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UNIVERSITY OF CINCINNATI
_______July 16________ / 951
I hereby recommend that the thesis prepared under my
supervision by Lawrence e. swasb, jr._____________________________
entitled_ A KINETIC STUDY OF THE CATALYTIC VAPOR PHASE_________
ADDITION OF HYDROGEN CHLORIDE TO PROPYLENE
be accepted as fulfilling this part of the requirements for the
degree of DQCfJ'
or of p h ilo so p h y _____________________________________________
Approved byi
FORM 668—G. S. & T. C—J00—5-48
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A KINETIC STUDY OF THE CATALYTIC
VAPOR PHASE ADDITION OF HYDROGEN CHLORIDE
TO PROPYLENE
A d issertation submitted to the
Graduate School of Arts and Sciences
of the U niversity of Cincinnati
in p a rtia l fulfillm ent of the
requirements for the degree of
DOCTOR OF PHILOSOPHY
1951
by
Lawrence E. Swabb, Jr.
Ch.E. U niversity of Cincinnati 1948
M.S. U niversity of Cincinnati 1949
195]
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UMI Number: DP16100
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ACKNOWLEDGEMENT
The author wishes to express his sincere appre
ciation for the valuable guidance and suggestions given by
Dr. H. E. Hoelscher under whose direction this work was
accomplished. The author also wishes to thank hr. S. Ruven
Smith of Ohio State U niversity for performing the mass
spectrographic analyses. The receipt of a Laws Fellowship,
for which the author is duly grateful, fa c ilita te d the
completion of this work.
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ABSTRACT
This thesis is a kinetic study of the vapor phase
addition of hydrogen chloride to propylene using activated
alumina as a cataly st. Preliminary work on this reaction
V. rvr? r r* i.S n'npori'vT clll OT*ids ?_ c th s OHlV f~2.SC O*'1 S
product formed at temperatures of 80°C or less when this cata
ly st is used. Second, the catalyst activ ity decreases with
time possibly due to the formation of non-volatile polymerized
product on the surface. The rate of decreasing catalyst ac
tiv ity is dependent on the temperature and on the conversion.
From the resu lts of the kinetic study i t is shown
that the addition reaction is not controlled eith er by the
adsorption of hydrogen chloride or by the adsorption of pro
pylene. The reaction may be controlled eith er by the desorp
tion of isopropyl chloride or by the surface reaction between
adsorbed molecules of hydrogen chloride and adsorbed molecules
of propylene. The kinetic data are correlated by rate equa
tions derived by two d ifferent methods based on the surface
reaction as the controlling mechanism. The reaction constants
in these equations are expressed as functions of process time
and temperature.
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TABLE OF CONTENTS
Chapter Page
I Introduction ............................................................................ 1
II Kinetic Theory of Heterogeneous Catalytic
Reactions ........................................................................... 3
III Description of Experimental Equipment . . . 17
IV M a te ria ls ................................................................................... 25
V Experimental Procedure ................................................... 27
VI Experimental Results ........................................................ 31
VII Determination of the M echanism............................... I4J4.
VIII Correlation of Kinetic D a t a .................................... 57
IX Discussion of R e s u lts ..................................................... 88
X Conclusions .............................................................................. 93
Nomenclature ........................................................................... 95
Bibliography ........................................................................... 97
Aooendix
Par>t Pn r-e
I Discussion of Experimental Equipment and
P ro c e su re .................................................................................. 98
R e a c to r................................................................................ 98
Catalyst A ctivity and the Purification
S ystem .................................................................................106
Method of A n a l y s i s ........................................................108
Reproducibility of R e s u l t s ....................................109
II Evaluation of Film Gradients due to Mass
T r a n s f e r .................................................................................112
III Derivation of Rate Equation Used in Corre
lation Method B 117
IV Thermodynamic Properties and Equilibrium
C o n sta n ts.................................................................................122
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Fart Page
V D etailed operating Procedure .............................. 126
VI Bibliography for the A p p e n d ix ......................... 13^
VII References to Catalysts ........................................... 136
VIII Experimental Data
Series 1 . 139
Series 2 .
Series 3 • lu6
Series \ . • • • • • # • • • • • • • • •
Conversion at process Time 0 Hours . . l £8
Conversion at Process Time 3 Hours . . 150
Conversion at Process Time 6 Hours . . i5 i
Results of Mass Spectrographic Analyses 152
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