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The Catalyst Group Resources, Inc.

Syngas Production and Conversion to Products A Strategic Assessment of the Technologies, Markets and Competitive Landscape

Volume 2: Syngas Conversion to Products Assessment

(completed April 2007) A MULTI-CLIENT STUDY IN TWO VOLUMES

CONTENTS

SECTION I - EXECUTIVE SUMMARY..................................................................1 A. B. CURRENT SITUATION AND INDUSTRY ISSUES......................................1 SYNGAS TO FUELS ........................................................................................3 1. 2. 3. 4. 5. 6. 7. 8. C. 1. 2. 3. 4. MegaMethanol® ........................................................................................3 Methanol to Gasoline (MTG) and Methanol to Olefins (MTO) Plus Conversion of Olefins to Distillate (COD)........................................5 Methanol to Propylene (MTP) ..................................................................7 Syngas to Dimethyl Ether (DME).............................................................9 Gas-to-Liquids (GTL) via Fischer-Tropsch (F-T) ..................................10 Coal-to-Liquids (CTL) via F-T ...............................................................12 F-T Specialty Products (Waxes) .............................................................13 Syngas to Fuels ­ Overall .......................................................................13 Ammonia.................................................................................................16 Hydrogen.................................................................................................17 Methanol..................................................................................................18 Oxo and Acetyl Chemicals......................................................................19 a) b) 5. Oxo Chemicals ...............................................................................19 Acetyl Chemicals ...........................................................................20

SYNGAS TO CHEMICALS ...........................................................................16

Syngas to Chemicals - Overall ................................................................21

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D. A. B. C. D. E. A.

SYNGAS TO POWER.....................................................................................23 INTRODUCTION............................................................................................27 BACKGROUND..............................................................................................28 SCOPE AND METHODOLOGY....................................................................29 THE STUDY TEAM .......................................................................................30 GLOSSARY OF TERMS AND ABBREVIATIONS .....................................33 MEGAMETHANOL®......................................................................................37 1. 2. 3. 4. Definition ................................................................................................37 Historical Background.............................................................................37 Methanol Market .....................................................................................38 Process Description and Technologies....................................................38 a) b) c) Lurgi ...............................................................................................39 Haldor-Topsøe................................................................................41 Other Process Developers ..............................................................41 i. ii. iii. iv. 5. 6. Syntroleum ............................................................................41 Starchem................................................................................41 Johnson Matthey ...................................................................42 Others ....................................................................................42

SECTION II - INTRODUCTION/BACKGROUND ..............................................27

SECTION III - SYNGAS CONVERSION TO FUELS..........................................37

Catalyst Suppliers....................................................................................43 Economics ...............................................................................................44

B.

METHANOL TO GASOLINE (MTG) AND METHANOL TO OLEFINS (MTO) + CONVERSION OF OLEFINS TO DISTILLATE (COD)...............................................................................................................48 1. 2. 3. 4. 5. Historical Background.............................................................................48 Gasoline and Diesel Market ....................................................................49 MTO + Oligomerization to Fuels Process Descriptions .........................49 Catalyst Suppliers....................................................................................52 Economics ...............................................................................................53 Historical Background.............................................................................58 Ethylene and Propylene Market ..............................................................59

C.

METHANOL TO PROPYLENE (MTP®) .......................................................58 1. 2.

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3. 4. 5. 6. D. 1. 2. 3. 4. 5. E.

MTP® Process Description......................................................................60 Catalyst Suppliers....................................................................................61 Economics ...............................................................................................61 Future Prospects of Olefins From Dimethyl Ether..................................65 Historical Background.............................................................................66 DME Process Description .......................................................................67 DME Catalyst Suppliers..........................................................................69 DME Economics .....................................................................................69 Specific Technical/Scale-up Issues with 5000 TPD+ Methanol and DME Plants .............................................................................................72

SYNGAS TO DIMETHYL ETHER (DME) ...................................................66

SYNGAS TO LIQUIDS USING FISCHER-TROPSCH (F-T) SYNTHESIS: GAS-TO-LIQUIDS (GTL).......................................................75 1. 2. 3. 4. 5. Historical Background.............................................................................76 Process Description .................................................................................77 Catalyst Suppliers....................................................................................80 Economics ...............................................................................................80 Current Commercial Opportunities and Future Challenges ....................83

F.

SYNGAS TO LIQUIDS USING FISCHER-TROPSCH (F-T) SYNTHESIS: COAL-TO-LIQUIDS (CTL) ....................................................84 1. 2. 3. 4. Historical Background.............................................................................84 Process Technologies ..............................................................................85 Catalysts ..................................................................................................85 Economics ...............................................................................................86

G. H.

SYNGAS TO FISCHER-TROPSCH (F-T) LIQUIDS WITH SPECIALTY PRODUCTS .....................................................................................................87 CATALYST MARKET SIZE AND GROWTH FOR GTL/CTL, MTO AND DME .............................................................................................89 1. Catalyst Market Size and Growth for GTL/CTL ....................................89 a) b) c) 2. GTL/CTL .......................................................................................89 The Situation in China....................................................................93 Catalyst Market Size and Growth for DME and MTO/MTP.........96

Competition in Catalyst Supply ..............................................................97

I.

REFERENCES.................................................................................................99

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SECTION IV - SYNGAS CONVERSION TO CHEMICALS ............................105 A. AMMONIA....................................................................................................105 1. Commercial Status ................................................................................105 a) b) c) 2. 3. 4. Global Market Situation ...............................................................105 Major Technologies......................................................................107 Market Leaders.............................................................................109

Emerging Technologies.........................................................................110 Process Technology Licensing..............................................................111 Relative Economics of Syngas Conversion to Ammonia .....................113 a) b) Prototypical Economics................................................................113 Sensitivity to Syngas Price Changes ............................................114

5. B. 1.

Implications of Relative Costs ..............................................................115 Commercial Status ................................................................................116 a) b) c) Global Market Situation ...............................................................116 Major Technologies......................................................................118 Market Leaders.............................................................................118

HYDROGEN .................................................................................................116

2. 3. 4.

Emerging Technologies.........................................................................119 Process Technology Licensing..............................................................120 Relative Economics of Syngas Conversion to Hydrogen .....................121 a) b) Prototypical Economics................................................................121 Sensitivity to Syngas Price Changes ............................................122

5. C. 1.

Implications of Relative Costs ..............................................................123 Commercial Status ................................................................................124 a) b) c) Global Market Situation ...............................................................124 Major Technologies......................................................................126 Market Leaders.............................................................................127

METHANOL .................................................................................................123

2. 3. 4.

Emerging Technologies.........................................................................128 Process Technology Licensing.............................................................130 Relative Economics of Syngas Conversion to Methanol ......................131 a) Prototypical Economics................................................................131

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b) 5. D. 1.

Sensitivity to Syngas Price Changes ............................................132

Implications of Relative Costs ..............................................................133 n-Butanol...............................................................................................134 a) Commercial Status .......................................................................134 i. Global Market Situation .........................................................134 ii. Major Technologies................................................................136 iii. Market Leaders.......................................................................136 b) c) d) Emerging Technologies................................................................136 Process Technology Licensing.....................................................136 Relative Economics of Syngas Conversion to n-Butanol ............136 i. Prototypical Economics..........................................................136 ii. Sensitivity to Syngas Price Changes ......................................138 e) Implications of Relative Costs .....................................................138

OXO CHEMICALS .......................................................................................134

2.

2-Ethyl hexanol .....................................................................................139 a) Commercial Status ..........................................................................139 i. Global Market Situation ............................................................139 ii. Major Technologies...................................................................140 iii. Market Leaders..........................................................................140 b) Emerging Technologies...................................................................140 c) Process Technology Licensing........................................................141 d) Relative Economics of Syngas Conversion to 2-EH......................141 i. Prototypical Economics.............................................................141 ii. Sensitivity to Syngas Price Changes .........................................142 e) Implications of Relative Costs ........................................................143

E.

ACETYLS......................................................................................................144 1. Acetic Acid............................................................................................144 a) Commercial Status ..........................................................................144 i. Global Market Situation ............................................................144 ii. Major Technologies...................................................................145 iii. Market Leaders..........................................................................153 b) Emerging Technologies...................................................................159 i. Carbonylation ............................................................................159

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ii. Ethane Oxidation ­ SABIC Process..........................................160 iii. Ethylene Oxidation ­ Showa Denko Process............................161 c) Process Technology Licensing........................................................162 d) Relative Economics of Syngas Conversion to Acetic Acid ............164 i. Prototypical Economics.............................................................164 ii. Sensitivity to Syngas Price Changes .........................................165 e) Implications of Relative Costs ........................................................167 2. Acetic Anhydride ..................................................................................167 a) Commercial Status ..........................................................................167 i. Global Market Situation ............................................................167 ii. Major Technologies...................................................................169 iii. Market Leaders..........................................................................174 b) Emerging Technologies...................................................................177 c) Process Technology Licensing........................................................178 d) Relative Economics of Syngas Conversion to Acetic Anhydride........................................................................................178 i. Prototypical Economics..........................................................178 ii. Sensitivity to Syngas Price Changes .....................................180 e) Implications of Relative Costs ........................................................181 F. CATALYST MARKET SIZE AND GROWTH FOR SYNGASDERIVED CHEMICALS ..............................................................................181 1. Catalysts for Chemicals.........................................................................182 a) Ammonia and Methanol..................................................................182 b) Hydrogen.........................................................................................183 c) Oxochemicals and Acetyls ..............................................................184 2. G. A. Competition in Catalyst Supply ............................................................185 REFERENCES...............................................................................................187 COMMERCIAL STATUS.............................................................................191 1. 2. 3. Projected Electric Supply Growth in the U.S. & Worldwide................191 Role of Coal in Power Generation ........................................................191 Tracking New Coal-Fired Plants (Coal's Resurgence in Power Generation) ...............................................................................................................192

SECTION V - SYNGAS CONVERSION TO POWER .......................................191

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B.

CHALLENGES IN ELECTRIC SUPPLY GROWTH..................................194 1. 2. 3. Air Pollution ­ and Other Environmental Issues ..................................194 Electric Supply Security........................................................................194 CO2 Emissions and the Global Climate Change Issue..........................195

C.

ROLE OF IGCC TECHNOLOGY IN RESOLVING CRITICAL ISSUES...........................................................................................................196 1. 2. 3. Technical and Environmental Issues.....................................................196 Investment and Economic Issues ..........................................................198 Commercial Issues ................................................................................199 Misperceptions of Gasification .............................................................203 Regulatory Uncertainty .........................................................................203 NOx Emissions ......................................................................................203 Capital Cost ...........................................................................................204 Technology Risk ...................................................................................204 Integration .............................................................................................204

D.

BARRIERS TO IGCC TECHNOLOGY IMPLEMENTATION ..................203 1. 2. 3. 4. 5. 6.

E. A. B.

REFERENCES...............................................................................................204 INDUSTRY ISSUES .....................................................................................207 FUELS............................................................................................................209 1. 2. 3. 4. 5. MegaMethanol® ....................................................................................209 MTO and Oligomerization to Fuels ......................................................211 Fischer-Tropsch (F-T) Conversion to Fuels..........................................212 Dimethyl Ether (DME)..........................................................................214 Syngas to Fuels ­ Overall .....................................................................216 Ammonia...............................................................................................219 Hydrogen...............................................................................................220 Methanol................................................................................................221 DME ......................................................................................................222 Oxo Chemicals ......................................................................................223 Acetyls...................................................................................................224 Syngas to Chemicals - Overall ..............................................................226

SECTION VI - RECOMMENDATIONS AND CONCLUSIONS ......................207

C.

CHEMICALS.................................................................................................218 1. 2. 3. 4. 5. 6. 7.

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D.

POWER..........................................................................................................228 1. 2. Market Needs / Drivers .........................................................................229 Technology Needs.................................................................................229 a) Process and Feeds............................................................................229 b) Refractory Liners.............................................................................230 c) Fundamental Studies .......................................................................230 3. Syngas to Power - Overall.....................................................................232

FIGURES

I-B-1 I-B-2 I-C-1 III-A-1 III-A-2 III-A-3 III-A-4 III-A-5 III-A-6 III-B-1 III-B-2 III-B-3 III-B-4 III-C-1 III-C-2 III-C-3 III-C-4 III-C-5 III-C-6 III-C-7 III-D-1 Methanol Transfer Price as a Function of Syngas Transfer Price................4 Effect of Syngas Cost on F-T Liquids Transfer Price...............................11 Schematic of Integrated Energy Facility (Trigeneration) .........................22 Lurgi's MegaMethanol® Process ...............................................................40 Alternative Reactor Configurations for Methanol Synthesis .....................40 The Tube-Cooled Converter (TCC) Reactor Configuration for Leading Concept Methanol (LCM)............................................................42 Syngas Transfer Price as a Function of Natural Gas Price ........................46 Methanol Transfer Price as a Function of Syngas Transfer Price..............46 Methanol Transfer Price as a Function of Capital Cost .............................47 Reactor Configurations for MTO Conversion ...........................................50 Process Configurations for Olefins or Liquid Fuels Products....................51 Effect of Syngas Price on Transfer Price for Fuels via MTO + Oligomerization..........................................................................................57 Effect of Capital on Transfer Price for Fuels via MTO + Oligomerization..........................................................................................58 Demand for Light Olefins ..........................................................................59 Prices for Light Olefins ..............................................................................60 Lurgi Methanol to Propylene (MTP®) Process ..........................................61 Effect of Gasoline By-product Price on Propylene Transfer Price ............62 Effect of Syngas Cost on Olefin Transfer Price.........................................63 Effect of Capital on Transfer Price for Olefins ..........................................63 Source of World Propylene, 2004 & 2020.................................................64 Effect of Syngas Ratio on DME and Methanol Yields ..............................68

The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447, Fax: (215) 628-2267, E-mail: [email protected], Website: www.catalystgrp.com

III-D-2 III-D-3 III-E-1 III-E-2 III-E-3 III-E-4 III-E-5 III-G-1 III-H-1 III-H-2 III-H-3 III-H-4 III-H-5 III-H-6 IV-A-1 IV-A-2 IV-A-3 IV-A-4 IV-A-5 IV-B-1 IV-C-1 IV-C-2 IV-C-3 IV-D-1 IV-D-2 IV-D-3 IV-D-4 IV-D-5 IV-D-6 IV-E-1 IV-E-2 IV-E-3 IV-E-4

DME Transfer Price as a Function of Syngas Cost....................................71 DME Transfer Price as a Function of Capital Cost....................................71 Development Interest in Fischer-Tropsch Technology..............................76 Fischer-Tropsch Plant Process Configuration............................................78 Fischer-Tropsch Reactor Configurations ...................................................79 Effect of Syngas Cost on F-T Liquids Transfer Price...............................81 Effect of Capital Cost on F-T Liquids Transfer Price................................82 History of Wax Prices ...............................................................................88 Syngas Integration to Fuels and Chemicals ...............................................89 GTL-Based Output (BPD) ........................................................................91 Catalyst Unit Operations of the F-T Train .................................................91 GTL - Catalyst Value (US $MIL) For F-T and Backcracking...................92 PRC's Fossil Energy (Oil, Coal) Resources...............................................95 DME Provides a Unique Solution for China..............................................95 Regional Ammonia Supply/Demand ­ 2006 ...........................................106 Global Ammonia Supply/Demand Trends ­ 2006-2010 .........................107 Uhde Dual Pressure Ammonia Process....................................................110 Lurgi Megammonia©...............................................................................111 Sensitivity of Ammonia Price to Syngas Price ........................................115 Sensitivity of Hydrogen Price to Syngas Price ........................................123 Regional Methanol Installed Capacity ­2006 and 2011 ..........................125 Lurgi Dual Reactor Concept for Methanol ..............................................129 Sensitivity of Methanol Price to Syngas Price .........................................133 Regional n-Butanol Supply/Demand ­ 2006 ...........................................135 Global n-Butanol Supply/Demand Trends ­ 2006-2010 .........................135 Sensitivity of n-Butanol Price to Syngas Price ........................................138 Regional 2-Ethyl hexanol Supply/Demand ­ 2006..................................139 Global 2-Ethylhexanol Supply/Demand Trends ­ 2006-2010.................140 Sensitivity of 2-Ethyl Hexanol Price to Syngas Price..............................143 Global Acetic Acid Supply/Demand Situation ........................................144 Global Acetic Acid Supply/Demand Situation ........................................145 Technology Breakdown of Global Acetic Acid Production Capacity .....147 Typical Monsanto Process Acetic Acid Plant ..........................................148

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IV-E-5 IV-E-6 IV-E-7 IV-E-8 IV-E-9

Monsanto Licensees' Published Capacity Increases................................151 Comparison of Carbonylation Batch Reaction Rates...............................152 Breakdown of Methanol Carbonylation Capacity by Process .................153 Chiyoda Reactor (and Catalyst) Concept ­ Acetica Process ...................160 Acetic Acid Transfer Price vs. Capacity ..................................................166

IV-E-10 Acetic Acid Transfer Price vs. Carbon Monoxide Price..........................166 IV-E-11 Global Acetic Anhydride Production Capacity ca. 2.2 million tonnes/year in 2006 ..................................................................................168 IV-E-12 Technology Breakdown of Acetic Anhydride Production Capacity ca. 2.2 million tonnes/year in 2006 ...........................................169 IV-E-13 The Ketene Process for Acetic Anhydride...............................................170 IV-E-14 Eastman's Reactive Distillation For Methyl Acetate Production ............173 IV-E-15 Simplified Methyl Acetate Carbonylation Process ..................................174 IV-E-16 Eastman's Coal-To-Chemicals Complex .................................................176 IV-E-17 SIPC Acetyls Complex.............................................................................178 IV-E-18 Acetic Anhydride Transfer Price vs. Capacity.........................................180 IV-E-19 Acetic Anhydride Transfer Price vs. Acetic Acid Price...........................180 V-C-1 VI-B-1 VI-B-2 VI-B-3 VI-B-4 VI-B-5 VI-B-6 VI-C-1 MIT's "The Future of Coal" Study - Comments/Perspectives/Issues......202 Syngas Transfer Price as a Function of Natural Gas Price ......................210 Methanol Transfer Price as a Function of Syngas Transfer Price............210 Effect of Syngas Cost on F-T Liquids Transfer Price..............................213 Effect of Capital Cost on F-T Liquids Transfer Price..............................213 DME Transfer Price as a Function of Syngas Cost..................................214 DME Transfer Price as a Function of Capital Cost..................................215 Schematic of Integrated Energy Facility (Trigeneration) ........................227

TABLES

I-A-1 I-B-1 I-B-2 I-B-3 I-B-4 I-B-5 Issues/Concerns for the Syngas and Syngas-to-Products Industries............2 Economics for MTO.....................................................................................6 Transfer Price for Fuels via MTO + Oligomerization from Syngas ............7 Propylene Transfer Price via Lurgi's MTP® Process ...................................8 Transfer Price for F-T liquids from Syngas ...............................................11 Comparison of Liquid Transfer Prices .......................................................14

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I-D-1 III-A-1 III-A-2 III-B-1 III-B-2 III-B-3 III-B-4 III-B-5 III-B-6 III-B-7 III-C-1 III-C-2 III-C-3 III-D-1 III-D-2 III-E-1 III-E-2 III-E-3 III-E-4 III-F-1 III-H-1 III-H-2 III-H-3 III-H-4 IV-A-1 IV-A-2 IV-B-1 IV-B-2 IV-C-1 IV-C-2

Normalized Capital Cost Comparison, IGCC vs. PCF ..............................24 Transfer Price for Methanol Using Conventional or MegaMethanol® Technology .....................................................................45 Transfer Price of Syngas From Combined Reforming at MegaMethanol® Scale ................................................................................45 Range of Olefin Yields for MTO Processes...............................................51 Economics for MTO...................................................................................54 Yield Variability for Olefin Oligomerization.............................................54 Economics for Olefin Oligomerization to Fuels ........................................55 Total Capital Requirement and Yields for Fuels via MTO + Oligomerization ............................................................................55 Transfer Price for Fuels via MTO + Oligomerization from Syngas ..........56 Properties of Hydrocarbon Fractions via Synthesis from Syngas..............57 Propylene Transfer Price via Lurgi's MTP® Process .................................62 Comparison of Products From MTO and DTO Processes.........................65 Typical Gas Compositions .........................................................................66 Transfer Price for DME from Syngas at Mega-scale.................................70 Single-Train Reformer Capacities..............................................................75 CTL/GTL Plants Using Fischer-Tropsch Technology...............................77 Transfer Price for F-T Liquids from Syngas..............................................81 Comparison of Liquid Transfer Prices .......................................................82 Transfer Price and Sensitivity Analysis For Sasol-Qatar Petroleum Oryx Ras Laffan Plant ................................................................................84 Commercially Proven Coal Gasification Scale (Holt, 2006) .....................86 Global GTL Capacity to 2012....................................................................90 Global CTL Capacity to 2012 ....................................................................93 Global DME Capacity to 2012...................................................................96 Catalyst Supplier Strengths/Weaknesses to GTL Producers......................98 Current Market Leaders ­ Ammonia ......................................................109 Prototypical Ammonia Process ................................................................114 Hydrogen Market Segments and Volumes...............................................117 Hydrogen via Steam-Methane Reforming ...............................................122 Market Leaders - Countries ­ Methanol ..................................................127 Market Leaders - Companies ­ Methanol ................................................128

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IV-C-3 IV-D-1 IV-D-2 IV-E-1 IV-E-2 IV-E-3 IV-E-4 IV-E-5 IV-E-6 IV-E-7 IV-E-8 IV-E-9 IV-F-1 IV-F-2 IV-F-3 IV-F-4 IV-F-5 V-C-1 V-C-2 V-C-3 VI-A-1 VI-B-1 VI-B-2 VI-B-3 VI-B-4 VI-B-5 VI-B-6

Prototypical Methanol Process.................................................................132 Prototypical n-Butanol Process ................................................................137 Prototypical 2-Ethyl Hexanol Process......................................................142 Major Acetic Acid Producers...................................................................154 Major Vinyl Acetate Producers................................................................155 British Petroleum Acetic Acid Position ...................................................157 Celanese Acetic Acid Position .................................................................158 Monsanto Methanol Carbonylation Licensees.........................................162 Acetic Acid Process Economics Comparison ..........................................165 Major Acetic Anhydride Producers..........................................................175 Celanese Acetic Anhydride Production Sites...........................................177 Acetic Anhydride Process Comparison....................................................179 Catalysts and Corresponding Poisons in Stream Reforming, Shift Conversion, Methanation, Ammonia and Methanol Synthesis .......182 Market Size and Growth of Ammonia and Methanol Production Catalysts, 2006 to 2010 (Mmt/yr = 000's mt/yr) ....................................183 Market Size and Growth for Oxochemicals and Acetyls Production Catalysts, 2006 to 2010 (mt/yr and $ MIL)..............................................184 Catalyst Volume and Growth for Syngas Chemical Applications, 2006-2010 (MIL mt/yr and $ MIL)..........................................................185 Chemical Catalyst Supply/Process Licenses: Strengths/Weaknesses ......186 Tracking Major U.S. IGCC Projects for Power Generation ....................198 Normalized Capital Cost Comparison, IGCC vs. PCF ............................199 Technology Issues and IGCC...................................................................201 Issues/Concerns for the Syngas and Syngas-to-Products Industries........207 Transfer Price of Syngas From Combined Reforming at MegaMethanol® Scale ..............................................................................209 Economics for Olefin Oligomerization to Fuels ......................................211 Transfer Price for Fuels via MTO + Oligomerization from Syngas ........212 Transfer Price for F-T Liquids from Syngas............................................212 Comparison of Products from MTO and DTO Processes........................215 Comparison of Liquid Transfer Prices .....................................................216

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