Table Of ContentThis thesis, having been approved by the
special Faculty Committee, is accepted by
the Graduate School of the
University of Wyoming,
in partial fulfillment of the requirements
for the degree of HQC_tor_ o f .Philosophy:
_________
Dean of the Graduate School.
Date Max 19iP___
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ISOLATION AND IDENTIFICATION OF SOME FIRROLES IN
SHALE-OIL NAPHTHA
by
Arthur Gray Janssen
A Thesis
Submitted to the Department
of Chemistry and the Graduate School
of the University of Wyoming in Partial
Fulfillment of the Requirements for the Degree of
Doctor of Philosophy
University of Wyoming
Laramie, Wyoming
June 5, 1950
UBRAKTfi
S rafs- fH E
fcARAMIE
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UMI Number: DP15232
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L*s»
DEDICATED TO
EVH N E S T W. B E C K
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ACKNOWLEDGEMENTS
The author wishes to express his sincere thanks for the coopera
tion and guidance offered by Ernest R. Schierz of the University of
Wyoming, and John S. Ball and Robin A* Van Meter of the Bureau of
Mines in the pursuit of this research. To Glenn L. Cook also goes the
author's thanks for his help in the interpretation of mass-spectrometer
analyses.
The assistance of the personnel and use of facilities at the
Petroleum and Oil-Shale Experiment Station of the Bureau of Mines in
Laramie, Wyoming, is gratefully acknowledged,
A portion of this thesis was presented at the Twenty-first Annual
Meeting of the Colorado-Wyoming Academy of Science at Fort Collins,
Colorado on May 12 and 13, 1950,
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TABLE GF CONTENTS
.Chapter Bags
I History and Introduction, ........... . . . . . . . 1
II Discussion......... 8
Separation of Pyrrolic Material From Shale-Oil
Naphtha. . . • • • • • • • • • • • • • . • • • • 8
Confirmation of the Presence of Pyrrole and
2-methylpyrrole, . . . . . . * . . . . 11
III Experimental ........... 25
Preparation of Shale-Oil Naphtha • • • • • • • • • 25
Determination of Nitrogen (Kjeldahl Method). ... 25
Removal of Tar Acids From Shale-Oil Naphtha. ... 26
Formation of Potassium Pyrroles................. 26
Purification of Potassium Pyrroles........... 27
Hydrolysis of Potassium Pyrroles . . . . . . . . . 28
Fractionation of fyrrole and Its Homologs. • • . • 28
Formation of fyrrole Phthalate ............. 29
Formation of Tetraiodopyrrole. •• ... 29
Preparation of 1-methylpyrrole . . . . . . . . . . 30
Formation of the Ketoxime of 2-methylpyrrole Vith
Hydroxylamine. . . . . . . . . . . . . . . . . . 30
Suggestions for Future Work......... 33
Bibliography • • • • • • • • • • 34
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LIST OP TABLES
Table Page
I Nitrogen Balance for Pyrrole Separation. .............. 12
II Refractive Indices of Pyrrolic Fractions Derived Froa
Shale-Oil Naphtha............ 13
III Effect of Alkyl Substitution on the Refractive Indices
of Various Compounds . . . . . . . . . . . ........ • 14
IV Boiling Points of Pyrrole and Substituted i^rroles . . . 18
V Bata on Fractions Containing Synthesised L-methylpyrrole 21
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LIST OF FIGURES
Figure Page
1 Schematic Diagram of Steps Involved in Potassium fyrrole
Formation, . . . . . . . . . . . . . . . . . . . . . . 10
2 Mass-spectrometer Analyses of Pyrrolic Fractions Derived
From Shale-Oil Naphtha . . . . . . . . . . . . . . . . 16
3 Mass Spectrogram of 1-methylpyrrole Showing Diffuse Peak
and Normal Peaks , . • • • • • • • • ............. • 19
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CHAPTER I
History and Introduction
Gasoline, prior to 1899, was a useless by-product of the petroleum
industry. With the commercial development of the gasoline engine in the
period 1909 to 1918 gasoline became the principal product of this rapidly
expanding industry. After World War I the estimated reserves of petroleum
had dropped to such a low point that supplemental sources such as oil from
oil shale were investigated. With the discovery of the east Texas fields
in the late twenties such investigations were dropped. The enormous need
for petroleum in World War II again brought out the need for supplemental
sources and synthetic fuels were again studied. Some of the sources
investigated include oil from natural gas, coal, agricultural products
and oil shale. Oil shale is defined as "a fine-grained sedimentary rock
containing organic matter (kerogen) which was derived chiefly from aquatic
organisms or waxy spores and pollen grains, which is only slightly soluble
in ordinary petroleum solvents, and of which a large proportion is dis-
tillable into artificial petroleum."10. The artificial petroleum referred
to in this definition has assumed the name of shale oil and by definition
it is the condensable product resulting from destructive distillation
(pyrolysis) of oil shale. This condensable product is known to consist
of aliphatic and aromatic hydrocarbons together with nitrogen-, oxygen-,
and sulfur-containing substances. Oil shale occurs in huge quantities in
the United States, the major deposits being in Colorado, Utah and Wyoming.
Gum formation in gasoline derived from shale oil is an undesirable
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