from waste cooking oil [25]. They found that by
addition of methanol, 100% removal of CaO is achieved, with also noticeable reduction in free
glycerol content.

Assawasaengrat and his team studied the usage of magnesium silicate as adsorbent to remove
FFAs, soap and glycerine in biodiesel [28]. His team varied the amount of adsorbent used and
found that the best removal efficiency of FFA, soap and glycerine were 77.39%, 77.11% and

9
82.92% respectively with SiO2/MgO ratio of 2.04:1 with 3 g of adsorbent used. Gomes and his
team on the other hand, prepared biodiesel from sunflower oil via transesterification using
alkaline NaOH as catalyst with methanol to conduct a comparison study between purification
methods such as conventional wet washing with hot water, usage of commercial adsorbent Select
450 and also newly developed natural adsorbents of cellulose and starch from different sources
[10]. It was found that by using the adsorbents, both commercial and novel, are able to purify the
biodiesel better than wet washing method using hot water. The different natural adsorbents used
included potato starch, corn starch and eucalyptus bleached Kraft cellulose were able to remove
impurities from biodiesel, reducing the acidity index, combined alkalinity, free glycerine and
turbidity.

Wall, Van Gerpen and Thompson investigated the removal of free glycerine and soap using ion
exchange resins as one of the alternatives to overcome problems associated with the
conventional wet washing methods [29]. Using biodiesel prepared from crude mustard seed oil
and canola oil via sodium methoxide transesterification, experiments were carried out using glass
columns filled with packed beds of resin ranging from 2.5 to 7.6 cm with mesh at the bottom to
allow flow of biodiesel down the bed. Using the treatment, soap and glycerine levels were
reduced from 1200 ppm to below 500 ppm and 0.08% to 0.02% respectively. Baroutian et al. on
the other hand studied the removal of residual KOH catalyst using activated carbon produced
from palm shell waste [9]. After washing the produced biodiesel using hot distilled water with
tannic acid, KOH content is around 5.74 mg/kg of biodiesel. Thus, using the adsorption
treatment, the KOH content was reduced to 4.37 mg/kg.

Alves and his team studied the dry purification of biodiesel to remove glycerol using different
forms of sugarcane bagasse i.e. raw sugarcane bagasse, sugarcane bagasses ash and stream
explosion pre-treated sugarcane bagasse as a low-cost adsorbent material [8]. Usage of sugarcane
bagasse allowed for achieved 80% adsorption efficiency, reducing the glycerol content to lower
than 0.02 wt%. Thus, dry purification methods offer an attractive way to purify biodiesel.
However, dry methods increase production cost due to added adsorbent materials cost. Also, the
production of the solid wastes must be rectified.

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2.3.3 Novel techniques in biodiesel purification

To overcome problems associated with wet and dry washing methods, novel techniques using
membrane processes are being extensively looked into. According to a review by Atadashi et al.,
membranes are semi-permeable barriers that restrict movement of substances across it [27]. In
biodiesel refining, membranes currently under study are microfiltration (MF), ultrafiltration
(UF), reverse osmosis (RO) and ceramic membranes. Atadashi and his team recently studied the
removal of free glycerol and soap using a ceramic membrane [7]. In the study, a multi-channel
tubular-type ultrafiltration Al2O3/TiO2 ceramic membrane was employed, varying parameters
such as transmembrane pressure, temperature and flow rate. Overall, best retention coefficient
for both glycerol and soap were 97.5% and 96.6% respectively.

Atadashi and team also carried out another study using the same kind of membrane to remove
residual KOH catalyst after producing biodiesel from transesterification of palm oil with
methanol [1]. From the experiment conducted, high quality biodiesel was produced. The residual
KOH content was reduced from 8.328 mg/L to 0.312 mg/L thus complying with the international
standards ASTMD6751 and EN14214. The retention coefficient achieved was 93.542%.
Nascimento et al. reported the application of microfiltration and ultrafiltration membranes for the
purification of biodiesel [30]. The membranes were used to reduce the soap content and glycerol
content to below than 0.02 wt%. Biodiesel was prepared using soybean oil and methanol, with
KOH as catalyst. However, it was found that the MF membrane was not efficient to reduce the
glycerol content as when using wet washing method. For UF membrane, the glycerol content
was able to be reduced to 0.02 wt% with pore size of 10 kDa.

Alves, Pereira, Cardoso and Reis found that the used ultrafiltration membrane was not able to
reduce the glycerol content was efficiently was conventional water washing, but is capable of
biodiesel refining and further analysis is required [31]. Another technique of membrane
separation for biodiesel refining is using a membrane contactor to perform a liquid-liquid
extraction. In a study conducted by Amelio and team, removal of methanol and glycerol were
studied using flat sheet membranes [32]. In the experiment, biodiesel and water were pumped

11
into a rectangular membrane module, where the flat sheet membrane was located. The
extractions were carried out using the module in co-current configurations to keep a constant
pressure difference. It was found that the transfer of substances in the membrane was highly
affected by mass transfer resistance. At a high flow rate, more recovery was achieved. Glycerol
removal of 2.5% was achieved in the contactor, suggesting the contactor is suitable for the
removal of glycerol.

2.4 Applications of DESs in Purification of Biodiesel

Deep eutectic solvents (DESs) are emerging ionic liquid analogous having many applications in
metal processing and synthesis applications [33]. DESs are liquids that exist as liquid below
100oC due to large freezing point depression which can be easily synthesized by mixing organic
halide salts such as choline chloride and hydrogen bond donors (HBDs) such as glycerol and
ethylene glycol [6]. Recently, several studies have been done in investigating the possible usages
of DESs in purification of biodiesel. Several studies have been done to classify different DESs
according to their physical properties viz. density, viscosity, surface tension and Walden rule
[34-36].

The usages of DESs in biodiesel purification is summarized in Table 2.1.

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 Table 2.1: Usages of DESs in biodiesel purification.

Researchers DESs used Substance removed Method Degree of removal of substances

Hui Min et al. [6] Choline chloride with Residual KOH catalyst. Agitating different Average removal efficiency of glycerol was
glycerol and ethylene ratios of DESs to 92.14% with the optimum DESs to biodiesel
glycol. biodiesel in an orbital ratio of 2.5
shaker. .

Shahbaz et al. Choline chloride and Residual KOH catalyst. Liquid-liquid Glycerol-based DESs were superior in
[37] methyl triphenyl extraction was removing KOH catalyst with ChCl:glycerol
phosphonium bromide performed in an DESs and MTPB:glycerol DESs exhibiting
(MTPB) with 2,2,2- orbital shaker by average removal efficiency of 98.59% and
trifluoroacetamide, mixing different 97.57% respectively.
ethylene glycol and ratios of biodiesel
triethylene glycol as and DESs.
HBDs.

Hayyan et al. [38] Low-cost quaternary Residual glycerol. Achieved by varying Glycerol can be removed efficiently.
ammonium salt and the biodiesel to DES
glycerol. ratio instead of
varying the
composition of the
DESs.

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Shahbaz et al. DESs synthesized with Removal of free Extraction processes Glycol-based DESs were able to eliminate all
[39] glycerol, ethylene glycerol, bound glycerol in an orbital shaker. free glycerol with 100% removal efficiency.
glycol and triethylene and total glycerol from
glycol. palm oil-based
biodiesel.
Chun Ho et al. Choline chloride and Remove residual free DESs and biodiesel By increasing the amount of glycerol in the
[40] glycerol/ethylene glycerol. were mixed at ratios DESs, glycerol extraction efficiency
glycol. 0.5:1, 1:1, 2:1 and decreased but with increasing amount of
2.5:1 in an orbital ethylene glycol in the DESs, the extraction
shaker. efficiency increased.

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2.5 Applications of Bulk Liquid Membranes (BLMs) in Purification Systems

Several studies have been done in using bulk liquid membranes (BLMs) as a tool for purification
to extract various different substances. A bulk liquid membrane is a system that combines all
three phases viz. material to be purified (feed phase), liquid membrane phase and strip phase. For
example, Ma et al. studied the transport of amino acids through di(2-ethylhexyl)phosporhic acid-
kerosene bulk liquid membrane as an attempt to simulate the biological membrane functions
[41]. Another study was carried out by Ng and co-workers using hydrophobic ionic liquids as
liquid membranes for removal of phenol [42]. The study was made as an attempt to replace
conventional extraction solvents. In the experiment, a bulk liquid membrane made from
rectangular glass cell of 12.1 cm x 5.6 cm x 11.9 cm dimensions was used.

Nabieyan and co-workers then studied the transportation of iodine using bulk liquid membrane
with kerosene as solvent and alkaline sodium sulfite as the strip phase [13]. The experiment was
carried out using a homemade rectangular glass container with dimensions of 300 mm x 300 mm
x 300 mm with a partition and four sampling port. Chakrabarty and team investigated the usage
of BLM system on the extraction and recovery of lignosulfate from its aqueous solution [14]. In
the experiment, dichloroethane in trioctylamine (TOA) was used as the organic membrane phase
with sodium hydroxide (NaOH) used as the strip phase. The effects of operating parameters such
as temperature, stirring of aqueous and organic phases and stirring speed were studied. It was
noticed that by increasing temperature and stirring speed of feed phase, transport of lignosulfate
can be enhanced.

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2.6 Summary

From the literatures cited, several key points have been identified:

1) Biodiesel is an alternative towards conventional fossil fuels produced from biomass such
as vegetable oil and corn oil. Biodiesel can be produced by four different methods
including microemulsification, direct blending of oils, thermal cracking and
transesterification.
2) The most common method in producing biodiesel is transesterification using either acid,
base or enzyme catalyst. From the literatures, production of biodiesel using base catalyst
is generally preferred due to faster reaction rate and lower reaction time. However, a
high-grade feed stock is required to prevent formation of soaps etc.
3) After separation of glycerol from the biodiesel rich phase, there is still other impurities
and residue of glycerol. These residues can be removed via conventional wet washing
method using water which adds to the production cost and generation of large amount of
wastewater.
4) Thus, dry washing and novel techniques using membrane have been studied. Dry
washing generally employs adsorbent to remove the impurities from biodiesel while
novel techniques include filtration using ultrafiltration and microfiltration membranes.
5) Recently, DESs have emerged as an ionic liquid analogous that is used as a cheap solvent
to remove impurities from biodiesel. Most experiments performed have been liquid-
liquid extraction whereby the DESs used have to be recovered in a separate step.
6) No studies have been done to purify biodiesel using a bulk liquid membrane system.
Thus, this study provides the opportunity to apply purification of biodiesel using a bulk
liquid membrane system, combining the extraction and stripping process of solvent
extraction in one equipment.

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3.0 Methodology

3.1 Experimental Flowchart

Preparation of biodiesel via

transesterification

Remove sludge from biodiesel

by centrifugation

Remove excess alcohol using

evaporation

Analyze initial glycerol content

using High Performance Liquid
Chromatography (HPLC)

Prepare deep eutectic solvents

(DESs) for purification

Perform removal of glycerol

using bulk liquid membrane
(BLM) system

Analyze final glycerol content

using HPLC

Figure 3.1: Experimental flowchart for the removal of glycerol from biodiesel using BLM system

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3.2 Materials

With Malaysia being one of the largest producers and exporters of palm oil and palm oil
products, accounting for 39% of world palm oil production and 44% of world exports, palm oil
has been chosen as the feedstock for biodiesel production [43]. The palm oil is supplied from
Sime Darby Sdn. Bhd. located in Pulau Carey, Selangor. Due to its abundance and low cost,
methanol (99.8%) has been chosen as the alcohol in the process while KOH (85%) is chosen as
catalyst to reduce reaction time and temperature. Both chemicals are supplied by R&M
Chemicals. As reported by Chun Ho et al., ethylene glycol based DESs are superior in extracting
free glycerol from biodiesel [40]. Thus, DESs prepared from ethylene glycol and choline
chloride have been chosen for this study. Ethylene glycol (99%) and choline chloride (98%) are
supplied by Merck Malaysia and Sigma-Aldrich respectively. NaOH (99%) is supplied from
R&M Chemicals to be used as the strip phase for the experiment. Deionized water is used to
prepare the NaOH of different concentrations.

3.3 Equipment

To carry out the transesterification, a multiunit reactor with reflux controller from VELP
Scientific is used. To remove excess alcohol and other impurities initially, oven is used to
vaporize the alcohol and the biodiesel is subjected to centrifugation using Table Top Low Speed
Centrifuge by Sastec. DESs are prepared by mixing in 250 mL conical flasks, with heating and
stirring of the mixture carried out via a hot plate with magnetic stirring from Fisher Scientific.
The bulk liquid membrane experiment to remove free glycerol from biodiesel is carried out using
Solteq BLM Model: BLF: 1.5 L with stirring capability from 0-3600 rpm. The equipment has
dimensions of 10 cm x 4.2 cm x 12 cm. Glycerol content is analyzed using HPLC model RF10A
XL Shimadzu Fluorescence Detector.

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3.4 Experimental Procedure

3.4.1 Preparation of Biodiesel

To carry out the transesterification to produce biodiesel, 15 g of crude palm oil is used for each
batch of production. Crude palm oil is weighed and loaded into the multiunit reactor with reflux
condenser. Methanol is then added into the reactor. The molar ratio of methanol to oil is 10:1 to
provided excess methanol for the reaction. 1 wt% of KOH catalyst with respect to weight of
palm oil is added to the reactor. The reaction is then carried out at 60oC for 2 hours with mixing
speed of 300 rpm. The biodiesel produced is then centrifuged at 2000 rpm for 10 minutes to
separate the biodiesel into the biodiesel and glycerol rich phase which is then pipetted out from
the biodiesel. Following the centrifugation, biodiesel is then heated in the oven at 70-80oC for 15
minutes to remove excess methanol from the biodiesel. Glycerol content in the biodiesel is then
analyzed using HPLC.

3.4.2 Preparation of DESs

For this experiment, five different DESs are prepared with different choline chloride (ChCl) to
ethylene glycol (EG) molar ratio. The composition of DESs are displayed in Table 3.1 below.
The desired amount of ChCl are mixed together with EG at different ratios in 250 mL conical
flasks. The mixtures are mixed initially at 10-50 rpm with speed up to 350 rpm to prevent loss of
ChCl to the wall of the flasks. The mixtures are simultaneously heated at 60-80oC for 1 hour
until homogeneous transparent liquids are formed. The DESs prepared are then stored in
desiccator to prevent interference of atmospheric moisture to the DESs.

Table 3.1: Different DESs of different molar ratios.

DESs Molar ratio
ChCl Ethylene glycol
1 1 1
2 1 2
3 1 1.25
4 1 3
5 1 4

19
3.4.3 Bulk Liquid Membrane (BLM) Experiment

The experiment is carried out using a bulk liquid membrane cell provided by Solteq. The system
is identified by BLM Model: BLF: 1.5 L with stirring capability from 0-3600 rpm with
dimensions of 10 cm length, 4.2 cm width and 12 cm height. The cell is separated into two equal
volume compartments (4.9 cm length) with a partition that is about 0.2 cm thick. Also, the cell
has 1 cm bottom opening as to allow the transport of glycerol from the biodiesel to the NaOH
solution acting as the strip phase. 100 mL of DES is measured and placed in the cell above the
clearance at the bottom. 180 mL biodiesel and 0.1 M NaOH each are placed in the feed and
stripping phase compartments respectively. The feed and strip phases are stirred with the
incorporated stirrers of the equipment. A magnetic stirrer is used to stir the membrane phase. The
experiment is run for 4 hours. At specified time intervals, i.e. every 30 minutes, 1 mL of sample
is collected using a pipette to be analyzed for glycerol content using a HPLC. The experiment is
repeated by changing the DESs, stirring speed of each phases (100-300 rpm) and concentration
of the strip phase (0-0.5 M NaOH). Experiments are also conducted using pure ethylene glycol
for comparison purposes.

Stirrer

Feed phase Strip phase

(Biodiesel) (NaOH)

DESs
membrane

Magnetic stirrer

20
 Figure 3.2: Experimental setup for BLM experiment

3.5 Data Analysis

3.5.1 Extraction and Stripping Efficiencies

The extraction and stripping efficiencies of glycerol from the biodiesel and into the NaOH
solution strip phase can be calculated based on the glycerol concentrations. The extraction
efficiency, E can be evaluated using:

(%) = 100 (1)

On the other hand, the stripping efficiencies, S are calculated by:

(%) = 100 (2)

Where:

A: Initial glycerol content in biodiesel.

B: Glycerol concentration in samples.

C: Glycerol concentration in strip phase.

3.6 Sample Data Collection

A sample of data at a specified condition can be tabulated for example at a specified strip phase
concentration. An example of planned data collection is attached in Appendix B1. The data can
be used to plot different results such as extraction efficiencies and stripping efficiencies against
time at a constant strip phase concentration for different DESs, effect of stirring speed on
extraction and stripping efficiencies for a DES membrane and effect of different strip phase
concentrations on the extraction and stripping efficiencies of glycerol.

21
 3.7 Job Safety Analysis
Table 3.2: Job safety analysis for purification of biodiesel using BLM experiment.
Job Sequence Possible Hazards
Preparing biodiesel by Hot surface of reactor unit
transesterification in the multiunit Inhalation of vaporized methanol
reactor with reflux Glassware might slip out of hand due to
slippery surface due to crude palm oil
Handling of corrosive catalyst
Centrifugation at high speed might cause
damage to equipment if not handled
properly
High temperature of surface of container
after heating of biodiesel in the oven to
remove alcohol
Preparation of DESs Hot surface of heated plate
22
Safety Measures
Use suitable gloves to handle hot surfaces of
equipment or containers as well as slippery
glassware
Cover connection between condenser and
multiunit reactor using parafilm to prevent
methanol from escaping
Handle hazardous substances such as KOH
and methanol in fume hood
Ensure that the centrifuge is in balance before
operation
Wear proper PPEs such as gloves, face mask
and lab coat
Use suitable gloves to handle hot surfaces of

Bulk liquid membrane (BLM)
experiment
Chemical spillage from the conical
flasks due to excess stirring
Chemicals come into contact with skin
Chemicals might come into contact with
skin during transferring of chemicals
into the membrane system
NaOH might cause skin burn
Chemical spillage due to excessive
stirring
23
equipment or containers
Handle chemicals involved such as choline
chloride and ethylene glycol in fume hood
Stir chemicals at moderate speed to prevent
chemical spillage
Wear proper PPEs such as gloves, face mask
and lab coat
Transfer chemical carefully using appropriate
sized equipment
Stir chemicals at moderate speed to prevent
chemical spillage
Wear proper PPEs such as gloves, face mask
and lab coat
 4.0 Working Schedule

Activity, Semester 1, 2016/2017 Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Topic allocation 16th September 2016
Briefing 1 23rd September 2016
Literature review, plan project, proposal writing
Talk on research methodology 30th September 2016

24
Talk on using EndNote for referencing 7th October 2016
Talk on design of experiments (DOE) 14th October 2016
Talk on proposal writing 21st October 2016
Laboratory work, data collection and analysis
Briefing 2 4th November 2016
Submission of literature review table 11th November 2016
Submission of proposal 2nd December 2016
Proposal presentation
Submission of corrected proposal

24
Activity, Semester 2, 2016/2017 Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Preparation and screening of DESs
Preparation of biodiesel feedstock
Preparation of strip phase
Bulk liquid membrane experiment
- Vary DESs for constant strip phase
- Vary strip phase concentration
- Effect of stirring speed on extraction
Data analysis
Article writing
ENGENIUS presentation
Article submission
URD poster presentation After final exam, Semester 2, 2016/2017

25
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[38] Hayyan, M., Mjalli, F. S., Hashim, M. A., & AlNashef, I. M. (2010). A novel technique for
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30
 Appendix A1: International standards of biodiesel
Table A1.1: Specifications of biodiesel according to EN 14214 and ASTM D 6751 standards.
Property EN 14214 ASTM D 6751
Test method Limits Test method Limits
Ester method EN 14103 96.5% (mol mol-1) min -
Linoleic acid content EN 14103 12.0% (mol mol-1) max -
Content of FAMEa with 4 double bonds - 1.0% (mol mol-1) max -
MAGb content EN 14105 0.80% (mol mol-1) max -
DAGc content EN 14105 0.20% (mol mol-1) max -
d -1
TAG content EN 14105 0.20% (mol mol ) max -
Free glycerine EN 14105 0.02% (mol mol-1) max ASTM D 6584 0.020% (w/w) max
Total glycerine EN 14105 0.25% (mol mol-1) max ASTM D 6584 0.240% (w/w) max
Water and sediment or water content EN ISO 12837 500 mg kg-1 max ASTM D 2709 0.050% (v/v) max
Methanol content EN14110 0.20% (mol mol-1) max - -
(Na+K) content EN14108 5.0 mg kg-1 max UOP 391 5 mg kg-1 max
(Ca+Mg) content prEN 14538 5.0 mg kg-1 max - -
P content EN 14107 10.0 mg kg-1 max ASTM D 4951 0.001% (w/w) max
Oxidative stability (110oc) EN 14112 6 h min - -
Density (15oC) EN ISO 3675 860-900 kgm-3 - -
Kinematic viscosity or viscosity (40oC) EN ISO 3104 3.5-5.0 mm2s-1 ASTM D 445 1.9-6.0 mm2s-1
Flash point EN ISO 3679 120oC min ASTM D 93 130oC min
Cloud point - - ASTM D 2500 Not specified

A1-1
Property EN 14214 ` ASTM D 6751
Test method Limits Test method Limits
Sulfur content EN ISO 20864 10 mg kg-1 max ASTM D 5453 0.05% (w/w) max
Cetane number EN ISO 5165 51 min ASTM D 613 47 min
Sulphated ash ISO 3987 0.02% (mol mol-1) max ASTM D 874 0.020% (w/w) max
Total contamination EN 12662 24 mg kg-1 max - -
o
Copper strip corrosion (3h, 50 C) EN ISO 2160 1 (degree of corrosion) ASTM D 130 No. 3 max
-1
Acid number or acid value EN 14104 0.50 mg KOH g max ASTM D 664 0.50 mg KOH g-1 max
Iodine value EN 14111 120 g 12.100 g-1 max - -
Distillation temperature (90% recovered) - - ASTM D 1160 360oC max

a = Fatty acid methyl ester

b = Monoacylglycerol
c = Diacylglycerol
d = Triacylglycerol

A1-2
Appendix B1: Sample of data collection
At a constant strip phase concentration, the following data can be tabulated.
Initial glycerol Glycerol content in Glycerol content in strip Extraction Stripping efficiency
DESs Time (min) content sample phase efficiency (%) (%)
1 0
120
240
2 0
120
240
3 0
120
240
4 0
120
240
5 0
120
240

B1-1
 Using the data at constant strip phase concentrations, effect of different concentrations can be plotted for example, a single DES.
NaOH
concentration Initial glycerol Glycerol content in Glycerol content in strip Extraction Stripping efficiency
(M) Time (min) content sample phase efficiency (%) (%)
0 0
120
240
0.1 0
120
240
0.2 0
120
240
0.3 0
120
240
0.4 0
120
240

B1-2