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Synthesis of New Heterogeneous Nanocatalyst Based On Carbon Nanocomposite through Formation of C-C Bonds And Investigation of the Kinetic Effect of Synthesized Heterogeneous Nanocatalyst on Gas Phase Unimolecular Reaction of Methan

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  1. Sc. Thesis in Chemistry- Physical Chemistry

Synthesis of New Heterogeneous Nanocatalyst Based On Carbon Nanocomposite through Formation of C-C Bonds

And

Investigation of the Kinetic Effect of Synthesized Heterogeneous Nanocatalyst on Gas Phase Unimolecular Reaction of Methane

In this work, a new method has been introduced to synthesize heterogeneous nanocatalyst based on C-C nanocomposite. Hot isostatic pressure (HIP) was used as thermal methods to made C-C composites supported on nickel surface. The produced catalyst was analyzed by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and the surface area by Brunauer, Emmett, Teller (BET) method for characterization. Then, a static system was adapted to investigate the role of the prepared heterogeneous nanocatalyst for decomposition of some light organic compounds. Using the C-C nanocomposite on nickel support contains active sites for thermal decomposition of methane and provides the possibility of catalyst recovery and the possibility of reaction at a lower temperature ~ 660 ̊ K, while increasing the efficiency of the reaction to 40% (w/w) and increasing hydrogen production to 24%.

 

List of content

 

Content                                                                                                                                        Page

 

CHAPTER ONE

Introduction. 2

1.1. Hydrogen production. 2

1.2. Methods for hydrogen production. 2

1.2.1. Hydrogen production from natural gas. 2

1.2.1.1. Steam reforming. 3

1.2.1.2. Partial oxidation. 3

1.2.1.3. Autothermal reforming. 3

1.3. Thermal decomposition of methane. 4

1.3.1. Thermo-catalytic decomposition of methane. 4

1.3.1.1. Metal catalysts for thermo-catalytic decomposition of methane. 5

1.3.1.2. Nickel-based catalyst 5

1.3.1.3. Effect of support in heterogeneous catalysts. 6

1.3.1.4. Methods of catalyst preparation. 7

1.3.1.4.1. Impregnation method for catalyst preparation. 7

1.3.1.4.2. Co-precipitation method for catalyst preparation. 7

1.3.1.5. Catalyst deactivation. 8

1.3.1.5.1. Causes of deactivation of catalysts. 8

1.3.2. Carbonaceous catalyst 9

1.3.2.1. Deactivation of carbonaceous catalysts. 10

1.4. Carbon-carbon composites. 11

1.4.1. Properties and applications of carbon-carbon composites. 11

1.4.2. C-C composite preparation. 12

Content                                                                                                         Page

1.4.2.1. Chemical vapor deposition. 13

1.4.2.2. Chemical vapor infiltration. 14

1.4.2.3. Liquid phase impregnation. 15

1.4.2.4. Hot isostatic pressure impregnation carbonization. 15

1.4.2.5. Hot pressing. 15

 

Chapter Two

Historical background and literature review.. 19

2.1. Metal catalysts for thermo-catalytic decomposition of methane. 19

2.2. Carbonaceous catalysts for thermo-catalytic methane decomposition. 21

2.3. Carbon-carbon composites. 24

The objective of this thesis. 29

CHAPTER THREE

3.1. Materials for catalyst synthesis. 31

3.1.1. Naphthalene. 31

3.1.2. Carbon nanotubes. 32

3.1.3. Carbon nanobud. 32

3.1.4. Polyacrylonitrile. 33

3.1.5. Epoxy resin. 33

3.2. Methods for synthesis of the catalyst. 33

3.3. Catalyst characterization. 34

3.4. Apparatus. 34

Content                                                                                                         Page

CHAPTER FOUR

Experimental 38

CHAPTER FIVE

Conclusions. 60

Recommendation for the future studies. 61

References. 62

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

List of Tables

 

Table                                                                                                             Page

Table 1-1. Range of properties for C-C composites. 12

Table 3-1. Physical properties of naphthalene. 31

Table 4-1. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T= 700±5 K and P = 100±10 Torr. Mass of catalyst= 5.582 g. 38

Table 4-2. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T= 800±5 K and P = 100±10 Torr. Mass of catalyst= 5.582 g. 39

Table 4-3. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T= 900±5 K and P = 100±10 Torr. Mass of catalyst= 5.582 g. 39

Table 4-4. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T= 1000±5 K and P = 100±10 Torr. Mass of catalyst= 5.582 g. 39

Table 4-5. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst= 5.678 g. 40

Table 4-6. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =200±10 Torr. Mass of catalyst= 5.668 g. 40

Table 4-7. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =50±10 Torr. Mass of catalyst= 5.668 g. 41

Table                                                                                                             Page

Table 4-8. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=5.668 g. 41

Table 4-9. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=5.668 g. In the presence of silica. 42

Table 4-10. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=5.668 g. 42

Table 4-11. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=5.668 g.In presence of epoxy resin and CO2.

. 43

Table 4-12. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=5.668 gr. In presence Ni nanoparticles. 43

Table 4-13. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=660±5 K and P =100±10 Torr. Mass of catalyst=5.753 g. With repeating 22 time sintering cycles. 44

Table 4-14. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=700±5 K and P =100±10 Torr. Mass of catalyst=9.574 g. When reflex system and powder include naphthalene and PAN was used. 44

Table                                                                                                             Page

Table 4-15. Concentration of products produced when methane gas is passed over catalyst (C-C composite surface coated on the Ni) at T=730±5 K and P =100±10 Torr. Mass of catalyst=5.749 g. 45

Table. 4-16. Properties of adsorption/desorption isotherm of nitrogen gas at 77 K for naphthalene/PAN. 50

Table. 4-17. Result of the BET plot for nitrogen adsorption gas at 77 K for naphthalene/PAN. Sample weight 0.2171 g, Saturated vapor pressure 90.2 KPa. 51

Table. 4-18. Result of pore size distribution of naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. Sample weight 0.2171 g, Saturated vapor pressure 90.2 KPa………………………………………..52

Table. 4-19. Result of the size distribution of holes with diameters less than 1 nm of naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. Sample weight 0.2171 g, Saturated vapor pressure 90.2 KPa . 53

Table. 4-20. Properties of adsorption/desorption isotherm of nitrogen gas at 77 K for SWCNT/Naphthalene/PAN composite. 54

Table. 4-21. Result of the BET plot for nitrogen adsorption gas at 77 K for SWCNT/Naphthalene/PAN composite. Sample weight 3.0300E-02 g, Saturated vapor pressure 89.940 KPa. 55

Table. 4-22. Result of pore size distribution of SWCNT/Naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. Sample weight 3.0300E-02 g, Saturated vapor pressure 89.940 KPa. 56

List of Figures

Figure                                                                                                                                    Page

Fig. 1.1. Carbon-carbon manufacturing processes. Liquid phase impregnation (LPI), hot isostatic pressure impregnation carbonization (HIPIC), Chemical vapor infiltration (CVI)………………….…………………………………………………………………….13

Fig. 1.2. Carbon-carbon manufacturing process – hot isostatic pressing (HIP) method  17

Fig. 3.1. A schematic diagram of the experimental setup. 36

Fig. 4.1. SEM images of the fracture surfaces of C-C nanocomposite. (a) Voltage: 26 kv, Resolution:  100x, Scale: 100μm. (b) Voltage: 26 kv, Resolution:  2.50 kx, Scale: 10μm. (c) Show the size of C-C composite particles; Voltage: 26 kv, Resolution: 10.0 kx, Scale: 1.0 μm. 46

Fig. 4.2. SEM images of the fracture surfaces of SWCNT/Naphthalene/PAN nanocomposite. (a) Voltage: 26 kv, Resolution:  40.0 kx, Scale: 1.0 μm. (b) Voltage: 26 kv, Resolution:  20.0 kx, Scale: 1.0 μm. (c) Show the size of C-C composite particles; Voltage: 26 kv, Resolution: 40.0 kx, Scale: 1.0 μm. 47

Fig. 4.3. Adsorption/desorption isotherm of nitrogen gas at 77 K for naphthalene/PAN composite. 50

Fig. 4.4. The BET plot equation for nitrogen adsorption gas at 77 K for naphthalene/PAN composite. 51

Fig. 4.5. Pore size distribution of naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. 52

Fig. 4.6. The size distribution of holes with diameters less than 1 nm of naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. 53

 

 

Figure                                                                                                                                    Page

Fig. 4.7. Adsorption/desorption isotherm of nitrogen gas at 77 K for SWCNT/Naphthalene/PAN composite. 54

Fig. 4.8. The BET plot equation for nitrogen adsorption gas at 77 K for SWCNT/Naphthalene/PAN composite. 55

Fig. 4.9. Pore size distribution of SWCNT/Naphthalene/PAN composite from nitrogen adsorption isotherms using BJH method. 56

Fig. 4.10. XRD spectra of C-C composite. a) XRD spectra of naphthalene. b) XRD spectra of PAN. 57

Fig. 4.11. XRD spectra of SWCNT/Naphthalene/PAN composite. 58

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