vii
TABLE OF CONTENTS
CHAPTER
1
2
TITLE
PAGE
TITLE
i
DECLARATION
ii
DEDICATION
iii
ACKNOWLGEMENT
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
x
LIST OF FIGURES
xi
LIST OF ABBREVIATIONS
xiii
LIST OF APPENDICES
xiv
INTRODUCTION
1.0
Background of Study
1
1.2
Statement of problem
3
1.3
Significant of research
4
1.4
Objectives
4
1.5
Scope of the research
5
LITERATURE REVIEW
2.1
Homogeneous and Heterogeneous catalyst
7
2.2
Zeolite
8
2.3
Nanozeolite
10
2.4
Sodalite
11
2.4.1
14
2.5
Synthesis of Sodalite
Acid base chemistry
17
viii
2.6
2.5.1 Solid Base Catalysts
18
2.5.2 Application of Solid Base Catalysts
18
2.5.3 Zeolite as Base Catalysts
19
2.5.4 Basic Zeolite
19
2.5.5 Basic Sites in Zeolites
21
2.5.6 Characterization of Basic Sites
23
Knoevenagel Condensation Reactions (KCR)
24
2.6.1 Catalysts in Knovenagel Condensation
25
Reaction
2.6.2 Solvents in Knoevenagel Condensation
27
Reaction
2.6.3 Solvent-free Technologies in Knoevenagel
27
Condensation Reaction
3
RESEARCH METHODOLOGY
3.1
Chemicals Reagents
29
3.2
Instrumentation and Equipments
30
3.3
Synthesis of Sodalite
30
3.4
Characterization of Sodalite
34
3.4.1 X-ray Diffraction (XRD)
34
3.4.2 Fourier Transform Infrared (FTIR)
35
3.4.3 Field Emission Scanning Electron
35
Microscope (FESEM)
3.6
4
3.4.4 Nitrogen Adsorption Analysis
37
3.4.5 CO2-IR Spectroscopy
38
3.4.6 Pyridine-IR Spectroscopy
38
Catalytic Testing in Knoevenagel Reaction
39
RESULTS AND DISCUSSION
4.1
Fumed Silica
40
4.2
Hydrothermal Synthesis Approach to Nanosodalite
42
ix
4.3
Effects of Temperature and Time Duration of
43
Heating
4.4
Structural Characterization
45
4.4.1 X-Ray Diffractogram (XRD)
45
4.4..1.1 Summary of Formation of Sodalite Based
57
on Different Temperature
4.4.2 Fourier Transform Infrared (FTIR)
59
4.4.3 Field Emission Scanning Electron
68
Microscope (FESEM)
4.4.4 Energy Dispersive of X-Ray Analysis
70
(EDAX)
4.5
4.4.5 Nitrogen Adsorption Analysis
72
4.4.6 Basicity Testing CO2 Monitoring FTIR
73
4.4.7 Acidity Testing Pyridine Monitoring FTIR
74
Catalytic Testing of Sodalite in Knoevenagel
75
Condensation Reaction
4.5.1 Analysis of Product
76
4.5.1.1 Reactivity of the Catalyst
76
4.5.1.2 Mechanism of the Knoevenagel reaction
80
using base catalyst
5
CONCLUSION AND RECOMMENDATIONS
5.1
Conclusion
82
5.2
Recommendations
83
REFERENCES
84
APPENDICES
95
x
LIST OF TABLES
TABLE NO.
TITLE
PAGE
3.1
Different Conditions Applied In the Synthesis of SOD by
33
Direct Hydrothermal Synthesis
4.1
Different Conditions Applied In the Synthesis of SOD by
44
Direct Hydrothermal Synthesis
4.2
Relative Crstallinity of Sodalite at 60°C at Different time
50
of heating.
4.3
Relative Intensity of sodalite formed in different time of
53
heating at 80°C
4.4
Relative Intensity of sodalite formed in different time of
56
heating at 90°C.
4.5
The time required for pure sodalite formation at different
58
temperature
4.6
4.7
Effect of temperature for hydrothermal treatment to the
crystallite particle size.
Summary of the Stretching Frequencies of Sodalite
58
61
Obtains at 60°C with Different time of heating.
4.8
Summary of the Stretching Frequencies of Sodalite
65
Obtains at 80°C with Different time of heating
4.9
Summary of the Stretching Frequencies of Sodalite
68
Obtains at 90°C with Different time of heating
4.10
The EDAX Elemental Analysis Data for S8 and S16
71
4.11
BET surface area for sample S8 and S16
72
4.12
The Time Required for Product Formation
77
4.13
Percentage Conversion of Reactant and Selectivity of
79
Product
xi
LIST OF FIGURES
FIGURE NO.
TITLE
PAGE
1.1
Flow Chart of the Experimental Research
6
2.1
Sodalite Structure Consisting of Space-Filling
12
Arrangement of β Cage
3.1
Flow Chart for the Synthesis of Nano Sodalite Without
32
Organic Additives.
3.3
Types of Nitrogen Physisorption Isotherm
37
4.1
IR spectra for fumed silica (Cab-O-Sil)
41
4.2
Diffractogram for Sample From Four Different Time of
46
Heating at 40º C (a) 16 hours, (b) 20 hours and, (c) 24
hours, (d) 28 hours.
4.3
Diffractogram for Sample from Four Different Time of
48
Heating at 60º C (a) 2 hours, (b) 3 hours and, (c) 4 hours,
(d) 5 hours.
4.4
Relative Crystallinity of Sodalite at 60°C at Different
50
time of heating
4.5
Diffractogram for Sample From Four Different Time of
52
Heating at 80º C (a) 1 hours, (b) 2 hours and, (c) 4 hours,
(d) 5 hours.
4.6
Relative Crystallinity of Sodalite at 80°C at Different
53
time of heating.
4.7
Diffractogram for Sample From Four Different Time of
55
Heating at 90º C (a) 1 hours, (b) 2 hours and, (c) 3 hours,
(d) 4 hours.
4.8
Relative Crystallinity of Sodalite at 90°C at Different
56
time of heating
4.9
FTIR of Sodalite with Heating Temperature 60°C with
61
xii
Different time of heating (a) 2 hours (b) 3 hours (c) 4
hours (d) 5 hours
4.10
FTIR of Sodalite with Heating Temperature 80°C with
64
Different time of heating(a) 1 hours (b) 2 hours (c) 3
hours (d) 4 hours.
4.11
FTIR of Sodalite with Heating Temperature 90°C with
67
Different time of heating(a) 1 hours (b) 2 hours (c) 3
hours (d) 4 hours
4.12
FESEM image of nanosodalite obtain from 5 hours of
69
hydrothermal treatment at 60°C
4.13
FESEM image of sodalite obtain from 4 hours of
70
hydrothermal treatment at 90°C
4.14
The EDAX Spectrum for Nanosodalite
71
4.15
Unidentate carbonate
73
4.16
FTIR spectra of S8 (nanosodalite) (a) before CO2
74
exposure (b) after CO2 exposure.
4.17
Proposed mechanisms for CO2 adsorption
74
4.18
FTIR spectra of S8 (nanosodalite) (a) before pyridine
75
exposure (b) after pyridine exposure
4.19
Chromatogram of the product of Knoevenagel Reaction
78
using Nanosodalite as Catalyst.
4.20
Reaction Mechanism Scheme of the Knoevenagel
Reaction using Base Catalyst.
81
xiii
LIST OF ABBREVIATIONS
XRD
– X-Ray Diffraction
FESEM
– Field Emission Scanning Electron Micrograph
EDX
– Energy Dispersive X-Ray
FTIR
– Fourier Transform Infrared Spectroscopy
IR
– Infrared Spectroscopy
SOD
– Sodalite
Pt
– Platinum
Au
– Aurum
GC-FID
– Gas chromatography – Flame ionization detector
GC-MSD
– Gas chromatography – Mass selective detector
PTFE
– Polytetrafluoroethane
xiv
LIST OF APPENDICES
APPENDICE
TITLE
PAGE
NO.
A
Chromatogram of Microsodalite (S16)
95
B
MS of Main Product Benzylidenemalononitrile
96
C
XRD of Sodalite (Standard)
97
D
XRD of Zeolite A (Standard)
97
E
XRD of Zeolite P
98
F
XRD of NanoSodalite (S8)
98
G
XRD of Microsodalite(S16)
99
H
References data of Infrared Spectroscopy
100