!
vii!
TABLE OF CONTENTS
CHAPTER
1
2
TITLE
PAGE
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENT
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xi
LIST OF FIGURES
xiii
LIST OF ABBREVIATIONS
xvi
LIST OF APPENDICES
xvii
INTRODUCTION
1
1.1
Background of Study
1
1.2
Problem Statement
4
1.3
Research Objectives
6
1.4
Scope of The Research
6
LITERATURE REVIEW
8
2.1
Coal Fly Ssh
8
2.2
Microwave Synthesis Technique
10
2.3
Zeolite
13
2.3.1
Synthesis of Zeolite
17
2.3.2
Sodalite
23
2.3.3
Basicity in Zeolite
25
!
viii!
2.4
Zeolite as Catalyst
29
2.5
Knoevenagel Reaction
31
2.5.1
Zeolite as Catalyst in Knoevenagel
32
Reaction
3
RESEARCH METHODOLOGY
35
3.1
Chemical Reagents
35
3.2
Instruments and Equipments
36
3.3
Synthesis of Zeolite from CFA
36
3.3.1
Synthesis of Zeolite via Conventional
37
Heating
3.3.2
Synthesis of zeolite via microwave
37
heating
3.4
Characterization of Sodalite
39
3.4.1
X-ray Dffraction (XRD)
39
3.4.2
Infrared Spectroscopy
39
3.4.3
Field Emission Scanning Electron
40
Microscopy(FESEM)
3.4.4 Electron Dispersive X-Ray (EDX)
3.4.5
29
41
Si MAS Non Magnetic Resonance
41
Spectroscopy (NMR)
3.4.6 Gravimetric Analysis of Unreacted
42
Silica Quartz
3.4.7
Elemental Analysis
42
3.4.8 Preparation of Samples Solution
3.5
3.6
43
Ion Exchange
43
3.5.1 Ion Exchange with Potassium Ion
43
3.5.2
Ion Exchange with Cesium Ion
44
3.5.3
Ion Exchange with Calcium Ion
44
3.5.4
Ion Exchange with Barium Ion
45
3.5.5
Ion Exchange with Strontium Ion
45
Temperature
(TPDCO2)
Programmed
Desorption
CO2
45
!
ix!
3.7
Catalytic Testing by Using Knoevenagel
46
Reaction
4
3.8
Reusability of catalyst
47
3.9
Flowchart
48
RESULTS AND DISCUSSION
49
4.1
Introduction
49
4.1.1
49
Basic Formation of Zeolite
4.2
Characteristics of Coal Fly Ash (CFA)
51
4.3
Synthesis of Sodalite by Oven Heating
52
4.4
Synthesis of Sodalite by Microwave
56
4.4.1
X-ray Diffraction (XRD)
57
4.4.2 Infrared Spectroscopy (FTIR)
63
4.4.3
65
29
Si MAS Nuclear Magnetic Resonance
4.4.4 Gravimetric Analysis of Unreacted
66
Silica
4.5
Modification of Sodalite
68
4.5.1
X-ray Diffraction (XRD)
68
4.5.2
Elemental Analysis
73
4.5.2.1 Energy Dispersive X-ray
73
Spectroscopy (EDX)
4.5.2.2 Flame Photometry
75
4.5.3 Field Emission Scanning Electron
76
Microscopy (FESEM)
4.6
Temperature Program Desorption – CO2
77
4.7
Catalytic Testing of Sodalite in Knoevenagel
81
Condensation Reaction
4.7.1 Reactivity of The Catalyst
82
4.7.2 Effect of Ion Exchange Temperature
83
4.7.3 Selectivity of The Catalyst
85
4.7.4
87
Effect of Reaction Temperature
4.7.5 Effect of Time
88
4.7.6 Reusability of The Catalyst
90
!
x!
4.8
Relationship of Physicocemical Properties of
91
The Catalyst for Knoevenagel Reaction
4.9
Mechanism of Knoevenagel reaction
92
4.9.1 Mechanism of Dimethyl-2-
92
benzylidenemalonate
4.9.2
Mechanism of Methyl cinnamate
94
4.9.3
Mechanism of Dimethyl-2,2-
95
bis(hydroxyl(phenyl)methyl) malonate
5
SUMMARY AND RECOMMENDATION
96
5.1
Summary
96
5.2
Recommendation
98
REFERENCES
99
Appendices A-L
113-117
!
!
xi!
!
LIST OF TABLES
TABLE NO.
TITLE
PAGE
1.1
Evolution of molecular sieve materials [13]
2
2.1
Summary of principal proposal for zeolite synthesis
21
mechanism [64]
3.1
Composition of raw coal fly ash
35
3.2
Summary of the treatment of CFA by conventional and
38
microwave heating
3.3
Standard series for the sodium ion
43
4.1
Percentage of phase exist in sample at different NaOH
54
concentration
4.2
Assignment of IR bands for sample synthesis at different
56
NaOH concentration
4.3
Table of XRD percentage phase of sample in microwave
58
heating with 3M of NaOH solution
4.4
Table of XRD percentage phase of sample in microwave
60
heating with 4M of NaOH solution
4.5
Table of XRD percentage phase of sample in microwave
61
heating with addition of sodium aluminate
4.6
FTIR assigned bands for sample synthesized with 3M of
63
NaOH
4.7
FTIR assigned bands for sample synthesized with 4M of
64
NaOH
4.8
FTIR assigned bands for sample synthesized with
64
addition of sodium aluminate and 45 minutes of heating
4.9
Result of gravimetric analysis of silica in the reaction
66
liquor
4.10
Crystallinity changes of the sodalite ion exchange with
70
!
xii!
potassium ion
4.11
Crystallinity changes of the sodalite ion exchange with
72
cesium ion
4.12
Crystallinity changes of the sodalite ion exchange with
73
group 2 metal ion
4.13
EDX elemental analysis data for Na-SOD,K-SOD60 and
74
Cs-SOD60
4.14
Elemental analysis of the samples
75
4.15
Lists of peaks for TPDCO2
80
4.16
Conversion percentage for catalyst with different ion
84
exchange temperature conducted at 150oC
4.17
Percent conversion for Na-SOD catalyst at different
88
temperature
4.18
Conversion percentage of catalyst first cycle and second
91
cycle
4.19
Relationship of catalyst basic strength and crystallinity
towards reactivity
!
!
!
92
!
xiii!
!
!
LIST OF FIGURES
FIGURE NO.
TITLE
PAGE
2.1
Cross section of an example of microwave radiation[42]
11
2.2
Zeolite!building!units![13]
14
2.3
Example structure of zeolite
15
2.4
NMR Ranges of 29Si chemical shifts of Si (nA1) units in
16
zeolites. The dotted lines for Si (4A1) units designate the
shift range for sodalites[56].
2.5
Basic synthesis of zeolite. The starting material are
18
converted by an influence of aqueous mineralizing agent
[64]
2.6
Concept of equilibrium model for zeolite synthesis
19
process [68]
2.7
Structure of sodalite
23
2.8
Sodalite structure after combination of building units
24
[79]
2.9
Base site and Lewis acid site of zeolite
26
2.10
Remarks on the ion exchange principle [91]
27
3.1
Flowchart of the study
48
4.1
XRD of the calcined CFA
51
4.2
IR spectrum for calcined CFA
52
4.3
XRD patterns of samples a) 3M NaOH b) 4M NaOH, c)
53
5 M NaOH d) sodalite xrd pattern from reference [54]
4.4
FTIR spectra of a) CFA treated with 3 M NaOH b) 4 M
55
NaOH c) 5 M NaOH
4.5
XRD patterns of microwave synthesis of zeolite with 3
M of NaOH at different time of heating a) 15 minutes b)
30 minutes c) 45 minutes d) XRD reference of sodalite
57
!
xiv!
[54].
4.6
XRD patterns of samples treated in 4M of NaOH, a) 15
59
minutes b) 30 minutes, c) 45 minutes d) XRD reference
of sodalite [54]
4.7
XRD patterns of sample treated with NaOH a)3M NaOH
61
b)3M NaOH + sodium aluminate c)reference XRD for
sodalite crytal phase [54].
4.8
29
4.9
Relationship of the remaining dissolved silica with that
66
Si MAS NMR spectroscopy of sample Na-SOD
67
of the percentage formation of sodalite.
4.10
XRD patterns of Sodalite ion exchange with 1M of
69
potassium acetate a) room temperature b) 60oC c)80oC
4.11
XRD diffractogram of Sodalite ion exchange with 1M of
71
Cesium nitrate a) 60oC b) 80oC
4.12
XRD difrractogram of Sodalite ion exchange with group
72
2 metal at 60 oC a) Ca-SOD60 b) Ba-SOD60 c) CsSOD60
4.13
Flame photometry regression line for sodium ion.
75
4.14
FESEM images of a)Na-SOD b)K-SOD60 c)Cs-SOD60
77
4.15
Proposed mechanism for CO2 desorption
78
4.16
TPDCO2 analysis for sample a) Na-SOD b) K-SOD60 c)
79
Cs-SOD60
4.17
and
81
GC-FID diffractogram for reaction by using K-SOD60 in
83
Knoeveagel
reaction
between
benzaldehyde
dimethyl malonate
4.18
6 hour
4.19
Selectivity of the catalysts
86
4.20
Percent conversion versus time of reaction for catalyst a)
89
Na-SOD b) K-SOD 60 c) Cs-SOD60
4.21
Reaction
mechanism
between
dimethyl
malonate
production
benzaldehyde
of
and
93
dimethyl-2-
benzylidenemalonate
4.22
Reaction
mechanism
between
benzaldehyde
and
94
!
xv!
dimethyl malonate production of methyl cinnamate.!
4.23
Mechanism
formation
of
bis(hydroxyl(phenyl)methyl) malonate.
!
!
!
dimethyl
2,2-
95
!
xvi!
!
!
!
ABBREVIATIONS
!
CFA
Coal fly ash
CuKα
X-ray diffraction from copper Kα energy levels
FTIR
Fourier Transform Infrared
SEM
Scanning Electron Microscopy
XRD
X-ray diffraction
2θ
Bragg angle
NaOH
Sodium hydroxide
CH3COOK
Potassium acetate
CsNO3
Cesium nitrate
CaCl2
Calcium chloride
Sr(NO3)2
Strontium nitrate
KBr
Potassium Bromide
GC
Gas chromatography
!
!
!
!
!
!
xvii!
LIST OF APPENDICES
APPENDIX
TITLE
PAGE
A
EDX spectrum for Na-SOD
113
B
EDX spectrum for K-SOD60
113
C
EDX spectrum for Cs-SOD60
114
D
Chromatogram of the products!
114
E
MS of dimethyl-2-benzylidenemalonate
115
F
MS of methyl cinnamate
115
G
MS of dimethyl-2,27bis(hydroxyl(phenyl)methyl)!
116
malonate
H
Calculation of the crystallinity
116
I
Calculation of the preparation of standard solution
116
J
Calculation of the percent conversion
117
K
Calculation of the selectivity
117
L
List of publications
117
!