PROCESS ECONOMICS PROGRAM Abstract Process Economics Program Report No. 158 SRI INTERNATIONAL Menlo Park, California 94025 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. most major chemicals The CHEMICAL ECONOMICS HANDBOOK Program covers 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.. 177 Institut Franlais du Petrole... 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
CONTENTS 9 PROPYLENE DIMATES (continued) Process Discussion..................... 201 Coat Estimates...................... 201 APPENDIX DESIGN AND COST BASES... 207 CITED REFERENCES... 211 PATENT REFERENCES... 215 V
ILLUSTRATIONS 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 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 Flow Sheet.......... 217 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... 22 25 26 27 29 30 35 39 45 47 48 49 50 52 54 55 62 70 74 78 81 ix
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 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 Bases and Assumptions... 185 Major Equipment... 186 Utilities Summary....... 186 Stream Flows... 187 Total Capital Investment.... 190 Production Costs... 191 Composition, Reid Vapor Pressure, Distillation Characteristics, and Octane Numbers of Propylene Dimates. 194 Bases and Assumptions........... 197 Stream Flows... 199 Major Equipment... 200 Utilities Summary... 200 Total Capital Investment... 203 Production Costs... 204 Xi