CATALYTIC AIR OXIDATION OF SEVERAL CONDENSED RING COMPOUNDS

188 Pages·07.377 MB·English

by  PINCUS, IRVING

The Pennsylvania State College
The Graduate School
Department of Mineral Technology
Division of Fuel Technology
The Catalytic Air Oxidation
of Several Condensed Ring Compounds
A thesis
by
Irving Plncus
Submitted in partial fulfillment
of the requirements
for the degree of
Doctor of Philosophy
September 1950
Approved:
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Professor of Fuel Technology
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Chief, Division of Fuel Technology
ACKNOWLEDGMENT
Many people have aided the author in carrying out the
investigation for this dissertation to a satisfactory conclu­
sion. First of all, sincere appreciation is expressed to the
people of this nation, who through their elected representa­
tives, passed Public Law 346, the "G.I. Bill,f. Without the
financial assistance from the Veterans Administration, an in­
strument of the federal government set up to aid the veteran,
this work would never have been possible.
The School of Mineral Industries of the Pennsylvania
State College through its Division of Fuel Technology has also
helped the present Investigator. Appreciation is gratefully
acknowledged to all the members of the Division from the Head
of the Division, Dr. C. G. Wright, down to the graduate as­
sistants. Special thanks are due Dr. C. R. Kinney, who sug­
gested the problem and supervised the work. His advice and
assistance yielded great comfort especially when the going was
toughest. Also, thanks are expressed by the author to the
members of the Analytical Laboratory for their assistance and
to his colleagues, Messieurs, Del Bel, Oclcert and Gillmore for
their kind assurances and confidence in him.
Thanks are also due to the Davison Chemical Company,
Baltimore, Maryland, the Hoppers' Company, Pittsburgh, Pennsyl
vania and the Laclede Gas Light Company, Saint Louis, Missouri
for their generosity in supplying the various samples employed
in this Investigation.
The draftsman, Mrs. E. L. Malloy and the typist, Mrs.
L. Friedman, were very helpful in the preparation of this dis­
sertation. They are to he commended for their very great pa­
tience with the author.
Finally, the present investigator wishes to express his
appreciation to his immediate family. He is indebted to his
wife, who with her good nature, undertook a greater part of her
family duties and to his two small children, who in their own
little way, were very confident that this work would come to a
successful culmination.
TABLE OP CONTENTS
Page
LIST OP TABLES v
LIST OF FIGURES viii
SUMMARY xi
I. INTRODUCTION 1
II. HISTORICAL 4
A. General 4
B. Catalysts 7
C. Apparatus 9
D. Effect of the Strongly Exothermic
Reaction on the Design of the Apparatus 11
E. Application to Various Condensed Ring
Systems: Naphthalene 12
Alkylnaphthalenes 17
Anthracene 18
Other Condensed Ring Systems 20
III. EXPERIMENTAL 23
A. Apparatus 23
B. Catalysts 25
C. Materials Oxidized 26
D. Auxiliary Materials 28
E. Oxidation Procedure 29
P. Analytical Procedure 31
G. Examination of the Catalyst Surface 33
1. Color of the Catalysts 33
2. Density of the Catalysts 33
3. Measurement of Void Space
in Catalyst Bed 33
4. Surface Area Measurements
of Catalysts 34
iii
TABLE OP CONTENTS (continued)
Page
H. Measurement of the Pressure Drop
across the Catalyst Bed 34
IV. DISCUSSION OP RESULTS 36
A. The General Problem of Diffusion in
Porous Catalysts 37
B. Catalytic Oxidation of Naphthalene 40
C. Catalytic Oxidation of the Alkyl­
naphthalenes 56
D. Catalytic Oxidation of Coal-Tar-
Fractlons 72
E. Catalytic Oxidation of Phenanthrene 75
F. Catalytic Oxidation of Anthracene 86
G. Catalytic Oxidation of Anthraquinone 103
H. Catalytic Oxidation of Carbazole 122
I. Catalytic Oxidation of the
"Anthracene Salts" 123
J. Catalytic Oxidation of Phthalic
Anhydride 134
K. Examination of the Catalyst Surface 149
1. Color 151
2. Density 152
3. Amount ofV oid Space 153
4. SurfaceA rea 153
V. CONCLUSIONS 158
BIBLIOGRAPHY 164
APPENDIX 167
iv
LIST OF TABLES
Table Page
I. Effect of Temperature on the Catalytic Air
Oxidation of Naphthalene (Catalyst 210) 43
II. Effect of Temperature on the Catalytic Air
Oxidation of Naphthalene (Catalyst 200A) 44
III. Effect of Temperature on the Catalytic Air
Oxidation of Naphthalene (Catalyst 200B) 45
IV. Effect of Catalyst Condition on the Catalytic
Air Oxidation of Naphthalene 51
V. Effect of Secondary Air on the Catalytic
Air Oxidation of Naphthalene 54
VI. Effect of Temperature on the Catalytic Air
Oxidation of 1-Methylnaphthalene 57
VII. Effect of Temperature on the Catalytic Air
Oxidation of 1-Methylnaphthalene 58
VIII. Effect of Temperature on the Catalytic Air
Oxidation of 2-Methylnaphthalene 62
IX. Effect of Temperature on the Catalytic Air
Oxidation of 2-Methylnaphthalene 63
X. Effect of Temperature on the Catalytic Air
Oxidation of 2,3-DImethylnaphthalene 67
XI. Effect of Temperature on the Catalytic Air
Oxidation of 2,3-Dlmethylnaphthalene 68
XII. Optimum Conversion of the Naphthalenes to
Phthalic Anhydride 71
XIII. Catalytic Air Oxidations of Coal-Tar-Fractions 74
XIV. Effect of Temperature on the Catalytic Air
Oxidation of Phenanthrene 77
XV. Effect of Temperature on the Catalytic Air
Oxidation of Phenanthrene 78
XVI. Effect of Secondary Air on the Catalytic
Air Oxidation of Phenanthrene 81
v
LIST OF TABLES (continued)
Table Page
XVII. Effect of Secondary Air on the Catalytic
Air Oxidation of Phenanthrene 82
XVIII. Effect of Temperature on the Catalytic
Air Oxidation of Anthracene 87
XIX. Effect of Secondary Air on the Catalytic
Air Oxidation of Anthracene 90
XX. Effect of Temperature on the Catalytic
Air Oxidation of Anthracene 93
XXI. A Comparison with Senseman and Nelson's Data 97
XXII. Comparison of the Catalytic Oxidations
of Phenanthrene and Anthracene 98
XXIII. Analysis of Exhaust Gases 99
XXIV. Catalytic.Air Oxidation of Anthracene
with the Treated 210 Catalyst 104
XXV. Effect of Temperature on the Catalytic
Air Oxidation of Anthraquinone 105
XXVI. Comparison of Products from the Catalytic
Oxidations of Anthracene and Anthraquinone 108
XXVII. Effect of Secondary Air on the Catalytic
Air Oxidation of Anthraquinone 110
XXVIII. Further Comparison of Products from the
Catalytic Oxidations of Anthracene and
Anthraquinone 111
XXIX. Effect of Temperature on the Catalytic
Air Oxidation of Anthraquinone 113
XXX. Effect of Higher Temperatures on the
Retardation of Catalytic Activity 119
XXXI. Effect of Treatment of Used Catalyst 200 on
the Catalytic Air Oxidation of
Anthraquinone 121
XXXII. Comparison of Treated and Untreated
Catalyst 200 122
vi
LIST OF TABLES (continued)
Table Page
XXXIII. Effect of Temperature on the Catalytic
Air Oxidation of the Anthracene Salts 125
XXXIV. Comparison of Yields from the Anthracene
Salts and from the Three Compounds
at Optimum Conversion Temperatures 127
XXXV. Comparison ox Yields from the Anthracene
Salts and from the Three Compounds
at 440°C. 127
XXXVI. Comparison of Yields from the Anthracene
Salts and from the Three Compounds
at 500 cc. per minute 128
XXXVII. Effect of Secondary Air on the Catalytic
Air Oxidation of the Anthracene Salts 130
XXXVIII. Catalytic Air Oxidation of Fractions
of the Anthracene Salts 133
XXXIX. Catalytic Air Oxidation of Phthalic
Anhydride (Catalyst 200) 135
XXXX. Catalytic Air Oxidation of Phthalic
Anhydride (Catalyst 210) 140
XXXXI. Pressure Drop over Catalyst Bed 147
XXXXII. Surface Area Measurements 156
vli
LIST OF FIGURES
Catalytic Air Oxidation Apparatus
Catalytic Oxidation of Naphthalene, Effect of
Temperature on Yield of Phthalic Anhydride 46
Catalytic Oxidation of Naphthalene, Effect of
Temperature on Yield of Maleic Anhydride
and Carbon Dioxide 47
Catalytic Oxidation of 1-Methylnaphthalene,
Effect of Temperature on Yield of Products 59
Catalytic Oxidation of 1-Methylnaphthalene,
Effect of Temperature on Yield of Carbon
Dioxide 59
Catalytic Oxidation of 2-Methylnaphthalene,
Effect of Temperature on Yield of Products 64
Catalytic Oxidation of 2-Methylnaphthalene,
Effect of Temperature on Yield of Carbon
Dioxide 64
Catalytic Oxidation of 2,3-Dimethylnaphthalene,
Effect of Temperature on Yield of Products 69
Catalytic Oxidation of 2,3-Dimethylnaphthalene,
Effect of Temperature on Yield of Carbon
Dioxide 69
Catalytic Oxidation of Phenanthrene, Effect
of Temperature on Yield of Products 79
Catalytic Oxidation of Phenanthrene, Effect
of Secondary Air on Yield of Products 83
Catalytic Oxidation of Phenanthrene, Effect
of Temperature on Yield of Carbon Dioxide 84
Catalytic Oxidation of Phenanthrene, Effect
of Secondary Air on Yield of Carbon Dioxide 84
Catalytic Oxidation of Anthracene, Effect
of Temperature on Yield of Products 88
Catalytic Oxidation of Anthracene, Effect of
Secondary Air on Yield of Products 91
viii
LIST OF FIGURES (continued)
Figure Page
16. Catalytic Oxidation of Anthracene, Showing
Decline of Catalytic Activity of
Catalyst 200 95
17. Catalytic Oxidation of Anthracene, Effect
of Temperature on Yield of Products--
Newly-Activated Catalyst 200 Used for
Each Run 96
18. Catalytic Oxidation of Anthraquinone, Effect
of Temperature on Yield of Products 106
19. Catalytic Oxidation of Anthraquinone, Effect
of Secondary Air on Yield of Products 106
20. Catalytic Oxidation of Anthraquinone, Effect
of Temperature on Yield of Carbon Dioxide 107
21. Catalytic Oxidation of Anthraquinone, Effect
of Secondary Air on Yield of Carbon Dioxide 107
22. Catalytic Oxidation of Anthraquinone, Showing
Decline of Catalytic Activity of Catalyst
200 115
23. Catalytic Oxidation of Anthraquinone, Effect
of Temperature on Yield of Products--
Newly-Activated Catalyst 200 Used for
Each Run 117
24. Catalytic Oxidation of the Anthracene Salts,
Effect of Temperature on the Yield of
Products 126
25. Catalytic Oxidation of the Anthracene Salts,
Effect of Secondary Air on the Yield
of Products 131
26. Oxidation of Phthalic Anhydride in Presence
of Catalyst 200 137
27. Oxidation of Phthalic Anhydride in Presence
of Catalyst 200 138
28. Oxidation of Phthalic Anhydride In Presence
of Catalyst 210 142
29. Oxidation of Phthalic -Anhydride In Presence
of Catalyst 210 143
ix