Oxo Alcohols, November 1966

Report No. 21

OX0 ALCOHOLS

by RICHARD G. DENNEY

contributions by Shigeyoshi Takaoka

November 1966

A private report by the

PROCESS ECONOMICS PROGRAM

I
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
I
 Oxo Alcohols, November 1966

I INTRODUCTION. ........................ 1

II SUMMARY ........................... 3
General Aspects ....................... 3
Technical Aspects ...................... 6

III INDUSTRY STATUS ....................... 15

IV CHEMISTRY OF OXO ALCOHOL PRODUCTION ............. 27

Stoichiometry ........................ 27
Mechanisms .......................... 28
Hydroformylation ...................... 28
Aldol Condensation ..................... 32
Kinetics ........................... 33
Product Distribution ..................... 34
Catalyst Addition and Removal ................ 38
Metal Cycle ........................ 39
Organic Salts Cycle .................... 39
Inorganic Salt Cycle .................... 41
Anionic Transfer Cycle ................... 42
Hydrogenation ........................ 43

V PROCESSES FOR OXO ALCOHOL PRODUCTION ............. 45

Low Pressure One-Step Process ................ 45
Review of Processes .................... 45
Process Description .................... 51
Process Discussion ...................... 61
Cost Estimates ....................... 62
Aldox Process ........................ 75
Review of Processes .................... 75
Process Description .................... 83
Process Discussion ..................... 102
Cost Estimates ....................... 105
Oxo-aldol Process ...................... 119
Review of Processes .................... 119
Process Description .................... 125
Process Discussion ..................... 143
Cost Estimates ....................... 146

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 Oxo Alcohols, November 1966

CONTENTS

V (continued)
Other 0x0 Processes ..................... 161
Review of Processes .................... 161

l
Process Description .................... 195
Process Discussion .................... 207
Cost Estimates ...................... 209

APPENDIX A DESIGN AND COST BASIS . . . . . . . . . . . . . . . 225

APPENDIX B HANDLING AND SAFETY . . . . . . . . . . . . . . . . 231

APPENDIX C PHYSICAL DATA . . . . . . . . . . . . . . . . . . . 235

APPENDIX D RAW MATERIAL AND PRODUCT SPECIFICATIONS . . . . . . 245

CITED REFERENCES . . . . . . . . . : . . . . . . . . . . . . . . 255

SUPPLEMENTARY REFERENCES . . . . . . . . . . . . . . . . . . . . 279

0

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 Oxo Alcohols, November 1966

ILLUSTRATIONS

History of 0x0 Capacity and Consumption in the United States

1948-1966........................... 20
Proposed Structures of Cobalt Hydrocarbonyl . . . . . . . . . . 30
Hydroformylation Rates of Olefins . . . . . . . . . . . . . . . 35
Specific Hydroformylation Rates of Olefins . . . . . , . . . . 36
0x0 Alcohols by a Low Pressure One-Step Process . . . . . . . . 53
0x0 Alcohols by a Low Pressure One-Step Process
Effect of 0x0 Reactor Liquid Hourly Space Velocity on
Process Unit and Utilities Investment . . . . . . . . . . . . . 67
7 0x0 Alcohols by a Low Pressure One-Step Process
Effect of Plant Capacity on Total Fixed Capital Cost . . . . . 68
8 0x0 Alcohols by a Low Pressure One-Step Process
Effect of Raw Material Costs and By-Product Credit on
a
Net Total Production Costs . . . . . . . . . . . . . . . . . . 72

9 0x0 Alcohols by a Low Pressure One-Step Process

Effect of Plant Capacity and Production Rate on
Net Total Production Cost . . . . . . . . . . . . . . . . . . . 73
10 0x0 Alcohols by the Aldox Process
Effect of C4 Aldehyde Recycle on Selectivity to Ca Products . . 81

11 0x0 Alcohols by the Aldox Process

Reaction and Catalyst Recovery . . . . . . . . . . . . . . . . 87
12 0x0 Alcohols by the Aldox Process
Aldehyde Separation and C4 Alcohol Production . . . . . . . . . 89

a 13 0x0 Alcohols by the Aldox Process

2-Ethylhexanol Production and Heavy Ends Reprocessing . . . . . 91
14 0x0 Alcohols by the Aldox Process
Effect of Plant Capacity on Total Fixed Capital Costs . . . . . 111

a
15 0x0 Alcohols by the Aldox Process
Effect of Raw Material Costs and By-Product Credit on
2-Ethylhexanol
Net Total Production Costs . . . . . . . . . . . . . . . . . . 116
16 0x0 Alcohols by the Aldox Process
Effect of Plant Capacity and Production Rate on 2-Ethylhexanol
Net Total Production Cost . . . . . . . . . . . . . . . . . . . 117

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 Oxo Alcohols, November 1966

ILLUSTRATIONS

17 0x0 Alcohols by the Oxo-Aldol Process

Reaction and Catalyst Recovery . . , . . . . . . . . . . . . . 127

18 0x0 Alcohols by the Oxo-Aldol Process

Aldehyde Separation and C4 Alcohol Production . . . . . . . . 129

19 0x0 Alcohols by the Oxo-Aldol Process

2-Ethylhexanol Production and Heavy Ends Reprocessing . . . . 131

20 0x0 Alcohols by the Oxo-Aldol Process

Effect of Plant Capacity on Capital Cost . . . . . . . . . . . 151

21 C4 Aldehydes and Alcohols by the 0x0 Process

Effect of Plant Capacity on Capital Cost . . . . . . . . . . . 152

22 0x0 Alcohols by the Oxo-Aldol Process

Effect of Raw Material Cost and By-Product Credit on
2-Ethylhexanol

23
Net Total Production Cost . . . . . . . . . . . . . . . . . .
Oxo Alcohols by the Oxo-Aldol Process
157
a-
Effect of Plant Capacity and Production Rate on
Net Total Production Cost . . . . . . . . . . . . . . . . . . 159

24 Cobalt Concentration in Liquid Reactants As a Function of

Reaction Temperature and Carbon Monoxide Partial Pressure . . 167

25 Stability of Cobalt Carbonyl Catalyst As A Function of

Reaction Temperature and Carbon Monoxide Partial Pressure . . 169

26 Typical Oil Soluble Organic Soap 0x0 Catalyst Cycle . . . . . 173

27 Typical Water Soluble Organic Cobalt Salt 0x0 Catalyst Cycle . 175

a-
28 Typical Inorganic Cobalt Salt 0x0 Catalyst Cycle . . , . . . . 179

29 Typical Anionic Transfer 0x0 Catalyst Cycle . . . . . . . . . 183

30 Oxo Alcohols by a Low Pressure Two-Step Process
Oxo Reaction and Catalyst Recovery . . . . . . . . . . . . . . 197
31 0x0 Alcohols by a Low Pressure Two-Step Process
Hydrogenation and Alcohol Finishing . . . . . . . . . . . . . 199
32 0x0 Alcohols by a Low Pressure Two-Step Process
0-
Effect of Plant Capacity on Total Fixed Capital Cost . . . . . 214
33 0x0 Alcohols by a Low Pressure Two-Step Process
.
Effect of Raw Material Costs and By-Product Credit on
Net Total Production Cost . . . . . . . . . . . . . . . . . . 219
0
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 Oxo Alcohols, November 1966

ILLUSTRATIONS

34 0x0 Alcohols by a Low Pressure Two-Step Process

Effect of Plant Capacity and Production Rate on
Net Total Production Cost . . . . . . . . . . . . . . . . . . . 221
35 Vapor-Liquid Equilibrium for Butyl Alcohol and 0x0 Heavy Ends . 239
a
36 Vapor-Liquid Equilibrium for Butyl Alcohol and 0x0 Light Ends . 240
37 Vapor-Liquid Equilibrium for Isobutyl and Normal Butyl Alcohol . 241
38 Equilibrium Constants for Hydrogen and Carbon Monoxide
atlOOOF............................ 242
39 Vapor Pressure--Aldehydes . . . . . . . . . . . . . . . . . . . 243
40 Vapor Pressure--Alcohols . . . . . . . . , . . . . . . . . . . . 244

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 Oxo Alcohols, November 1966

TABLES

l
Summary of Costs of Evaluated Processes . . . . . . . . . . . 4
Summary of Technical Aspects of Evaluated Processes . . . . . 7
Oxo Plant Capacities
Americas....................... . . . . 17
4 Oxo Plant Capacities
Europe........................ . . . . 23
5 Oxo Plant Capacities
Asia and Australia . . . . . . . . . . . . . . . . . . . . . . 25
6 0x0 Alcohols by a One-Step Process
Summary of Processes . . . . . . . . . . . . . . . . . . . . . 47
7 0x0 Alcohols by a Low Pressure One-Step Process
Major Process Equipment and Utilities Summary . . . . . . . . 52
a 0x0 Alcohols by a Low Pressure One-Step Process
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . . 55

9 0x0 Alcohols by a Low Pressure One-Step Process

Process Unit and Utilities Investment . . . . . . . . . . . . 63

10 0x0 Alcohols by a Low Pressure One-Step Process

Total Capital Investment . . . . . . . . . . . . . . . . . . . 65
11 0x0 Alcohols by a Low Pressure One-Step Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . . 69

12 0x0 Alcohols by the Aldox Process

Summary of Esso Research & Engineering Processes . . . . . . . 77

13 0x0 Alcohols by the Aldox Process

Major Process Equipment and Utilities Summary . . . . . . . . 85
0 14 0x0 Alcohols by the Aldox Process
Stream Flows
Aldox Reaction and Catalyst Recovery Sections . . . . . . . . 93
15 0x0 Alcohols by the Aldox Process
Stream Flows
Aldehyde Separation and C+ Alcohol Production Section . . . . 95
16 0x0 Alcohols by the Aldox Process
Stream Flows
2-Ethylhexanol Production and Heavy Ends Reprocessing
Sections....................... . . . . 97

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 Oxo Alcohols, November 1966

TABLES

17 Oxo Alcohols
by the Aldox Process
Process Unit and Utilities Investment . . . , . . . . . . . . . 107

18 0x0 Alcohols by the Aldox Process

Total Capital Investment . . . . . . . . . . . . . . . . . . . 110
0
19 0x0 Alcohols by the Aldox Process
Production Costs . . . . . . . . . . . . . . . . . . . . . . . 113
20 0x0 Aldehyde by the Hydroformylation of Olefins
Summary of Mitsubishi Processes . . . . . . . . . . . . . . . . 121
21 Effect of Reaction Temperature on the Reaction Rate and
Normal Iso-Ratio in the Hydroformylation of Propylene to
Butyraldehydes . . . . . . . . . . . . . . . . . . . . . . . . 124

22 Oxo Alcohols by the Oxo-Aldol Process

Major Process Equipment and Utilities Summary . . . . . . . . . 126
23 Oxo Alcohols by the Oxo-Aldol Process a
Stream Flows
0x0 Reaction and Catalyst Recovery . . . . . . . . . . . . . . 133
24 0x0 Alcohols by the Oxo-Aldol Process
Stream Flows
Aldehyde Separation and C+ Alcohol Production . . . . . . . . . 137

25 0x0 Alcohols by the Oxo-Aldol Process

Stream Flows
2-Ethylhexanol Production and Heavy Ends Reprocessing . . . . . 139
26 0x0 Alcohols by the Oxo-Aldol Process
Process Unit and Utilities Investment . . . . . . . . . . . . . 147
27 0x0 Alcohols by the Oxo-Aldol Process
0
Total Captial Investment . . . . . . . . . . . . . . . . . . . 149

28 0x0 Alcohols by the Oxo-Aldol Process

Production Cost . . . . . . . . . . . . . . . . . . . . . . . . 155
29 Oxo Alcohols by the Hydroformylation of Olefins
Summary of Other Processes . . . . . . . . . . . . . . . . . . 163
0
30 Comparison of 0x0 Catalysts Recovery and Recycle Methods . . . 185
31 Hydrogenation of 0x0 Aldehydes to Alcohols
Summary of Processes . . . . . . . . . . . . . . . . . . . . . 189

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 Oxo Alcohols, November 1966

TABLES

32 Comparison of 0x0 Alcohols Pretreatment Methods . . . . . . . . 193

33 0x0 Alcohols by a Low Pressure Two-Step Process

Major Process Equipment and Utilities Summary . . . . . . . . . 196

34 0x0 Alcohols by a Low Pressure Two-Step Process

Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . . 201

35 0x0 Alcohols by a Low Pressure Two-Step Process

Process Unit and Utilities Investment . . . . . . . . . . . . . 211
36 Oxo Alcohols by a Low Pressure Two-Step Process
Total Capital Investment . . . . . . . . . . . . . . . . . . . 213

37 0x0 Alcohols by a Low Pressure Two-Step Process

Production Costs . . . . . . . . . . . . . . . . . . . . . . . 217

38 Heats of Combustion and Vaporization for Various Compounds

Associated with 0x0 Alcohols . . . . . . . . . . . . . . . . . 237

39 Specifications and Typical Properties of 0x0 Alcohols . . . . . 251

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