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PROCESS ECONOMICS
PROGRAM SRI INTERNATIONAL
Abstract Menlo Park, California
94025
Process Economics Program Report No. 158
OCTANE IMPROVERS FOR GASOLINE
(November 1983)
There la currently worldwide interest in the use of exotic octane
improvers for gasoline-primarily oxygenated compounds. This study
examines the present industrial status (together with the technology
and economics of manufacture) of the major additives: including
methanol, ethanol, tert-butanol (TBA), and methyl tert-butyl ether
(MTBE) .
One of the major factors likely to.affect future additive usage is
anticipated structural changes in gasoline markets-in particular the
growth of unleaded gasoline in an otherwise static (or shrinking)
gasoline pool. Against this background an assessment la made of the
value of additives to gasoline blenders and to major refiners using
conventional gasoline components such as light naphtha, reformate, FCC
gasoline, alkylate, and polymer gasoline. Comparisons are made between
additive value and estimated production coat for two crude oil price
growth scenarios.
PEP ‘81 WSF DG SF
Report No. 158
OCTANE IMPROVERS FOR GASOLINE
by WING SIEN FONG
DONALD GREENAWAY
STAN FIELD
November 1983
A private report by the
PROCESS ECONOMICS PROGRAM
Menlo Park, California 94025
For detailed marketing data and information, the reader is
referred to one of the SRI programs specializing in marketing
research. The CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicals and chemical products produced in the
United States and the WORLD PETROCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.
ii
CONTENTS
1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY .......................... 3
Industry Status ...................... 3
Commercial Prospects .................... 6
Additive Valuation and Gasoline Economics ......... 7
Additive Production Technology and Costs .......... 14
Cost/Value Comparisons ................... 16
3 INDUSTRY STATUS ...................... 21
Ethanol .......................... 21 Methanol .......................... 23 Methyl tert-Butyl Ether .................. 28 tert-Butanol ........................ 28
tert-Amy1 Methyl Ether ................... 31 Dimates .......................... 31
4 COMMERCIAL PROSPECTS FOR OCTANE IMPROVERS ......... 33
Gasoline Demand and Quality in the United States ....... 34 The Importance of Front-End Octane Improvers ........ 47
Methyl tert-Butyl Ether .................. 51 Ethanol .......................... 59 Propylene Dimer ...................... 60 Methanol and tert-Butanol ................. 64
5 PRODUCTION TECHNOLOGY AND ECONOMICS FOR TBE FOUR MOST PROMINENT ADDITIVES . . . . . . . . . . . . . . . 67
Ethanol Production ........ ............. 67
Process Description ...... ............. 67
Cost Estimates ......... ............. 68
Methanol Production ....... ............. 73
Process Description ...... ............. 73
Cost Estimates ......... ............. 73 Methyl tert-Butyl Ether Production ............. 76
Review of Processes ...... ............. 76
Process Description ...... ............. 77
Cost Estimates ......... ............. 77 tert-Butanol Production ..... ............. 80
Process Description ...... ............. 80
Cost Estimates ......... ............. 80
iii
CONTENTS
6 ADDITIVE BLENDING PROPERTIES ................ 83
Ethanol .......................... 83 Methanol .......................... 87 Oxinol@, a Commercial Methanol-TBA Blend .......... 93 Methyl tert-Butyl Ether .................. 96 tert-Butanol ........................ 99
7 GASOLINE ECONOMICS ...................
General Approach ..................... Additive Blendstock Valuation .............. Refinery Octane Valuation (1990 compared with 1982) ... General Refinery Octane Valuation ............ Refinery Additive Valuation --Higher Molecular Weight Range Refinery Additive Valuation-- Lower Molecular Weight Range Market Value--Octanes and Additives ........... C4 Values and Alkylation Economics ............ Additive Valuation and Production Costs ......... Generalized Production Costs .............. Crude Oil Price Trends ................ MTBE .......................... TBA .......................... Ethanol ........................ Methanol ........................ Oxinol@ ........................
. 101
. 101
. 103 , 112
: 119 128 . 136 . 146 . 152 . 157 . 157 . 160 : 165 161
. 165
. 167
. 171
8 TERTIARY-AMYL METHYL ETHER ................ 175
Chemistry ......................... 175 Review of Processes .................... 177 GulfCanada . . Institut Franlais du Petrole ..................................
177 179
Standard Oil (Ohio) ................... 182 Texaco ......................... 183
Process Description .................... 184 Process Discussion ..................... 188 Cost Estimates ....................... 189
9 PROPYLENBDIMATES ..................... 193
Review of Processes .................... 193 Process Description .................... 196
IV
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CONTENTS
9 PROPYLENE DIMATES (continued)
Process Discussion . . . . . . . . . . . . . . . . . . . . . 201 Coat Estimates . . . . . . . . . . . . . . . . . . . . . . 201
APPENDIX DESIGN AND COST BASES ............. 207
CITED REFERENCES ...................... 211
PATENT REFERENCES ...................... 215
V
l 2.1
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
5.1
6.1
6.2
7.1
ILLUSTRATIONS
Gasoline Improvement. ................... 10
Octane Number and Boiling Point for a Variety of High Octane Gasoline Components ............. 36
Historical and Projected Gasoline Demand In the United States .................... 40
Historical and Projected Octane Number of the Average U.S. Gasoline Pool ............. 41
Effect of Compression Ratio on Fuel Economy and Octane Requirement for Gasoline Engines ........ 42
Average Compression Ratio of New Cars in the United States .................... 43
Passenger Cars as a Function of Disposable Income in the United States .................... 44
Passenger Car Gasoline Expenditures as a Percentage of Disposable Income In the United States ......... 46
Estimated World MTBE Capacity ............... 56
Effect of Base Gasoline Octane Number on the Octane Improvement Capabllltlea of MTBE .......... 57
Effect of Base Gasoline Octane Number on the Blending Octane Number of MTBE ............... 58
Options for Diapoaitlon of Propylene ............ 61
Propylene Dimerization Material Balance .......... 63
Estimated Consumption of Methanol for Use in Gasoline in the United States .............. 65
Ethanol from Corn Effect of Corn Price and DDGS Credit on Production Coat ..................... 72
Methanol RVP Blending Characteristics ........... 91
Effect of a Methanol-TBA Mixture (Oxlnol?) on Octane Number, RVP, and Water Tolerance ......... 94
Octane-Barrel Addition ................... 106
VII
ILLUSTRATIONS
7.2
7.3
7.4
7.5
7.6
8.1
9.1
Oxygenate Heating Values ................. 111
Hypothetical Refinery Gasoline Pool ........... 115
Octane Barrel Valuation Identification of Cases ................. 121
Effect of Mileage per Gallon Improvement on Methanol Value .................... 149
Alkylation ........................ 153
TAME Production from a C5 Fraction Flow Sheet .. .. . .. ................ 217
Propylene Dimates Production from a C3 Stream Flow Sheet ... ..... ... . . .......... 219
Viii
TABLES
3.1
3.2
3.3
3.4
3.5
3.6
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
5.1
5.2
5.3
5.4
Some of the Major Existing and Potential Ethanol Producers in the United States ..........
U.S. Methanol Producers .................
West European Methanol Producers .............
Summary of Anticipated New Methanol Capacity Worldwide . .
U.S. Methyl tert-Butyl Ether Producers ..........
Some European Methyl tert-Butyl Ether Producers .....
Value of Individual Octane Improvers in the U.S. Gasoline Pool ................
Gasoline Demand and Quality in the United States .....
Historical Expenditures for Passenger Car Gasoline Use in the United States ............
Gasoline Demand in the United States, Western Europe, and Japan ................
High Octane Front-End Components of Gasoline .......
Important Characteristics of Various Gasoline Octane Improvers ............
Typical Clear Octane Numbers ...............
Estimated World Supply of Isobutylene ..........
World Potential Supply of MTBE ..............
Estimated World Capacity and Production of MTBE .....
Profitability of Propylene Dimer Production and the Value of Refinery C3's in 1982 ..........
Ethanol from Corn Production Costs .....................
Methanol from Natural Gas by the ICI Copper-Based Catalyst Process Production Costs .....................
MTBE from Mixed Butenes Production Costs .....................
TBA from Mixed Butenes Production Costs .....................
iX
22
25
26
27
29
30
35
39
45
47
48
49
50
52
54
55
62
70
74
78
81
TABLES
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
7.11
7.12
7.13
.7.14
7.15
Physical and Thermal Properties of Ethanol ........ 84
Effect of Ethanol on Octane Numbers ........... 85
Effect of Ethanol on RVP and Distillation ........ 86
Physical and Thermal Properties of Methanol ....... 89
Effect of Methanol on Octane Numbers ........... 90
Effect of Methanol on RVP and Distillation ........ 92
Effect of a Methanol-TBA Mixture (Oxinol®) on Distillation ..................... 95
Physical and Thermal Properties of MTBE and the Composition of a Commercial MTBE Product ..... 97
Effect of MTBE on Octane Numbers ............. 98
Arconol® A Commercial TBA for Gasoline Blending ..... 100
Typical Additive Valuation (Blendstock Basis) .................... 108
Oxygenate Heating Values and Other Data ......... 110
Refining Operations 1982 and 1990 ............ 117
Octane Valuation at Constant Octane ........... 123
Octane Valuation at Constant Volume ........... 125
Additive Valuation at 120 Blending Octane Number ..... 131
Additive Valuation: Sensitivity to RVP at 120 Blending Octane Number .............. 132
Additive Valuation: Sensitivity to RVP at 110 Blending Octane Number .............. 133
Additive Valuation: Sensitivity to RVP at 100 Blending Octane Number .............. 134
Additive Valuation: Restricted FCC Capacity ....... 137
Methanol Valuation in Refining Operations ........ 139
Ethanol Valuation in Refining Operations ......... 140
Oxinol® Valuation in Refining Operations ......... 141
Low Molecular Weight Additives, Refinery Valuation .... 144
Methanol Valuation in Refining Operations, Thermal Efficiency Sensitivity .............. 147
X
TABLES
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0
7.16
7.17
7.18
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
9.1
9.2
9.3
9.4
9.5
9.6
9.7
Variation of Methanol Value with Improved Miles/Gallon ................ 148
Gasoline Prices and Market Valuation of Octanes and Additives (February 1983) ..................... 150
Additive Production Costs ................ 158
Physical Properties of TAME ............... 176
Octane Numbers of Some TAME-Containing Blends ...... 177
TAME Production from a C5 Fraction Bases and Assumptions .................. 185
TAME Production from a C5 Fraction Major Equipment ..................... 186
TAME Production from a C5 Fraction Utilities Summary . . .. ................ 186
TAME Production from a C5 Fraction Stream Flows ...................... 187
TAME Production from a C5 Fraction Total Capital Investment . ................ 190
TAME Production from a C5 Fraction Production Costs ..................... 191
Composition, Reid Vapor Pressure, Distillation Characteristics, and Octane Numbers of Propylene Dimates . 194
Propylene Dimates Production from a C3 Stream Bases and Assumptions ... ... . . .......... 197
Propylene Dimates Production from a C3 Stream Stream Flows ....................... 199
Propylene Dimates Production from a C3 Stream Major Equipment ..................... 200
Propylene Dimates Production from a C3 Stream Utilities Summary .................... 200
Propylene Dimates Production from a C3 Stream Total Capital Investment ................. 203
Propylene Dimates Production from a C3 Stream Production Costs ..................... 204
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