photocatalytic reduction of carbon dioxide and...
TRANSCRIPT
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PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE AND METHANE TO
LIGHT HYDROCARBONS OVER NITROGEN DOPED TITANIUM DIOXIDE
MOHAMMADREZA DASTAN
A dissertation submitted in partial fulfilment of the
requirements for the award of the degree of
Master of (Chemical Engineering)
Faculty of Chemical Engineering
Universiti Teknologi Malaysia
AUGUST 2014
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To my beloved father, mother and sister
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ACKNOWLEDGEMENT
I would like to express my deepest gratitude to Allah Almighty as with the
blessing this project has successfully been concluded.
Foremost, I would like to express my sincere gratitude to my supervisor Professor
Dr Nor Aishah Saidina Amin for the continuous support of my research, for her patience,
motivation, enthusiasm, and immense knowledge. Her guidance helped me in all the time
of research and writing of this dissertation. I could not have imagined having a better
supervisor and mentor for my master study. I would like to thanks Dr Muhammad Tahir
for introducing me to the topic as well for the support on the way. Aside, I would like to
express my warmest thanks to Chemical Reaction Engineering Group (CREG) members,
and other UTM friends for their support and valuable inputs regarding the research.
Words cannot express how grateful I am to my mother, my father and sister for all
of the sacrifices that you’ve made on my behalf. Your prayer for me was what sustained
me thus far. I would also like to thanks to all my family members, especially my dear
uncle, Mohsen Dastan for supported me in this long journey.
I also wish to express my gratitude to my beloved partner who will always be in
my heart for being with me through thick and thin.
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ABSTRACT
Concerns of fossil fuel reserves depletion and environmental pollution
problems have led to increased demand for alternative fuels. Therefore, methods for
converting natural gas into useful fuels were considered. The main objective of this
study is to develop pathways for photolysis reduction of carbon dioxide and methane.
Initially nanocatalyst were investigated using cell type photoreactor with C2H6 and
C3H8 as main products during CO2 reduction with CH4 over nitrogen (N) /TiO2
nanocatalyst. The yield of C2H6 over TiO2 was 35 µmole g-1 catal-1 enhanced to 166
µmole g-1 catal-1 using 15% N doped TiO2. Besides, the effects of parameters such as,
CH4/CO2 feed ratio, reaction temperature and light irradiation time on yield of
reduction of CO2 was studied. Finally, the central composite design (CCD) was
employed to find individual and interactive effects of the mentioned parameter on
yields of C2H6 was studied. The predicted values of the yield of C2H6 were found to
be in good agreement with experimental values (R2= 0.97), which indicate the
suitability of the CCD model.
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ABSTRAK
Kebimbangan terhadap pengurangan rizab bahan api fosil dan masalah
pencemaran alam sekitar telah membawa kepada peningkatan permintaan bagi bahan
api alternatif. Oleh itu, kaedah menukarkan gas asli kepada bahan api berguna dipilih.
Objektif utama kajian ini adalah untuk membangunkan laluan bagi pengurangan
photolysis terhadap karbon dioksida dan metana. Pada permulaan, naocatalyst dikaji
dengan menggunakan sel photoreactor dengan C2H6 dan C3H8 sebagai produk utama
bagi pengurangan CO2 bersama dengan CH4 terhadap nanocatalyst nitrogen (N)/TiO.
Kadar hasil bagi C2H6 C terhadap TiO2 adalah 35 µmole g-1 catal-1, dipertingkatkan
kepada 166 catal-1 g µmole-1 menggunakan 15% N disaluti oleh TiO2. Selain itu, kesan
parameter seperti, nisbah suapan CH4/CO2, suhu tindak balas dan sinaran cahaya masa
bagi hasil pengurangan CO2 telah dikaji. Akhirnya, pusat rekabentuk komposit (CCD)
digunakan untuk mencari kesan parameter yang dirujuk di atas secara individu dan
interaktif bagi pengahsilan C2H6 telah dikaji. Nilai ramalan bagi penghasilan C2H6
menunjukkan keputusan yang baik dengan nilai eksperimen (R2= 0.97), sekaligus
menunjukkan kesesuaian penggunaan CCD model.
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TABLE OF CONTENTS
CAHPTER TITLE PAGE
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xi
LIST OF FIGURES xii
LIST OF SYMBOLS xiv
LIST OF ABBREVIATIONS xvi
LIST OF APPENDICES xvii
1 INTRODUCTION
1.1 Background of research 1
1.2 Problem Statement of Research 3
1.3 Objectives of Research 4
1.4 Scope of Research 4
1.5 Research Hypothesis 5
2 LITERATURE REVIEW 6
2.1 Introduction 6
2.2 Energy Concern and Global Warming 7
2.3 Importance of the Methane Utilization 9
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2.4 Developments of Methane Conversion 10
2.4.1 Conversion to Hydrocarbon 10
2.4.2 Oxidation 10
2.4.3 Reforming 12
2.5 Photocatalysit Conversion of Methane 15
2.6 Fundamentals of photocatalysis 16
2.7 Titanium Dioxide Semiconductor 18
2.7.1 Improvemnet of TiO2 Photocatalytic
Activity
21
2.7.1.1 Nanosized TiO2 materials 21
2.7.1.2 Non- Metal Modify TiO2 Nanocatalysts 22
2.8 Synthesis and Characterization of TiO2
Nanocatalysts
23
2.8.1 Technologies for Developing
Nanoparticles
23
2.8.2 Sol-Gel Synthesis of TiO2 Nanoparticles 23
2.9 Characterization of Nanocatalysts 29
2.9.1 X-ray Diffraction (XRD) 29
2.9.2 Scanning electron microscopy (SEM) 33
2.9.3 Transmission Electron Microscopy
(TEM)
33
2.9.4 Fourier Transfer Infrared Spectroscopy
(FTIR)
33
2.9.5 Brunauer-Emmerr-Teller (BET) Surface
Area
32
2.9.6 UV-Visible Spectrophotometer 32
3 METHODOLOGY 33
3.1 Introduction 33
3.2 Materials of research 33
3.3 Synthesis of TiO2 Nanoparticles 35
3.3.1 Synthesis of N doped TiO2 Nanoparticles 36
3.4 Photocatlytic Carbon Dioxide and Methane 37
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Reductions into Fuel
3.4.1 Cell Type Phorocatalytic Reactor 37
3.5 Response Surface Methodology 33
4 RESULT AND DISCUSSION 43
4.1 Introduction 43
4.2 Characterization of Nanocatalysts 42
4.2.3 X-ray Diffraction Analysis 42
4.2.2 FESEM Analysis 43
4.2.3 TEM Analysis 44
4.2.4 FTIR Analysis 45
4.2.5 Adsorption Isotherm, Surface Area and
Pore Structure Analysis
46
4.2.6 DR UV-Vis Spectrophotometer
Analysis
43
4.3 Carbon Dioxide Reduction with Methane Using
Cell Type Photoreactor
50
4.3.1 Effect of Nitrogen Loading on TiO2
Photoactivity
50
4.3.2 Effect of CO2/CH4 Feed Ratio on
Hydrocarbon Yield
51
4.3.3 The effect of reaction Temperature on
Yield of Product
52
4.3.4 Effect of Irradiation Time on
Hydrocarbon
Yield
53
4.4 Mechanism of CO2 Photoreduction with CH4 54
4.5 Experimental Design and Optimization 55
4.5.1 Central Composite Design Model
Development and Validation
56
4.5.2 Analysis of Variance 58
4.5.3 Effect of Variable as Response Surface
and Counter Plots on Photocatalytic Process
60
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4.5.4 Optimal Condition of Photocatalytic
Reduction of CO2
63
4.6 Summary 64
5 CONCLUSION AND RECOMMENDATIONS 66
5.1 Conclusions 66
5.2 Recommendation for Future Research 67
REFERENCES 69
Appendixes 75-78
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LIST OF TABLE
TABLE NO TITLE PAGE
1.1 Location of Natural Gas Reserves 2
2.1 Change of Gibbs free energy for various reactions 14
2.2 Properties of anatase, rutile and brookite [45] 20
2.3 TiO2 based photocatalytic synthesis method 24
2.4 Important element used in the various steps of a sol-gel
process [45]
26
3.1 Type and characterization of materials used for catalyst
synthesis
34
3.2 Types of gases used for experiments 34
4.1 The physiochemical characteristic of TiO2 and N-doped
TiO2
48
4.2 Experimental range and levels of the independent variables 56
4.3 The 3-factor central composite design matrix and the value
of response function
57
4.4 ANOVA for Response Surface Quadratic Model for Yield
of Ethane
59
4.5 Optimization result using response surface method
64
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LIST OF FIGURE
FIGURE NO. TITLE PAGE
1.1 World proven reserves of natural gas (1012 m3) [1] 2
2.1 Schematic representation of band potential of several
semicundactor [37]
17
2.2 Mechanism and patways for photocatalytic oxidaction
[39]
18
2.3 Crystalline structure of TiO2 based maerials; Rutil,
Antase, Brookite [45]
20
2.4 Schematic Presentation of particle size on TiO2
photoactivity [49]
22
3.1 sol-gel methods for preparation of TiO2 nanoparticles 35
3.2 sol-gel method for preparation of N doped TiO2
nanoparticles
36
3.3 Schematic of cell type photoreactor system for CO2
reduction with CH4 to hydrocarbons
38
3.4 Central composite designs for the optimization of: (a)
two variables (b) three variables (●) Points of factorial
design, (○) axial points and (□) [61]
39
3.5 Flow chart of general research methodology 40
4.1 XRD pattern of anatase TiO2 and N/TiO2 catalyst 42
4.2 FESM micrographs of TiO2 nanoparticles (a-b) and N
doped TiO2 nanoparticle (c-d) at different magnification
43
4.3 TEM and HRTEM images of TiO2 and N/TiO2
nanoparticles
44
4.4 FTIR spectra of bare TiO2 and 15%N/TiO2 catalysts 45
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4.5 N2 adsorption –desorption isotherms of TiO2 and
N/TiO2 samples
47
4.6 Pore size distribution of TiO2 and N/TiO2 samples 47
4.7 Uv-Vis absorption spectra of TiO2 and N modified TiO2
nanocatalysts
49
4.8 Effect of Nitrogen loading on TiO2 photoactivity for
photocatalytic CO2 reduction (PCO2= .175 bar, PCH4 =
0.175, reaction temperature 100 (˚C), reaction time 3h)
51
4.9 Yield of C2H6 at various initial CO2/CH4 feed ratio over
15% N/TiO2 (Irradiation time 3h, reaction temperature
100 ˚C)
52
4.10 Effect of temperature on photocatalytic CO2 reduction
to C2H6 and C3H8 over 15% N/TiO2 photocatalyst
(reaction time 3h, CO2/CH4 feed ratio 1)
53
4.11 Effect of irradiation time on photocatalytic CO2
reduction to C2H6 and C3H8 over 15% N/TiO2
photocatalyst (reaction temperature, CO2/CH4 feed ratio
1)
54
4.12 Comparison between predicted and observed Ethane
yield (a), the predicted value and studentized residual
plot (b).
60
4.13 The response surface and counter plots function of
reaction temperature and irradiation time
61
4.14 The response surface and counter plots function of
nitrogen loading and reaction time
63
4.15 Desirability ramp for optimal condition of model 64
4.16 Perturbation plot of reaction time, reaction temperature
and nitrogen loading
65
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LIST OF SYMPOLS
𝛼 - Intensity factor
𝛽 - Full width at half maximum
c - Speed of light
D - Average Particle size
e- - Electron
Egap - Gap energy
Ebg - Energy band gap
E - Activation energy
Ep - Energy of photon
f - Photon flux
h - Planks constant
∆𝐻 - Change in enthalpy of reaction (Kj/mole
h+ - Hole
H - Heat of reaction
I - Light intensity (mW/cm2)
Ip - Photon Irradiance
k - Reaction rate constant
kl - Reduction rate constant
Kj - Kilo Joule
k2 - Oxidation rate constant
M - Metal
nm - Nanometer
N - Nitrogen
S - Active Site
TiO2 - Titanium dioxide
Ti - Titanium
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Hg - mercury
V - Volt
W - Watt
𝜆 - Wavelength
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LIST OF ABBREVIATIONS
C - Concentration
CVD - Chemical vapor deposition
CSD - Chemical solvent deposition
GHG - Greenhouse gas
NHE - Normal Hydrogen Electrode
BET - Braunaure-Element-Teller
FTIR - Fourier Transform Infrared Spectroscopy
FESEM - Field Emission Scanning Electron Microscopy
HRTEM - High Resolution Transmission Electron Microscopy
SEM - Scanning Electron Microscopy
XRD - X-ray Diffraction
UV-Vis - Ultraviolent-Visible
VLR - Visible light responses
CCD - Central composite design
RSM - Response surface methodology
ANOVA - Analysis of variance
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LIST OF APPENDICES
APPENDIX TITLE PAGE
A Photographs of photocatalytic reactor 79
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CHAPTER 1
INTRODUCTION
1.1 Background of Research
Currently, much of the energy used is produced by fossil fuels.
Unfortunately, deposits of fossil fuels reducing too fast owing to industrial
developments and other energy requirement. The use of fossil fuels increases air
pollution problem, as well as the effect of climate change and global warming. To
prevent environmental catastrophe and depleting of the fossil fuel resources a
generating notice has developed to replace non-fossil and environmentally friendly
energy sources.
Methane is introduced as a greenhouse gas. In the form of natural gas,
capacious volumes of methane are extensively accessible in nature. The great supply
of this gas cusses it attractive raw substance for fuels and chemical synthesis. Based
on the newest reports presently, proven world natural gas supplies are approximate to
6609 trillion cubic feet or about 187 trillion cubic (Figure 1.1) [1]. Because of a
large quantity of natural gas are predominantly found in far-off areas (Table 1),
Therefore gas exploitation and transportation is so expensive. This problem raises
the demand for converting gas into liquids on-site [2-6]. Pipeline and tanker can be
transported natural gas liquefied by refrigeration. Though, compressed gas to 80 atm
is necessary for transfer gas via these pipelines also for distant market it is possible
sometimes pipeline not be accessed [2, 4].
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Figure 1.1 World proven reserves of natural gas (1012 m3) [1]
Table 1.1: Location of Natural Gas Reserves (1012 m3) [1]
The most common method for converting methane into higher oxygenates
and hydrocarbons are not economical because these methods need to specific
conditions like high pressure, temperature and particular catalyst. Thus Scientists
encourage finding another method for conversion of carbon dioxide and methane to
valuable compounds. Methanol is a favorable compound between the products of
methane oxidation because it saves so much of energy of methane. In addition, carry
out transportation and storage needs. Methanol can be transformed into useful
product and oxygenated fuels or may be used straightly as fuel in industry [7].
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Heterogeneous photocatalysis is a developing technology also significant for
organic synthesis moreover for water and air cleaning. Scientists have worked in this
field for years. Heterogeneous photocatalysis has developed as a specific technique
for many usages, with the synthesis processing and characterization of new wide
band gap and narrow band gap semiconductor materials. In photocatalysis the
selectivity of light source is a very significant [7]. The main goal of this study is the
reduction of CO2 and CH4 to higher hydrocarbon with mild condition using
semiconductor photocatalyst and light.
1.2 Problem Statement of Research
Concerns of fossil fuel reserves depletion and environmental pollution
problems have led to increased demand for alternative fuels. Therefore, methods for
converting natural gas into useful fuels were considered. One of these methods
which is our interest is the photocatalyst reduction of carbon dioxide and methane to
hydrocarbons. However, breaking stable CO2 molecule through thermal reforming
requires higher energy. The basic problem in front in this study are explained as
below:
i. CO2 reduction with CH4 to hydrocarbon fuels is a two-step process which
demanded higher energy. However, on industrial, input energy provided by
composition of CH4 causes more greenhouse gases effect, it is also
uneconomical as well as unfriendly process to the environment.
ii. CO2 photocatalysts reduction to fuels have many advantages, yet
photocatalysts and reactors under investigations have lower efficiency due to
incompetent yield and repartition of light irradiation over the catalyst surface.
iii. TiO2 semiconductor is widely studied due to great availability, cheap and
many other benefits. It’s also has lower light adsorption performance,
obvious photoactivity and selectivity for photocatalytic CO2 reduction to
fuels
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1.3 Objectives of Research
The following are the objectives of this research:
i. To prepare, characterize and test the nitrogen modified TiO2
nanocatalysts (N-TiO2) for CO2 reduction to fuels.
ii. To investigate the effectiveness of various operating parameters on the
photoactivity of nanocatalysts in terms of yield
iii. To study central composite design matrix and response surface
methodology to design the experiments and evaluate the interactive
effects of the three most important operating variables.
1.4 Scope of Research
The following are the scope of this research:
i. TiO2 nanoparticle, N/TiO2 nanoparticle are prepared using sol-gel
single step method to study the path of CO2 photoreduction to
hydrocarbon fuels. Nanaocatalysts were characterized using X-ray
Diffraction (XRD), Field Emission Scanning Electron Microscopy
(FESEM), High Resolution Electron Microscopy (HRTEM), Fourier
Transfer infrared spectroscopy (FTIR), Brunauer-Emmerr-Teller
(BET) Surface Area and UV-Visible Spectrophotometer
ii. Operating parameter such as light intensity, N loading, reaction
temperature, feed ratio and irradiation time were investigated in cell
photoreactor.
iii. Design expert software was used to study the response surface
methodology (RSM) and the effect of three most elements on yield of
hydrocarbon and find optimum condition for CO2 and CH4
photoreduction.
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1.5 Research Hypothesis
Developing photocatalytic system for efficiently converting CO2
molecule to hydrocarbon fuels is the main focus of this study. Nanosized
catalysts and good designed photoreactor could help to achieve this aim. Hence,
most hypotheses of the research described as follows:
i. The single step CO2 reduction to hydrocarbon fuels is possible through
photochemical process. Nanostructured semiconductor catalyst is
organized to be designed in such a way which could enable to overcome
obstacles by providing higher light absorption capacity, controlling of
surface reaction for increasing selectivity and steps ahead toward higher
CO2 reduction. For this aim TiO2 nanoparticles doped with structured
material.
ii. Improved photocativity of CO2 reduction to hydrocarbon fuels will be
possible by modified Nonmetal ions to titanium structure. Nitrogen was
used because of their determine features and selective production of
hydrocarbon fuels.
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REFERENCES
1 U. S. Energy Information Administration, International Energy Outlook 2010
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