vii
TABLE OF CONTENTS
CHAPTER
1.
TITLE
PAGE
TITLE
i
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENTS
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xii
LIST OF FIGURES
xiv
LIST OF SYMBOLS
xxii
LIST OF ABBREVIATIONS
xxiv
LIST OF PUBLICATIONS
xxvii
LIST OF APPENDICES
xxix
INTRODUCTION
1
1.1 General Background
1
1.2 Direct Catalytic Conversion of Methane to Higher
2.
Hydrocarbons
6
1.3 Problem Statements
8
1.4 Research Objectives
9
1.5 Research Scope
9
LITERATURE REVIEW
13
2.1 General Introduction
13
2.2 Natural Gas as Fuels
15
viii
2.3 Natural Gas to Hydrocarbon Processing
2.3.1 Indirect Processes Natural Gas to Gasoline
17
18
2.3.2 Direct Synthesis Natural Gas to Higher
Hydrocarbons
3.
24
2.4 Catalyst Support
38
2.5 Zeolite ZSM –5
40
RESEARCH METHODOLOGY
46
3.1 Material and Chemicals
46
3.2 Catalysts Synthesis
48
3.2.1 Tungsten Supported on Various Zeolites
Catalysts
48
3.2.2 W-Modified Li-HZSM-5 Catalysts
49
3.2.3 HZSM-5 Loaded with 2 % wt. of Tungsten
49
3.3 Catalyst Characterization
50
3.3.1 BET Surface Area Measurement
52
3.3.2 X-ray Diffraction (XRD)
52
3.3.3 UV-Vis Diffuse Reflectance Spectroscopy
(UV-Vis DR)
53
3.3.4 Temperature-programmed Desorption and
Oxidation (TPD and TPO)
54
3.3.5 Fourier Transform Infrared Spectroscopy
(FTIR) Pyridine
3.3.6 Thermogravimetric Analysis (TGA)
3.4 Catalytic Performance Test
55
55
55
3.4.1 Dehydroaromatization of Methane over
Supported W Catalysts in The Absence of
Oxygen
56
ix
3.4.2 Dehydroaromatization of Methane with and
without O2 Addition over W/HZSM-5
Catalysts
57
3.4.3 Conversion of Methane to Gasoline Range
Hydrocarbons over W/HZSM-5
58
3.4.4 Conversion of Methane to Gasoline Range
Hydrocarbons: Effect of Co-Feeding
58
3.4.5 Kinetic Study for The Conversion of Methane
in The Presence of Co-Feeding to Gasoline
4.
Hydrocarbons
60
3.5 Analysis of Product Composition
60
3.6 Design of Experiments (DOE)
64
3.6.1 Process Models for DOE
65
3.6.2 Full Factorial Designs
66
3.6.3 Response Surface Designs
67
DUAL EFFECTS OF SUPPORTED TUNGSTEN
CATALYSTS FOR DEHYDROAROMATIZATION
OF METHANE IN THE ABSENCE OF OXYGEN
70
4.1 Introduction
70
4.2 Experimental
71
4.3 Results and Discussion
71
4.3.1 Catalytic Performance of Supported W
Catalysts
71
4.3.2 Correlation between Activity and Properties of
Supported W Catalysts
4.4 Conclusions
82
92
x
5.
IMPROVED PERFORMANCE OF W/HZSM-5
BASED CATALYSTS FOR
DEHYDROAROMATIZATION OF METHANE
93
5.1 Introduction
93
5.2 Experimental
95
5.3 Results and Discussion
95
5.3.1 Characterization of Fresh Catalysts
5.3.2 Results of Catalytic Testing
5.4 Conclusions
6.
95
102
116
PRODUCTION OF GASOLINE FROM CATALYTIC
REACTION OF METHANE IN THE PRESENCE OF
7.
ETHYLENE OVER W/HZSM-5
117
6.1 Introduction
117
6.2 Experimental Procedure
118
6.2.1 Catalyst Preparation
118
6.2.2 Activity Testing
119
6.3 Results and Discussion
119
6.4 Conclusions
125
CONVERSION OF METHANE TO GASOLINE
RANGE HYDROCARBONS OVER W/HZSM-5
CATALYST: EFFECT OF CO-FEEDING
126
7.1 Introduction
126
7.2 Experimental Procedure
128
7.2.1 Catalyst Preparation
128
7.2.2 Catalyst Testing
129
7.3 Results and Discussion
129
xi
7.4 Conclusion
8.
136
KINETICS STUDY FOR THE CONVERSION OF
METHANE IN THE PRESENCE OF CO-FEEDING
TO GASOLINE HYDROCARBONS OVER W/HZSM-
9.
5 CATALYST
137
8.1 Introduction
137
8.2 Experimental Procedure
140
8.2.1 Catalyst Preparation
140
8.2.2 Catalytic Activity
140
8.3 Reaction Mechanism and Kinetic Model
140
8.4 Kinetic Parameters Estimation
144
8.5 Results and Discussion
149
8.5.1 Effect of Temperature
149
8.5.2 Effect of CH4 Concentration
151
8.5.3 Kinetic Parameters
152
8.6 Conclusion
155
CONCLUSIONS AND RECOMMENDATIONS
156
9.1 Conclusions
156
9.2 Recommendations
159
REFERENCES
161
APPENDICES A-B
178
xii
LIST OF TABLES
TABLE NO
TITLE
1.1
Characteristics of fuel oils (De Jong, 1996).
2.1
The contents of natural gas ( Abella and Gallardo,
PAGE
2
2001 )
14
2.2
Process reaction for syngas production
20
2.3
Laboratory investigations of oxidative coupling of
methane (Zaman, 1999)
2.4
26
Literature references on heterogeneous partial
oxidation of natural gas to methanol using oxygen or
air as oxidant
28
2.5
A wide variety of support catalyst
39
3.1
Physical properties of the catalyst supports
46
3.2
Precursor used for catalyst preparation
47
3.3
Physical properties of the reactant gaseous (Air
Liquide Ltd., 2002)
48
3.4
GC FID temperature program
62
3.5
GC TCD valve switching program
63
3.6
Number of runs for a 2k Full Factorial
67
4.1
BET surface areas and micropore volumes of W
supported catalysts
4.2
82
The amount of NH3 desorption and total number of
acid sites of the various catalysts supports and W
supported HZSM-5 catalysts
84
xiii
5.1
NH3-TPD data of fresh catalysts
5.2
Integrated band area of Brønsted and Lewis acid sites
98
and the number of Brønsted and Lewis acid sites in the
fresh catalysts
5.3
BET surface areas and pore volumes of fresh and used
catalysts
6.1
118
Independent variables with the operating range of each
variable
6.3
116
Properties of HZSM-5 (Si/Al=30) zeolite and
W/HZSM-5 catalysts
6.2
101
119
An experimental plan based on CCD and the three
responses
120
6.4
ANOVA for the second order model equations
122
7.1
Conversion of methane and ethylene at two different
CH4/C2H4 molar ratios: 10/80 and 86/14, respectively
7.2
Conversion of methane in the presence co-feedings
methanol and ethylene
8.1
129
131
Results of catalytic activity the conversion of methane
in the presence co-feeding to gasoline products over
W/HZSM-5 catalyst at temperature range of 9731073K
8.2
150
Estimated kinetic and equilibrium constants krs, K1,
and K2 obtained from a non linear regression of the
8.3
model
152
Comparison of kinetic parameter with literature values
153
xiv
LIST OF FIGURES
FIGURE NO
1.1
TITLE
World energy demand, 1970-2020
(www.eia.doe.gov/iea/)
1.2
PAGE
1
Proven world oil and natural gas reserves
(http://www.eia.doe.gov/emeu/aer/resource.html)
3
1.3
A brief utilization of natural gas (Peterson et al., 2001)
5
2.1
World natural gas production in 2003
14
2.2
The world natural gas consuming.
15
2.3
Fuel Chains from NG and crude oil based. (Hekkert,
2005)
2.4
Chemical conversion of methane to higher
hydrocarbons
2.5
16
18
Shell Middle Distillate Syhthesis (SMDS) in Bintulu
(Shell Malaysia, 2001)
22
2.6
New Zealand Methanol to Gasoline (MTG)
23
2.7
Infrared spectra of 2 wt% Cr/H-ZSM-5 that contained
different concentration of Brönsted acid sites
(Weckhuysen, 1998)
2.8
32
NH3-TPD spectra of the Mg2+ doped 3 % W-1.5 %
Zn/HZSM-5 systems with different Mg2+ doping
amounts (Xiong, 2001)
2.9
The proposed reaction mechanism of methane
34
xv
conversion into C5+
2.10
35
The structure of the secondary building unit of HZSM5. The positions of the tetrahedral “T-atoms”, silicon or
aluminium are indicated by circles.
2.11
The addition of secondary building units leading to the
crystalline framework of ZSM-5
2.12
40
41
The three diemensional channel network of HZSM-5.
There are linkings between the straight and sinusoidal
channels
2.13
42
Cross-sectional dimensions of (a) straight and (b)
sinusoidal channels in ZSM-5. The large circles
represent oxygen and the small circles represent the Tatoms (either Si or Al)
2.14
42
Schematic representation of molecular shape
selectivity effects: (a) reactant selectivity; (b) product
selectivity; (c) restricted transition state selectivity; (d)
molecular traffic selectivity (in ZSM-5) (Smart and
Moore, 1992)
2.15
Scheme for the generation of Brönsted and Lewis acid
sites in zeolites (Weitkamp, 1994)
3.1
45
Schematic diagram of testing rig for the single step
conversion of methane to higher hydrocarbons
3.2
43
56
Experimental rig set up for the conversion of methane
in the presence of co-feeding to gasoline range
hydrocarbons
3.3
59
The arrangement of columns and valve switching
program
62
xvi
3.4
A schematic ‘Black Box’ process model
3.5
A Response surface types: A) “Peak”, B)”Hillside”, C)
“Rising Ridge”, and D) “Saddle”
4.1
65
69
Methane conversion over the 3 wt.%-loading W
catalysts with various supports for DHAM at 973 K ,
GHSV=1800 ml/(g.h) , Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (z)W-H2SO4/HZSM- (Si/Al=30) ;
(|)W/HZSM-5 (Si/Al=30); („)W/Hβ(Si/Al=25);
(S)W/USY(Si/Al=5.1); (U)W/Al2O3
4.2
72
Aromatic selectivities over the 3 wt.%-loading W
catalysts with various supports for DHAM at 973 K ,
GHSV=1800 ml/(g.h) , Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (z)W-H2SO4/HZSM-5 (Si/Al=30) ;
(|)W/HZSM-5 (Si/Al=30); („)W/Hβ(Si/Al=25);
(S)W/USY(Si/Al=5.1); (U)W/Al2O3
4.3
73
C2 selectivities over the 3 wt.%-loading W catalysts
with various supports for DHAM at 973 K ,
GHSV=1800 ml/(g.h) , Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (z)W-H2SO4/HZSM- (Si/Al=30) ;
(|)W/HZSM-5 (Si/Al=30); („)W/Hβ(Si/Al=25);
(S)W/USY(Si/Al=5.1); (U)W/Al2O3
4.4
74
Effect of Si/Al ratio of HZSM-5 on the methane
conversion over 3 wt.% W-H2SO4/HZSM-5 catalysts
for dehydroaromatization of methane at 1073 K ,
GHSV=1800 ml/(g.h). Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (|)W-H2SO4/HZSM-5 (Si/Al=30);
(…)W-H2SO4/HZSM-5 (Si/Al=50) ; (U) WH2SO4/HZSM-5 (Si/Al=80)
75
xvii
4.5
Effect of Si/Al ratio of HZSM-5 on aromatics
selectivities over 3 wt.% W-H2SO4/HZSM-5 catalysts
for dehydroaromatization of methane at 1073 K ,
GHSV=1800 ml/(g.h). Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (|)W-H2SO4/HZSM-5 (Si/Al=30);
(…)W-H2SO4/HZSM-5 (Si/Al=50) ; (U) WH2SO4/HZSM-5 (Si/Al=80)
4.6
76
Effect of Si/Al ratio of HZSM-5 on C2 selectivities
over 3 wt.% W-H2SO4/HZSM-5 catalysts for
dehydroaromatization of methane at 1073 K ,
GHSV=1800 ml/(g.h). Feed Gas = CH4 + 10% N2, 1
atm. Catalysts : (|)W-H2SO4/HZSM-5 (Si/Al=30);
(…)W-H2SO4/HZSM-5 (Si/Al=50) ; (U) WH2SO4/HZSM-5 (Si/Al=80)
4.7
77
Effect of GHSV on methane conversion. Catalysts :
(|)W-H2SO4/HZSM-5 (Si/Al=30); (…)WH2SO4/HZSM-5 (Si/Al=50) ; (U) W-H2SO4/HZSM-5
(Si/Al=80). Reaction conditions : 1073 K, feed gas :
CH4 + N2, 1 atm, The data taken at 1 h after the
reaction starts
4.8
78
Effect of GHSV on aromatics selectivity
(|)W-H2SO4/HZSM-5 (Si/Al=30); (…)WH2SO4/HZSM-5 (Si/Al=50) ; (U) W-H2SO4/HZSM-5
(Si/Al=80). Reaction conditions : 1073 K, feed gas :
CH4 + N2, 1 atm, The data taken at 1 h after the
reaction starts
4.9
Effect of GHSV on C2 hydrocarbons.
Catalysts : (|)W-H2SO4/HZSM-5 (Si/Al=30); (…)WH2SO4/HZSM-5 (Si/Al=50) ; (U) W-H2SO4/HZSM-5
79
xviii
(Si/Al=80). Reaction conditions : 1073 K, feed gas :
CH4 + N2, 1 atm, The data taken at 1 h after the
reaction starts
4.10
80
Comparison between oxidative and non oxidative of
DHAM reaction over 3 %W-H2SO4/HZSM-5.
(Si/Al=30) at 1073 K, GHSV=3000 ml/(g.h), 1 atm
4.11
81
Ammonia-TPD profile of catalyst supports used in the
present study: (a) USY (b) Hβ (c) HZSM-5 (Si/Al =30)
(d) Al2O3
4.12
85
UV-DRS of 3 % W based catalyst on different
supports : (a) Al2O3 ; (b) USY ; (c) Hβ ; (d) HZSM-5
(Si/Al=30)
4.13
UV- DRS of (a) 3 % W-H2SO4/HZSM-5 (Si/Al=30)
and (b) 3 % W/HZSM-5 (Si/Al=30).
4.14
88
UV-DRS of 3 %W-H2SO4/HZSM-5 with different
Si/Al ratios: (a) 30 ; (b) 50 ; (c) 80.
4.15
87
89
Effect of Si/Al ratio of HZSM-5 on A220 and A310 ratio
attributed to monomeric and polymeric concentration
of tungsten species
5.1
91
XRD patterns of HZSM-5 (a), 3WH-Z (b), 3WHLi-Z
(5:1) (c), 3WHLi-Z (4:1) (d), 3WHLi-Z (1:1) (e),
3WLi-Z (f), and WO3 (g) catalysts
5.2
96
NH3-TPD spectra of catalysts (a) HZSM-5, (b) 3WHZ, (c) 3WHLi-Z(5:1), (d) 3WHLi-Z(4:1), (e) 3WHLiZ(1:1), (f) 3WLi-Z
5.3
IR spectra of pyridine adsorption at room temperature
followed by desorption at 423 K on HZSM-5 (a),
97
xix
3WH-Z(b), 3WHLi-Z(5:1) (c), 3WHLi-Z(4:1) (d),
3WHLi-Z(1:1) (e), 3WLi-Z (f)
5.4
100
Results of catalytic testing for the conversion of
methane to aromatics hydrocarbons in the absence of
oxygen over the catalysts. Methane conversion vs time
on stream. (1) 3WH-Z, (2) 3WHLi-Z(5:1), (3) 3WHLiZ(4:1), (4) 3WHLi- Z(1:1) (Reaction conditions used
were 1 atm, T=1073 K, WHSV: 1800 ml/(g.h).
5.5
104
Results of catalytic testing for the conversion of
methane to aromatics hydrocarbons in the absence of
oxygen over the catalysts. C2 selectivity vs time on
stream. (Reaction conditions used were 1 atm, T=1073
K, WHSV: 1800 ml/(g.h). (1) 3WH-Z, (2) 3WHLiZ(5:1), (3) 3WHLi-Z(4:1), (4) 3WHLi- Z(1:1)
5.6
105
Results of catalytic testing for the conversion of
methane to aromatics hydrocarbons in the absence of
oxygen over the catalysts. Aromatics selectivity vs
time on stream (Reaction conditions used were 1 atm,
T=1073 K, WHSV: 1800 ml/(g.h). (1) 3WH-Z, (2)
3WHLi-Z(5:1), (3) 3WHLi-Z(4:1), (4) 3WHLi- Z(1:1)
5.7
107
Results of catalytic testing for the conversion of
methane to aromatic hydrocarbons with the presence of
7.6% oxygen in feed over the catalysts. Methane
conversion vs time on stream (Reaction conditions
used were 1 atm, T=1073 K, WHSV: 20868 ml/(g.h)).
(1) 3WH-Z, (2) 3WHLi-Z(5:1), (3) 3WHLi-Z(4:1), (4)
3WHLi- Z(1:1), (5) 3WLi-Z
5.8
Results of catalytic testing for the conversion of
110
xx
methane to aromatic hydrocarbons with the presence of
7.6% oxygen in feed over the catalysts. C2 selectivity
vs time on stream (Reaction conditions used were 1
atm, T=1073 K, WHSV: 20868 ml/(g.h)). (1) 3WH-Z,
(2) 3WHLi-Z(5:1), (3) 3WHLi-Z(4:1), (4) 3WHLiZ(1:1), (5) 3WLi-Z
5.9
111
Results of catalytic testing for the conversion of
methane to aromatic hydrocarbons with the presence of
7.6% oxygen in feed over the catalysts. Aromatic
selectivity vs time on stream (Reaction conditions used
were 1 atm, T=1073 K, WHSV: 20868 ml/(g.h)). (1)
3WH-Z, (2) 3WHLi-Z(5:1), (3) 3WHLi-Z(4:1), (4)
3WHLi- Z(1:1), (5) 3WLi-Z
5.10
112
TPO profiles of used catalysts in the absence of oxygen
on samples (1) 3WH-Z (2) 3WHLi-Z (5:1) and (3) with
addition of 7.6% oxygen in methane feed over 3WH-Z
catalyst
5.11
114
TG profile of the coked catalysts after the reaction with
and without oxygen on the catalysts: (a ) 3WH-Z (b)
3WHLi-Z (5:1) and (c) 3WH-Z with addition of 7.6%
oxygen in methane feed.
6.1
115
Correlation of the observed and predicted value for (a)
selectivity of C5-C10 non-aromatics hydrocarbons (b)
selectivity of aromatics hydrocarbons
6.2
Response surface methodology for the C5-10 nonaromatics hydrocarbons selectivity
7.1
123
Hydrocarbons products distribution as a function of
reaction temperature with methane and ethylene as a
124
xxi
feed. GHSV(CH4+C2H4) =1200 ml/g h, CH4:C2H4
molar ratio=86:14.
7.2
132
Ethylene conversion with time on stream for the
reaction of methane and ethylene over W/HZSM-5 and
HZSM-5 catalysts. Reaction condition : T=400 C,
GHSV(CH4+C2H4) =1200 ml/g h, CH4:C2H4 molar
ratio=86:14
7.3
134
Product distribution for the reaction of methane and
ethylene over HZSM-5 and W/HZSM-5 catalysts, T =
400 ◦C, and GHSV(CH4+C2H4) =1200 ml/g h,
CH4:C2H4 molar ratio=86:14
8.1
135
Calculation and optimization of the krs, K1 and K2
flowchart
146
8.2
Verification Rcalc compared to Rexp
148
8.3
Effect of temperature on methane conversion under
different methane concentrations
8.4
Experimental reaction rate as a function of methane
concentration at different temperatures
8.5
8.6
149
151
Van’t Hoff and Arrhenius plots for equilibrium and
rate constants
154
Experimental versus calculated reaction rate
154
xxii
LIST OF SYMBOLS
α
-
Level of significance
β 0 , β1 , β 2
-
Regression coefficient, the linier term
β11, β 22 , β33 -
Regression coefficient, the squared term
β12, β13 , β 23 -
Regression coefficient, the interaction term
θ
-
Diffraction Angle
Cv
-
Molar concentration of vacant sites
Ci.s
-
Molar concentration of sites occupied by species i
λ
-
Wavelength usually 1.54056 Å for Cu Kα radiation
ΔG
-
Gibbs free energy, J/mol
ΔHads
-
Adsorption enthalpy, J/mol
ΔHi
-
Heat of reaction i, J/mol
ΔSads
-
Adsorption entropy, J/mol.K
ΔSi
-
Entropy of reaction i, J/mol.K
Ea
-
Activation energy, J/mol
FT
-
Total gas flow (ml/h)
F
-
Objective function
FCH4
-
Molar flow rate of methane, kmol/h
F-value
-
The ratio of mean squares due to regression to mean squares due to
residual
xxiii
Ki
-
Equilibrium constant
ki
-
Reaction rate constant, kmol/kgcat.h.atm
krs
-
Surface reaction rate constant (controlling step), kmol/kgcat.h atm
N-p
-
Degrees of freedom for residual
p-1
-
Degrees of freedom for regression
Pj
-
Partial pressure of component j, atm
Po
-
Saturation pressure of adsorbate gas at the experimental
temperature
R
-
Constant of ideal gas, 8.314 J/mol.K
R2
-
The coefficient of determination
ri
-
Reaction rate, kmol/kgmol.h
T
-
Temperature
V
Volume of gas adsorbed at pressure P
Vm
-
Volume of gas adsorbed in monolayer
W
-
Mass of catalyst, kg
X1, X2, X3
-
Independent variables of temperature, concentration of ethylene in
a mixture of methane-ethylene in the feed and catalyst loading,
respectively
XCH4
-
Methane conversion
Y1,Y2,Y3
-
The response variables corresponding to selectivity of C5+ liquid
hydrocarbons, C5-C10 non-aromatics, and aromatics
xxiv
LIST OF ABBREVIATIONS
ANOVA
-
Analysis of variance
ATR
-
Auto thermal reforming
BET
-
Brunauer-Emmet-Teller
CCD
-
Central composite design
CNG
-
Compressed natural gas
DF
-
Degree of freedom
DHAM
-
Dehydroaromatization of methane
DME
-
Dimethyl ether
DOE
-
Design of experiments
FCC
-
Fluid catalytic cracking
FCV
-
Fuel cell vehicle
FID
-
Flame ionization detector
FT
-
Fischer Tropsch
FT-IR
-
Fourier transform infrared
GC
-
Gas chromatography
GHSV
-
Gas hourly space velocity
GTL
-
Gas-to-liquid
HC
-
Hydrocracking
HDS
-
Hydrodesulfurisation
ICEV
-
Internal combustion engine vehicle
xxv
LPG
-
Liquefied petroleum gas
MAS NMR
-
Magic-Angle-Spinning Nuclear Magnetic Resonance
MeOH
-
Methanol
MFI
-
Mobile Number Five
MOGD
-
Mobil Olefin to Gasoline and Distillate
MS
-
Mean square
MTG
-
Methanol to gasoline
NA
-
Nitrogen adsorption
NG
-
Natural gas
NGV
-
Natural gas vehicles
OCM
-
Oxidative coupling of methane
OGD
-
Olefin to gasoline and distillate
POM
-
Partial oxidation of methane
RSM
-
Response surface methodology
SA
-
Total surface area
Si/Al
-
Silica to alumina ratio
SMDS
-
Shell middle distillate synthesis
SR
-
Steam reforming
SRM
-
Steam reforming of methane
SS
-
Sum of squares
SSE
-
Sum of squares due to residuals
SSR
-
Sum of squares due to regression
xxvi
SST
-
Total of sum of squares
Syngas
-
Synthetic gas
TCD
-
Thermal conductivity detector
TCF
-
Trillion Cubic Feet
TGA
-
Thermogravimetric analysis
TMI
-
Transition metal ions
TPD/TPR/TPO
-
Temperature-programmed desorption/reduction/oxidation
USY
-
Ultra stable Y zeolite
UV
-
Ultraviolet
UV-Vis DR
-
UV-Vis diffuse reflectance spectroscopy
VIS
-
Visible
WGS
-
Water-gas shift
WHSV
-
Weight hourly space velocity
XPS
-
X-ray photoelectron spectroscopy
XRD
-
X-ray diffraction
ZSM-5
-
Zeolite secony mobil five
xxvii
LIST OF PUBLICATIONS
International refereed journals
1.
Kusmiyati and N.A.S. Amin, (2005), Production of gasoline range
hydrocarbons from catalytic reaction of methane in the presence of ethylene
over W/HZSM-5, Catalysis Today, Vol 106, No 1-4, p. 271-274.Elsevier B.V.
2.
Kusmiyati and N.A.S. Amin, (2005), Dual effects of supported W Catalysts for
Dehydroaromatization of Methane in the Absence of Oxygen, Catalysis Letters,
Vol. 102, No. 1-2, p.69-78, Springer Science.
3.
Nor Aishah Saidina Amin and Kusmiyati, (2004), Improved Performance of
W/HZSM-5 Catalysts for Dehydroaromatization of Methane, Journal of
Natural Gas Chemistry, Vol. 13, No. 3, p. 148-159, Science Press.
4.
Kusmiyati and N.A.S. Amin, (2006), Conversion of Methane to Gasoline
Range Hydrocarbons over W/HZSM-5 Catalyst: Effect of Co-Feeding. Fuel.
Elsevier B.V. (submitted)
5.
Kusmiyati and N.A.S. Amin, (2006), Kinetics Study of Methane Conversion to
Higher Hydrocarbons in Gasoline Range over W/HZSM-5 Catalyst. Reaction
Kinetics and Catalysis Letters. Springer Science. (submitted)
International refereed conferences and proceedings
1.
Kusmiyati and N.A.S. Amin, (2005), Production of Gasoline Range
Hydrocarbons from Catalytic Reaction of Methane in the Presence of Ethylene
over W/HZSM-5, International Conference on Gas-Fuel 2005, Brugge,
Belgium, 14-15 November 2005.
2.
Kusmiyati and Nor Aishah S.A. (2006), Conversion of Methane to Gasoline
Range Hydrocarbons Over W/HZSM-5 Catalyst : Effect of Co-Feeding,
Annual Fundamental Science Seminar (AFSS 2006), UTM, 6 -7th June 2006.
xxviii
3.
Kusmiyati and N.A.S. Amin, (2005), Bifunctional Catalyst of Modified
W/HZSM-5 for Dehydroaromatization of Methane in the Absence of Oxygen,
Annual Fundamental Science Seminar (AFSS 2005), UTM, 4 -5th July 2005.
4.
Kusmiyati and N.A.S. Amin, (2004), Dehydroaromatization of Methane in the
Absence of Oxygen over W Based Catalysts. Presented in 18 th Symposium of
Malaysian Chemical Engineers (SOMChE 2004), Perak, Malaysia, 13-14
December 2004.
5.
Kusmiyati and Nor Aishah Saidina Amin, (2004), Application of Central
Composite Design (CCD) and Response Surface Methodology (RSM) in the
Catalytic Conversion of Methane and Ethylene into Liquid Fuel Product,
Annual Fundamental Science Seminar (AFSS 2004), UTM, 14 -15th June
2004
xxix
LIST OF APPENDICES
APPENDIX
A
B
TITLE
PAGE
Gas Chromatogram Analysis and
Calculation of Conversion and Products Selectivity
Using Internal Standard
179
Mathcad Program for the Kinetic Studies
183