Beruflich Dokumente
Kultur Dokumente
FACULTY OF ENGINEERING
UNIVERSITY OF MALAYA
KUALA LUMPUR
2012
Candidates Signature
Date: 21-11-2012
Date: 21-11-2012
Name:
Designation: Department of Chemical Engineering,
Faculty of Engineering, University of Malaya, Kuala Lumpur, 50603, Malaysia
Tel. /Fax: +60 123002949/+60 379675311
ii
ABSTRACT
Exploring new bio-sources for fuel production is one of the priorities of
industrial oriented research. Alternatively, there are large amounts of acidic
crude palm oil (ACPO) with high FFA content produced from industrial mills
of oil palm. These could be converted to fatty acid methyl esters (FAME). The
main obstacle against producing biodiesel from ACPO is its high FFA content.
Therefore, it is required to undergo a pre-treatment stage in order to convert the
FFA into fatty acid methyl ester (FAME) before proceeding for biodiesel
production. An acid-catalyzed esterification process was carried out in
pretreatment of ACPO with alcohol to esterify the free fatty acid (FFA) before
trasestifying the triacylglycerols (TAG) with an alkaline catalyst to produce
biodiesel fuel. In this study, characterization of ACPO was investigated in
terms of fatty acid composition and physical properties. The first phase in this
study was screening of different types homogenous acids such as
ethanesulfonic acid (ESA), methanesulfonic acid (MSA), chromosulfuric acid
(CSA), benzenesulfonic acid (BZSA) and toluene-4-sulfonic acid monohydrate
(PTSA). The second phase of this study is conversion of selected homogenous
acid such as PTSA to deep eutectic solvent (DES) in order to improve the
physical properties of the acid. Different types of ammonium such as choline
chloride and phosphonium salts such as allyltriphenylphosphonium bromide
were used to prepare DES. DES was introduced as a solvent and catalyst in
esterification reaction of ACPO. This study develops a pre-treatment process
using DES to reduce the free fatty acid to the minimum acceptable limit for
biodiesel production. Conversion of PTSA to DES was improved the physical
properties of PTSA and this DES shows high catalytic activity in the
esterification reaction. There are unlimited possibilities, studies and
applications to synthesize potential DES for esterification and
transesterification reactions of wide range of oils and fats. The biodiesel
produced from ACPO was favorable as compared to EN 14214 and ASTM
D6751 standards.
iii
ACKNOWLEGMENTS
In the name of Allah, the Most Gracious and the Most Merciful.
In the first place, all the praises and thanks are to Allah Almighty for
granting us success in this work and giving us patience and strength to
complete this study as a fulfillment of the requirement of Doctorate of
Philosophy in Chemical Engineering successfully.
The author would like to extend his sincere thanks and gratitude to the
head of Centre for Ionic Liquids (UMCiL), Professor Dr. Mohd Ali Hashim for
his continued support, supervision, encouragement and valuable guidance
throughout the duration of this research study. The author wishes to express his
profound appreciation and gratitude to Assoc. Prof. Dr. Inas M. AlNashef and
Assoc. Prof. Dr. Farouq S. Mjalli for their support.
Finally, the author presents his most sincere thanks and warmest
gratitude to the great parents (may ALLAH SWT bless and reward them). The
warm gratitude and thanks are extended to all other authors family members,
especially his wife, for their support during the period of study.
iv
TABLE OF CONTENTS
vi
Characteristics
of
ACPO
Physical
properties
of
ACPO...54
4.2. Screening of Different Types of Acids..58
4.2.1
Effect
of
BZSA
in
the
Reduction
of
FFA
in
ACPO
....................................................75
4.2.4 Effect of PTSA in the Reduction of FFA in ACPO (Presented in 2nd
International Conferences on Process Engineering and Advanced Materials
2012)..82
4.2
4.2.1 PTSA
converison
to
DES
using
phosphonium
Salt
............................................................................86
4.4
PTSA
converison
to
DES
using
Ammonium
Salt
............................98
106
vii
CHAPTER I
INTRODUCTION
1.1
Overview
sell CPO to palm oil refineries as a raw material for food processing. In view of
the above mentioned facts, many obstacles exist for the commercialization of
biodiesel produced from CPO. Hence, finding and highlighting new bioindustrial resources for biodiesel production is one of the urgent priorities of the
industrial and academic community in order to make biodiesel production
economical and commercially feasible. Acidic crude palm oil (ACPO) is an
unfavorable type of CPO produced from palm oil mills due to different
operational and processing factors. Possible reasons for producing ACPO
involve technical milling problems, long time oil storage, delay of fruit
harvesting, unexpected climate changes, in addition to the variation of storage
environment and temperature. Usually, CPO with FFA lower than 5% is
considered as an acceptable CPO grade which can be sent directly to the palm
oil refinery. ACPO has an FFA content higher than 5% and consequently it
needs to undergo a pre-treatment stage to remove the high FFA before
proceeding to other palm oil refinery processing stages. FFA content is the
controlling key factor for pricing different verities of oils and fats. ACPO as an
agricultural raw material with a much lower price compared to CPO due to the
unfavorable higher FFA content of ACPO in addition to existence of other
undesirable impurities. From an economical point of view, ACPO is a
significant raw material for biodiesel production which can reduce the total cost
of biodiesel processing. Based on the abovementioned discussion, this study
proposes ACPO as a cheap alternative raw material for the biodiesel industry.
The cost of feedstock accounts for 6075% of the total production cost of
biodiesel fuel (Krawczyk, 1996; Ma and Hanna, 1999).
using
different
types
of
homogenous
catalysts
such
as
procedure of preparation (Cooper et al., 2004). In addition, DESs share with ILs
other environmental merits such as biodegradability and non-flammability (Hu
et al., 2004; Abbott et al., 2008; Olivier-Bourbigou et al., 2010). A DES can be
prepared via mixing of hydrogen bond donor (HBD) such as urea and salt such
as choline chloride (ChCl) (Abbott et al., 2003). ChCl is the common salt used
for preparation of DES with a wide range of HBDs. Nevertheless, limited
studies were found in the literature for using DES as a catalyst in chemical
reactions. For instance, a ChCl-based DES was used as a catalyst in the carbon
carbon bond formation in the rapid synthesis of -hydroxy functionalized
derivatives (Singh et al., 2012). However, DES was not yet studied as catalyst
for pre-treatment of industrial acidic oils such as ACPO for biodiesel
production.
1.2
Acidic crude palm oil has an FFA content higher than 5% up to 15%. Above
this limit the oil is consider as SPO. ACPO is a promising renewable raw
material for biodiesel production which can significantly reduce the total cost
of biodiesel processing due to the huge quantity of LGCPO produced from the
palm oil industry.
The main obstacle against producing biodiesel from LGCPO is its high FFA
content. Due to this acidic oil high FFA content, it is required to undergo a pretreatment stage in order to convert the FFA into fatty acid methyl ester (FAME)
before proceeding to other palm oil refinery processes or for biodiesel
production.
DES containing PTSA as a hydrogen bond donor has not been investigated
as a reaction solvent and as a catalyst for the practical FFA reduction in
industrial acidic oils, such as ACPO. Although PTSA has been used as a
catalyst in esterification reactions, its hygroscopic nature and storage and its
handling difficulties have prevented its commercial usage. Conversion of solid
organic acids such as PTSA into DES using simple technique will provide
opportunity to improve a wide range of catalysts in esterification and a host of
other chemical reactions. In addition, catalysts based on DESs are potential
alternatives to heterogeneous catalysts and their applications can simplify
downstream operation, such as the elimination of filtration and catalyst pretreatment.
There are unlimited research waiting of further studies to carry on
experiments using ILs or DES with wide range of acids for deep investigation
in terms of catalytic activity, recycling study, kinetics study and reaction
parameters. In addition, results of this study using IL supporting technique can
be applied and used for other types of reactions using homogenous catalyst and
potential to increase the selectivity of desired products and reduce the cost of
production significantly via recycling the homogenous catalysts.
1.3
Research Philosophy
It is vital to target the direct utilization energy for domestic and industrial
applications. A recent literature survey by the authors reveals a big gap between
the availability of different energy resources and their potential applications.
Technology is the main link between earth energy sources and their
applications. Therefore, improvement of technology using available sources to
generate energy is the main focal issue in research concerning energy and fuel.
5
Research Objectives
To treat the high acidic oils via esterification process and to reduce the
biodiesel production. To develop this raw material via dilution with different
types of oils.
3.
new liquid and solid acids and to screen the conventional acidic catalysts in
FFA content reduction.
4.
Research Methodology
2)
esterification process.
4)
solvent dosage, molar ratio, reaction time, reaction temperature and recycling
runs of DES after reaction.
6)
1.6
results
and
discussions.
Chapter
includes
conclusions
and
CHAPTER II
LITERATURE REVIEW
2.1 Historical Background of Biodiesel
Transesterification of a vegetable oil was conducted as early as 1853, by
scientists E. Duffy and J. Patrick, many years before the first diesel engine
became functional. Life for the diesel engine began in 1893 when the famous
German inventor Dr. Rudolf Diesel published a paper entitled The theory and
construction of a rational heat engine (Gunstone and Hamilton, 2001). What
the paper described was a revolutionary engine in which air would be
compressed by a piston to a very high pressure thereby causing a high
temperature. Dr. Diesel designed the original diesel engine to run on vegetable
oil. Diesel received a patent in 1893 and demonstrated a workable engine in
1897. Today, diesel engines are classified as compression-ignition engines.
Dr. Diesels prime model, a single 3 m iron cylinder with a flywheel at its base,
ran on its own power for the first time in Augsburg, Germany on August 10,
1893. Diesel later demonstrated his engine and received the Grand Prix
(highest prize) at the World Fair in Paris, France in 1900 (Gunstone and
Hamilton, 2001). This engine stood as an example of Diesels vision because it
was powered by peanut oil, a biofuel, though not strictly biodiesel, since it was
not transesterified. Dr. Diesel believed that the utilization of a biomass fuel was
the real future of his engine.
In a 1912 speech, Dr. Diesel said the use of vegetable oils for engine fuels
may seem insignificant today, but such oils may become, in the course of time,
as important as petroleum and the coal-tar products of the present time. Dr.
Diesel pointed out in any case, they (vegetable oil) make it certain that motor8
power can still be produced from the heat of the sun, which is always available
for agricultural purposes, even when all our natural stores of solid and liquid
fuels are exhausted. Up to approximately 1950, numerous other reports exist
on the use of vegetable oils as biofuel. The background at that time, as already
mentioned by Dr. Diesel (1912b), was largely that several European nations
wanted to provide their colonies in the tropical climate zone with a certain
degree of energy self-sufficiency. Several reports from that time are
noteworthy. In 1937, Chavanne received a patent on what now would be called
biodiesel. Chavanne (1937) claimed that a mixture of fatty acids and their
glycerol esters was converted into esters with alcohols of low molecular weight
in the presence of an acid catalyst. Acid-catalyzed formation of the ethyl esters
of palm oil was described in some suitable as a liquid fuel. The background of
this work was described by Chavanne (1943) in an additional publication. Van
den Abeele (1942) wrote an extensive report describing synthesis and use of
ethyl esters of palm oil. After 1950, the use of vegetable oils and their
derivatives as diesel fuel remained largely dormant (Gunstone and Hamilton,
2001). After 1950, the use of vegetable oils and their derivatives as diesel fuel
remained largely dormant. Bruwer et al., (1980) reported the use of sunflower
oil esters as alternative diesel fuel. Since about 1980 there has been significant
interest in the utilization of vegetable oils and their derivatives as alternative
fuels. Since the 1980s, biodiesel plants have opened in many European
countries, and some cities have run busses on biodiesel, or blends of petrodisesl
and biodiesel. Recent environmental and domestic economic concerns have
prompted resurgence in the use of biodiesel throughout the world. Commercial
production of biodiesel fuel did not begin until the late 1990. In 1991, The
9
European community proposed a 90% tax deduction for the use of biofuels,
including biodiesel. Biodiesel plants are now being built by several companies
in Europe; each of these plants will produce up to 1.5 million gallons of fuel per
year. The European Union accounted for nearly 89% of all biodiesel production
worldwide in 2005 (Demirbas, 2009a).
2.2 Definitions and Characteristics of Biodiesel Fuel
Biodiesel made from renewable biological sources, such as vegetable oils,
animal fats (Ma and Hanna, 1999; Demirbas, 2009a). Biodiesel, defined as
substitute for, or an additive to diesel fuel that is derive from the oils and fats
of plants and animals. Chemical definition of biodiesel is monoalkyl esters of
long chain fatty acids derived from a renewable lipid feedstock, such as
vegetable oil or animal fat according to the American Society for Testing and
Materials (ASTM). Bio represents its renewable and biological source in
contrast to traditional petroleum-based diesel fuel; diesel refers to its use in
diesel engines. Biodiesel is known as monoalkyl, such as fatty acid methyl ester
(FAME) and fatty acid ethyl esters (FAEE) derived from a renewable lipid
feedstock, such as vegetable oil or animal fat (Demirbas, 2009a). Biodiesel is a
mixture of methyl esters of long chain fatty acids like lauric, palmitic, steric,
oleic, etc. Typical examples are palm oil, rapeseed oil, canola oil, soybean oil,
and sunflower oil and its derivatives from vegetable sources. Beef and sheep
tallow and poultry oil from animal sources and cooking oil are also the sources
of raw materials. Biodiesel reaction is a reaction between oil or fat with alcohol
the presence of catalyst alkaline or acid to form biodiesel, and glycerin and this
reaction call transesterification reaction. The common international standard for
biodiesel is EN 14214 and ASTM D6751 (Hayyan et al., 2010). Biodiesel can
10
i.
ii.
iii.
The exhaust emissions from biodiesel are lower than with regular diesel
fuel.
iv.
FFA + Methanol
FAME + Water
(2.1)
Triacylglycerols + Methanol
3 FAME +
Glycerol
(2.2)
RCOOH
CH3OH
RCOOCH3
H2O
(2.3)
FFA
Methanol
FAME
Water
The esterification may be driven to the right either by using a significant excess
of one of the reactants or by removing one of the products. Water will form as
by product of reaction (Chi, 1999). Water may be removed either by distillation
or by the addition of a dehydrating agent such as magnesium sulfate or
molecular sieves. The mechanism of Fischer esterification involves an acidcatalyzed nucleophilic acyl substitution. An alcohol is not a strong enough
nucleophile to attack the carbonyl group of a carboxylic acid; however, the acid
catalyst protonates the carbonyl group and activates it toward nucleophilic
attack. Loss of a proton gives the hydrate of an ester. Protonation of the alkoxyl
group allow it to leave as water, this protonated ester then loses a proton, giving
the ester. The mechanism of Fischer esterification of fatty acid by methanol is
illustrated in Equation (2.4) (Chi, 1999).
13
(2.4)
TG
Methanol
FAME
Glycerol
15
TG
Methanol
DG
FAME
DG
Methanol
MG
FAME
MG
Methanol
Glycerol
FAME
The stoichiometry of the reaction requires a 3:1 molar ratio of alcohol to TG.
Because esters and alcohols appear on both sides of the equation it might be
expected that equilibrium contents would be close to unity. However, the
16
glycerol moiety is usually not such a good nucleophile as the alcohol and
typically only a 6: 1 molar ratio is required to drive the transesterification to >
95% completion (Chi, 1999). Therefore, the presence of MG and DG at the end
of the reaction must be anticipated.
2.5 Overview of Cheap Sustainable Sources
Economic growth is mainly based on the diversity and availability of energy
sources. Energy is essential input for social development of countries and
improving the quality of life (Sahoo et al., 2007). Throughout the technological
age, many industrialized countries have focused on utilizing the earths
resources to generate renewable energy (Hayyan et al., 2008). Since their
exploration, fossil fuels continued to be the major conventional energy source.
The increasing trend of modernization and industrialization resulted in a surge
of growth of the world energy demand. This continuously escalating demand
has drawn the attention to utilize other fuel alternatives such as biodiesel.
Biodiesel as a fuel is receiving an upsurge interest as an alternative, sustainable
and renewable energy resource (Sahoo et al., 2007; Ma and Hana, 1999;
Demirbas, 2009; Hayyan et al., 2010a). Biodiesel has becomes more attractive
as an alternative fuel to petroleum diesel fuel (Pandey, 2009). Moreover,
recently, the increase in crude oil prices has participated in focusing the
attention for considering biodiesel as an alternative, relatively cheaper fuel.
Vegetable oils and animal fats are regarded as the major sources for producing
biodiesel fuels (Ma and Hana, 1999; Canakci and Van Gerpen, 2001). Biodiesel
production has many merits as an alternative, renewable, non-toxic fuel,
biodegradable and environment friendly (Canakci, M., Van Gerpen, 2003;
Hayyan et al., 2009a; Demirbas, 2009). However, various obstacles scenarios
17
have been faced biodiesel production. The availability of resources and the cost
of processing are the most important factors (Krawczyk, 1996; Ma and Hana,
1999; Demirbas, 2009; Hayyan et al., 2010b). The high cost of biodiesel
compared to petroleum diesel has been a major obstacle for the
commercialization of biodiesel (Canakci and Van Gerpen, 2001; Hayyan et al.,
2010a). Currently, edible vegetable oils, such as palm oil, soybean, rapeseed
and sunflower are the prevalent feedstocks for biodiesel production (Antolin et
al., 2002; Hayyan et al., 2010b; Hayyan et al., 2010c). Production of biodiesel
from edible vegetable oil results in the high price of biodiesel. Consequently,
exploring ways to reduce the cost of raw materials is the main focus in current
biodiesel research (Canakci and Van Gerpen, 2001; Canakci, 2007; Hayyan et
al., 2009a; Hayyan et al., 2010c). Mainly, there are three cheap sustainable
sources (CSS) for biodiesel production namely: Non-edible plant oils (Ghadge
and Raheman, 2005; Veljkovic et al., 2006), low grade by-products of oil
refinery industries (Chongkhong, et al., 2007; Echim, et al., 2009; Hayyan et
al., 2009b; Hayyan et al., 2010b) and waste cooking oils (WCO) or waste fats
from restaurants (Leung and Guo, 2006; Canakci and Van Gerpen, 2001;
Canakci, 2007; Bhatti et al., 2008). The use of CSS may lower the cost of
biodiesel production significantly. The problem facing these raw materials is
often the large amount of free fatty acid (FFA) that cannot be converted to
biodiesel using an alkaline catalyst (Canakci and Van Gerpen, 2001; Ma and
Hana, 1999). Usually, raw materials (oils or fats) from CSS are of very low
grade containing water, FFA, impurities and contaminants such as WCO or byproduct of oil industries (Canakci, 2007). However, developing a pre-treatment
process to treat low grade oils and fats from CSS before transesterification
18
the rationale for the variously proposed pre-treatment techniques are reviewed
in terms of their effectiveness, efficiency, merits, effect of conditions and
costing. A brief discussion of selected pre-treatment technologies was included
in order to present advantages and disadvantages of using the technology and to
investigate the potential use of each technology for a pilot plant scale.
20
Acid Catayst
RCOOH + CH 3OH
At present, fatty acid alkyl esters (FAAE) are obtained by reacting TAG with
lower alcohols, such as methanol or ethanol, in the presence of a strong base
used as catalyst. The reaction yields glycerol as by-product. Oils and fats used
in alkaline transesterification reactions should contain no more than 1% FFA
(Sahoo et al., 2007; Ma and Hana, 1999; Canakci and Van Gerpen, 2001;
Demirbas, 2009). If the FFA level exceeds this threshold, saponification
hinders separation of the ester from glycerol and reduces the yield and
formation rate of biodiesel. A number of researchers have worked on many
types of feedstock that have elevated FFA levels (Canakci and Van Gerpen,
2001). Due to high FFA content in waste cooking oils, the alkali catalyzed
transesterification to produce biodiesel gives low biodiesel yield because FFA
reacts with alkali to form soap, resulting in serious emulsification and
separation problems (Freedman et al., 1984; Canakci and Van Gerpen, 2001;
Demirbas, 2009). Researchers reported that the oil should not contain more
than 1% FFA for alkalinecatalyst transesterification reactions (Freedman et
al., 1984; Ma and Hana, 1999; Canakci and Van Gerpen, 2001; Demirbas,
2009). Pre-treatment of oils or fats before biodiesel production is an important
21
step in the production process especially if the raw material used is waste
cooking oils or oils and fats with high FFA such as palm oil fatty distillate
(Chongkhong et al., 2007), mahua (Ghadge and Raheman, 2005), sludge palm
oil (SPO) (Hayyan et al., 2008; 2009; 2010a), rubber seed oil (Ramadhas et al.,
2004), tobacco (nicotiana tabacum L.) seed oil (Veljkovic et al., 2006), mahua
(madhuca indica) (Ghadge and Raheman, 2005), Karanja (pongammia pinnata)
(Naik et al., 2008), yellow and brown grease (Canakci and Van Gerpen, 2001).
Thus, an acidcatalyzed pre-treatment step by esterification reaction to convert
the FFA to fatty acid methyl ester (FAME) followed by an alkalicatalyzed step
to convert the triglycerides to methyl esters and glycerol should provide an
effective and efficient method to convert high FFA feedstock to biodiesel
(Canakci and Van Gerpen, 2001; Naik et al., 2008). This pre-treatment process
usually utilizes an acid catalyst. The most commonly preferred acid catalysts
are sulfonic, hydrochloric, and sulfuric acid (Ma and Hana, 1999). Organic
sulfonic acid such as p-toluene sulfonic acid (PTSA) (Ma and Hanna, 1999;
Shahidi, 2005) has been used in the pretreatment of SPO (Hayyan et al., 2009)
and to reduce the high FFA content in soybean oil. It was reported that using
6.4x10-5 mol of PTSA as acid catalyst can decrease the FFA content in soybean
oil from 20.5% to 1.1% and the yield obtained after reaction obtained was 48%
with the reaction conditions of 12:1 molar ratio, 180oC reaction temperature,
and 60 minutes reaction time (Di Serio et al., 2008).
22
Table 1: Advantages and disadvantages of common acids used in the pretreatment process (esterification reaction) (Paolo, 2001).
Acid catalyst
Advantages
Disadvantages
Sulfuric acid
Corrosion problems.
Low price.
bonds.
neutralization.
glycerol refiners.
esterification reaction
Transesterification very
difficult.
Dark colour of final product.
Hydrochloric
Low price.
Corrosion problems.
acid
neutralization.
reaction
PTSA
reaction mixture.
bonds.
Transesterification very
difficult.
grade.
23
It can be observed that both acid catalysts sulfuric acid and hydrochloric acid
cause corrosion problems in the chemical reactor and pipelines of the pilot plant
during production of biodiesel, however, PTSA was not reported as corrosive
acid in the biodiesel production. Sulfuric acid was reported to react with the
double bonds of oils and fats. The main disadvantage of using sulfuric acid was
the resulting ash sulfates in the crude glycerol. Purification of glycerol is very
difficult in case the crude glycerol contains sulfates ash. However, the main
advantage of using sulfuric acid in the pre-treatment of oils and fats and
biodiesel production is its high catalytic activity compared to other acid
catalysts in addition to its cheapest cost among other acids. Because of these
merits, sulfuric acid was used widely in pilot plants worldwide.
Hydrochloric acid was reported as the one of the difficult acids to storage and
handling because of its vapor which is very harmful. In addition it is important
to take special care in its handling and storage and use very expensive
containers and sophisticated safety precautions.
The catalytic efficiency of HCl is lower compared to sulfuric acid and PTSA
(Hayyan et al., 2008). However, these disadvantages were not found in PTSA.
The main advantage to propose PTSA as a suitable acid catalyst was the high
activity of PTSA in pre-treatment of oils and fats with high FFA such as SPO.
The FFA content was reduced from 46% to less than 2% FFA using 2% of
PTSA in the pre-treatment of SPO which was suitable to produce acceptable
yield of treated SPO and very pure biodiesel after the transesterification
reaction (Hayyan et al., 2008). However, the main drawback of using PTSA as
acid catalyst is its high price when compared to sulfuric acid. For industrial use,
24
the PTSA cost can be reduced when dealing with large quantities of
commercial grade instead of analytical grade.
Oils pre-treatment using solid catalysts involves an additional cost for the
removal of the spent catalyst from the biodiesel product before using it in
combustion engines. An improper purification process may cause serious
problems such as induced corrosion in the fuel tank, engine, pipes and
eventually wreak havoc on the overall vehicle. In terms of capital cost of the
pre-treatment process, it should be noted that the process with an acid-catalyzed
pretreatment step is more complex in terms of instrumentation due to the
addition of a pretreatment unit to the main production unit (transesterification)
resulting in an increase in the overall plant cost. For these reasons, it is a
common industrial practice to use alkaline-catalyzed processes with fewer and
simpler process equipment units (Leung et al., 2006; Guo et al., 2004).
glycerol and carotenoide) will assess the direct and indirect impacts on the
national economy.
26
heating has been used for SPO and acidic crude palm oil because at room
temperature SPO usually exists in semisolid phase (Hayyan et al. 2010; 2011).
In case of used cooking oils (UCO) analysis showed that the differences
between UCO and virgin oil are not very substantial (Knothe, et al. 1997).
Therefore, in most cases, heating and removal by filtration of solid particles
suffices for subsequent transesterification (Enweremadu and Mbarawa, 2009).
However, in some cases the products of oil decomposition cause deterioration
in oil quality, which can lead to reduced ester yield during biodiesel production
and the formation of unwanted products. The negative effects of the undesirable
compounds can be avoided by the proper treatment of the UCO (Enweremadu
and Mbarawa, 2009).
Supple et al. (2002) used steam and sedimentation method to investigate the
effects of oil pre-treatment on the properties of UCO and the produced esters.
The study was carried out in two stages consisting of pretreatment and heating
of the oil at 65o C followed by sedimentation in both stages. The effects of
these treatments on the physical and chemical properties of UCO were studied.
Results after both stages of pretreatment showed that there was a reduction in
moisture content, free fatty acid and a substantial reduction in viscosity while
the calorific value increased. The pretreated UCO was transesterified with
methanol (6:1 molar ratio) using 1% KOH as the catalyst at 60o C. The
decrease in FFA (6.34.3%) and moisture content (1.40.4%), respectively
accounted for the substantial increase in ester yield (from 67.5% to 83.5%)
(Enweremadu and Mbarawa, 2009; Supple et al. 2002).
27
catalyst that remain with the glycerol after its separation from the methyl esters.
FFA was converted into salts and soaps, which was miscible to the crude
glycerol-rich phase and leave the oil-rich phase. This proposed neutralization
step helps to reduce the acid value of the oil and also helps to remove traces of
catalyst from crude glycerol (Sousa et al., 2010). In case that if the glycerol has
been used in the process the recovery, reclaiming and reusing a residue of
alkaline catalyst which contains in the crude glycerol will be highly desirable
process because this process had used the cycling the waste materials in a
closed loop, therefore recycling process results in a reduction of the total cost of
biodiesel production in many steps such as handling, managing and disposal of
the waste. Figure 1 shows proposed industrial flowchart to produce biodiesel
using pretreatment of caster oil by its crude glycerol. However, the process is
suitable if FFA was low in the raw materials such as waste cooking oils but it is
not suitable if the raw materials have high FFA such as yellow and brown
grease from restaurant. However, Glycerolysis technique involves adding
glycerol to the raw material and heating it to high temperature (200oC), can be
done without catalyst or by adding catalyst such as zinc chloride. The glycerol
reacts with the FFA to form monoacylglycerol (MAG) and diacylglycerols
(DAG) (Gerpen et al., 2004). Figure 2 shows the rate of decrease of the fatty
acid level in a batch of animal fat. The conditions were 100 g animal fat, 13 g
glycerol, 0.1 g ZnCl, 200 oC, 11 psi vacuum.
investigate the effect of sonication time on the reduction of FFA in SPO. The
results showed that the conversion of FFA to FAME by applying ultrasonic
energy is related to length of sonication time. The FFA content of SPO was
reduced from 24.5% to less than 3% using molar ratio 10:1, reaction
temperature 50oC and 2% wt/wt sulfuric acid to SPO in 300 minutes sonication
time. Santos et al. (2010) have used ultrasound assisted pretreatment of Nile
tilapia oil (Oreochromis niloticus) to produce biodiesel. Nile tilapia oil is a low
cost feedstocks and generally contains high amounts of FFA. The reaction was
carried out by applying low-frequency high-intensity ultrasound (40 kHz) under
atmospheric pressure and ambient temperature. The hypothesis of using
ultrasonic waves in pretreatment of oils and fats and producing biodiesel was
ultrasonic irradiation causes cavitation of bubbles near the phase boundary
between the alcohol and oil phases. As a result, micro fine bubbles are formed.
The asymmetric collapse of the cavitation bubbles disrupts the phase boundary.
Impinging of the liquids creates micro jets leading to intensive mixing of the
system near the phase boundary. The cavitation may also lead to a localized
increase in temperature at the phase boundary enhancing the transesterification
reaction. Neither agitation nor heating are required to produce biodiesel by
ultrasound application because of the formation of micro jets and localized
temperature increase (Stavarache et al., 2005; Stavaracheet al., 2006).
the rate of reactions and selectivity (Mazzocchia, et al., 2002). Hence, it was
possible to prepare biodiesel rapidly and with good conversions by microwave
heating (Mazzocchia et al., 2002).
Hayyan et al.(2008) have used microwave in order to evaporate the water
content, melt and purify SPO from the particles and other impurities before
using a chemical reactor for the esterification reaction. Saifuddin and Chua
(2004) have used microwave in the pre-treatment of UCO. The study used
filtration and drying using microwave oven at 60o C for 10 min.
32
33
35
Type of catalyst
Reaction temperature
in the two-steps method was 97.22% at a reaction time of 4 hours, molar ration
10:1, while the conversion of acid catalyzed process was 90% at a reaction time
of 10 hours, molar ratio 20:1. Hence ferric sulfate showed much higher
catalytic activity compared to the acid catalyzed method. It was reported that
sulfuric acid is the most common acid catalyzed used in esterification because
of its low cost and availability (Canakci and Van Genpen, 2001). Naik et al.,
(2008) proposed Karanja oil as a new source for biodiesel production. The
study used sulfuric acid as a catalyst to treat the Karanja oil which has up to
20% FFA, 0.5% of sulfuric acid has reduced FFA content from 20% to less than
2% within 1 hour and 6:1 molar ratio methanol to FFA of Karanja oil. In
another study, Bhatti, et al., (2008) used waste tallow as low cost sustainable
potential feed stock for biodiesel production. The process was acid catalyzed
esterfication using sulfuric acid followed by base catalyzed transesterification
using potassium hydroxide. The optimal conditions for processing 5g of tallow
were: reaction temperature of 50 and 60oC; molar ratio oil/methanol of 1:30 and
1:30, amount of sulfuric acid 1.25 and 2.5 g for chicken and mutton tallow,
respectively. Under optimal conditions, chicken and mutton fat methyl esters
formation of 99.01% and 93.21% respectively were obtained after 24 hours in
the presence of sulfuric acid.
(Ramadhas, et al., 2004). Canakci and Van Gerpan, (1999; 2001) advocated the
use of large excess quantity of methanol (15:1-35:1) while using the sulfuric
acid as catalyst. Di Serio et al., (2008) have used 12:1 molar ratio to decrease
the FFA content in soybean oil from 20.5% to 1.1% using PTSA as acid
catalyst. (Chongkhong et al., 2007) have used 8:1 molar ratio methanol to palm
fatty acid distillate with 1.834 wt% of sulfuric acid at 70C under its own
pressure with a retention time of 60 minutes. A study by Veljkovic et al., (2006)
used tobacco seed oil as an alternative raw material to produce biodiesel. The
results showed that the FFA content was reduced from 17 wt% to less than 2
wt% using a pretreatment step followed by alkali transesterification reaction.
The conditions of pretreatment were; a molar ratio of 18:1 of methanol to oil,
60 C reaction temperature, at 25 minutes. For the case of waste cooking oil
catalyzed by sulfuric acid, biodiesel production increased rapidly within 1-6
hours and then dropped down, and when the molar ratio of methanol to oil
exceeded 16, waste cooking oil conversion increased rapidly, in addition waste
cooking oil conversion increased with the amount of sulfuric acid up to 4 wt%
(Wang, et al., 2006). Increasing the molar ratio of the methanol to oil increases
the rate of formation of the methyl esters. The reaction was faster with a high
molar, whereas longer reaction time was required for the lower molar ratio to
get the same conversion (Pandey, 2009).
time (Freedman et al., 1984). A reaction temperature above the boiling point of
the alcohol is avoided because at high temperature, it tends to accelerate the
saponification of the glycerides by the alkaline catalyst before completion of
the alcoholysis (Dorado et al. 2004). A study by Leung and Guo (2006) showed
that a temperature higher than 50oC has a negative impact on the product yield
for neat oil, but a positive effect for waste oil with higher viscosities. However,
The FFA of WCO were esterified with methanol catalyzed by ferric sulfate in
the first step, and the TG in WCO were transesterified with methanol catalyzed
by potassium hydroxide in the second step. The results showed that ferric
sulfate had high activity to catalyze the esterification of FFA with methanol.
The conversion rate of FFA reached 97.22% when 2 wt% of ferric sulfate was
added to the reaction system containing molar ratio of 10:1 composition and
reacted at 95oC for 4 h. The methanol was vacuum evaporated, and
transesterification of the remained TG was performed at 65oC for 1 h in a
reaction system containing 1 wt% of KOH and 6:1 mole ratio of methanol to
TG. The final product consisted of 97.02% biodiesel. Using heterogeneous
catalysts such as ferric acid necessitates
homogenous acid catalysts. On the other hand, there are other merits of using
ferric acid heterogeneous catalyst such as its high efficiency, no acidic waste
water, low equipment cost and easy recovery of the catalyst. A two-step
technique combining pre-esterification catalyzed by cation exchange resin with
transesterification catalyzed by base alkali was developed to produce biodiesel
from rapeseed oil deodorizer distillate. The FFA in the rapeseed oil deodorizer
distillate was converted to FAME in the pre-esterification step using a column
reactor packed with cation exchange resin. The acid value of oil was reduced
40
from the initial 97.60 mg-KOH/g oil to 1.12 mgKOH/g oil under the conditions
of cation exchange resin D002 catalyst packed dosage of 18 wt%, oil to
methanol molar ratio 1:9, reaction temperature 60 C, and reaction time 4 h.
The biodiesel yield by transesterification was 97.4% in 1.5 h using 0.8 wt%
KOH as catalyst and a molar ratio of oil to methanol 1:4 at 60C. The
properties of rapeseed oil deodorizer distillate biodiesel production in a packed
column reactor followed by KOH catalyzed transesterification were measured
up the standards of EN14214 and ASTM6751-03.
Adding more acid or methanol did not significantly affected the methyl esters
content (Pandey, 2009). Production of FAME from palm fatty acid distillate
(PFAD) having high free fatty acids (FFA) was investigated by chongkhong et
al., (2007). The optimum condition for the continuous esterification process
was a molar ratio of methanol to PFAD at 8:1 with 1.834wt% of sulfuric acid at
70oC under its own pressure with a retention time of 60 min. The amount of
FFA was reduced from 93 wt% to less than 2 wt% at the end of the
esterification process. The FAME was purified by neutralization with 3M
sodium hydroxide in water solution at a reaction temperature of 80oC for 15
min followed by transesterification process with 0.396M sodium hydroxide in
methanol solution at a reaction temperature of 65oC for 15 min.
starts after adding the regents and operating the reactor mixer (Demirbas,
2009). A pre-treatment study of waste rapeseed oil with high FFA using 400
rpm has been conducted by Yuan, et al., (2008). Sahoo et al., (2007) have
carried out experiments to produce biodiesel from polanga seed oil with 450
rpm continuous stirring using a mechanical stirrer speed of 450 rpm. AlWidyan and Al-Shyoukh, (2002) produced biodiesel from waste palm oil by
efficient boiling of the reactants. Lifka and Ondruschka, (2004) compared
different methods of mixing using (magnetic stirrer, ultrasound and ultra turrax)
using PTSA as a catalyst. The study found that ultrasonic mixing was the
lowest in energy consumption.
43
applied in the pre-treatment of acidic oils such as acid exchange resins (Tesset
et al., 2010), ferric sulfate (Zhang et al., 2012; Montefrio et al., 2010) and
carbon nano tube based solid acid catalysts (Shu et al., 2009; Shu et al., 2010).
Recently, ligninderived carbonaceous catalyst (LCC) was used to reduce the
FFA content in acidic soybean soapstock for biodiesel production (Guo et al.,
2012). The reaction time for the esterification reaction using LCC was too long
compared to the corresponding homogenous catalyst. In addition, LCC needs
special equipment and conditions for the catalyst preparation. The common
acidic catalysts used for the esterification reaction are p-toluenesulfonic acid
(PTSA) (Di Serio et al., 2008), trifluoromethanesulfonic acid (Hashim et al.,
2011), sulfuric acid (Hayyan et al., 2011a) and methanesulfonic acid (Aranda et
al., 2008). These types of acids are readily commercially available and can be
used directly in the synthesis of materials and chemical reactions. The common
industrial catalyst for the esterification reaction is sulfuric acid (Haas et al.,
2003; Atadashi, 2012). The main obstacle for using homogeneous catalyst in
the biodiesel production is the separation of catalyst and purification of product.
Thus, recycling of homogeneous catalysts is one of the main reasons for losing
the catalyst in chemical reactions. Recently ionic liquids (ILs) and their
applications have triggered the interest of researchers in many fields (OlivierBourbigou et al., 2010). ILs have applied successfully in versatile biological,
chemical, and electrochemical applications (Yue et al., 2011; Xue et al., 2006;
Hayyan et al., 2012). ILs have many advantages for the industrial use including
their undetectable vapor pressure and liquidity at a wide temperature range
(Xue et al., 2006; Naushad et al., 2012). ILs are usually expensive and
unavailable at industrial scale. Deep eutectic solvents (DESs) are categorized as
45
a cheap class of ILs (Abbott et al., 2003; Abbott 2008). DESs share many
merits and physical properties with ILs (Abbott 2008). In addition, the DES
preparation is very simple compared to conventional ILs (Cooper et al., 2004).
Choline chloride (ChCl) is the common salt used as the main ingredient in a
wide range of available DESs. The ChCl-urea based DES was one of the first
reported in literature, and was used later in many applications (Kareem et al.,
2010; Zhang et al., 2012). ChCl-based DESs were also used in
electrodeposition of zinctin alloys (Abbott et al., 2007), synthesis of
polyoxometalate based hybrids (Wang et al., 2010) and preparation of zeolite
(Cooper et al., 2004). A metal halide-based DES was made of ChCl.xZnCl2 and
introduced as a catalyst in the transesterification reaction (Long et al., 2010).
De Santi et al (2012) used quaternary ammonium methanesulfonate salts based
DES for esterification of carboxylic acids. Few studies reported the use of DES
with palm oil; examples are the removal of alkaline transesterification catalyst
and the separation of glycerol from biodiesel (Shahbaz et al., 2011). DESs
continging PTSA and ammoimum or phosphonium salts have not been
investigated as a reaction solvent and as a catalyst for the practical FFA
reduction in industrial acidic oils, such as ACPO. Although PTSA has been
used as a catalyst in esterification reactions, its hygroscopic nature and storage
and its handling difficulties have prevented its commercial usage (Di Serio et al
2008). Conversion of solid organic acids such as PTSA into DES using simple
technique will provide opportunity to improve a wide range of catalysts in
esterification and a host of other chemical reactions.
46
47
CHAPTER III
Experimental Methodology
3.1 ASPO Sample Collection and Preparation
ACPO sample was obtained from West Oil Mill, Carey Island, Selangor,
Malaysia. ACPO was preheated because it usually exists in semisolid phase
under ambient conditions The SPO was melted in an oven at 80oC. Melting
process also helped to evaporate the water and settled the impurities in ACPO.
In this study ACPO with different FFA content was used for pretreatment
process.
3.2
Materials
The studied salts and acids were purchased from different suppliers as listed in
Table 3.1 and 3.1. The structures of salts and PTSA are shown in Scheme 3.1.
Table 3.1: Name, Formula and Mwt of Acids used in this study
Acid name
Formula
C7H8O3S.H2O
Mwt
(g/mol)
190.22
C6H5SO3H
158.17
Methanesulfonic acid
CH4O3S
96.11
Ethanesulfonic acid
C2H6O3S
110.13
Trifluoromethanesulfonic acid
CHF3O3S
150.08
Chromosulfuric acid
mixture
48
Table 0.2: Name, formula and Mwt of salts used in this study
Salt name
Formula
Mwt(g/mol)
M.P
C
Choline Chloride
C5H14ClNO
139.62
302
C6H16ClNO
153.65
133 -
(2-hydroxyethyltrimethylammonium)
N,NDiethylethanolammonium
136
chloride
Methyltriphenylphosphonium
C19H18BrP
357.22
bromide
230 233
Benzyltriphenylphosphonium
337
C25H22ClP
388.87
C21H20BrP
383.26
chloride
Allyltriphenylphosphonium
222 -
bromide
225
49
50
column
DB-wax
122-7032.
Ester
content,
mono-,
diand
triacylglycerols (TAG), free and total glycerol content were determined using
GC/FID (Perkin Elmer Clarus 500).
period of 30 min from reaction startup time. The FFA content of the treated
ACPO was measured and reported for all experiments. Biodiesel was produced
from ACPO via two catalyzed reactions (esterification and transesterification).
In the pre-treatment stage, the ACPO sample weight for each experiment was
500 gm. While in the second reaction potassium hydroxide (KOH) was used as
a catalyst in order to convert the triacylglycerols (TAG) to fatty acid methyl
ester (FAME). The product of the esterification reaction is considered as a raw
material for the transesterification reaction. Following transesterification
reaction, gravity separation and evaporation of excess methanol were
performed. The product was then treated by water washing to remove the
impurities, free glycerol, soap and residuals of alkaline catalyst. Validation
experiments were conducted several times in order to investigate the optimum
conditions of ACPO pre-treatment process. In the second stage, 1% wt KOH
was dissolved in methanol (10:1 M ratio) and then the mixture was added to the
pre-treated ACPO in the transesterification reactor after a period of 30 min
from reaction startup. Recyclability of acid catalyst was examined via
separating the spent catalyst and reusing it to treat ACPO for further
consecutive runs. The last stage of this study was the characterization of the
produced biodiesel using the EN 14214 and ASTM D6751 international
biodiesel standards. All experimental runs were performed in a lab scale batch
multiunit reactor system with methanol reflex. The reaction temperature and
mixing intensity were monitored and controlled using specially designed
feedback controllers. Figure 3.1 shows the flow chart of biodiesel production
from ACPO.
52
TRANSESTERIFICAT
ION PROCES
ESTERIFICATION
PROCES
Acid
Catalyzed
ESTERFICATION
Potassium
TRANSESTERIFICATION
Methoxide
Crude Biodiesel
PURIFICATION PROCES
EVAPORATION
Crude
SETTLING PHASES
Glycerol
WASHING PROCESS
PURE BIODIESEL
Alcohol
CHAPTER IV
quality compared to crude palm oil in terms of FFA, moisture and other
contaminants contents. Table 1 shows the similarities and differences between SPO
and ACPO. Generally, industrial mill byproducts such as SPO and ACPO are
traded based on FFA, moisture and impurities contents (Lin, 1989). Due to its
lower specifications, ACPO has less cost per ton than that of CPO. Table 1 shows
that the peroxide value of ACPO is higher than that of SPO. While the FFA
content in ACPO lies between that of SPO and CPO which indicates that ACPO
ranks after CPO and before SPO in terms of quality. ACPO and SPO are of lower
quality compared to CPO in terms of FFA, moisture and other contaminants
contents. The FFA content of ACPO in this study was 8.8% while the
corresponding CPO value was below 5% (Tan et al., 2009). An oil with FFA
content higher than 15% is considered as SPO (Lin, 1989). The water content in
SPO and ACPO was higher than that of CPO. Based on the saponification value of
ACPO, the calculated average molecular weight was 827 which was used in the
molar ratio calculation. ACPO has low grade characterization parameters such as
FFA, peroxide value and moisture content due to long storage conditions. Products
and byproducts of industrial palm oil mills such as CPO and SPO are generally
traded based on FFA, moisture and impurities contents (Lin, 1989). Table1 shows
a comparison of properties between SPO and ACPO. It is clear that ACPO has the
highest FFA content and poor quality indicators which highlight the importance of
a reliable pretreatment stage in its processing. Accordingly, an acid-based
esterification is needed prior to the main transesterification stage. Pretreatment of
acidic oils and fats via esterification reaction was proposed in different previous
studies (Canakci and Van Gerpen, 2001; Naik et al., 2008; Hayyan et al., 2010b;
55
SPO*
22.330.77
1.52 0.40
1.20 0.06
53.4 0.71
0.05 0.007
190 1.41
1.47 0.26
0.015 0.001
48.88 1.70
0.550.03
ACPO
8.6 0.40
7.45 0.55
1.1050.2
56 0.52
0.0560.006
197.00 1.70
6.70 0.26
0.011 0.001
3.3 0.052
17.02 0.5
1.80 0.033
47.17 wt% while the unsaturated fatty acids were 50.83 wt%. The chemical
compositions of fatty acids from various products and by-products of industrial
mills are very similar in many aspects.
FFA content of ACPO increased proportionally with storage time. It was observed
that FFA content of ACPO increased at room temperature by an amount of 1% after
6 months storage time. There are many other factors that affect the degree of oils
decomposition and increase the FFA content such as water content of oil, storage
time, environment and temperature of the storage place also the type of container
can effect if the container isolated or it was opened to air for long time etc. Solar
energy increases the oxidation reaction of oil and eventually decreases the quality
of oil. Storage time has a significant effect on the increase of high FFA content of
ACPO. ACPO exists in a semisolid or solid form at room temperature (27 2oC)
due to the availability of saturated fatty acids and the high content of FFA
compared to CPO or refined palm oil. Therefore, ACPO has higher pour and cloud
points as compared to crude palm oil low FFA content. Consequently, ACPO
should be preheated before proceeding to the pretreatment stage using the
esterification reaction. On the other hand, higher saturated fatty acids in oils give a
higher cetane number and make the oil less prone to oxidation (Canakci and Van
Gerpen, 2001).
57
Structure
Type of
fatty acid
Lauric acid
Myristic
acid
Palmitic
acid
Palmitoleic
C12:0
C14:0
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
C20:0
Saturated
Saturated
Saturated
Unsaturated
Saturated
Unsaturated
Unsaturated
Unsaturated
Saturated
Stearic
acid acid
Oleic
Linoleic
acid
AlphaLinolenic
Arachidic
Fatty
acids
wt%
0.284+
1.00+
0.04
44.8+
1.95
0.30+
0.01
3.80+
0.8
39.90+
1.70
9.28+
1.0
0.22+
0.03
0.35+
4.3.2
Catalyst dosage plays a very important role during the esterification reaction.
Finding the optimum dosage of catalyst has the priority among all reaction
parameters due to its effectiveness to the whole process. Figure 4.1 shows the
effect of ESA dosages on reducing of FFA content in ACPO, conversion of FFA to
FAME and yield of treated ACPO. The FFA content was reduced from 8.6% to less
than 1% in the ranges of 0.753.5 wt%. Low ESA dosage such as 0.25 and 0.5 was
insufficient to decrease FFA content to less than 1%. It has been reported in Figure
1 that using 0.25% (ESA to ACPO) the FFA content was 2.22% while using 0.5%
the FFA content was 1.3%. Dosage at 0.5% was very close the limit and slightly
higher than 1% FFA content. According to study by Hayyan., et al., (2010b; 2011)
and Ramadhas et al., (2005) were noted that the FFA content below 2% can be
58
59
120
100
FFA%
80
FFA%
60
Limits of FFA%
Yield% of ACPO
40
20
0
0
0.5
1.5
2
2.5
Dosage of ESA wt%
3.5
Figure 4.1 Effect of ESA dosages on FFA content reduction, conversion of FFA to
FAME and yield of treated ACPO
4.2.1.2 Effect of Molar Ratio
Methanol one is of the essential reactant in the pretreatment process via
esterification reaction. Molar ratio is significantly affecting the conversion of FFA
to FAME during the course of reaction. In economical point of view, controlling
the molar ratio results in the reduction of the overall production cost of biodiesel.
In this study molar ratio was studied in the range (1:1-20:1). Figure 4.2 shows the
effect of molar ration on the reduction of high FFA content in ACPO, conversion of
FFA to FAME and yield of treated ACPO. Low loading of methanol makes the
reaction insufficient to decrease FFA content to the target FFA level. According to
Figure 4.2, reduction of FFA content using molar ratio at 1:1 and 5:1 were 5.66%
and 2.32% respectively. It is mentioned that the stoichiometry of the esterification
reaction a molar ratio of 1:1 is needed in order to drive the reaction towards
60
10
completion (Demirbas, 2009; Park et al., 2010). On the other hand, results of this
study showed that 1:1 molar ration was very low amount to reduce the FFA content
to 1%. Practically, the molar ratio of esterification reaction should be much higher
than 5:1. Hence, further molar ratios were studied in order to select the optimum
molar ratio and to satisfy the pretreatment economically. The FFA content was
decreased from 8.6% to less than 1% in the range of 10:1- 20:1. Molar ratio at 10:1
was sufficient to decrease the high FFA content in ACPO from 8.6% to 0.56%.
Excess molar ratio did not show any improvement in the reduction of FFA content.
Therefore, 10:1 was selected as optimum molar ratio for esterification reaction
using ESA catalyst. Yield of treated ACPO was 96% while the conversion of FFA
to FAME was 93.47%. Hayyan et al., (2010b: 2011) was used 10:1 also as
optimum condition to teat SPO for biodiesel production.
FFA%
Limits of FFA%
120
100
FFA%
80
6
60
4
40
2
20
10
12
14
Molar Ratio
16
18
20
Figure 4.2 Effect of molar ratio on FFA content reduction, conversion of FFA to
FAME and yield of treated ACPO
61
22
10
62
Limits of FFA%
10
120
100
80
60
4
40
20
0
0
10
20
30
40
50
60
Temperature oC
70
80
90
FFA%
FFA%
reaction. Conversion of FFA to FAME was 94.9% while the yield was 95%.
Reaction time at 30 minutes was achieved successfully FFA content 0.5%, 98%
yield of treated ACPO and 94.14% conversion of FFA to FAME. According to
Hayyan et al., (2010b) used sludge palm oil with 22.33% and the time of
pretreatment process was 60 minutes while in this study the reaction time required
to treat the high FFA content in ACPO was 15-30 minutes. Therefore, it can be
estimated simple correlation between FFA content and reaction time which is every
1% FFA content equal 2.5-3.5 minutes. However, this correlation is approximately
can give an idea about the reaction time because there are other conditions can
affect the reaction time such as the quality of oils and the oil source.
120
100
FFA%
6
4
FFA%
80
Limits of FFA%
60
40
20
0
0
30
60
90
120
150
10
30 minutes reaction time. Using these optimum conditions the FFA was reduced
from 8.6% to 0.8%, with 96% yield of treated ACPO and 90.7% conversion of FFA
to FAME.
The catalyst dosage is an essential factor with an important role in the reaction and
the total production cost. Fig. 4.5 shows the effect of the MSA dosage on reducing
acidity in the ACPO, conversion of FFAs to FAMEs and the corresponding yield of
the treated ACPO. The oils or fats should have an acid value of no more than 1 mg
KOH g1 which is equivalent to approximately 0.5 % FFA content (Ma & Hanna,
1999; Sharma et al., 2008; Demirbas, 2009). All materials or chemicals or fatty
acid sources for biodiesel production should be substantially anhydrous (Ma &
Hanna, 1999). Use of a small dosage of MSA has a large effect on reducing the
acidity of the ACPO. Acid dosages of 0.25 % and 0.5 % were insufficient to
reduce the acid value to the target limit for the transesterification reaction. A
dosage of 0.75 % resulted in an acid value reduction to the limit of the acceptable
value, while 1 % showed more catalytic activity. Higher MSA dosages did not
contribute to the reduction of oil acidity and might increase the cost of the pretreatment process due to extra and unnecessary catalyst use. Hence, a 1 % MSA
catalyst dosage was selected as the optimum operating value for the esterification
reaction. The yield of the treated ACPO did not change with varying MSA
dosages. However, the yield of the treated ACPO attained a maximum of 96 %.
Triacylglycerols (TAGs) were measured using a GC-FID after the pre-treatment
65
reaction with MSA. It was found that 26.5 % of TAGs contained in the ACPO
were converted to FAMEs. Accordingly, conversion to FAMEs reduced the
20
120
15
90
10
60
30
Yield /%
0
0
Dosage of MSA /%
Fig 4.5 Effect of MSA dosages on acid value reduction and yield of treated ACPO
at 10 : 1 molar ratio, 60 C reaction temperature, 60 min reaction time, and 400
rpm stirrer speed. () Acid value, (-) limit of acidity, () yield of treated
ACPO.
20
120
15
90
10
60
30
Yield /%
12
16
20
Molar ratio
Fig. 4.6 Effect of molar ratio on acid value reduction and yield of treated ACPO at
1 % dosage of MSA to ACPO, 60 C reaction temperature, 60 min reaction time,
and 400 rpm stirrer speed. () Acid value, (-) limit of acidity, () yield of
treated ACPO.
68
120
15
90
10
60
30
0
0
30
60
Yield /%
20
90
Temperature /C
Fig. 4.7 Effect of reaction temperature on acid value reduction and yield of treated
ACPO at 1 % dosage of MSA to ACPO, 8 : 1 molar ratio, 60 min reaction time,
and 400 rpm stirrer speed. () Acid value, (-) limit of acidity, () yield of
treated ACPO.
was selected as the optimum reaction time for pre-treatment of the ACPO using
MSA.
Many studies have reported one hour as the optimum reaction time for the
esterification reaction (Chongkhong et al., 2007; Di Serio et al., 2008; Hayyan et
al., 2010a, 2011a). This study reports half that period (30 min) of reaction in order
to obtain a high yield and acidity reduction in comparison with previous studies.
However, the reaction time is affected by the level of the FFAs content, which is
20
120
15
90
10
60
30
Yield /%
0
0
40
80
120
160
Fig. 4.8 Effect of reaction time on acid value reduction and yield of treated ACPO
at 1 % dosage of MSA to ACPO, 8 : 1 molar ratio, 60 C reaction temperature, and
400 rpm stirrer speed. () Acid value, (-) limit of acidity, () yield of
treated ACPO.
ACPO) of 8 : 1, the temperature of 60 C and the 30 min reaction time. Using these
optimum conditions, the acidity was reduced from 18 mg KOH g1 to slightly
below the acceptable limit with a yield of the treated ACPO of 9398 %.
71
72
Figure 4.10 Effect of molar ratio on FFA content reduction, conversion of FFA to
FAME and yield of treated LGCPO
73
Figure 4.11
11 Effect of reaction temperature on FFA content reduction, conversion
of FFA to FAME and yield of treated LGCPO
min there was no improvement in the reduction of the acidity along reaction time.
Hence, in order to optimize the reaction time, 30 minute
minutes was selected as the
shortest reaction time for the pre-treatment
pre treatment of LGCPO. The shortest reaction time
can be considered as the optimum value due to the additional cost entailed with
longer reaction time.
Figure 4.12
12 Effect of reaction time on FFA content
ent reduction, conversion of FFA
to FAME and yield of treated LGCPO
75
76
methyl ester using BZSA. The FAME conversion was less than 10% at 1 hour
reaction time. This result give conclusion that BZSA is suitable catalyst for
esterification while in trasesterification it shows low catalytic activity. Therefore,
BZSA in
the esterification
followed
by potassium hydroxide in
the
trasesterification will be perfect method to save the time to produce high quality
biodiesel.
10
120
100
FFA%
60
Limits of FFA%
40
Yield% of treated LGCPO
2
20
0
0
0.5
1.5
2
2.5
Dosage of BZSA wt%
3.5
Figure 4.13. Effect of BZSA dosage on the FFA reduction and yield of treated
LGCPO
77
Yield%
FFA%
80
6
reduction was from 9.3% to 2.4%. As mentioned earlier, the FFA target in this study is
1%, therefore, the ratio of 4:1 did not achieve this target. The FFA content using a
molar ratio of 6:1 was 1.93% which is still slightly higher than the recommended FFA
limit in this study. Figure 4.14 shows that there is no significant improvement in the
reaction by increasing the molar ratio from 8:1 to 20:1. The economy of the process is
highly affected by using higher reactants molar ratio. Hence, in order to save energy
the optimum ratio of methanol to LGCPO was selected to be 8:1 which reduced the
FFA content from 9.3% to 0.6% which is below the targeted FFA content. The FAME
conversion was 92.8% and the yield of treated LGCPO was 96%. Based on the study
of Hayyan et al., (Hayyan et al., 2011a) and the findings of this study, lower loading of
methanol can be used effectively to reduce the high acidity of oils such as SPO and
LGCPO.
FFA%
Limits of FFA%
10
120
100
60
4
Yield%
FFA%
80
6
40
2
20
10
12
Molar Ratio
14
16
18
20
22
Figure 4.14 Effect of molar ratio on the FFA reduction and the yield of treated LGCPO at
0.75 % dosage of BZSA to LGCPO, 60oC reaction temperature, 60 min reaction time, and
300 min-1 stirrer speed.
78
79
Limits of FFA%
10
120
100
80
60
4
40
20
0
0
10
20
30
40
50
60
o
Temperature C
70
80
Yield%
FFA%
FFA%
90
Figure 4.15 Effect of reaction temperature on the FFA reduction and the yield of treated
LGCPO at 0.75 % dosage of BZSA to LGCPO, 8:1 molar ratio, 60 min reaction time, and
300 min1 stirrer speed.
80
to reduce the FFA from 9.3% to less than 1%. Yield of treated LGCPO at these
conditions was 96% with a 90.93% FAME conversion.
10
120
100
60
Limits of FFA%
40
20
0
0
30
60
90
120
150
Fig. 4.16 Effect of reaction time on the FFA reduction and yield of treated LGCPO at 0.75
% dosage of BZSA to LGCPO, 8: 1 molar ratio, 60oC reaction temperature, and 300 min1
stirrer speed.
81
Yield%
FFA%
80
FFA%
4.2.4 Effect of PTSA in the Reduction of FFA in ACPO (Presented in 2nd International
Conferences on Process Engineering and Advanced Materials 2012)
4.2.4.1 Effect of PTSA Dosage
Catalyst dosage was varied in order to achieve low FFA content reduction, high
yield of treated oil and high conversion of FFA to FAME. In this study, the FFA
content was set to the recommended minimum FFA content level of 1%. Figure
4.17 shows the effect of different dosages of PTSA on the reduction of FFA
content in LGCPO and the corresponding yield of treated LGCPO. The dosage of
PTSA to LGCPO ranged from (0.25-3.5 wt/wt %). The results showed that PTSA
is a very active catalyst in the pre-treatment of LGCPO via esterification reaction.
The dosages values of 0.25 and 0.5 wt% PTSA to LGCPO attained a lower
reduction of the FFA in LGCPO. The high FFA content in LGCPO after reaction
exceeded the target limit because the PTSA loading was low and the catalytic
activity was insufficient to enhance the pre-treatment reaction. The targeted FFA
content for the transesterification reaction was below 1% and the results of this
study showed that the PTSA catalyst has the ability to achieve this limit at a
catalyst dosage of 0.75%. The FFA content was reduced in LGCPO significantly
from 9.5% to less than 1% using 0.75% up to 3.5%. Figure 1 illustrates that there
was no further reduction of FFA content using a dosage higher than 0.75%.
82
Fig. 4.17 Effect of PTSA dosages on acid value reduction and yield of treated LGCPO
83
Fig.4.18 Effect of molar ratio on FFA content reduction and yield of treated LGCPO
4.2.4.3 Effect of reaction temperature
In the current study, the reaction temperature was varied from 40C to 80C in
order to determine the optimum conditions for the ppre-treatment
treatment reaction. Figure
4.19 shows the effect of the reaction temperature on the reduction of the FFA
content and yield of treated LGCPO. It was found that an optimum reaction
temperature of 60oC is needed. At this temperature, the FFA content was de
decreased
from 9.5% to 0.30%, and the conversion of FFA to FAME was 96.7%. The yield
of treated LGCPO was 98% which is considered a high yield for biodiesel
production. With an increase in reaction temperature higher than 60oC, no
significant change in the yield
yield of treated LGCPO was observed. Higher reaction
temperature has many disadvantages such as high consumption of energy and the
loss of methanol due to the high degree of evaporation. Therefore it is not
recommended to use high reaction temperature in th
the pre--treatment of LGCPO.
84
Fig. 4.19 Effect of reaction temperature on FFA reduction and yield of treated LGCPO
4.2.4.4 Effect of reaction time
The reaction time was varied in a wide range (3
(3-150
150 min) as shown in Figure 4.20.
It was observed that the reduction of FFA content increased with an increase in
reaction time. During the first 10 minutes of reaction, the FFA content was
decreased from 9.5% to 2.5. After 15 minutes of reaction, the FFA content was
1.40%, which is slightly
slightly higher than the limits of FFA for the alkaline
transesterification reaction. On the other hand, less 1% FFA was achieved for 30
up to 120 minutes of reaction time. In order to optimize the cost of the
pretreatment reaction, 30 minutes of reaction time is very suitable for the
completion of the esterification reaction.
It was found that after 60 minutes of LGCPO esterification reaction, 3-6%
3
of the
triacylglycerols were converted to FAME. Conversion of FFA and some of
triacylglycols to FAME during este
esterification
rification results in decreasing the reaction time
of the transesterification reaction. The final FFA content after 30 minutes was
85
0.20%.
This
low
FFA
content
promotes
the
potential
of
successful
transesterification reaction.
Fig. 4.20 Effect of reaction time on FFA content reduction and yield of treated LGCPO
4.2.4.5Validation
Validation of optimum esterification conditions
After optimizing the esterification reaction conditions it was found that the
optimum conditions for the pre-treatment
pre
stage were: 0.75% (wt/wt) PTSA to
LGCPO,, 8:1 molar ratio, 60oC temperature, 30 minutes reaction time. Using these
optimum conditions the FFA was reduced from 9.5% to 1%.
4.4
87
FFA + Methanol
FAME + Water
Fig.4.22 Esterification reaction using P-DES
LGCPO) resulted in 1.91% FFA content and the treated LGCPO yield was 96.6%
and a FAME conversion was 79.4%. Its worth mentioning that Hayyan et al.
(2010a) used 0.75% of PTSA to reduce the high FFA content (22.33%) in SPO to
less than 2% while Di Serio et al. (2008) used 6.4X10-5 mol of PTSA to treat the
FFA content in soybean oil from 20.5% to 1.1%.
120
100
80
FFA%
FFA%
60
Limits of FFA%
Yield% of LGCPO
40
20
0
0
0.5
1.5
2
2.5
3
Dosage of P-DES wt%
3.5
Fig.4.23 Effect of P-DES dosage on the FFA reduction and yield of treated
LGCPO
10
methanol such as 1:1 or 1:5 resulted in a low reduction in FFA content. Based on
these results, reacting the FFA with insufficient amount of methanol, the reaction
tends to be slower, thus decreasing the FAME conversion significantly. A molar
ratio of 10:1 can reduce the FFA content significantly to less than 2%. Molar ratio
more than 10:1 did not enhance the FFA reduction. Therefore, in order to minimize
the consumption of methanol and to save the energy required to evaporate the
excess methanol, 10:1 molar ratio is selected as the optimum ratio for the pretreatment LGCPO using P-DES. At this molar ratio the FFA content was reduced
from 9.3% to 1.10% and the FAME conversion was 88.1%. While the yield of
treated LGCPO was in the range of 94-98% and there is no significant reduction
achieved at higher molar ratios. Hayyan et al (2010a) used PTSA to treat the high
FFA content in SPO and their study reported a similar optimum molar ratio. Man et
al.(2013), used 15:1 to treat the FFA content (3.49%) in CPO.
FFA%
Limits of FFA%
10
120
FFA%
80
6
60
4
40
2
20
10
12
14
Molar Ratio
90
16
18
20
22
100
Fig.4.24 Effect of molar ratio on the FFA reduction, conversion of FFA to FAME
and the yield of treated LGCPO
91
Limits of FFA%
10
120
100
80
60
4
40
20
0
0
10
20
30
40
50
60
o
Temperature C
70
80
90
FFA%
FFA%
reaction time more than 30 minutes did not contributed in improving the reaction.
The fact that short reaction time is needed to complete the reaction indicates the
high catalytic activity of P-DES due the presence of the sulfonic group SO3H from
hydrogen bond donor (PTSA). The current results are much better than those
reported
by
recent
imidazolium hydrogensulfate
application
of
the
[bmim][HSO4]
IL
and
1-butyl-3-methyltriethylammoium
120
100
FFA%
FFA%
80
Limits of FFA%
60
Yield% of treated
LGCPO
40
4
2
20
0
0
30
60
90
120
150
93
10
94
100
80
60
40
20
0
1
Recycle Runs
Fig 4.27. FFA to FAME conversion at different catalyst recycling runs
reaction. Untreated biodiesel and the crude glycerol are fed to the evaporator and
centrifuge in order to purify the products from excess methanol and to facilitate
fast separation. The crude biodiesel is finally fed to the washing vessel to purify
the product from contaminants, soap and traces of crude glycerol. The studied PDES will be then recycled for four times with the same experimental conditions as
indicated previously. The temperature is set at 60oC, and the molar ratio to 10:1.
96
Allyl triphenyl
phosphonium
bromide
PTSA
Methanol
Tank
P-DES
KOH
LGCPO
Tank
1
4
Excess
Methanol
2
Treated
LGCPO
5
Recycled
P-DES
7
PURE
CRUDE
GLYCEROL
Fig.4.28. Proposed schematic for the pre-treatment and biodiesel production form
of LGCPO. 1. Esterification reactor, 2. Evaporator, 3. Centrifuge,
4.Transesterification reactor, 5. Evaporator, 6. Centrifuge, 7.washing vessel.
97
needed to reduce the FFA content to the acceptable limit prior to the
transesterification reaction is 0.75%.
PTSA
ChCl Salt
ChCl-DES
ChCl-DES
Figure 4.29 Preparation of ChCl based DES
99
3.3.
.3. Effect of molar ratio
The alcohol is one of the ingredients that affects to the overall production cost of
biodiesel. In this study the molar ratio of methanol to ACPO was varied in the
range of 3:1 to 20:1. Figure 4.31 depicts the effect of molar ratio on conversion of
FFA to FAME and the corresponding yield of treated ACPO. No significant FAME
conversion change was observed for molar ratios larger than 10:1. The yield of
treated oil was almost constant for the differen
differentt ratios of methanol to ACPO. A
minimum of 10:1 molar ratio was required to covert the FFA content of ACPO to
FAME with high conversion (96.6%) suitable for transesterification reaction.
100
110
100
90
80
70
60
50
40
30
20
10
0
8
10
12
Molar Ratio
14
16
18
20
Figure 4.31: Effect of molar ratio on conversion of FFA to FAME and the
corresponding yield of treated ACPO
3.4. Effect of reaction temperature
Figure 4.32 shows the influence of temperature on the esterification reaction. The
results indicated that the increase in reaction temperature enhanced the reaction to
completion within 30-60 minutes. Figure 4.32 indicates that a reaction temperature
of 60oC was kinetically enough to reach a stable high conversion and further
increase in the reaction temperature did not show any significant effect in the
conversion of FFA to FAME and yield of treated ACPO. Both yield of treated oil
and conversion were high at 60oC compared to the lower reaction temperature of
40oC and 50oC. Hence, an optimum reaction temperature of 60oC was selected for
esterification of FFA content in ACPO in order to minimize use of energy and to
make the pre-treatment process economically feasible.
101
22
110
100
90
80
70
60
50
40
30
20
10
0
0
10
20
30
40
50
60
Temperature oC
70
80
90
catalyst with enough reaction time increases the conversion significantly. After 30
minutes of reaction, the FAME conversion to reached equilibrium. Therefore, it is
concluded that a reaction time of 30 minters was sufficient to complete the
esterification reaction. Many studies found 60 min as an optimum reaction time
for esterification of acidic oils such as waste cooking oil, SPO and ACPO.
110
100
90
80
70
60
50
40
30
20
10
0
0
30
60
90
Reaction Time min
120
150
Figure 4.33: Effect of reaction time on the conversion of FFA to FAME and
the corresponding yield of treated ACPO
3.6. Validation of Optimal Pre-treatment Conditions
From the previous sections, the optimum conditions using the ChCl-DES catalyst
were: 0.75% (wt/wt) dosage of acid to ACPO, 10:1 molar ratio, 60oC reaction
temperature at 30 minutes reaction time. The use of this catalyst was verified by
conducting the esterification reaction at these optimum operating. Using these
103
optimum conditions, the amount of FFA was reduced from 9% to less than 1%.
FFA conversion to FAME was 96% while the yield of treated ACPO was 97%.
Conversion
Yield
(%)
(%)
97
96
96
95
89
95
104
order to separate the two products (crude glycerol and biodiesel), a settling vessel
is used. After settling, crude biodiesel is washed with water to remove impurities
of soap and the traces of catalyst.
ChCl
PTSA
Methanol
ChCl-DES
Mixing
Mixing
Methanol and
ChCl-DES
ACP
Pre-heating
Esterification
Evaporation
Methanol
Washing
Biodiesel
Centrifugatio
Treated
ACPO
and KOH
Transesterificatio
Evaporation
Settling
Crude Glycerol
Figure 4.34 Proposed process flowchart to produce biodiesel from ACPO using
ChCl-DES
106
CHAPTER V
using ESA as a catalyst. The optimum conditions for esterification reaction using
homogenous catalyst such as ESA, MSA, CSA and BZSA and PTSA were 0.75%
wt/wt acid to ACPO with 10:1 molar ratio, 60oC reaction temperature at 30
minutes. After validating, the FFA content was reduced from 8-10 % to less than
1% with high yield of treated ACPO and conversion of FFA to FAME. Results of
this study showed that these types of homogenous acids have high catalytic
activity. The biodiesel produced met the standards specifications for biodiesel fuel
(EN 14214 and ASTM D6751). PTSA was used for further studies due to low cost
of this acid and the high catalytic activity.
5.3 Development of Homogenous Acids via Conversion these Acids to DES
This study was conducted in order to evaluate the feasibility of producing
biodiesel from ACPO using a DES as a catalyst. The study revealed that ACPO is a
suitable feedstock for biodiesel production using a pre-treatment stage with
ammonium or phosphonium based DES. The treated ACPO is a promising
industrial raw material for biodiesel production using a second stage
transesterification reaction. The produced biodiesel was characterized and
compared to other standard biodiesels. The optimum esterification reaction
conditions were 0.75% wt/wt (catalyst to ACPO) for ammonium based DES while
the optimum dosage of catalyst for phosphnuim was 1%. The molar ratio of both
DES is 10:1 molar ratio at 30 minutes reaction time and 60oC. Using these
conditions the conversion of FAME was 96% and the yield of treated ACPO was
97%. The catalytic activity of ammonium based DES is higher than phosphnuim
based DES. The yield of biodiesel was 92% with 0.07% FFA content (0.14% acid
value) while ester content was 96%. The biodiesel produced from ACPO met the
108
This is the first work in the world for DES application in biodiesel
This study proposed new class of deep eutectic solvent as alternative to ILs
The current study converted PTSA to DES and we reported for first time
recycling of the catalyst. This technique can be applied for wide a range of acids.
5-
DES can be design according to the application and then can be applied for
Because DES can be synthesized in such a way that it is solid form at room
temperature, then the storage and transport will be much easier than powder or
liquid forms.
7-
DES can be directly applied for industrial applications due to their above-
mentioned merits.
8-
There are limited studies in the application of industrial low grade crude
palm oil, and in our paper we highlighted the importance of using this Bioindustrial resource for biodiesel production.
109
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APPENDICES
APPENDIX A
List of Achievements
Patents
1)
Invention Title: A Method for Producing Biodiesel from crude plantderived oil using deep eutectic solvent
Adeeb Hayyan, Farouq S. Mjalli, Mohd Ali Hashim, Maan Hayyan, Inas M.
AlNashef, Saeed M. Al-Zahrani, Mohammed A. Al-Saadi. (2011). Ethanesulfonic
acid-based esterification of industrial acidic crude palm oil for biodiesel
production. Bioresource Technology 102 (2011) 95649570. (ISI-Cited
Publication/ Elsevier).
2)
(Accepted)
Adeeb Hayyan, Mohd Ali Hashim, Farouq S. Mjalli, Maan Hayyan, Inas M.
AlNashef. A Novel Phosphonium-Based Deep Eutectic Catalyst for Biodiesel
Production from Low grade Crude Palm Oil. (ISI-Cited Publication/ Elsevier).
4)
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