The Vapor Phase Hydration of Ethylene Oxide

158 Pages·08.066 MB·English

by  Horner, John Francis

PURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
John Francis Horner
by______________________
THE VAPOR PHASE HYDRATION OP ETHYLENE OXIDE
ENTITLED
COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES
AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS
FOR THE DEGREE OF
Doctor, of Philosophy
toFBssoR in Charge of Thesis
of School or Department
TO THE LIBRARIAN:----
m
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.

THE VAPOR PHASE HYDRATION OF ETHYLENE OXIDE
A Thesis
Submitted to the Faculty
of
Purdue University
by
John Francis Horner
In P artial Fulfillm ent of the
Requirements for the Degree
of
Doctor of Philosophy
February, 1950
ACKNOWLEDGMENT
The author wishes to express his appreciation
to Dr# J. M. Smith, the director of this research,
for his in terest, encouragement, and advice during
the course of these investigations, and to Messrs*
Cartmell, Galloway, Olson, Trice, and Langer for
their contributions to the prelim inary phases of
this work.
ProQuest Number: 27714099
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TABLE OF CONTENTS
Page
ABSTRACT ................................................................................................... i
INTRODUCTION .......................................................................................... 1
Uses and Properties of the Ethylene Glycols . . . . . . 1
Ethylene Glycol .......................................................... 1
Diethylene Glycol ............................................................ 2
Triethylene G lycol........................................................... 2
Manufacture of Ethylene Glycol . . . . . . . . . . . . . . . . . . . 3
Chlorohydrin Process ........................................ !
Dichloride Process ...........................................................
duPont Synthesis ............................................
Processes Based upon Ethylene Oxide ..............
Liquid Phase Hydration ............................... 6
Vapor Phase H ydration................................. 6
Purpose of the Project ................................................. 7
Review of Previous Experimental Work . . . . . . . . . . . . . 8
Thermodynamic Considerations .................................. 8
Equipment for Preliminary Studies •••.............. 10
Results of Preliminary Work .................. 11
DESCRIPTION OF EQUIPMENT ............................................................... 15
* Design Conditions .......................................................... 15
Metering and Control System for Ethylene Oxide ••• 19
Metering and Control System for Steam .................. 23
Preheating the Reactants .................................................... 25
The Catalytic R eacto r........................................................ 28
Dowtherm System ............................................................... 31
Product Separation and Collection System ............ 33
Temperature Recording ........................................... 35
TABLE OF CONTENTS (Continued)
PRELIMINARY EXPERIMENTAL WORK....................................................
Development and Calibration of the Ethylene Oxide
Metering System ...........................................
Development and Calibration of the Steam Metering
and Control System ............................................
Product Analysis by D is tilla tio n ................
Analysis for Ethylene Oxide in Mixtures with
Glycols .......................................................................................
Analysis for Total Converted Organics by Oxidation
COMPLETE OPERATING PROCEDURE......................................................
The Warm-up Period ..............................................................
Run Operation .....................................................
Shut-down.......................................................................................
Mis cellaneous .................................................
RESULTS.....................................................................................................
Study of the Variance of Catalytic A ctivity ..........
Physical Condition of the Catalyst . . . . . . . . .
Effect of On-Stream Time on A ctivity . . . . . . . . .
Study of the Effect of Operating Variables on
Total Conversion .....................................................
SUMMARY OF RESULTS AND CONCLUSIONS ........................................
BIBLIOGRAPHY ...................................................................................
APPENDIX A. COMPLETE RUN DATA..................................................
APPENDIX B. CALIBRATION OF ETHYLENE OXIDE FLOWRATOR• •
Bl. Tempe rature-Density Plot .............................
B2. Calibration Data ...................................
B3* Calibration Curves .......................................
TABLE OF CONTENTS (Continued)
Page
APPENDIX C. CALIBRATION CURVES FOR WATER FLOWRATOR .. 105
APPENDIX D« SAMPLE CALCULATIONS .......................... 108
Dl# Calculation of Flowmeter Settings «....109
D2« Calculation of Yields and Conversions
from D istillatio n Analysis Data ........... 110
D3« Total Conversion Calculation from
Oxidation Analysis Data • ............. 112
Dlj-* Sample Calculation for Preparation of
Catalyst Number 3 ........................................ lli{-
APPENDIX E, REFRACTIVE INDEX - COMPOSITION PLOTS ... I l6
APPENDIX F. PHYSICAL CONSTANTS FOR THE ETHYLENE
GLYCOLS .................................................................... 120
VITA...................................................................................................... 122
LISTS OF TABLES AND FIGURES
L ist of Tables
Table Page
1. Tabulation of Data for Check Runs on
Catalytic A ctivity ..................................... 70
2. Tabulation of Data for Check Runs on
Catalytic A ctivity - Total Conversion. ... 74
3. Data for Conversion Studies at l53- l 60°C •••• 79
4* Data for Conversion Studies at 129-132°C .. .. 82
5. Data for Conversion Studies at 188-190°C .... 84
6# Data for Yield Studies at 188-190° C ................... 86
7. Conversion Studies with Temperature and
Pressure as Variables ................................. 86
8. Table of Complete Run Data .......................... 97
9- Ethylene Oxide Flowrator Calibration Data
Steel Float ....................................................... 100
10. Ethylene Oxide Flowrator Calibration Data
Glass Float .................... 101
11. Physical Constants for the Ethylene Glycols . 120
List of Figures
Figure Page
1. Pilot Plant Flow Sheet ......................... l 6
2. Panel View Photograph of Equipment ............. 17
3. Rear View Photograph of Equipment •••................. 18
4* E lectrical C ircuits Diagram .............. 21
5. Preheater .............................. 26
6. Reactor ........................... 29
List of Figures (Continued)
Figure Page
7# Photograph of New and Used Catalyst
P a rtic le s................. 66
8» Section View of a Particle from Catalyst No.7 6?
9* Section View of a Particle from Catalyst No.3 68
10. Effect of On-Stream Time on Conversion and
Yield at Constant Conditions ...................... 71
11. Effect of On-Stream Time on Total Conversion
at Constant Conditions ..................... 75
12. Conversion Studies at l 53- l60°C ....................... 80
13. Conversion Studies at 129-132°C ........... 83
li|.. Conversion Studies at l 88-190°C ............... 85
15. Effect of Temperature on Total Conversion at
Constant Conditions ............... 89
16. Temperature - Density Plot for Ethylene Oxide 99
17. Calibration Curve for the Ethylene Oxide
Flowrator with Steel Float «................................ 103
18. Calibration Curve for the Ethylene Oxide
Flowrator with Glass Float ............... lOij.
19. Calibration Curve for the Water Flowrator
with Light Float ...................................... 106
20. Calibration Curve for the Water Flowrator
with Heavy Float ........................ 107
21. Refractive Index - Composition Plot for the
Water - Glycol System ............. 117
22. Refractive Index - Composition Plot for the
Glycol - Diethylene Glycol System . . . . . . . . . 118
23. Refractive Index - Composition Plot for the
Di- Triethylene Glycol System ............. 119