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Iron-Induced Deactivation of Supported Nickel Methanation Catalysts - 1978.

Dumesic, James A.

University of Wisconsin

In this pdf format, this document has 161 pages and is 4.61 MB.

Table of Contents

 

I.

Mossbauer Spectroscopy Cell for in situ Catalyst Characterization and Reaction Kinetics studies at high pressure

7

I. A.

Introduction

7

I. B.

Apparatus

4

I.B.1.

The High-Pressure Cell

9

I.B.2.

The Prereactor and Postreactor

12

I.C.

Performance

12

I.D.

References

19

II.

Deactivation Studies of Ni/Al2O3 Methanation Catalysts

28

II.A.

Experimental

29

II.B.

Results

31

II.C.

Discussion

33

II.D.

Conclusions

40

II.E.

References

42

III.

Appendix A.  Criteria for Stable Ni Particle size under Methanation Reaction Conditions:  Nickel Transport and Particle Size Growth via Nickel Carbonyl

62

III.A.

Experimental

63

III.A.1.

High Pressure Reaction System

63

III.A.2.

Particle Size Determinations

64

III.A.3.

Catalyst reparation and Treatment

64

III.B.

Results

67

III.C.

Discussion

70

III.C.1.

Nickel Transportation and Particle Size Growth

70

III.C.2.

Kinetic and Thermodynamic Aspects of Ni(CO)4 Formation

74

III.C.3.

Blockage of Surface Sites

79

III.C.4.

Methanation Kinetics

80

III.D.

Conclusions

82

III.E.

References

83

IV.

Appendix B - Iron Pentacarbonyl Decomposition over Grafoil

97

IV.

Production of Small Metallic Iron Particles

97

IV.A.

Experimental

98

IV.A.1.

Iron Pentacarbonyl Handling

98

IV.A.2.

Mossbauer Spectroscopy

99

IV.A.3.

Graphite Sample

100

IV.B.

Results

100

IV.C.

Discussion

102

IV.C.1.

Fe(CO)5 Adsorbed on Graphite Spectrum 1

102

IV.C.2.

Interaction of Metallic Iron with Graphite Spectra 2, 3, and 4

103

IV.C.3.

Quantitative Spectral Analysis Spectra 2 and 3

107

IV.C.4.

Proposed Iron Morphology

113

 

IV.D.

References

115

V.

Appendix C. Iron Pentacarbonyl Decomposition over Grafoil

133

V.

Effect of Sample Outgassing on Decomposition Kinetics

133

V.A.

Experimental

134

V.A.1.

Graphite Sample

134

V.A.2.

Mossbauer Spectroscopy

134

V.A.3.

Volumetric Gas Phase Measurements

135

V.B.

Results

137

V.B.1.

Mossbauer Spectroscopy

137

V.B.2.

Volumetric Gas Phase Measurements

138

V.C.

Discussion

140

V.C.1.

Mossbauer Spectroscopy

140

V.C.2

Volumetric Gas Phase Measurements

142

V.D.

Conclusions

148

V.E.

References

149