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Low Severity Upgrading of F-T Waxes With Solid Superacids - 1995

Wender, Irving
Tierney, John W.

University Of Pittsburgh

In the pdf format this document has 115 pages
1-19 640kb 40-59 721kb 80-99 630kb
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Table of Contents

Preface i
Abstract ii
Nomenclature xi
1.0 Introduction 1
2.0 Scientific Discussion 3
 

2.1

 Hydrocarbon Conversion by Hydrocracking and Hydroisomerization 3
  2.1.1 Hydrocracking 3
2.1.2 Hydroisomerization 4

2.2

 Catalysis in Hydrocracking and Hydroisomerization 5
 

2.2.1

 Catalytic Hydrocracking 5

2.2.2

 Catalytic Hydroisomerization 6

2.2.3

 Thermodynamic Considerations for Isomerization 7

2.3

 Superacid Catalysis 7
 

2.3.2

 Characterization of Solid Acids 8

2.3.3

 Hydrocarbon Transformation in Superacids 9

2.4

 Sulfate Promoted Metal Oxides 10
 

2.4.2

 Structure and Properties of Sulfate Promoted Metal Oxides  11

2.4.3

 Hydrocarbon Reactions Catalyzed by Sulfate Promoted Metal Oxides 12

3.0

 Research Objectives 19

4.0

 Synthesis of Anion-Modified Metal Oxides 20
 

4.1

 Objectives 20

4.2

 Background 20

4.3

 Experimental 21
 

4.3.1

 Chemicals and Materials Used 21

4.3.2

 Heterogeneous Precipitation Method 21
 

4.3.2.1

 Synthesis of ZrO2/SO4 and Pt/ZrO2/SO4 Using Zr(SO4)24H2O 21

4.3.2.2

 Synthesis of Pt/ZrO2/SO4 Using Zirconium Oxide Dichloride and Zirconium Oxide Dinitrate 23

4.3.2.3

 Synthesis of Pt/ZrO2/SO4 With Various Pt Loadings, PtO2/ZrO2/SO4 and PtO2+ZrO2/SO4 24

4.3.2.4

 Synthesis of Pd/ZrO2/SO4 and Ni/ZrO3/SO4 24

4.3.2.5

 Synthesis of Pt/HfO3/SO4 and Pt/ZrO2/MoO3 25

4.3.2.6

 Synthesis of Pt/HfO3/SO4 and Pt/ZrO2·HfO3/SO4 25

4.3.3

 Homogeneous Precipitation Method 26

4.4

 Final Remarks 26

5.0

 Catalyst Characterization 29
  5.1 Objectives 29
5.2 Background 29
5.3 Experimental 30
 

5.3.1

 Characterization of the Physical Properties 30
 

5.3.1.1

 Crystalline Structures and Average Particle Size 30

5.3.1.2

 BET Surface Area, Pore Volume and Area Distributions 30

5.3.1.3

 Sulfur Analysis 31

5.3.1.4

 Thermal Stability 31

5.3.2

 Characterization of Acidic Properties 31
 

5.3.2.1

 Nature of Acid Sites by FTIR 31

5.3.2.2

 Temperature-Programmed Desorption 32

5.4

 Results and Discussion 33
 

5.4.1

 Effect of Addition of Sulfate Group on Properties of Zirconium Oxide 33

5.4.2

 Effect of the Preparation Procedures on Properties of Pt/ZrO2/SO4 35
 

5.4.2.1

 Precipitation Methods 35

5.4.2.2

 Effect of Calcination Temperature 36

5.4.2.3

 Effect of the Nature of the Anion 38

5.4.2.4

  Effect of the Concentration of Sulfuric Acid 38

5.4.3

 Properties of Pt and Sulfate-Promoted Mixed Zirconium and Hafnium Oxides 40

5.4.4

  Effect of Addition of Hydrogenation Metals on the Acidic Properties of ZrO2/SO4 41

5.5

  Summary 42

6.0

  Activity of Anion-Modified Metal Oxides for Hydrocracking and Hydroisomerization of Alkanes 44
 

6.1

  Objectives 44

6.2

  Background 44

6.3

  Experimental 45
 

6.3.1

 Experimental Setup 45

6.3.2

  Reaction Procedure 46

6.4

  Results and Discussion 47
 

6.4.1

  Effect of Preparation Procedure on Catalytic Activity 47
  6.4.1.1  Effect of the Precipitation Method and Nature of Zirconia Precursor 47
6.4.1.2  Effect of Calcination Temperature 49
6.4.1.3  Effect of the Nature of the Anion 51
6.4.1.4  Effect of H2SO4 Concentration 52

6.4.2

  Effect of Addition of Hydrogenation Metals on the Catalytic Activity of ZrO2/SO4 55
  6.4.2.1  Hydrogenation Metal 55
6.4.2.2  Platinum Loading 59
6.4.2.3  Catalytic Activity of Sulfate-Promoted Bimetallic Oxides (Pt/ZrO2·HfO2/SO4) 63

6.5

  Summary 66

7.0

  Effect of Reaction Conditions on Catalytic Activity in Hydrocracking and Hydroisomerization of Alkanes 68
 

7.1

  Objectives 68

7.2

  Background 68

7.3

  Experimental 68

7.4

  Results and Discussion 70
 

7.4.1

  Catalytic Activity of Pt/ZrO2/SO4 Toward Different Long Chain Hydrocarbons 70

7.4.2

  Effect of Reaction Conditions 70
  7.4.2.1  Reaction of n-Dotriacontane 71
7.4.2.2  Effect of Initial Hydrogen Pressure 73
7.4.2.3  Long-Term Performance of Pt/ZrO2/SO4 74
7.4.2.4  Effect of Reaction Temperature 75
7.4.2.5  Effect of Addition of Hydride Transfer Agents (Methylcyclopentane and Adamantane) 76
7.4.2.6  Effect of Addition of Olefins 76

7.4.3

  Further Comments on the Mechanism of Hydrocracking and Hydroisomerization 79

7.5

  Summary 80

8.0

 Kinetic Modeling of Hydrocracking and Hydroisomerization of n-Hexadecane 81
  8.1  Objectives 81
8.2  Background 81
8.3  Experimental 82
8.4  Results and Discussion 82
  8.4.1  Kinetic Model 82
8.4.2  Kinetic Parameter Estimation 85
8.4.3  Application of the Kinetic Model 87

8.5

  Summary 90

9.0

  Conclusions 91
Bibliography 94