Section 1
889kb

1.0 

Objective

1

2.0 

Introduction

1

2.1

Problem Statement

1

2.2

Background Work

3

2.2.1

Fischer-Tropsch Synthesis Reaction Mechanism

3

2.2.1.1

Dissociative Chemisorption of CO

3

2.2.1.2

Carbon Species in/on Working Fischer-Tropsch Catalysts

7

2.2.1.2.1

Reaction Intermediate Carbon

7

2.2.1.2.2

Less Active Form of Carbon

7

2.2.1.2.3

Poison Carbon

8

2.2.1.2.4

Bulk Carbide

9

2.2.1.3

Chain Growth and Termination

10

2.2.1.4

Water Gas Shift Reaction

10

2.2.1.4.1

Water Gas Shift Catalysts

10

2.2.1.4.2

Water Gas Shift Reaction Mechanism

11

2.2.1.4.3

Water Gas Shift Activity of Cobalt

12

2.2.1.4.4

Water Gas Shift Activity of Ruthenium

13

2.2.2

 State-of-the Art Catalysts

13

2.2.3

Review of Literature Reports on Hydrocarbon Cutoff

15

2.2.4

Review of Literature Reports on Particle Size Effects with Supported Ruthenium Catalysts in Fischer-Tropsch Synthesis

19

2.2.5

Review of Micelle Literature

21

2.2.5.1

Principles of Micelle Formation

21

2.2.5.2

Reverse Micelle Procedure for Making Catalysts

22

2.3

Research Approach

24

2.4

Project Team

24

Section 2
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3.0

Summary

26

3.1

Newly Developed Catalyst

26

3.1.1

Current Performance

26

3.1.2

Potential for Improvement of the New Catalyst

28

3.1.2.1

Effect of Modifiers

28

3.1.2.2

Effect of Metal-Support Interaction

28

3.1.2.3

Effect of a Second Bimetallic Component

28

3.1.2.4

Strategy for Spent Catalyst

29

3.1.2.5

Overall Assessment

30

3.1.3

Activation and Start-Up Procedure

30

3.1.4

Reproducibility of the New Catalyst

31

3.2

Elucidating the Relationship Between Properties and Function of Ruthenium Catalysts

31

3.2.1

Ruthenium Metal Agglomeration

31

3.2.2

Water Gas Shift Reaction

32

3.2.3

Hydrocarbon Synthesis Activity

33

3.2.4

Olefin-to-Paraffin Ratio

33

3.2.5

Chain Growth Probability

33

3.2.6

General Applicability of Catalyst Preparation and Characterization Method

34

3.3

Hydrocarbon Cutoff Hypothesis

314

3.4

Characterization of Coke on Ruthenium Catalysts

35

3.5

Elucidation of the Role of Modifier n the Improved Catalytic Stability Observed

37

4.0

Experimental

40

4.1

Pretreatment Procedure for the C-73-1-101 Iron Reference Catalyst

41

4.2

SAXS Procedure for Characterizing Micelle Solutions

42

4.3

Catalyst Characterization Techniques

42

4.3.1

Gas Adsorption

44

4.3.2

STEM

46

4.3.3

EXAFS

47

4.3.4

XRD

51

4.3.5

XPS

52

4.3.6

CO FTIR

53

4.3.7

IR

55

4.3.8

X-Ray Fluorescence

55

4.3.9

HRMS

56

4.3.10

NMR

57

4.3.11

DSC

58

4.3.12

TGA

59

Section 3
921kb

4.4

Catalyst Testing Plant and Procedure

59

4.4.1

Fixed-Bed Reactor System

59

4.4.2

Product Collection and Overview of Analytical Procedures

59

4.4.3

Pilot Plant On-Line Analytical Equipment

62

4.4.4

Off-Line Analytical Procedures

64

4.4.4.1

Analysis of Gas Leaving the O°C Separator

64

4.4.4.2

Analysis of Oxygenates

65

4.4.4.3

Analysis of Organic Phase by GC

66

4.4.4.4

Analysis of Organic Phase by Gel Permeation Chromatography

66

4.4.5

Conversion and Selectivity Calculations

67

4.4.6

Catalyst Testing Procedure

69

4.4.7

Catalyst Testing Conditions

70

5.0

Results and Discussion

71

5.1

Establishment of Experimental Procedures

81

5.1.1

Applications of Gel Permeation Chromatography to Analysis of Fischer-Tropsch Wax

81

Section 4
513kb

5.1.2

Establishment of Catalyst Testing and Analytical Procedures with Reference C-73-1-101 Iron Catalyst

93

5.1.2.1

Characterization of Reference Iron Catalyst

93

5.1.2.2

Testing of the Reduced C-73-1-101 Iron Catalyst in Fixed-Bed Pilot Plant

101

5.1.2.2.1

Tests Under the First Set of Reference Conditions (Runs 1-3)

101

5.1.2.2.2

Tests Under the Second Set of Reference Conditions (Runs 4-6)

106

5.1.2.2.3

Test Under the Third Set of Reference Conditions (Run 7)

112

Section 5
833kb

5.1.2.2.4

Test Under the Fourth Set of Reference  Conditions (Run 8)

117

5.1.2.2.5

Analyses of Wax Fractions Extracted from Used Catalysts

117

5.1.2.2.6

Repeated Test Under the Third Set of Reference Conditions (Run 10)

122

5.1.3

Application of the Reverse Micelle Technique to Ruthenium Catalysts

143

5.1.3.1

Characterization of Reverse Micelle Solutions by SAXS

143

Section 6
716kb

5.1.3.2

Control of Ruthenium Particle Size by the Reverse Micelle Technique

154

5.1.3.2.1

Catalysts with -5 mm Ruthenium Particles

154

5.1.3.2.2

Catalysts with <2-4 mm Ruthenium Particles on Alumina

166

5.1.3.2.3

Ruthenium Catalyst on Titania

168

5.1.3.2.4

Ruthenium Catalyst on Alumina-Titania

168

5.1.3.3

XRD Examination of Ruthenium Catalysts Prepared by Reverse Micelles

173

5.1.4

Application of Conventional Aqueous Impregnation to the Preparation of Highly Dispersed Ruthenium Catalysts

178

Section 7
906kb

5.1.5

Application of EXAFS to Characterization of Ruthenium Catalysts

181

5.1.5.1

Measurements at CHESS

181

5.1.5.2

Measurements at Brookhaven National Laboratory

187

5.2

Selection of the Most Promising Catalyst Development Approach

196

5.2.1

Performance of Al₂O₃-Supported Catalysts with Different Size Ruthenium Particles

196

5.2.1.1

Highly Dispersed Ruthenium Catalysts with -1% Ru

196

5.2.1.1.1

Test at H₂:CO Feed Ratio = 0.9, 208°C at Inlet and 35 atm (Run 16)

196

Section 8
853kb

5.2.1.1.2

Tests at H₂:CO Feed Ratio = 2.9, 208°C at Inlet and 35 atm (Runs 18, 21)

208

Section 9
1002kb

5.2.1.1.3

Test Under Maximum Water Gas Shift Conditions (Run 25)

230

5.2.1.1.4

Test at H₂:CO Feed Ratio = 2.0, 225°C at Inlet and 35 atm (Run 32)

237

5.2.1.2

Catalysts with <2-4 mm Ru Particles with -1% Run

243

5.2.1.2.1

Test at 0.9 H₂:CO Feed Ratio, 208°C at Inlet and 35 atm (Run 17)

243

Section 10
776kb

5.2.1.2.2

Test at 2.9 H₂:CO Feed Ratio, 208°C at Inlet and 35 atm  (Run 19)

254

5.2.1.2.3

Test at 1.5 H₂:CO Feed Ratio, 200°C at Inlet and 14.3 atm (Run 20)

264

5.2.1.3

Catalysts with 3-500 mm Ruthenium Particles wiht -1% Ru (Runs 9, 11-14)

272

5.2.1.4

Catalysts with -5 mm Average Size Ruthenium Particlese with -1% Ru

274

Section 11
541kb

5.2.1.4.1

Test at 0.9 H₂:CO Feed Ratio, 208°C at Inlet and 35 atm (Run 15)

275

5.2.1.4.2

Test with Inactive Catalyst (Run 26)

290

Section 12
921kb

5.2.1.4.3

Establishment of the Effect of Operational Conditions with Tests at H₂: CO Feed Ration = 2, 208-250°C, 35-103 atm (Runs 23, 24 and 33)

293

Section 13
867kb

5.2.1.4.4

Establishment of Catalytic Stability with Tests at H₂:CO Feed Ratio = 2, 225°C at Inlet and 35 atm (Runs 34-36)

317

Section 14
909kb

5.2.1.4.5

Establishment of Catalytic Stability with a Test at H₂:CO Feed Ratio = 2, 208°C at Inlet and 62 atm (Run 37)

337

5.2.2

 Performance of Ruthenium Catalysts Prepared on Other Supports

348

5.2.2.1

Ruthenium on Y-Zeolite (Runs 27 and 28)

348

Section 15
763kb

5.2.2.2

Highly Dispersed Ruthenium on Titania (Runs 29 and 30)

361

5.2.2.3

3-10 mm Ruthenium on Titania (Run 31)

374

Section 16
1314kb

5.2.2.4

Ruthenium on Alumina-Titania (Runs 39, 41-43)

379

Section 17
811kb

5.2.3

Ruthenium Metal Agglomeration Phenomenon Results Summary

408

5.2.3.1

Effect of Particle Size on Ruthenium Metal Agglomeration

408

5.2.3.2

Effect of Support on Ruthenium Metal Agglomeration

410

5.2.3.2.1

Y-Zeolite vs. Alumina

410

5.2.3.2.2

Titania vs. Alumina

410

5.2.4

Hydrocarbon Cutoff Hypothesis Investigation Summary

414

5.2.5

Ruthenium Metal Particle Size Effects in Fischer-Tropsch Synthesis

414

5.2.5.1

Activity Effect

414

5.2.5.2

Selectivity Effects

416

5.2.5.2.1

Water Gas Shift Reaction

416

5.2.5.2.2

 Olefin-to-Paraffin Ratio

419

5.2.5.2.3

Chain Growth Probability

423

5.2.6

Support Effects on Ruthenium Catalytic Performance in Fischer-Tropsch Synthesis

432

5.2.6.1

Y-Zeolite vs. Al₂O₃

432

Section 18
790kb

5.2.6.2

Titania vs. Alumina

435

5.2.7

Selection of the Most Suitable Catalyst Development Approach

436

5.3

Modification of Alumina-Supported Ruthenium Catalyst Composition to Improve Stability

436

5.3.1

Iron-Modified Ruthenium Catalyst with 1% Ru

436

5.3.2

Ruthenium Catalyst with 2.8% Ru

443

Section 19
1253kb

5.3.3

Iridium-Modified Ruthenium Catalyst with 2.8% Ru

455

5.3.4

New Modified-Ruthenium Catalyst Demonstration

462

Section 20
815kb

5.3.5

Elucidation of the Relation Between Properties and Function of the New Modified Ruthenium Catalyst

489

5.3.5.1

Characterization of Fresh Catalysts

489

5.3.5.1.1

EXAFS Measurements

491

5.3.5.1.2

CO FTIR Measurements

491

5.3.5.1.3

XPS Measurements

495

5.3.5.2

Characterization of Used Catalysts

501

5.3.5.2.1

STEM Examination

501

5.3.5.2.2

XPS Measurements

508

Section 21
676kb

5.3.5.2.3

NMR Measurements

515

5.3.5.2.3.1

Establishment of Experimental Procedures with Catalyst 4966-124 Tested in Run 39

515

5.3.5.2.3.2

Examination of the Al2O3-Supported New Modified Ruthenium Catalyst 4966-180 and the Unmodified Ruthenium Catalyst 4966-198 After Testing in Runs 46 and 47

525

5.3.5.2.3.3

Overview of NMR Measurements

522

5.3.5.2.4

Analysis of Materials Extracted from Used Catalysts

530

5.3.5.2.4.1

 Establishment of Experimental Procedures with Catalyst 4966-124 Tested in Run 39

530

Section 22
594kb

5.3.5.2.4.2

Analyses of Material Extracted from Modified Ruthenium Catalyst 4966-180 Used in Run 46 and from Unmodified Ruthenium Catalyst 4966-198 Used in Run 47

540

5.3.5.2.5

Burning Characteristics of Carbon on Used Catalysts

544

5.3.5.2.5.1

 Establishment of DSC and TGA Experimental Procedures with Catalyst 4966-124 Test in Run 39

545

5.3.5.2.5.2

DSC and TGA Analyses with Modified Ruthenium Catalyst 4966-180 After Use in Run 46 and with Modified Ruthenium Catalyst 4966-198 After Use in Run 47

550

Section 23
465kb

5.3.5.2.6

Overall Summary of Used Catalyst Characterization

566

5.3.5.3

Elucidation of the Role of Modifier in the Improved Catalytic Stability Observed

568

6.0 

Appendix

571

7.0 

References

573