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TABLE OF CONTENTS

TITLE PAGE
1.0 INTRODUCTION ......................................................................................................... 1

2.0 PROBLEM STATEMENT ........................................................................................... 2

3.0 RESEARCH OBJECTIVE ........................................................................................... 3

4.0 SCOPE OF WORK ....................................................................................................... 3

5.0 LITERATURE REVIEW ............................................................................................. 4

5.1 Epoxide ................................................................................................................... 4

5.2 Epoxide from Vegetable Oil (VO) ....................................................................... 5

5.3 Epoxidation of Vegetable Oil ............................................................................... 5

5.3.1 Yield of Epoxide .............................................................................................. 6

5.3.2 Oxirane Ring Stability ................................................................................... 6

5.4 Parameter Optimization using Response Surface Methodology (RSM) .......... 7

5.4.1 Response Surface Methodology (RSM) ........................................................ 7

5.4.2 Effect of Temperature .................................................................................... 7

5.4.3 Effect of Catalyst Loading ............................................................................. 8

6.0 RESEARCH METHODOLOGY ................................................................................. 8

6.1 Flowchart ............................................................................................................... 8

6.2 Design of Experiment (DoE) ................................................................................ 9

6.3 Experimental Work .............................................................................................. 9

6.3.1 Experimental Set-up ..................................................................................... 10

6.3.2 Experimental Procedure .............................................................................. 10

6.4 Analytical Techniques ......................................................................................... 10

6.5 Response Surface Methodology (RSM) Optimization ..................................... 11

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7.0 EXPECTED FINDINGS ............................................................................................. 11

8.0 GANTT CHART .......................................................................................................... 13

9.0 REFERENCES............................................................................................................. 14

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1.0 INTRODUCTION

Day-to-day, the utilization and demand for epoxide has increased significantly.
Epoxy resin or epoxide has been used in a wide range of fields with its excellent bonding
property, mechanical strength and chemical resistance [1]. Nevertheless, globalisation and
advanced research on technology has increased the awareness on “green epoxide” which is
derived from plant oil instead of petroleum-based epoxide. Epoxide or oxirane from plant
oil possess several advantages over the petroleum-based epoxides. Plant oil such as palm oil,
are abundant in feedstock, stable in price, easily available and having similar properties
compared to the petroleum-based counterparts [2]. This can be proven through the statistic
provided by Malaysian Palm Oil Board (MPOB), which states that the production of crude
palm oil (CPO) for year of 2017 is at 1.8 million metric tonne per annum [3]. CPO has been
chosen as the raw material for epoxidation reaction due to the presence of double bonds in
unsaturated fatty acids of the oil. CPO contains 50% of saturated fatty acids and 50% of
unsaturated fatty acids. Saturated fatty acids of CPO consist of 45.48% of palmitic acid,
3.49% of stearic acid and 0.93% of myristic acid. Meanwhile, unsaturated fatty acid consists
of 40.17% of oleic acid and 9.92% of linoleic acid [4].

Epoxide from vegetable oils has been widely used in application to produce bio-
lubricant, polymer, stabilizers in PVC, intermediate, adhesive, paints and also coatings [5-
9]. The epoxidation of palm oil is carried out by reacting the double bonds in the unsaturated
fatty acids of the oil with percarboxylic acid such as performic acid or peracetic acid [5]. For
safety reason, the epoxidations reaction is carried out using peracids formed in-situ, in which
the carboxylic acid would be reacted with 30 wt% hydrogen peroxide in the presence of a
mineral acid such as sulphuric acid as catalyst [6]. The reaction mechanism for epoxidation
can be seen from the equations below:

Peracid formation
H2O2 + HCOOH H+ HCO2OH+ H2O (1.1)
Epoxidation
R-CH=CH-R’ + HCO2OH  R-CH-CH-R + HCOOH (1.2)

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The reaction initiates with peracid formation (Eq. 1.1) and followed by epoxidation
reaction (Eq. 1.2) [7]. At the same time, reversible reaction of the peracids formation from
hydrogen peroxide and carboxylic acid will occur simultaneously with the epoxidation of
unsaturated compounds. The carboxylic acid formed in reaction reacts again with the
hydrogen peroxide to form peracid [8]. Epoxidation causes formation of cyclic ether at the
sites of ethylenic unsaturation (C=C) which is located along the fatty acid chain. The
breaking of the bond would make a new bond angle at about 60° which making it highly
strained and reactive [7]. This occurrence would make it difficult for the process of
maintaining the epoxide structure and thus, allowing other side reactions to occur which
would decrease the yield of epoxide and epoxide’s capability to be used as raw materials.

Hence, with so many extensive studies reported in the literature on epoxidation of


palm oil, the task for process optimization of CPO epoxidation can be embarked by using
statistical optimization method, such as Response Surface Methodology (RSM). It is an
efficient statistical tool to investigate the parameters that affects the desired response by
predicting the impact of various process parameters on the responses studied [9]. In this
study, the effects of temperature and catalyst loading on the yield of epoxide and oxirane
ring stability would be investigated.

2.0 PROBLEM STATEMENT

The utilization of epoxides in multi aspects of industrial applications proves that


demand of epoxides is increasing from time to time. Epoxides derived from palm oil which
is superior than petroleum-based epoxides in term of its cost and biodegradability shows the
significance in providing more sustainable sources for the future.

However, the exceedingly reactive oxirane ring opening of epoxidized palm oil has
become an obstacle in obtaining high yield of epoxide. The usage of strong mineral inorganic
acid such as sulphuric acid (H2SO4) as catalyst in epoxidation process, would contributes to
many side reactions which includes oxirane ring opening to diols, hydroxyl esters, estelloids
and other dimer formation even though the H+ ion in H2SO4 aids in increasing the rate of
reaction [10]. At low pH value, the oxirane oxygen would partially protonated and readily

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attacked by a nucleophilic at the less sterically hindered site [11]. Epoxides that are highly
reactive due to the inherent ring strain and would readily react with nucleophiles causing
ring opening and thus degradation of the oxirane. Higher temperature is also being associated
with more chances of the oxirane degradation. As temperature increased, the kinetic energy
increased and more collisions between molecules takes place which causing higher degree
of oxirane degradation and thus formation of side products [12]. The occurrence of side
reaction in preparation of epoxidation of palm oil is undesirable as it will diminish the
attractiveness as starting material and causing expensive purification of the epoxides [13].

Thus, a method to improve the yield and epoxy ring stability is crucial. In this study,
optimization of reaction parameters in order to improve yield of epoxide and ring stability
is conducted by using Response Surface Methodology (RSM) statistical method.

3.0 RESEARCH OBJECTIVE

1. To optimize the reaction parameters such as catalyst loading and reaction


temperature of crude palm oil epoxidation using Response Surface Methodology
(RSM) in order to obtain higher epoxide yield and oxirane ring stability.

4.0 SCOPE OF WORK

In order to achieve the objective, a deep study on the process parameters for
epoxidation of palm oil is carried out. This was done by designing the experiments through
the use of Minitab software. Under design of experiments, the parameters and levels of
experiments was determined to obtain the most suitable experimental design. From the
design provided, the in situ epoxidation will be carried out using the prepared experimental
set-up. The epoxide sample obtained from the reaction are analysed using wet analytical
method to measure the percentage of the Oxirane Oxygen Content (OOC) by using standard
method AOCS CD 5-92. The analysis would provide the relative conversion to oxirane (%
RCO) as a function of reaction time. Functional group of epoxides is confirmed by FTIR.
Then, optimization of the process parameters would be carried out by using Response
Surface Methodology (RSM) method. RSM would give the best process parameters needed
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to obtain the highest yield of epoxy and ring stability. Confirmation experiment would be
conducted to verify the accuracy of the RSM optimization by running the experiment at the
parameters provided.

5.0 LITERATURE REVIEW

5.1 Epoxide

Epoxide or also known as oxirane are ethers having the oxygen atom in a three-
membered ring. Epoxides have the same leaving group as ethers, OR-. However, epoxide do
contain C-O-C bond angle at 60° through addition of a nucleophile to a ring carbon which
making it highly strained and reactive. For this reason, epoxides become an important class
of industrial chemicals that have been used as chemical intermediates.

Figure 5.1: Epoxy ring structure.

Epoxide are widely used in polymers, paints, adhesive, metal coatings, electronics
and electrical components, insulators, paint brush manufacturing, composites, constructions
and even in medical to bind the root of teeth [14–23]. Petrochemical based is widely used as
the main sources for epoxide with its desirable properties such as high stiffness and strength
[24]. However, due to the increase in the price and depletion of fossil reserves, there has
been a growing interest in the utilization of renewable resources such as vegetable oil as
substitution for raw materials in producing epoxide [25]. Vegetable oil are abundant in
feedstock, having a low and stable price, biodegradable and possess the same properties as
petroleum-based epoxides.

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5.2 Epoxide from Vegetable Oil (VO)

The epoxidation of vegetable oil has been studied due to the rising demand of green-
based epoxide and the commercial importance of these compounds as additives of polymers,
lubricants and detergents [26,27]. Furthermore, the world total production of vegetable oils
that was more than 150 million tons in 2012 proves that vegetable oil is abundant in
feedstock and able to replace petrochemical based material in production of epoxide [28].
The long fatty acid chains of vegetable oils also impart desirable flexibility and toughness
to epoxy resin [29].

5.3 Epoxidation of Vegetable Oil

Epoxidation is a method of functionalizing vegetable oils and derivatives which


partially oxidizing the fat acids by introducing an atom of oxygen to the unsaturation in the
chain of the molecule. The epoxidation using vegetable oil with its high content of
unsaturated fatty acids, functionalize its double bonds by transforming them into more
reactive oxirane rings [30]. The widely used method for epoxidation of vegetable oils are by
epoxidation with percarboxylic acid generated in situ as it is easy process and can be
catalysed by acids or enzymes [25]. The mechanism to yield epoxide starts with formation
of percarboxylic acid from reaction of hydrogen peroxide and carboxylic acids such as
formic acid. The percarboxylic acid formed would be reacted with unsaturated double bond
of fatty acids to form epoxide. As an example, Figure 5.2 shows the reaction between formic
acid and hydrogen peroxide to form performic acid, meanwhile, Figure 5.3 shows the
reaction between performic acid and unsaturated fatty acid to form epoxide.

Figure 5.2: Reaction between hydrogen peroxide and carboxylic acid to form
percarboxylic acid.

Figure 5.3: Reaction between percarboxylic acid and unsaturated double bond to form
epoxide.

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5.3.1 Yield of Epoxide

The typical conversions of double bonds to epoxy groups are found to be at about
90% [31]. Table 5.1 shows some findings for yield of epoxidation by using different
vegetable oils at different operating conditions.

Table 5.1: Findings on yield of epoxidation based on previous studies


Epoxidation Findings Authors
Epoxidation of Palm Kernel - A maximum of 99% relative conversion of [32] (2011)
Oil Fatty Acids ethylenic oxirane was obtained within 120
minutes of reaction time.
Epoxidation of Palm Oil - Yield obtained is 85% at OOC value 3.42%. [33] (2017)
Epoxidation of Palm Olein - The OOC value obtained was 3.57% [34] (2014)
compared to theoretical OOC value 3.74%
- The optimum oxirane conversion was 95.5%
with 90% yield.
Epoxidation of RBD Palm Oil - The epoxidized RBD Palm oil yield was [35] (2018)
86% with oxirane oxygen content of 3.46%.
Epoxidation of Palm Kernel - Higher concentrations of formic acid during [5] (2018)
Oil-Based Crude Oleic Acid in situ epoxidation decrease the net yield of
epoxides.
Epoxidation of Rapeseed Oil - The largest yield of epoxidized oil is at 66 [8] (2010)
mol% at temperature 51.5°C.
Epoxidation of Jatropha Oil - The greatest conversion rate is at 87.4%. [10] (2011)

5.3.2 Oxirane Ring Stability

Ring opening or named as degradation of oxiranes, occurs through the cleavage of


one of the C=O=C bonds. Table 5.2 lists findings on the factors related to the oxirane ring
stability for epoxidation of vegetable oil.

Table 5.2: Findings on epoxy ring stability of epoxidation based on previous studies.
Epoxidation Findings Authors
Epoxidation of Soybean Oil - Large content of acid causes the cleavage of [36] (2016)
the oxirane producing large number of by-
products.
Epoxidation of Sunflower Oil - The higher the concentration of hydrogen [37] (2006)
peroxide, the faster the rate of oxirane
degradation.
Epoxidation of Palm Olein - The stability of the oxirane ring was very [38] (2010)
poor for the high concentration of hydrogen
peroxide.

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5.4 Parameter Optimization using Response Surface Methodology (RSM)

5.4.1 Response Surface Methodology (RSM)

Response Surface Methodology (RSM) basically combines statistical and


experimental methods with data-fitting techniques. The first step is the Design of
Experiments at which the number of run for experimental design is determined. Then, based
on the responses acquired in the experiments, Regression Analysis is utilized to identify the
relationships between the responses and the variables to establish a mathematical model that
satisfies the relationship between a group of test factors and objective functions. This model
is then used to explore the optimal solution in the experimental data [39] .The optimum
condition is represented through response surface which is then analysed through the fitting
surface. In this study, the Response Surface Methodology utilizes Second-Order model
where Central Composite Design (CCD) experiments are performed. CCD provides
favourable predictions and the fitting model shows consistent and stable variance for the
prediction of input point [9].

5.4.2 Effect of Temperature

Epoxidation usually are carried out at lower temperature since the reaction has
possibility for side reactions due to the oxirane cleavage [40]. Table 5.3 shows the optimum
temperature for epoxidation of different vegetable oils from previous research.

Table 5.3: Optimum temperature of epoxidation based on previous studies


Epoxidation Findings Authors
Epoxidation of Palm Olein - The highest percentage of RCO% [40] (2017)
obtained was 2.22% at 60°C.
Epoxidation of RBD Palm Oil - The optimum condition for [35] (2018)
epoxidation was at reaction
temperature 40°C.
Epoxidation of Soybean Oil - Epoxidation reached maximum [25] (2008)
values at 75°C and decrease with
further increase in reaction time.
Epoxidation of Palm Kernel Oil- - The highest complete conversion [41] (2014)
Based Crude Oleic Acid oxirane (88%) happens at moderate
temperature 55°C.
Epoxidation of Rubber Seed Oil - The optimum levels of epoxidation [42] (2002)
could be attained at moderate
temperatures (50°C-60°C).

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5.4.3 Effect of Catalyst Loading

The uses of acidic catalyst play an important role in increasing the yield of
epoxidation. Table 5.4 shows some findings that relates catalyst loading with yield of
epoxidation and oxirane stability.

Table 5.4: Findings on catalyst loading for epoxidation based on previous studies
Epoxidation Findings Authors
Epoxidation of Soybean Oil - Maximum yield of epoxy content is [36] (2016)
obtainable in shorter time with
greater loading of resin and that
this maximum yield increases with
loading.
- However, if the loading is larger
than 15 wt%, it is possible to
promote cleavage of oxirane.
Epoxidation of Palm Kernel Oil- - Extra hydrogen ions from external [41] (2014)
Based Crude Oleic Acid acid catalyst contribute to the
increase in oxirane formation.

6.0 RESEARCH METHODOLOGY

6.1 Flowchart

The experimental work flowchart for this research is shown in Figure 6.1:

Figure 6.1: Experimental flowchart

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6.2 Design of Experiment (DoE)

One of the important aspect in Response Surface Methodology (RSM) is the design
of experiments (DoE). In order to evaluate the pure error in the experiment, a total of 13
experiments were amplified. The design of experiments carried out are shown as the table
below:

Table 6.1: The order and conditions for three level Central Composite Design (CCD).

Run Order Catalyst Loading Temperature (°C)


(g)
1 1.0 45
2 0.5 65
3 0.5 55
4 1.0 65
5 0.5 55
6 0.5 45
7 0.0 45
8 0.0 65
9 0.5 55
10 0.5 55
11 0.0 55
12 0.5 55
13 1.0 55

6.3 Experimental Work

The reaction parameters for epoxidation of CPO can be seen as Table 6.2.

Table 6.2: Reaction parameters for epoxidation of CPO.


Reaction parameters Value Units
Agitation speed 600 rpm
Catalyst loading 0-1 gram
Temperature 45-65 °C
Formic acid to unsaturated double bond molar ratio 2 :1 -
Hydrogen peroxide to unsaturated double bond molar 4:1 -
ratio

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6.3.1 Experimental Set-up

4
3 6
1
2

Figure 6.2: Schematic diagram for epoxidation of CPO: (1) peristaltic pump; (2) hot plate;
(3) stirrer; (4) beaker; (5) thermometer; (6) water bath

6.3.2 Experimental Procedure

The epoxidation of palm oil with performic acid generated in situ was carried out in
a 500 ml beaker equipped with motored stirrer with low shear impeller, thermometer, and
water bath [32]. The required amount of CPO, sulphuric acid and formic acid is added in
beaker. The mixture of the CPO and formic acid were heated to the reaction temperature by
controlling the temperature of hot plate [43] and continuously stirred at 600 rpm. Then,
aqueous hydrogen peroxide was added dropwise by peristaltic pump [44]. Samples are taken
every 5 minutes interval for Oxirane Oxygen Content (OOC) analysis. Once the OOC
reached maximum value, the heating is stopped. The epoxidation reaction was repeated with
different parameters of temperature and catalyst loading. The sample are analysed by using
FTIR to detect the presence of epoxide’s functional group.

6.4 Analytical Techniques

The sample was retrieved every 5 minutes to determine the experimental oxirane
oxygen content (OOC). The data from OOC analysis would be compared with OOC
theoretical to obtain the percentage of relative conversion oxirane (RCO%). Graph of RCO%
versus reaction time would be plotted. Then, the sample was tested for its functionality group
by using FTIR spectrum.

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6.5 Response Surface Methodology (RSM) Optimization

RSM was applied to optimize the amount of catalyst loading and temperature of the
reaction. Analysis of Variance (ANOVA) is used as multivariate techniques to determine the
optimum reaction conditions of epoxidation [9]. The significance of model was decided
based on the P-value. The P-value that is less than 0.05 indicates that the model is significant
[45]. Furthermore, the precision of model can be evaluated by the regression coefficient (R2).
Regression coefficient denotes the accuracy and good ability of the polynomial model. The
R2 must be in the range of 0 to 1. The closer the value to one indicates a better statistical
model. [46]. Meanwhile, the adjusted coefficient of determination (adj R2) value indicates
the goodness of the model [35]. Lastly, the model was assessed through lack-of-fit test. It is
used to compare the variation due to the changes in combination of variable levels with the
variation due to the random errors inherent to the measurement of the generated responses
[47]. The optimum conditions chosen were tested in order to confirm the model prediction.

7.0 EXPECTED FINDINGS


Figure 7.1 shows an example of graph for percentage relative conversion of oxirane
(RCO%) versus reaction time from previous study [32]. From the graph, it can be seen that
the oxirane formation is increasing until it reaches the highest peak. Then, the oxirane ring
would losses its stability and starts to degrade as the reaction time proceeds.

Figure 7.1: Graph of % RCO versus reaction time [32].

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The temperature and catalyst loading that gives the highest yield and longer oxirane
stability will be analyzed by using Response Surface Methodology (RSM) and optimization
would be carried out. The optimization would give response surface as Figure 7.2.

Figure 7.2: The effect of catalyst loading and temperature on OOC.

From Figure 7.2, the optimum temperature and catalyst loading will be obtained. It
is expected that the optimum conversion and ring stability are achieved at temperature
between 50°C to 80°C. This is based on the study made by Campanella [26] that states at 70
°C, the conversion is at 71.4%. This can be supported with the study made by Petrovic et. al
[31] that temperature lower than 80°C is preferable to prevent undesirable extent of side
reactions. Other than that, it was also found that the extent of epoxidation reached maximum
values for epoxidation at 75°C and then decreased with further increased in reaction time
[48]. Meanwhile, for effect of catalyst loading on epoxidation, it was expected that the higher
amount of catalyst would provide higher yield of epoxy. This can be supported from
research made by Jalil et al. [41] that states extra hydrogen ions from catalyst would give
higher oxirane formation. However, according to Picollo [36], the amount of catalyst
loading that higher than 15 wt% is possible to promote cleavage of oxirane ring. Since, the
range of the catalyst loading used in this study is in between 0 gram to 1 gram, the oxirane
ring structure are believed could be retained.

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8.0 GANTT CHART
Table 8.1: Gantt Chart for Final Year Project 1 (Sept-Jan 2018)
ACTIVITIES WK1 WK2 WK3 WK4 WK5 WK6 WK7 WK8 WK9 WK WK WK WK WK
10 11 12 13 14
Selection of title
FYP briefing
Research proposal (1.0-5.0)
Research proposal (6.0-9.0)
1st draft of proposal
2nd draft of poposal
Correction of proposal
Proposal report submission
Presentation of proposal
Submission final report (C1-C3)
FYP workshop

Table 8.2: Gantt Chart for Final Year Project 2 (March-June 2019)
ACTIVITIES WK1 WK2 WK3 WK4 WK5 WK6 WK7 WK8 WK9 WK WK WK WK WK
10 11 12 13 14
Correction for final report (C1-C3)
HIRARC
FYP briefing
Experimental works
Final report (C4-C5)
Correction final report (C4-C5)
Submission final report (C1-C5)
Manuscript
Poster presentation
Hardbound+thesis+manuscript+CDs

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