Disclaimer

ii

Table of Contents

iii

List of Figures

iv

List of Tables

viii

Abstract

1

1.

Objective and Scope

3

1.

Background

3

2.

Objectives

4

2.

Technical Progress

5

2.1

Summary of Results

5

2.2

Stability of Iron Nitride Catalysts

6

2.2.1

Introduction

6

2.2.2

Experimental Techniques

8

2.2.3

Preparation of Iron Nitride Catalysts

11

2.2.4

Iron Nitride Stability

21

2.2.5

Nitride Stability During Fischer-Tropsch Synthesis

27

2.3

Iron Nitride as Fischer-Tropsch Catalysts

30

2.3.1

Introduction

30

2.3.2

Steady State Fischer Tropsch Reaction over the Iron Nitrides

32

2.3.3

Kinetic Behavior at 458 K

37

2.3.4

Phase Behavior at 458 K

41

2.3.5

A-Fe Carburization at 458 K

41

2.3.6

γ-Fe₂N Carburization at 458K

45

2.3.7

e-Fe₂N Carburization at 458 K

48

2.3.8

ζ-Fe₂N Carburization at 458 K

50

2.3.9

Effect of CO Pretreatment on FTS

52

2.3.10

Kinetic Behavior of Preoxidized ζ-Fe₂N

58

2.3.11

Phase Behavior of Preoxidized ζ-Fe₂N

60

2.3.12

Hydrogenation of Catalysts After Reaction

65

2.3.13

Carburization of Iron and Iron Nitrides at 523 K

70

2.4

Modification of Iron Nitride Chemistry by Supports and by Gas Pha. Ammonia

93

2.4.1

Selectivity and Stability of Synthesis Reactions Over Iron Nitrides

93

2.4.2

Catalysts Preparation

94

2.4.3

Addition of Ammonia to Synthesis Gas

95

2.4.4

Small Particle Iron Carbon

101

3.

References

108

4.

Appendices

110

1.

Report Distribution List

110

2.

DOE Form RA 427

112