Methyl tertiary-Butyl Ether (MTBE)

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TABLE OF CONTENTS
Page I SUMMARY A. INTRODUCTION B. GLOBAL SUPPLY AND DEMAND C. PRODUCTION ECONOMICS COMMERCIAL TECHNOLOGY A. RAW MATERIAL AND COPRODUCT VALUATIONS 1. Feedstocks (a) Isobutylene from Steam Crackers (b) Isobutylene from Refineries (c) Isobutylene from TBA Dehydration (d) Isobutane Dehydrogenation 2. Feedstock Valuation (a) Isobutylene (b) Field Butanes (c) tertiary-Butyl Alcohol (d) Other Raw Materials and Byproducts B. CHEMISTRY C. CONVENTIONAL MTBE PROCESS DESIGN 1. Conventional Technology - ABB Lummus Crest (a) Isomerization (b) Dehydrogenation (Catofin Process) (c) Etherification (CDTech) D. NEWER DEVELOPMENTS 1. UOPs MTBE Process (a) Isomerization (Butamer Process) (b) Dehydrogenation (Oleflex Process) (c) Etherification (Ethermax Process) (1) Reaction Section/C4 Column (2) Oxygenate Removal Unit (ORU) (3) Complete Saturation Process (CSP) 2. Texaco Propylene Oxide/Methyl tertiary Butyl Ether 1 1 2 4 7 7 7 7 7 9 9 10 10 10 12 12 15 18 20 20 22 25 27 27 27 30 35 35 38 38 38

II

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Page Phillipss High Conversion Etherification MTBE Production Associated With Butylene Isomerization (a) Skeletal Isomerization (1) Chemistry (2) Economics 5. New Dehydrogenation Catalysts (a) Overview (b) Zeolites PROCESS ECONOMICS 1. Conventional (a) MTBE From Field Butanes (b) MTBE From Steam Cracker Mixed Butylenes (c) MTBE From Refinery Mixed Butylenes (d) MTBE from tertiary-Butyl Alcohol (e) MTBE From Steam Cracker Mixed Butylene Associated with Butylene Isomerization (f) Comparative Economics 2. ETBE 3. 4. 41 44 44 45 46 48 48 50 57 57 57 58 61 61 63 63 66

E.

III

PHYSICAL AND BLENDING PROPERTIES OF OXYGENATES IN GASOLINE A. INTRODUCTION B. BLENDING PROPERTIES C. OXYGENATES VALUE 1. Blend Value Calculation (a) Volumetric Value (b) Vapor Pressure (c) Octane Credit (d) Oxygen Credit

72 72 73 78 78 78 80 80 81

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Page IV COMMERCIAL STATUS A. MTBE SUPPLY AND DEMAND B. CAPACITY ENVIRONMENTAL LEGISLATION A. REGIONAL OVERVIEW 1. North America 2. Western Europe 3. South America 4. Asia 5. Other Regions B. CURRENT U.S. 1. Introduction 2. Gasoline (a) Oxygenated Gasoline (b) Reformulated Gasoline (1) Covered Areas (2) Simple Model Certification (3) Complex Model Certification (4) Antidumping Provisions (5) Opt-In Provisions (6) Opt-Out (7) Renewable Oxygenate Proposal (c) California Gasoline (d) Volatility Trends (e) Gasoline Composition Trends C. CURRENT WEST EUROPEAN REGULATORY CLIMATE 1. Overview 2. Lead Levels 3. Benzene and Aromatics Levels 82 82 89 96 96 96 97 97 98 99 99 99 99 99 102 103 103 104 110 110 112 113 116 119 123 126 126 127 128

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Page RVP and Evaporative Hydrocarbon Emissions Exhaust Emissions Oxygenates Gasohol and ETBE Customer Requirements Individual Countries (a) Belgium (b) Netherlands (c) Luxemburg (d) Denmark (e) France (f) Germany (g) Greece (h) Ireland (i) Italy (j) Portugal (k) Spain (l) United Kingdom (m) Austria (n) Switzerland (o) Finland (p) Norway (q) Sweden CURRENT JAPANESE REGULATORY CLIMATE 1. Octane Levels 2. Reformulation 4. 5. 6. 7. 8. 9. 128 130 131 132 133 133 133 134 134 134 135 135 136 136 136 136 137 137 137 137 138 138 138 138 138 139 140 141

D.

REFERENCES PERP TITLE INDEX

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TABLES
Page Table I.A.1. Table I.B.1 Table I.B.2 Table I.C.1 Table I.C.2 Table II.A.1 Table II.A.2 Table II.A.3 Table II.C.1 Table II.D.1 Table II.D.2 Table II.D.3 Table II.D.4 Table II.D.5 Table II.E.1 Table II.E.2 Table II.E.3 Table II.E.4 Table II.E.5 Table II.E.6 Table II.E.7 Table II.E.8 Table II.E.9 Table II.E.10 MTBE Competitive Strengths and Weaknesses Global MTBE Demand, 1994-2010 Global MTBE Net Trade, 1994-2010 Summary of MTBE Production Costs ETBE Cost Comparison Typical Butene Isomer Distribution in C4 Product Stream Cost Estimate of tertiary-Butyl Alcohol Production via TBA (Allocated Cost) Raw Material and Byproduct Prices Lummus Isomerization Projects Production Cost Estimate of MTBE Production via Texaco: Hydroperoxide/Propylene Oxide Coproduct MTBE Material Balance MTBE Plus Isomerization Material Balance Commercial Isobutane Dehydrogenation Technologies Dehydrogenation of Isobutane with Isobutane Feed and Atmospheric Pressure MTBE Plant Capacity, 1995 ISBL Capital Cost of MTBE from Field Butanes Cost Estimate of MTBE Production via Field Butanes Cost Estimate of MTBE Production from Steam Cracker Mixed Butylenes Production Cost Summary of MTBE from Fluid Catalytic Cracker ISBL Capital Cost of MTBE Production from TBA Cost Estimate of MTBE Production from TBA Cost Estimate of MTBE Production from SC Mixed Butylenes with Isomerization Summary of MTBE Production Costs Cost Estimate of ETBE Production from a Fluid Catalytic Cracker in a Modified Conventional Fixed Bed MTBE Plant 1 3 2 5 6 9 14 15 22 42 46 48 49 54 57 58 59 60 62 61 64 65 66 69

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Page Table II.E.11 Table II.E.12 Table II.E.13 Cost Estimate of ETBE Production from a Fluid Catalytic Cracker for the Phillips High Conversion Etherificatiion Technology Cost Estimate of MTBE Production from a Fluid Catalytic Cracker Summary of Production Costs of ETBE (Conventional), ETBE (Phillips), and MTBE (Phillips)

70 71 68

Table III.A.1 Table III.B.1 Table III.B.2

MTBE Competitive Strengths and Weaknesses 72 Physical and Blending Properties of Oxygenates used in Gasoline Blending (Ethers) 74-75 Physical and Blending Properties of Oxygenates used in Gasoline Blending (Alcohols) 76-77 Global MTBE Demand, 1994-2010 Global MTBE Net Trade, 1994-2010 Global MTBE Supply/Demand Balance Regional MTBE Capacity, 1995 83 85 86-88 89-93

Table IV.A.1 Table IV.A.2 Table IV.A.3 Table IV.B.1 Table V.B.1 Table V.B.2 Table V.B.3 Table V.B.4 Table V.B.5 Table V.B.6 Table V.B.7 Table V.B.8 Table V.B.9 Table V.B.10 Table V.B.11

Key Dates for Fuel-Related CAA Mobile Source Provisions 100 Summary of Reformulated Gasoline Program 102 Simple Model Requirements for RFG, Jan. 1995 through Dec. 1997 104 RFG Complex Model Parameters with Most Effect on Emissions 105 Complex Model Performance for Phase I RFG, 1995-1999 106 CAA Baseline Fuel Compositions 106 Typical Simple Model Fuels Using MTBE 107 Performance of Typical Simple Model Fuels under Phase I Complex Model 107 Complex Model Performance Requirements for Phase II RFG, 2000+ 108 Opt-In Areas at Outset of RFG Program as per the EPA, by State, Ozone Nonattainment Status, and County 111 California Reformulated Gasoline: Phase 2 Specifications 116

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TABLES (Continued)
Page Table V.B.12 Table V.B.13 Table V.C.1 Table V.C.2 Table V.C.3 Table V.C.4 Table V.C.5 National Gasoline Volatility - Average RVP Estimated U.S. Gasoline Pool Composition, 1984-2010 E.U. Legislated Product Specifications Summary of Draft Stage 1 Proposals Summary of Draft Stage 2 Proposals E.U. Consolidated Vehicle Emission Limits Oxygenate Limits in the European Community 120 124 127 129 130 131 132

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FIGURES Page
Figure II.A.1 Figure II.A.2 Figure II.A.3 Figure II.C.1 Figure II.C.2 Figure II.C.3 Figure II.C.4 Figure II.D.1 Figure II.D.2 Figure II.D.3 Figure II.D.4 Figure II.D.5 Figure II.D.6 Figure II.D.7 Figure II.D.8 Figure II.D.9 Figure II.D.10 Figure III.C.1 Figure IV.A.1 Figure IV.B.1 Figure IV.B.2 Figure V.B.1 Figure V.B.2 Figure V.B.3 Isobutylene Supply Sources Factors Influencing MTBE Processing Route Selection Cost Assumptions of TBA Production via PO/TBA Plant Operations MTBE Production Processes Lummus Crest Butane Isomerization Process Flow Diagram Catofin Process: Isobutane Dehydrogenation DETech MTBE Process Flow Diagram UOP Butamer Process Flow Diagram UOP Oleflex Process Flow Diagram UOP/Oleflex Dehydrogenation Catalyst Regeneration Ethermax MTBE Process Flow Diagram Phillips High Conversion MTBE Process Flow Diagram MTBE Production from Steam Cracker C4s Integration of Skeletal Isomerization BP Zeolite Dehydrogenation Catalyst: Life Performance BP Dehydrogenation Catalyst: Temperature Response Mobil Zeolite Dehydrogenation Catalyst Life Performance Gasoline Blending Octane and RVP Selected Oxygenates Global MTBE Demand Global MTBE Capacity Regional Capacity Additions Effect of Sulfur Content on Gasoline Nox Reduction Estimated RVP Specifications Mandated and Opt-In RFG Areas to Date 8 11 13 19 21 23 26 29 31 32 36 43 47 47 52 53 56 79 84 94 95 109 121 122

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