i

SYNTHESIS OF TRIACETIN FROM GLYCEROL

HENG WEPOH

A project report submitted in partial fulfilment of the requirements for the award of
Bachelor of Engineering (Hons.) Petrochemical Engineering
Faculty of Engineering and Green Technology

Universiti Tunku Abdul Rahman

September 2015
ii

DECLARATION

I hereby declare that this project report is based on my original work except for citations and
quotations which have been duly acknowledged. I also declare that it has not been previously
and concurrently submitted for any other degree or award at UTAR or other institutions.

Signature
:

Name
:

HENG WEPOH

ID No.
:

10AGB04286

Date
:

th
10 SEPTEMBER 2015
iii

APPROVAL FOR SUBMISSION

I certify that this project report entitled SYNTHESIS OF TRIACETIN FROM

GLYCEROL was prepared by HENG WEPOH has met the required standard for
submission in partial fulfillment of the requirements for the award of Bachelor of Engineering
(Hons.) Petrochemical at Universiti Tunku Abdul Rahman.

Approved by,

Signature
:

Supervisor
: Dr. Tan Kok Tat
Date
:

th
10 SEPTEMBER 2015
iv

The copyright of this report belongs to the author under the terms of the copyright Act 1987
as qualified by Intellectual Property Policy of Universiti Tunku Abdul Rahman. Due
acknowledgement shall always be made of the use of any material contained in, or derived
from, this report.

2015, Heng WePoh. All right reserved.

v

ACKNOWLEDGEMENTS

I would like to thank everyone who had contributed to the successful completion of this
project. I would like to express my gratitude to my research supervisor, Dr. Tan Kok Tat for
his invaluable advice, guidance and her enormous patience throughout the development of the
research.

In addition, I would also like to express my gratitude to my loving parent and friends who had
helped and given me encouragement. Besides, I would also like to express my warm thanks
and appreciation for the crucial role performed by the staff of Petrochemical Laboratory, who
permitted all the required equipment and knowledgeable advices to complete the research
study. Last but not least, I would like to thank my moderator, Ms Leong Siew Yoong for her
considerable help in this research.

Lastly, I would like to thank Universiti Tunku Abdul Rahman (UTAR) for providing me a
good environment and also platform to learn and done my research.
vi

SYNTHESIS OF TRIACETIN FROM GLYCEROL

ABSTRACT

Glycerol is the by-product of biodiesel with about 10 wt% of its production. The excessive
amount of glycerol is a very promising feedstock for converting into more valuable product.
One of the prospective glycerols derivatives is triacetin which produce by glycerol
acetylation. Synthesis of triacetin from glycerol with acetic acid using homogeneous acid
catalyst has been carried out in a batch reaction and was analyzed by gas chromatography.
The parameters that were manipulated are glycerol to acetic molar ratio of 1:3, 1:6, and 1:9
mol/mol and the reaction times are 30, 60 and 120 minutes. Besides, the catalyst amount used
were glycerol to sulphuric acid molar ratio of 1:0.00, 1:0.02 and 1:0.04 mol/mol and the
o
temperatures being manipulated were between 90 to 120 C. After manipulating among the
parameters, a set of parameter that produce highest yield of triacetin will be obtained and
studied. In the study, the triacetin production efficiency was further improved by determining
the optimum operating condition for the process. The optimum conditions for triacetin
production were molar ratio of glycerol to sulphuric acid 1:0.02 mol/mol, 1:9 mol/mol molar
o
ratio of glycerol to acetic acid, 60 minutes of reaction time and 105 C of reaction
temperature. The highest yield for the triacetin synthesis through the research is 31.89% with
the help of full factorial design.
vii

TABLE OF CONTENTS

DECLARATION

ii
 APPROVAL FOR i
ACKNOWLEG

ABSTRACT

vi
TABLE
 LIST

viii
CHAPTER

1
INTRODUCTION
1

1.1
Background
1

1.2
Glycerol
2

1.3
Triacetin
3

1.4
Problem Statements
4

1.5
Aims and Objectives
5
2
LITERATURE REVIEW
6

2.1
Acetylation
6

2.2
Trans-esterification
7

2.3
Interesterification
8

2.4
Method
10
2.4.1
Batch reaction
10

2.4.2
Continous acetylation reaction
11

2.5
Type of catalyst
11

2.5.1
Homogenous catalyst
12

2.5.2
Heterogenous catalyst
13
3
METHODOLOGYX
15X

3.1
Overview of Experiment
15

3.2
Material and Chemicals
15

3.3
Equipment
16

3.4
Reactant and Catalyst Preparation
16

3.5
Acetylation
16

3.6
Design of Experiment (DOE)
18
3.7
Product Analysis
20

3.7.1 Triacetin Yield

20

ix

3.7.2
Preparation of Diluted Triacetin Sample
21

3.7.3
Determination of Yield of Triacetin
21

3.7.4
Fourier Transform Infrared Spectroscopy (FTIR)
21
3.8
Research Flow Diagram
22

4
RESULT AND DISCUSSION

4.1
Preliminary Study
23

4.2
Glycerol Acetylation Reaction
25

4.2.1
Screening Study via Statistical Analysis By using

Design of Experiment (DOE)

25
4.2.2
Statistical Analysis
25

4.2.3
Variables Interaction
30

4.2.4
Optimization Study
40

4.3
Product Analysis
41
5
CONCLUSION AND RECOMMENDATIONS
42

5.1
Conclusion
42

5.2
Recommendation
42

REFERENCEX
42

APPENDIXX
48
x

LIST OF FIGURE

FIGURE
TITLE
PAGE
2.1
The steps of acetylation of glycerol reaction

mechanism
7
2.2
Trans-esterification of triglycerides and methyl

acetate
8
2.3
Interesterification reaction of triglycerides
with

methyl acetate
9
2.4
Comparison of main advantages and disadvantages

of homogenous and heterogeneous catalyst

12
3.1
Reflux condensation Machine
17
3.2
Recirculating Water Respirator
17
3.3
Recirculating Water Respirator
18
3.4
Research Flow Diagram of this Study
22
4.1
Predicted Yields against Experimental Yields for

Acetylation Rection
28
4.2
Effect of reaction temperature (A) and glycerol to
sulphuric acid catalyst mole ratio (B) on the

triacetin content in (a) two-dimension and (b)

three-dimension interaction plots for acetylation

reaction
31
x

4.3
Effect of reaction temperature (A) and reaction

time (C) on the triacetin content in (a) two-

dimension and (b) three-dimension interaction

plots for acetylation reaction

33
4.4
Effect of reaction temperature (A) and molar ratio

of glycerol to acetic acid (D) on the triacetin

content in (a) two-dimension and (b) three-

dimension interaction plots for acetylation reaction

34
4.5
Effect of molar ratio of glycerol to sulphuric acid

catalyst (B) and reaction time (C) on the triacetin

content in (a) two-dimension and (b) three-

dimension interaction plots for acetylation reaction

36
4.6
Effect of molar ratio of glycerol to acetic acid (D)

and reaction time (C) on the triacetin content in (a)

two-dimension and (b) three-dimension interaction

plots for acetylation reaction

37
4.7
Effect of molar ratio of glycerol to acetic acid (D)
and molar ratio of glycerol to sulphuric acid (B) on

the triacetin content in (a) two-dimension and (b)

three-dimension interaction plots for acetylation

reaction
39
4.8
FTIR Analysis of Triacetin
41
B.1
Chromatograph Analysis of Mono-, di- and Tri-

acetin
49
B.2
Chromatograph Analysis of Glycerol
49
B.3
Chromatograph Analysis of Acetic Acid
50
xi

LIST OF TABLE

TABLE
TITLE
PAGE
3.1
List of Chemicals used in Reasearch Experiment
15
3.2
List of equipment used in this Research

Experiement
16
3.3
Range and levels of independent variables
19
3.4
Gas Chromatography Specification
20
4.1
Experimental Condition and Triacetin Yield
24
4.2
Result of Sequential Model Sum of Square
25
4.3
Analysis of Variance (ANOVA) of the Variable
26
4.4
ANOVA Study for R-Square Value
27
4.5
Summary of Optimum Conditions for Glycerol

Acetylation and Predicted Yield

40
4.6
Comparison between Predicted and Experimental

Triacetin Content of Acetylation Reaction

40
xii

LIST OF SYMBOLS / ABBREVIATIONS

Ai acid methyl esters

Ais Fourier transforms infrared

spectroscopy
Ci
Gas chromatography
FAME
peak area, i = component
FTIR
peak area of internal standard
GC (methyl heptadecanoate)
Fatty
content of components, %
xii

LIST OF APPENDICES

APPENDIX
TITTLE
PAGES
A
Gantt Chart
48
B
Triacetin GC Analysis
49
C
Triacetin Yield Sample Calculation
51
1

CHAPTER 1

INTRODUCTION

1.1 Background

In recent years, biodiesel has increased greatly as a renewable transportation fuel. There is
noticeable concern in growing biodiesel as a substitute fuel because it is environmental
friendly compare to petrol-diesel fuel that is extracted from the fossil fuels. It is also a
biodegradable fuel which has a higher octane number and superior ignition properties compare
to petroleum-diesel fuel. Biodiesel is also known as fatty acid methyl esters (FAME). FAMEs
are normally produced from renewable sources such as animal fats or vegetable. Biodiesel
production involves transesterification of triglycerides with ethanol or methanol in the
presence of alkali-based catalyst (Corma et al., 2007). The reaction occurs with the production
of three methyl esters of fatty acid molecules (biodiesel) and glycerol as by product.

Glycerol is a by-product of biodiesel production as mentioned earlier. Glycerol commonly

formed with 10wt% mass balance from the reaction (C.H. Zhou, 2008). The global glycerol
production in the biodiesel market is estimated to reach 36.9 million metric tons in 2020 and
this means that there will be around 3.7 million metrics tons of crude glycerol produced as a
by-product of biodiesel (B. Katryniok, S. Paul, F. Dumeignil, ACS Catal, 2013). The fast
increase in the biodiesel production has resulted in a large surplus of crude glycerol. However,
the use of glycerol is restricted because of the contaminant of poisonous methanol and fatty
acid (soaps) (Yuan et al., 2010). Hence, researchers have paid more consideration and
attention to
2

the utilization of glycerol from the biodiesel production in order to overcome the production
cost and encourage the biodiesel production in a wide range. In other words, there is an
advantage of the glycerol co-product as it is a promising option for lowering the production
cost. Besides, researchers have been putting in effort to seek out different ways for disposal
and utilization of this crude glycerol including compositing, combustion anaerobic digestion
and thermochemical/biological conversion to value added products.

One of the chemical transformations of glycerol can be achieved by acetylation (Ferreira et

al., 2009). Acetylation is an acid catalyzed reaction. The glycerol produced from the biodiesel
process can be greatly utilized in acetylation processes. The products produce via acetylation
of glycerol are mono-acetyl glycerides, di-acetyl glycerides and tri-acetyl glycerides. The tri-
acetylated glycerides derivative is also known as triacetin which can be formed from the
glycerol acetylation reaction with solvent named acetic acid. Triacetin has applications such
as cosmetics, pharmaceutical and fuel additive. Besides, biodiesel also uses triacetin as an
additive in lowering the emission of nitrogen oxide to an acceptable amount. The fuel mixed
with triacetin can reduce the engine exhaust smoke because it lowers down the carbon
molecules in the fuel.

1.2 Glycerol

Glycerol is an organic compound with a molecular formula C3H8O3. It is colorless, clear,

sweet tasting, and a viscous liquid. The boiling point, melting point and flash point of
o o o
glycerol are 290 C, 18 C and 177 C respectively (Speight, 2002). Glycerol is also known as
glycerine, propane-1, 2, 3-triol. It is mainly produced during biodiesel transesterification,
saponification and hydrolysis reaction. Glycerol is a valuable by-product of biodiesel
produced from animal, vegetable fats and oils as feed stock. Crude glycerol produced during
the transesterification in biodiesel production would consist of impurities such as soap, ash,
water, methanol and other organic materials Tan HW et al., 2013. Glycerol has multiple
functions in food, cosmetic and pharmaceutical industries.

The improvement of transformation of glycerol to other value-added products is being

intensively studied. Lately, researches have been done on the
3

catalytic of glycerol to produce usefulness chemicals such as glyceric acid and ester glycerol
(Climent et al., 2010). Among all the glycerol conversion reactions, acetylation reaction is one
the most promising process that transforms the glycerol into applicable biodiesel additives by
enhancing the fuel properties. The intended result by converting of glycerol into desired
chemicals such as triacetin has successfully reduced both economic losses and environment
pollutions.

1.3 Triacetin

Triacetin is also known as 1,2,3-triacetoypropane or glycerin triacetate. It is the ester of

glycerol that forms with acetic acid. Triacetin can be produced through the acid catalyzed
reaction of acetic acid or acetic anhydride with glycerol. Triacetin is greatly used in industrial
application such as pharmaceutical, cosmetic and fuel additives. In biodiesel, triacetin is used
as an additive which can improve the cetane number in order to decrease the nitrogen oxide
emission to an acceptable emission level. Addition of 10% of triacetin in biodiesel can lead to
the enhancement of the engine in performance as compared to the pure biodiesel (P. V. Rao et
al., 2011).

Besides, triacetin can also be applied as a fuel additives as an anti-knocking agent to

minimize the engine knocking in the gasoline engine. Researchers found that triacetin can be
used to enhance cold and viscosity properties in final fuel produced (Melero et al., 2007).
4

1.4 Problem Statements

Biomass is a renewable and clean energy to replace diesel fuel. Due to the emission of
greenhouse gases, researchers had been working more on rectifying these problems caused in
the environment. There are problems arising from production of biodiesel, which is glycerol.
The rapid increase in biodiesel production has resulted in an increase of low value crude
glycerol in the world market.

In order to overcome the problem of excessive glycerol, it is recommended to convert the

glycerol into useful and valuable products such as mono-, di- and tri-acetin. Utilization of
glycerol can reduce both of the environment and economic losses (A. Yuksel, 2010). Triacetin
is the most desired product produced from acetylation of glycerol with acetic acid. Most
scientists are now drawing attention towards the triacetin production with different types of
processes and different type catalysts used.

In previous studies by Mufrodi et al. (2014), it is shown that the optimum condition to
achieve highest conversion of glycerol acetylation is at 373-393K in the presence of catalyst
with a mole ratio of sulfuric acid to glycerol at 2.5, with 30 minute of reaction time

In this study, the optimum conditions for acetylation of glycerol and acetic acid will be
investigated using batch reactor, where sulfuric acid homogenous catalyst and amberlyst-35
heterogeneous were used.
5

1.5 Aims and Objectives

The aims and objectives for this thesis are listed below:

To determine the optimum conditions for conversion of glycerol to triacetin.

II.To set up an experiment of batch reaction for glycerol acetylation.

III.To characterize the product using various characterization tests.

6

CHAPTER 2

LITERATURE REVIEW

2.1 Acetylation

Glycerol produced as a by-product from biodiesel is an extremely low cost feedstock.

Variables chemical reactions of low value glycerol to other valuable chemicals can be done by
using several catalytic processes, such as the selective oxidation to glyceric acid or hydrox-
yacetone(S. Sato et al., 2012), dehydration to acrolein (H. Atiaet et. al., 2008), hydrogenation
to 1,2- or1,3-propanediol (I. Gandarias et al., 2012), etherification to alkyl ethers (N. Ozbay et
al., 2013), condensation to dimers or oligomers and the acetylation to ester of glycerol.

Acetylation of glycerol is one of the most common ways to produce mono-acetin, diacetin
and triacetin. Acetylation is also known as ethanoylation in the IUPAC nomenclature. It is a
reaction that initiates an acetyl functional group into a chemical compound. Acetylation
including the substitution of the hydrogen atom of a hydroxyl group with an acetyl group
resulting in an acetoxy group. The chemical compounds used are glycerol which has a
hydroxyl group and acetic acid which has an acetyl functional group.
7

Figure 2.1: The Steps of Acetylation of Glycerol Reaction Mechanism (Zahrul,Mufrodi,

Rochmandi, Sutijan & Arief Budiman, 2014)

Basically, acetylation can be synthesized by two different types of reaction, which are the
batch reactor reaction and the continuous reactive distillation column reaction. Acetylation can
be carried out with or without the uses of catalyst. However, the presence of catalyst can
highly increase the rate of reaction and the product selectivity. There are many researches and
experiments had been done on the glycerol acetylation process. From most researches, it is
proven that acetylation can used either heterogeneous catalyst or homogenous catalyst.

2.2 Trans-esterification

Production of glycerol cant be avoided during the trans-esterification of biodiesel fuel

production. Therefore, many studies have been carried out to investigate the decrease in
production of glycerol from vegetable oil during the biodiesel production. Triacetin can be
produced via trans-esterification reaction between triglycerides and methyl acetate via
supercritical conditions. In this reaction, the triacetin produced as
8

side product with is targeted for resolving the issues of high glycerol yield in biodiesel
production in conventional processes.

Saka and Isayama studied supercritical methyl acetate by transforming the rapeseed oil into
triacetin and fatty acid methyl ester (FAME). They found that the trans-esterification by
supercritical conditions can be processed in the absence of catalyst which produces FAME
and triacetin. Besides, they also found that high yield of FAME and triacetin can be produced
by supercritical process (Saka and Isayama, 2009). The reaction formula for the trans-
esterification of triglycerides and methyl acetate is shown below.

Figure 2.2: Trans-esterification of Triglycerides and Methyl Acetate (Tan, Lee and
Mohamed, 2011)

2.3 Interesterification

Another research had been done by Casas, Ramos and Prez. Methyl acetate and triglycerides
were used to produce triacetin and biodiesel. They proposed a study on chemical reaction of
sun flower oil with methyl acetate by using different catalyst such as potassium hydroxide,
methoxide, and polyethylene. This chemical reaction is known as interesterification. However
this reaction has only been studied using vegetable oils. Interesterification has been mostly
studied in the presence of enzymes (Du et al., 2004) (Ognjanovic, Bezbradica and Knezevic-
Jugovic, 2009) or under supercritical condition (Casas, Ramos and Prez, 2011). The Figure
2.3 shows the reaction formula for interesterification.
9

Figure 2.3: Inter-Esterification Reaction of Triglycerides with Methyl Acetate (Casas,

Ramos and Prez, 2011)
10

2.4 Method

2.4.1 Batch Reaction

Batch reactor is commonly used in the process industries. The catalyst and reactants are put in
a closed reactor and the reaction is let to run for a specific time. This is the mechanism of a
batch reactor. Batch reactors are a simple and need some supporting equipment to carry out
the process. It is used for small amount of material and produces high-value products.
Synthesis of triacetin from glycerol is carry out in a batch reactor and the research was done
by (Mufrodi et al., 2014). The aim of this study is to identify by two different processes for
glycerol acetylation.

In this research, the conversion of glycerol from continuous distillation column is 98.51% and
batch reactor is 96.30%. Both of the reactions use sulfuric acid as the catalyst. Sulphuric acid
is a homogenous catalyst and it achieved the best performance during the acetylation of
glycerol amongst the various type of heterogeneous catalyst used. Although the conversion of
glycerol in a batch reactor is lower than the continuous distillation column, but the selectivity
of triacetin produced in a batch reactor is higher. The selectivity of triacetin in a batch reactor
is 13.96% and the reactive distillation column is only 8.98%.

Besides, temperature is also one of parameters that need to be considered during the batch
reaction in order to increase the selectivity of triacetin. From the research, monoacetin,
diacetin and triacetin selectivity can be increased by increasing temperature in the batch
reactor. The highest yield of triacetin is 13.69% at temperature of 388K (Mufrodi et al.,
2014). However, the boiling point of acetic acid is 391K, if the temperature increase to this
temperature, the acetic acid will start to evaporate and thus decreasing the selectivity of
triacetin.
11

2.4.2 Continuous Acetylation Reaction

Continuous acetylation processes was studied as early as the 1960s by morrissette (1964).
Continuous acetylation reaction is a process for the continuous production of triacetin
consisting essentially of continuously charging liquid glycerol into liquid reaction area
through which acetic acid vapors and water vapors flows.

Normally the triacetin are produce using batch reactor tank. However, batch reactor is very
versatile for small production. For the large scale production of triacetin, batch reactor is
labor intensive and low in productivity. Therefore, continuous acetylation process is more
suitable in commercial production compare to the batch process.

There are several parameters that will affect the selectivity of production of triacetin in the
continuous acetylation reaction. In other researches, the parameters include the effect of
height packing and the effect ratio of glycerol to acetic acid. In the continuous acetylation, the
height of packing can affect the yields of triacetin due to contacting time between acetic acid
and glycerol. For example, by increasing height packing of the distillation column, more time
is given to the reactants to contact each other and thus higher selectivity of triacetin can be
formed. Next, from the stoichiometric calculation, 1 mole of glycerol needs 3 mole of acetic
acid to produce one mole of triacetin. Therefore, by increasing the ratio of acetic acid to
glycerol, there will be an increase in triacetin production.

2.5 Type of Catalyst

Acetylation of glycerol with acetic acids produces fuel additives like triacetin. Acetylation of
glycerol can be carried out using different types of suitable mineral acid catalyst. Catalysts are
classified into two categories, which are homogenous catalyst and heterogeneous catalyst.
12

Table 2.1: Comparison of Main Advantages and Disadvantages of Homogenous and

Heterogeneous Catalyst (Erica Farnetti, Roberta Di Monte and Jan kaspar, n.d.)
Property
Homogeneous
Heterogeneous

Catalyst recovery
Difficult and expensive
Easy and cheap

Thermal stability
Poor
Good

Selectivity
Excellent/good- single
Good/poor-multiple active

active site
sites

2.5.1 Homogeneous Catalyst

The homogenous catalyst operates respectively in the same phase where the reaction involves
a liquid catalyst with the reactants as in either liquid or gases. Strong acid must be used in
order perform well the glycerol acetylation. This reaction is performed using the homogeneous
catalyst such as sulphuric acid, hydrofluoric or p-toluene sulfonic acid (Kale et al., 2015).
Khayoon et al. (2011) studied the performance of H3PO4, HCl, HNO3 and H2SO4 as
homogeneous catalysts for glycerol esterification. Among these H2SO4 showed the highest
glycerol conversion. Synthesis of triacetin from glycerol and acetic acid acid required 72 hours
in the existents of homogeneous catalyst (Lu & Ma, 1991).

However, these strong acids are not beneficial because they are hazardous, corrosive and
difficult to remove from the glycerol acetylation (Kale et al., 2015). Besides, homogeneous
catalyst also suffers from the inherent problems in terms of catalyst separation, reactor
corrosions and environment protections as well as economical inconveniences (Zhu et al.,
2013). Therefore, quite a number of researchers did their research by changing the catalyst and
developing the heterogeneous solid acid catalyst system for the glycerol acetylation.
13

2.5.2 Heterogeneous Catalyst

The heterogeneous catalyst includes the use of catalyst in a different phase where the reaction
involves a solid catalyst with the reactants as either liquid or gases. Different types of solids
are used in heterogeneous catalysis. For example metals, metal oxides, metal sulphides and
these materials may be used in their pure form or in the form of their mixtures. Besides,
catalyst can be both in acidic and alkaline based. Generally, acetylation of glycerol is using
solid acid catalyst.

In order to overcome the environment problems and economical inconvenience, a huge

number of heterogeneous solid acid catalyst has been developed in recent works. Studies had
been made using solid acid catalyst such as Amberlyst-15, K-10 montmorillnite, HUSY,
niobic acid, and HZSM-5 (Gonalves et al., 2008). All the reaction times are carried out
o
within 30 minutes and temperature used is 150 C to monitor the initial products. The results
display the selectivity of mono-, di- and tri- acetin are different for each different catalyst
used and conversion degree. Amberlyst-15 is more active compare to niobic acid, HUSY,
HZSM-5 and catalysts (T.A Peters et al., 2006). After reaction time of 30 minutes, the
conversion of glycerol was as high as 97% with a selectivity of 31% to monoacetin, 54% to
diacetin and 13% to triacetin. However, they find out the conversion and selectively can be
increased by increasing the reaction time.(Gonalves et al., 2008). Zeolite HZSM-5 and
HUSY showed the bad achievement among all the catalyst as their glycerol conversion are
only 30% and 14 % respectively, probably due to the acid site deactivation and diffusion
problem.

Liao et al. (2009) did glycerol acetylation with two-step method in order to get a higher
selectivity and conversion. The esterification of glycerol with acetic acid was performed using
resins and zeolites. Amberlyst-35 was discovered to be an outstanding catalyst among the
catalyst used in this research. The reaction parameters were enhanced by using catalysts at
different temperatures, feedstock ratios and catalyst loading. Optimum conditions have been
found where the molar ratio of acetic acid to glycerol is 9:1 at the temperature of 105C with
0.5g of catalyst and a reaction time of 4 hours. Acetic anhydride was then added there to
increase the selectivity of triacetin. Besides, the result shows that the reaction needed to
increase
14

the amount of acetic acid used in order to push equilibrium toward the improvement of the
conversion of glycerol and triacetin.

Zhu et al. 2009 proposed silver-exchanged phosphotungstic acid (AgPW) catalysts for
glycerol acetylation with acetic acid. Among the catalysts partially silver-exchanged
phosphotungstic acid (Ag1PW) showed high activity and good performance in the reaction.
o
The conversion of glycerol is 96.8% at 120 C within 15 min of reaction time. The reason is
because Ag1PW shows remarkable stability, unique kegging structure, high acidity as well as
excellent water-tolerance property. The selectivity of acetylated products is 5.2% for triacetin,
46.4% for diacetin and 48.4% for monoacetin. Compare with others exploited mixed metal
oxides such as MoO3/ZrO2, WO3/ZrO2, and Nb2O5/ZrO2, their reactivity were very low,
which might be due to their low acidity.

Rodriguez et al.(2007) researched glycerol acetylation by using sulfated zirconia with acetic
acid. The catalyst is also named as AC-SA5. This catalyst is produced from activated carbon
o
(AC) at 85 C for 4 hours with the help of sulphuric acid in order to initial the functionalities
of the catalyst surfaces. The surface interaction between the acyl group and the glycerol
molecules can be enhanced due to the presence of sulphur that consist functional group on the
AC surface.

The conversion of glycerol by using this catalyst was about 91% after 24 hours of reaction at
o
120 C. The selectivity of monoacetin, diacetin and triacetin in glycerol conversion was 38%,
28% and 24% respectively. However, the selectivity and the conversion of glycerol
acetylation are still affected by the time, temperature and the molar ratio of glycerol to acetic
acid (Khayoon and Hameed, 2011)

The use of sulfated zirconia catalysts showed acetylation yields up to 63% and 91% of
glycerol conversion after 24 h of reaction. This catalyst also shows the selectivity result of
38% for mono-acetin, 28% for di-acetin and 34% for tri-acetin with the optimized conditions
o
at 120 C and 3 hours of reaction time.
15

CHAPTER 3

METHODOLOGY

3.1 Overview of Experiment

In this study, the main purpose was to investigate the optimal conditions which could result in
highest yield of Triacetin for acetylation with catalyst which where sulphuric acid (H2SO4) act as
a homogenous catalyst. The parameters involved for preliminary study reaction temperature (90
o
and 120 C), reaction time (30 60 minutes), glycerol to acetic acid ratio ( 1:3, 1:6 and 1:9 ), and
glycerol to sulphuric acid ratio (1:0.00, 1:0,02 and 1:0.04). Full factorial design was used to study
the effects of those parameters.

3.2 Material and Chemicals

The material used in this research is glycerol which is a colourless liquid. While the chemicals
used throughout the whole research are listed in Table 3.1.

Table 3.1: List of Chemicals Used in Research Experiment

Chemicals
Supplier
Purpose

Glycerol
R & M Chemical, Malaysia
Solvent in Acetylation
Acetic acid
R & M Chemical, Malaysia
Solvent in acetylation
Sulphuric acid
QReC, Malaysia
Catalyst for acetylation
Ethanol
Chem Sol, Malaysia
Internal standard for GC
16

3.3 Equipment

The equipment used throughout this research studies are listed as in Table 3.2.

Besides, the supplier of the equipment is provided as well.

Table 3.2: List of equipment used in this research study

Equipment
Brand

Gas Chromatography
Perkin Elmer, USA

Gas Chromatography-Mass Spectrometry

Shimadzu, Japan

Heating Mantle
Favorit, Malaysia

Hot Plate
Favorit, Malaysia

Rotary Evaporator
Buchi, Switzerland

Reflux Condensation Reactor

Favorit, Malaysia

Fourier Transform Infrared Spectroscopy

Perkin Elmer, USA

3.4
Reactant and Catalyst Preparation

All the chemicals were obtained commercially and used without any further purification. 98%
of Acetic acid was obtained from R & M Chemical, Malaysia, 93% of glycerol was obtained
from R & M Chemical, Malaysia and 98.9% of sulfuric acid was obtained from QReC,
Malaysia. 99.9% of GC grade ethanol used for Gas chromatography (GC) test was made from
Chem Sol, Malaysia.
3.5 Acetylation

Synthesis of triacetin in the presence and absence of catalyst was carried out in a stirred
o
reactor at atmospheric pressure and 290 rpm of stirring speed, temperatures of 90 to 120 C.
Synthesis of triacetin has been carried out previously by using different types of catalyst which
including the heterogeneous catalyst and homogenous catalyst. In this research, the catalyst
used is homogeneous catalyst sulfuric acid. It was revealed that this catalyst has functionalized
as the best homogeneous catalyst among several types of catalyst used.
17

The reaction carries out in three-neck flask equipment with heating mantle, stirrer and
thermometer as shown in Figure 3.1. The reactants glycerol and acetic acid were mixed
directly into the three neck flask along with the sulfuric acid catalyst. The reaction carries out
at a mixing time from 30 minutes to 60 minute. The mixing was continuously stirred during
the reaction using a magnetic stirrer. Next, the products which contain sulfuric acid catalyst
were neutralized by adding same ratio of sodium hydroxide in container. After neutralized, the
contaminated catalyst was removed by using the recirculating water respirator equipment as
shown in Figure 3.2. Lastly, the product containing mono-acetin, di-acetin, tri-acetin, glycerol
and unreacted acetic acid were poured into a rotatory evaporator to remove the solvent from
the product as shown in Figure 3.3.

Figure 3.1: Reflux Condensation Set Up

Figure 3.2: Recirculating Water Respirator

18

Figure 3.3: Rotatory Evaporator

3.6 Design of Experiment (DOE)

Design-Expert software version 6.0.6 (STAT-EASE Inc., Minneapolis, USA) was employed
to utilize Response Surface Methodology (RSM) for acetylation of glycerol. This design
method allowed analysis of statistical data and optimization of desired response to be
determined. There are three major steps involved in this experimental design, including
statistical design experiments, validation of a mathematical model with response prediction
and optimization of response. Central composite design (CCD) was selected as the
experimental design to study the effect of operating parameters (independent variables) on the
acetylation of glycerol with acetic acid into triacetin (response). The optimum operating
parameters for acetylation were determined in order to maximize the triacetin yield. The
independent variables studied in this experimental design were reaction time, reaction
temperature, molar ratio of glycerol to acetic acid and molar ratio of glycerol to sulphuric acid
catalyst.
19

Table 3.3 lists the range and levels of the four independent variables studied.

Table 3.3: Range and levels of independent variables

Code
Variable
Units
Low
High

A
Reaction Temperature
o
C
90
120
B
Molar Ratio of Glycerol to
mol/mol
0.00
0.04

Acetic Acid

C
Reaction Time
minutes
30
60
D
Molar Ratio of Glycerol to
mol/mol
3
9

Sulphuric Acid
Therefore, 29 runs of experiment were conducted where the first 24 runs were organized in a
factorial design and additional 5 runs were carried out at the center points to estimate the
overall curvature effect. Statistical analysis and regression analysis of the experimental data
of the experimental data were conducted by using Design Expert software. The response (Y)
or yield of triacetin obtained in each acetylation process was utilized to develop a
mathematical model that correlates the conversion of glycerol with acetic acid into triacetin
(response) as a function of the independent variables.

Successively, correlation coefficient (R-Square) was employed to evaluate the quality of the
proposed model whereas the statistical significance of the model and the Lack of Fit test of
the model were evaluated using analysis of variance (ANOVA). In addition, interactions
between independent variables were studied in two-dimensional and three-dimensional plots
and the region of optimum conditions was evaluated.

Furthermore, numerical feature of Design Expert software was practiced in optimization

study to identify the optimum operating parameters which lead to optimum yield of triacetin.
The independent parameters were set within the range of low (-1) and high (+1) while the
yield was set to maximum value. As a result, several solutions were generated and solution
with the best desirability based on optimum yield was identified as the optimum parameters.
20

3.7 Product Analysis

The properties of the triacetin obtained from the glycerol acetylation went through several
analytical tests which include Fourier transform infrared spectroscopy (FTIR) and Gas
chromatography (GC) in order to identify the yield, components and impurity.

3.7.1 Triacetin Yield

Gas Chromatography (GC) equipped with flame ionization detector with model PerkinElmer
Clarus 500 was used to determine Triacetin in the sample collected. The principle of GC is to
study the different in retention time of vaporized component in sample though a capillary
column. BPX5 capillary column used have 0.25 m of film thickness, 0.25mm of internal
diameter and 30 m length. Samples were prepared

by mixing 500 of product with 20 of the ethanol (GC grade) as internal standard. About 0.5 of
the sample was then injected into the column. Table 3.4 shows the summary of GC
specification.

Table 3.4 Gas Chromatography Specification

Specification
(GC)

Analytical Column
BPX5 capillary column
Carrier Gas
Helium gas (38.3 mL/min)
Initial Temperature
o
60 C (2 min)
Initial Ramp
o o
10 C/min to 260 C
Final Ramp
o o
30 C/min to 300 C
FIP
o
350 C
Injection temperature
o
250 C with split ratio 20
The area under the peak is proportional to the amount of triacetin present in the sample.
Concentration of triacetin presented in the sample was determined through the area under peak
obtained by referring the calibration curve prepared based on
21

interval standard. Triacetin yield was calculated and the sample calculation was inserted in
Appendix C.

3.7.2 Preparation of Diluted Triacetin Sample

Firstly, internal standard, GC ethanol was prepared. Samples were mixed 500L of product
with 20l of ethanol as internal standard. Hence, the dilution factor of the sample was 20.
About 1.5l of diluted sample was injected into the column of gas chromatography and the
peak areas of each individual component and internal standard (IS) were recorded as
Areasample and AreaIS respectively.

3.7.3 Determination of Yield of Triacetin

According to modified EN 14103 standard, the content of every individual component of

sample could be obtained by using the following Equation 3.1:

(3.1)

where

Ci = content of different component in the sample in %

Ai = component peak area

A = total peak area

3.7.4 Fourier Transform Infrared Spectroscopy (FTIR)

Fourier transform infrared spectroscopy (FTIR) was employed in this studies to determine the
functional group of each component obtained in the triacetin. The analysis is carried out by
using Perkin Elmer FTIR.
22

3.8 Research Flow Diagram

Figure 3.4 shows the flow diagram of the research experiments. This optimization of

glycerol acetylation which involved four parameters and were carried out by utilizing

Response Surface Methodology (RSM) to obtain their respective optimum conditions

Process Method and Optimization

The raw materials glycerol, acetic acid and sulphuric catalyst acid are placed into reflux
condensation reactor.

Glycerol acetylation reaction is carried out in the reactor and triacetin is formed.

The effect of different process parameters such as reaction time, reaction temperature, molar
ratio of glycerol to acetic acid and molar ratio of glycerol to sulphuric acid catalyst were
studied.
Product Analysis
FTIR and GC were used for characterization of product.

Figure 3.4: Research Flow Diagram of this

Study
23

CHAPTER 4

RESULT AND DISCUSSION

In this section, there were major parts which were preliminary study and optimisation study.
In preliminary study, triacetin yield for prepared by those parameters would be studied. After
decided the parameters, optimisation study would proceeded with. Thus, an optimum
condition to produce triacetin yield could be determined.

4.1 Preliminary Study

Preliminary study investigated the relation between reaction time, reaction temperature,
catalyst quantity and also glycerol to acetic ratio on the triacetin yield. Besides, preliminary
study helped to define the feasible range for each process parameters before the optimisation.
In preliminary study, the feasible range of reaction time, reaction temperature, catalyst ratio
and glycerol to acetic acid ratio were defined. Thus the feasible range for those parameters
will be used during the optimisation experiments.

During the preliminary study, 29 experiments runs were designed using Design Expert
software. The reaction performance was defined based on biodiesel yield. Sample calculation
for the biodiesel yield was shown in Appendix C.

24

Table 4.1: Experimental Condition and Triacetin Yield

Run
Reaction
Glycerol
Reaction
Glycerol
Triacetin

Temperature
To
Time
To Acetic
Yield

o
( C)
Sulphuric
(minute)
Acid Ratio
(%)

Acid

Ratio

1
105.00
1:0.02
45.00
1:6
25.50
2
105.00
1:0.02
45.00
1:6
28.80
3
105.00
1:0.02
60.00
1:3
29.76
4
105.00
1:0.04
45.00
1:9
26.71
5
105.00
1:0.02
45.00
1:6
25.26
6
90.00
1:0.02
45.00
1:3
18.65
7
105.00
1:0.02
45.00
1:6
26.78
8
120.00
1:0.02
60.00
1:6
31.12
9
90.00
1:0.02
30.00
1:6
17.58
10
105.00
1:0.00
60.00
1:6
6.56
11
105.00
1:0.02
60.00
1:9
31.89
12
120.00
1:0.04
45.00
1:6
21.98
13
105.00
1:0.02
30.00
1:9
18.45
14
120.00
1:0.02
30.00
1:6
30.53
15
105.00
1:0.02
45.00
1:6
25.55
16
120.00
1:0.00
45.00
1:6
5.67
17
105.00
1:0.00
45.00
1:3
4.45
18
120.00
1:0.02
45.00
1:3
21.45
19
105.00
1:0.00
30.00
1:6
4.65
20
105.00
1:0.02
30.00
1:3
15.76
21
105.00
1:0.04
45.00
1:3
30.76
22
90.00
1:0.02
45.00
1:9
19.47
23
105.00
1:0.04
60.00
1:6
31.34
24
105.00
1:0.04
30.00
1:6
21.76
25
90.00
1:0.00
45.00
1:6
2.34
26
120.00
1:0.02
45.00
1:9
32.5
27
105.00
1:0.00
45.00
1:9
5.76
28
90.00
1:0.04
45.00
1:6
23.45
29
90.00
1:0.02
60.00
1:6
25.30
25

4.2 Glycerol Acetylation Reaction

4.2.1 Screening Study via Statistical Analysis by using Design of Experiment (DOE)

The feasible range for each parameter (catalyst ratio, glycerol to acetic acid ratio, reaction
temperature, and reaction time) was determined again using statistical analysis.

Table 4.1 displays the complete experimental design matrix and the corresponding yield of
triacetin. As shown in the table, the yield ranged 2.34% to 31.89%. A reaction time of 60
minutes, molar ratio of glycerol to methanol of 1:9, molar ratio of glycerol to sulphuric acid
o
catalyst of 1: 0.02 and reaction temperature of 105 C gave the highest yield whereas a
reaction time of 45 minutes, molar ratio of glycerol to methanol of 1:6, molar ratio of glycerol
o
to sulphuric acid catalyst of 1:0.00 and a reaction temperature of 90 C gave the lowest.

4.2.2 Statistical Analysis

Statistical analysis was done to determine how the variables affect the response. Table 4.2
shows the result of the sequential model sum of square analysis. As shown in the table, a
quadratic model was suggested as the most appropriate approach to optimize the acetylation
reaction with the Prob > F value being 0.0001.

Table 4.2: Result of Sequential Model Sum of Square

Source

Sum
of DF
Mean
F Value
p-valvue

Square
Square

Prob > F

Mean
12818.00
1

12818.00

Linear
1646.27
4

411.57

10.90

<0.0001

2FI
66.36

6
11.06

0.24

0.9585

Quadratic

665.03

166.26

12.34

0.0001

Suggested
26

Cubic
131.62
8
16.45
2.30
0.1625
Aliased
Residual
42.84
6
7.12

Total
15370.13
29
530.00

Data for ANOVA was summarized in Table 4.3. Prob > F less than 0.05 indicated the model terms are
2
significant. In this case A, B, C, and B were significant model terms. Thus, the triacein yield heavily
dependents on the factors of reaction temperature, catalyst amount, and reaction time. Furthermore, the
F-value of 13.63 indicates that the model is significant and is reliable in predicting the triacetin yield. For
the model, the Prob > F value is only < 0.0001 which means that there is less than 0.0001% chance
that a F-value this large could occur due to noise factor, further proving the reliability of the model.
Besides, the F-value of lack of fit is only 7.59, this indicating that is insignificant. The prob > F value
of 0.0328 proves that there is only 3.28% chance that Lack of Fit F-value this small could occur due
to noise factor.

Table 4.3: Analysis of Variance (ANOVA) of the Variable

Source
Sum of
DF
Mean Square
F Value
p-value
Square

Prob > F

Model
2377.66
14
169.83
13.63
< 0.0001
significant

A
110.78
1
110.78
8.89
0.0099

B
1333.10
1
1333.10
106.97
< 0.0001

C
185.97
1
185.97
14.92
0.0017

D
16.43
1
16.43
1.32
0.2702

2
A
22.02
1
22.02
1.77
0.2050

B2
639.58
1
639.58
51.32
< 0.0001

2
C
0.000627
1
0.000627
0.00005033
0.9944

2
D
8.69
1
8.69
0.70
0.4178

AB
5.76
1
5.76
0.46
0.5077

AC
12.71
1
12.71
1.02
0.3297
AD
26.16
1
26.16
2.10
0.1694

BC
14.71
1
14.7
1.18
0.2957

BD
6.94
1
6.94
0.56
0.4678
27

CD
0.078
1
0.078
0.00629
0.9379

Residual
174.47
14
12.46

Lack of fit
165.73
10
16.57
7.59
0.0328
significant

Pure Error
8.73
4
2.18

Cor Total
2552.13
28
Data for ANOVA Study for R-Square Value was summarized in Table 4.4.

Table 4.4 ANOVA Study for R-Square Value

R-Squared
0.9316

Adj R-Squared
0.8633

Pred R-Squared
0.6206

Adeq Precision
13.000

The R-Square value shown in Table 4.4 for the empirical model was 0.9316, which implies that 93.16%
of the variation in the result was attributed by the independent variable studies. This indicated that the
empirical model developed well fitted the experimental data. The Pred R-Squared of 0.6206 is in
reasonable agreement with the Adj R-Squared of 0.8633.

As the R-Square value is relatively near to one, a good agreement between predicted and actual yield
was achieved in this regression model. Figure 4.1 shows a graph of predicted yield against actual yield
using the model development in order to show the correlation between these two parameters.
28

Figure 4.1: Predicted Yields against Experimental Yields for Acetylation

Reaction

The final equation in term of coded factors after eliminating parts of the insignificant terms is
outlined in Equation 4.1
( ) ( ) ) )
( ) ) )

( )

( )
29

From the Equation 4.1, terms with a positive sign indicates synergistic effects whereas terms
with negative sign indicates antagonistic effect. According to Equation 4.1, parameter B
which contains highest value of coefficient from 4 parameters plays an important role in
reaction producing triacetin. The Final equation in terms of actual factors is outlined in
Equation 4.2
mole temperature * mole ratio of
ratio catalyst) (0.0079222 * reaction
Tricetin of temperature * reaction time) +
glycer (0.056833 * temperature * mole
ol to ratio of glycerol to acetic acid) +
= -136.11838 + (2.02599 * reaction acetic (7.17661 * mole ratio of catalyst
temperature) + (2120.57027 * mole ratio of acid2) * reaction time) - (24.65497 *
catalyst) + (0.97559 * reaction time) mole ratio of catalyst * mole
(3.40899 * mole ratio of glycerol to acetic (4.491 ratio of glycerol to acetic acid) -
acid) (0.00818815 * reaction temperature2) 2 * (0.000311111 * reaction time *
(31296.24295 * mole ratio of catalyst2) reacti mole ratio of glycerol to acetic
(0.000004.3703 * reaction time2) (0.12859 * on acid)
(4.2)
30

4.2.3 Variables Interaction

Variable interactions are important throughout the study to determine the optimum condition
required to achieve desired result. Therefore, interactions of variable are studied.

Figure 4.2 shows the interaction between reaction temperature (A) and mole ratio of glycerol
to sulphuric acid catalyst (B) on the yield of triacetin produced. Figure 4.2 (a) describes the
plot in two-dimension and Figure 4.2 (b) in three-dimension. From the Figures 4.2 (a) and (b),
when no catalyst was used in the reaction, the yield was its lowest. Furthermore, at lower
reaction temperature, the yield seems to be at its lowest too. When the temperature increased
o o
from 90 C to 120 C, with an increment in the catalyst from a mole ratio of glycerol to
sulphuric acid 1:0.02 mol/mol to 1:0.04 mol/mol, an increasing trend in yield is observed. The
elevated temperatures enhanced the formation of higher glycerol acetates due to the
protonation of the remaining hydroxyl groups of glycerol molecule by steric factors and/or
interaction with the active sites on the catalyst surface (Khayoon and Hameed, 2011). The rate
of formation of acylium ions on the catalyst surface represents the fastest and determining
step during the acetylation reaction (Lilja et al., 2005). However, a decreasing trend in yield
o
was observed when passing a temperature of 112.5 C with a catalyst percent of 1:0.04. A
desired yield is obtained when the temperature reaches its optimum value together with an
o
optimum catalyst amount. Beyond 112.5 C, the activity decreases in the reaction due to the
certain chemical changes taking place between the catalysts in high temperature. An
observation was made during this research. Addition of too much catalyst at a high
temperature entirely changes the final product colour. Hence, the optimum temperature and
o
catalyst amount are 105 C with 1:0.02 mol/mol ratios.
31

(a)

(b)
Figure 4.2: Effect of Reaction Temperature (A) and Glycerol to Sulphuric Acid Catalyst
Mole Ratio (B) on the Triacetin Content in (a) Two-Dimension and (b) Three-Dimension
Interaction Plots for Acetylation Reaction.
32

Figure 4.3 (a) and (b) illustrate the effect of reaction temperature (A) and reaction time (C) on
the yield triacetin. Melero et al. (2007) have acclaimed that reaction temperature and molar
ratio of glycerol with acetic acid are the most influential parameters on the esterification of
glycerol, as evidence by multivariate analysis. Theoretically, a long reaction time and a higher
reaction temperature produce a higher yield of the triacetin. Thus from Figures 4.3 (a) and (b),
o
it is observed that the influence of reaction time in acetylation at 90 C is more prominent
o
compare to the reaction conducted at 120 C. This shows that at a lower reaction temperature,
longer reaction time is needed to enhance of yield of triacetin. Hence, at lower temperature, a
longer time is needed to eliminate the yield of triacetin. Observation from Figures 4.3 (a) and
o
(b), reviews after 118 C, yield starts to deteriorate. This is because when the temperature
o
exceeding 118 C, the acetic acid tends to evaporate at a higher rate, disturbing the reaction
hence resulting in a lower yield of triacetin. Therefore in this study, the optimum time for the
o
reaction to take place is 60 minutes at 105 C.

(a)
33

(b)

Figure 4.3: Effect of Reaction Temperature (A) and Reaction Time (C) on the Triacetin
Content in (a) Two-Dimension and (b) Three-Dimension Interaction Plots for
Acetylation Reaction.

Figure 4.4 shows the interaction between reaction temperature (A) and mole ratio of glycerol
to acetic acid (D) on the yield of triacetin produced. Figure 4.4 (a) describes the plot in two-
dimension and Figure 4.4 (b) in three-dimension. At higher molar ratio of glycerol to acetic
o o
acid (1:9 mol/mol), the increment of temperature from 90 C to 120 C encourages increase in
triacetin yield. An excess of carboxylic acid utilized in acetylation reactions might shorten the
time required to reach reaction equilibrium (Pagliaro et al., 2007) and provide more
acetylating agent which undertakes the formation of tricetin through further acetylation
reactions. These data correlates with those already reported (Balaraju et al., 2010; Ferreira et
al., 2009). In contrast, at lower molar ratio a similar trend is observed, yield increases until the
o
temperature of 105 C and start decreasing at a higher temperature. This phenomena can be
explained further because at a higher molar ratio and temperature, there is an excess of
solvent thus evaporation of solvent doesnt disturb the reaction whereas for a smaller molar
ratio, when the solvent evaporates there is no excess to run the remaining reaction. Therefore
in this study, the optimum temperature for the reaction to take place is 60 minutes with molar
ratio of glycerol to acetic acid of 1:9.
34

(a)

(b)
Figure 4.4: Effect of Reaction Temperature (A) and Molar Ratio of Glycerol to Acetic
acid (D) on the Triacetin Content in (a) Two-Dimension and (b) Three-Dimension
Interaction Plots for Acetylation Reaction.
35

Figure 4.5 (a) and (b) display the interaction between molar ratio of glycerol to sulphuric acid
catalyst (B) and reaction time (C) on the yield of triacetin production in both two-dimensional
and three-dimensional respectively. These figures revealed the effect of different amount of
catalyst and reaction time on triacetin yield obtained. It is observed from the figures that
increasing the molar ratio of catalyst not only increase the final triacetin content, but also
increased the rate of reaction. From the figures (a) and (b), the triacetin yield increases as
catalyst load and reaction time increases. The highest Triacetin yield of 31.89% was obtained
in 60 minutes reaction time at a molar ratio catalyst of 1:0.02. It was explained by Liu et al.,
2014 that the amount of catalyst represents the total number of acid sites or active sites
available for reaction and the total surface area of the catalyst. But at the molar ratio of
1:0.04, the yield of triacetin started to decrease with the increment of time. This could be
explained as increased in catalyst load, the acidity of the reaction also increased. Thus the
adsorption of the product molecules by excessive of catalyst load could cause higher mass
transfer resistance (Liu et al., 2014). However, in Figure 4.5 (a) and (b), the highest amount of
triacetin yield was obtained at 60 minutes reaction times, and for longer reaction time, the
triacetin yield started to decrease after 60 minutes. Longer reaction time will cause the active
sites of the catalyst to be blocked by the product (Patel, Brahmkhatri and Singh, 2013). Thus,
the optimum catalyst weight is molar ratio of 1:0.02 with a reaction time of 60 minutes.

(a)
36

(b)

Figure 4.5: Effect of Molar Ratio of Glycerol to Sulphuric Acid Catalyst (B) and
Reaction Time (C) on the Triacetin Content in (a) Two-Dimension and (b) Three-
Dimension Interaction Plots for Acetylation Reaction.

Figure 4.6 (a) and (b) display the interaction between molar ratio of glycerol to acetic acid (D)
and reaction time (C) on the yield of triacetin production in both two-dimensional and three-
dimensional respectively. From the figures, it is observed the triacetin yield increased with the
increase of molar ratio of glycerol to acetic acid and the reaction time. From Figure 4.6 (b), it
shows that the interaction effect between reaction temperature (C) and molar ratio of glycerol
to acetic acid (D) is insignificant. The effect of reaction time in the production of triacetin is
more prominent at molar ratio of 1:9 mol/mol compared to at molar ratio at 1:3 mol/mol. This
shows that at higher molar ratio with a longer reaction time induces high rate of reaction and
subsequently increases the yield of triacetin content. However, the yield was still increasing
when it approached 60 minutes of reaction time for both molar ratio of 1:3 mol/mol and 1:9
mol/mol. This implies that although a higher yield percent can be achieved by increasing the
molar ratio of glycerol to acetic acid, a long reaction time is required. Thus, the optimum
mole ratio of glycerol to acetic acid is 1:9 mol/mol with a reaction time of 60 minutes.
37

(a)

(b)
Figure 4.6: Effect of Molar Ratio of Glycerol to Acetic Acid (D) and Reaction Time (C)
on the Triacetin Content in (a) Two-Dimension and (b) Three-Dimension Interaction
Plots for Acetylation Reaction
38

Figure 4.7 (a) and (b) display the interaction between molar ratio of glycerol to sulphuric acid
catalyst (B) and molar ratio of glycerol to acetic acid (D) on the yield of triacetin production
in both two-dimensional and three-dimensional respectively. From Figure 4.7 (a), the molar
ratio of glycerol to acetic acid 1:9 mol/mol has a higher yield compare to molar ratio of 1:3
mol/mol. This shows the molar ratio of glycerol to acetic acid affect the yield of triacetin is
more than the molar ratio of catalyst used. Besides, there is no increment in rate of reaction
and the yield when the molar ratio of catalyst is 1: 0.04 mol/mol with the increasing of molar
ratio of glycerol to acetic acid. There will be unused active site when there is huge amount of
active site with the limited amount of reactant. Therefore, further increment amount of
catalyst will not affect the rate of reaction and the yield of the product and molar ratio of
catalyst with 1:0.04 mol/mol is said to be overloaded. Both the plot did not intercept each
other, indicating there was minimal interaction between the variables B and D. Thus, the
optimum molar ratio of catalyst is 1:0.02 mol/mol with a molar ratio of glycerol to acetic acid
of 1:9 mol/mol.

(a)
39
(b)

Figure 4.7: Effect of Molar Ratio of Glycerol to Acetic Acid (D) and Molar Ratio of
Glycerol to Sulphuric Acid (B) on the Triacetin Content in (a) Two-Dimension and (b)
Three-Dimension Interaction Plots for Acetylation Reaction
40

4.2.4 Optimization Study

From the Design Expert software, the combination of optimum conditions had been
determined. The optimum conditions are listed in the Table 4.5.

Table 4.5 Summary of Optimum Conditions for Glycerol Acetylation and Predicted Yield

Condition
Value

o
Reaction Temperature (A), ( C)
105
Glycerol to Sulphuric Ratio (B), mol/mol
1:0.02
Reaction Time (C), minute
60
Glycerol to Acetic Acid Ratio (D), mol/mol
1:9
Predicted Yield
29.378

Table 4.6 shows the comparison between the predicted and experimental yield of triacetin.
Addition independent run was conducted to validate the proposed conditions. Actual
experiment based on the optimum conditions produced 31.89 of triacetin with percent error of
8.55%. This small percent error proves that the actual values and predicted values are in strong
agreement with each other. Thus, the regression model was successfully proven to be reliable
in predicting the yield of triacetin content for the given conditions studied.

Table 4.6: Comparison between Predicted and Experimental Triacetin Content of

Acetylation Reaction
Run
Predicted Triacetin
Experimental Triacetin
Error (%)

Content (%)
Content (%)
1
29.378
31.89
8.55%
41

4.3 Product Analysis

4.3.1 Fourier Transform Infrared Spectroscopy Analysis

Fourier transform infrared spectroscopy (FTIR) is used to identify the component and
impurities in the triacetin obtained from the glycerol acetylation. As shown in Figure 4.8,
several peaks can be obtained and each peak represents different functional group of different
compounds

Figure 4.8: FTIR Analysis of Triacetin

-1
The peak at 3390 cm represents the functional group of O-H stretch of alcohol, this
-1
indicating there was unreacted ethanol in the product. Besides, the peak at 1625 cm
indicates O-H stretch of carboxylic acid, indicating the unreacted acetic acid in the product.
The peak at 2952 represents a C-H stretch in an alkane hydrocarbon. On the other hand, the
 -1
peak at 1727 cm represents a C=O stretch represents the ester molecules. Lastly, the peak at
-1
1257 cm indicates a C-C(O)-C stretch of ester of acetates group, further proving the
presence of the triacetin in the product.
42

CHAPTER 5

CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion

The batch reaction of glycerol acetylation was conducted using the reflux condensation
machine. The glycerol acetylation was optimized using different parameters. The parameter
used to optimize the reaction were reaction temperature, reaction time, molar ratio of glycerol
to acetic acid and molar ratio of glycerol to sulphuric acid catalyst. The highest yield of
triacetin obtained in this research was 31.89% with the condition of 1:0.02 molar ratio of
glycerol to sulphuric acid, 1: 9 molar ratio of glycerol to acetic acid, 60 minutes of reaction
o
time and 105 C of reaction temperature. The Fourier Transform Infrared Spectroscopy
Analysis reviews that the present of triacetin is seen through the ester of acetates group stretch
-1
at 1257 cm peak. Finally through the GC and FITR test conducted, it was proven that the
experiment is a success.

5.2 Recommendation

The experiment was conducted in batch mode by using reflux condensation machine,
although it is a convenient method to produce triacetin but the amount of triacetin production
is limited due to the size of the machine. Therefore, increasing the size of the machine will
take more advantages for the production of triacetin. Besides, batch reaction which may
different from the condition in mass production, there for continuous reaction is
recommended for further study.
43

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48

APPENDICES

APPENDIX A: Gantt Chart

Gantt Chart for First Long Trimester

Details/Week
1
2
3
4
5
6
7
8
9
10
11
12
13
14

Project Proposal/Selection

Preliminary Research Work

Project Work

Progress Report Submission

Oral Presentation

Gantt Chart for Second Long Trimester

Details/Week
1
2
3
4
5
6
7
8
9
10
11
12
13
14

Project Work (continue)

Progress Report Submission

Final Report Submission

Oral Presentation

Hard bound submission

49

APPENDIX B: Triacein GC Analysis

Figure B.1: Chromatograph Analysis of Mono-, di- and Tri-acetin

Figure B.2: Chromatograph Analysis of Glycerol
50

Figure B.3: Chromatograph Analysis of Acetic Acid

51

APPENDIX C: Sample Calculation

Based on Figure B, the area and retention time of Triacetin obtained for set number 11 in Table
4.2 was summarized in Table C.1. It is given that,

Total peak area

= 803007

Table C.1: Retention Time and Area of Traicetin obtained in Figure B

Component
Retention Time
Area
Content, Ci (%)

(min)

Triacetin
12.699
146414
31.89

According to modified EN 14103 standards, the content of each individual component of

samples were calculated by using Equation 3.2.

Ci
Ai
100%

AA
IS

For example:

Content of triacetin, C
=
Ai
100%

AA
IS

x 100%

= 31.89%