AN INVESTIGATION OF THE REACTION BETWEEN CARBON-MONOXIDE AND HYDROGEN ON A NICKEL CATALYST AT PRESSURES ABOVE ONE ATMOSPHERE

151 Pages·05.331 MB·English

by  PURSLEY, JOHN ARDELL

AN INVESTIGATION CF THE REACTION BETWEEN
CARBON MCI I OX IDE AMD HYDROGEN
CN A NICKEL CATALYST
AT PRESSURES ABOVE ONE ATMOSPHERE
by
John Ardell Pursley
A Dissertation Submitted in partial Fulfillment of
the Requirements for the Degree of Doctor of Philosophy
in the University of Michigan
Doctoral Committee:
Professor R. R. White, Chairman
Associate Professor M. J. Sinnott
Assistant Professor C. M. Sliepcevich
'ssociate Frofessor iC. F. '/Yestrum, Jr.
ssociate Professor 3. R. Williams
January, 19 %1
- ii-
TO
HENRY K. DICE
- iii -
ACKNOWLEDGEMENT
Itie author -wishes to express his appreciation to all those
who have directly or indirectly aided in this investigation and in
particular to:
Professor R.R. White, chairman of the doctoral committee
and supervisor of the Michigan Gas Association Fellowship,
whose foresight and guidance have created an integrated
research program on the fundamentals of catalysis of which
this manuscript represents but a small part.
The doctoral committee members for their advice and criticism.
The wisdom of the Michigan Gas Association by which this
fellowship was established and has been supported for the
past fifty years.
To John N. Dev/, friend and professional associate, who has
been concerned with all the details of this research program.
To the graduate students and, in particular, to William A.
Doemer of the Department of Chemical and Metallurgical En­
gineering for suggestions and criticisms.
TABLE OF CONTENTS
Page
LIST OF FIGURES vii
LIST OF TABLES vii
LIST OF GRAPHS viii
TABLE CF NOMENCLATURE X
SUMMARY xvi
INTRODU CTION 1
THEORETICAL BASIS 3
EQUIPMENT AND OPERATING PROCEDURE 1U
General
2h
Equipment Rack
2h
Control Panels 25
Piping 25
Valves 26
Wiring 27
Flov/ and Pressure Control 28
Hydrogen Control 28
Carbon Monoxide Control 31
'.Thermostat 32
Startup and Operation 33
Gas Sampling
35
Thermal Conductivity Cells 36
Voltage Regulator 37
Sampling System 37
Reactor 38
Preheater 39
Reaction Tube 39
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TABLE OF CONTENTS (cont'd)
Page
Product Condenser 1+0
Jacket 1+0
Jacket Temperature Control 1+1
Temperature Measurement 1+2
Compression System 1+3
Flow 1+3
Compressor uu
Power
Control 1+5
Startup and Opera-Mcn 1+6
Methods of Analysis 1+7
PRELIMINARY TESTS 1+9
Wall Effect 1+9
Catalyst Stability 55
Carbon Deposition 55
Poisoning 56
Thermal Deactivation 57
Pretreatmcnt 61
EXPERIMENTAL DATA 61+
Materials 61+
Experimental Errors 66
Catalyst Test Data 70
CORRELATION OF DATA 85
Effect of Products 85
Effect of Temperature 86
P
- vi -
TABLE OF CONTENTS (cont'd)
Page
Effect of Mass Transfer 88
Between Bulk of Gas Stream and Catalyst Particle 89
Diffusion in the Catalyst Particle 90
Surface Reaction 97
CONCLUSIONS 113
APPENDIX H U
BIBLIOGRAPHY I36
- vii -
LIST CF FIGURES
No. Title Page
la. Catalyst Testing Unit, Front View 15
lb. Catalyst Testing Unit, Rear View 16
2. Sampling System 17
3a. Control panel, Rear View 18
3L. Control Panel, Rear View Details 19
lia • Flow Diagram, Reactor Control System 20
Ub. Flow Diagram, Reactor 21
Uc • Flow Diagram, Compressor System 22
—/
p1 . Wiring Diagram, Control System 23
LIST OF TABLES
1. Experimental Data
7S
2a. Possible Rate Controlling Steps
83
2b. Rate Equation Constants
10U
3. Material Balances 128
Experimental Errors
129
5. Spectrometer Calibration Data 132
6. Pressure Gauge Calibration Data
1—
1
7. Equipment Manufacturers 131;
- viii -
LIST OF GRAPHS
Title Page
Ho.
la. Wall Effect (Reactangular Coordinates) 53
lb. Wall Effect (Logrithmic Coordinates) 5U
2. Carbon Deposition 58
3. Poisoning 59
Thermal Deactivation 60
h-
5. Pretreated Catalyst Stability 63
6a a Feed Compositions 73
6b. Feed Rates 7h
7. Catalyst Bod Temperature Rise 37
8a. Effect of Hass Velocity on Reaction Rate 91
8b. Effect of Mass Velocity on Conversion 92
9a. Diffusion in the Catalyst Particle (Pressure Effect) 95
9b. Diffusion in the Catalyst Particle (Concentration Effect) 96
10a. Reaction Rate Constants; P/r0) vs. (P)°-S 99
10b. Reaction Rate Constants; 100
PC0/ro) vs- (PH2)0*^
10c. Reaction Rate Constants; pc(/ r0) vs. (p^) 101
11a. Reaction Rate Constants: P ^ A o ) VS. (P) 102
lib. Reaction Rate Constants: 103
PC0)(PH2)0‘5/ro vs‘ (PH2>
12a. Effect of Pressure on the Reaction Itate (500°F) 105
12b. Effect of Pressure on the Reaction Rate (550°F) 106
12c. Effect of Pressure on the Reaction Rate (600°F) 107-
13a. Effect of Concentration on the Reaction Rate (250 psia) 100
13b. Effect of Concentration on the Reaction Rate (175 psia) 109
13c. Effect of Concentration on the Reaction Rate (100 psia) 110
■MM
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LIST OF GRAPHS (cont'd)
No. Title Page
13d. Effect of Concentration on the Reaction Rate (15 psia) 111
111. Infra-Red Spectrophotometer Calibration 133
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TABLE OF NOMENCLATURE
1
A constant 1/(k)JT
A reactant A in the overall reaction
a number of mols of A consumed in the overall reaction
activity of reactant A in the fluid phase
a3 activity of reactant B in the fluid phase
D
a ^ activity of carbon monoxide in the gas phase
ap activity of any component, F, in the fluid phase
a„ activity of the diffusing component in the gas phase
O
a^2 activity of hydrogen in the gas phase
aj activity of the inert components I in the fluid phase
am mean surface of pellets per unit mass
ap surface area per single nellet
a^ activity of product R in the fluid phase
aQ activity of product S in the fluid phase
B constant b/(k)fT
B reactant B in the overall reaction
b constant Kjj(l-X)^
b number of mols of B consumed in the overall reaction
C active center
1
C constant c/(k)ff
C observed overall rate factor for a reaction
c constant KC0(X) f KH2(1-X)
c empirical constant
c average radius of pores in a particle
c the molal concentration of vacant active centers per unit mass of catalyst