Abstract Process Economics Program Report 12D LINEAR ALPHA OLEFINS (June 2001)

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1 Abstract Process Economics Program Report 12D LINEAR ALPHA OLEFINS (June 2001) This report updates the Process Economics Program technical and economic appraisal of linear alpha olefin processes for Shell and Chevron that were last examined in PEP Report 12C (July 1990). In addition, the following new technologies are evaluated: BP Amoco: Total Butene-Recycle technology. Institut Français du Pétrole: AlphaSelect TM technology. UOP/Union Carbide: Linear-1 technology. Phillips Petroleum: Ethylene Trimerization technology. Sasol: 1-Hexene Recovery technology. Shell uses a proprietary liganded nickel catalyst system for ethylene oligomerization compared with Chevron and BP Amoco, which employ a Ziegler-type catalyst. Institut Français du Pétrole s AlphaSelect TM targets the maximizing of alpha olefin production in the C 4 C 10 range using zirconium-based catalysts. Like Shell, UOP/Union Carbide s Linear-1 oligomerization technology is founded on liganded nickel compounds and, although focusing on producing C 4 C 10 alpha olefins, produces detergent-grade alpha olefins as well. Both AlphaSelect TM and Linear-1 produce C 4 s in appreciably high amounts. Phillips selectively produces 1-hexene from ethylene. Using chromium-based catalysts, the Phillips ethylene trimerization technology can give a high yield of 1-hexene with a purity of above 90%. Sasol produces 1-hexene primarily because of its high market demand and as an alternative for its gasoline product via a proprietary extractive distillation process. This report also presents a brief discussion of the state of the industry with particular reference to manufacturing capacities and consumption rates. PEP 00 SNN

2 CONTENTS GLOSSARY... xiii 1 INTRODUCTION SUMMARY INDUSTRY STATUS LINEAR ALPHA OLEFINS TECHNOLOGIES Shell Higher Olefins Process for Linear Alpha and Internal Olefins Chevron Linear Alpha Olefins Process BP Amoco Linear Alpha Olefins Process IFP Linear Alpha Olefins Process UOP/UCC Linear Alpha Olefins Process Phillips Ethylene Trimerization Technology Sasol 1-Hexene Recovery Process PROCESS ECONOMICS INDUSTRY STATUS SHELL HIGHER OLEFINS PROCESS FOR LINEAR ALPHA AND INTERNAL OLEFINS PROCESS REVIEW Catalyst System Reactors and Reaction Conditions Product Separation Product Purity PROCESS DESCRIPTION Section 100 Ethylene Oligomerization Section 200 Alpha Olefins Separation Section 300 Isomerization and Disproportionation PROCESS DISCUSSION Process Waste Effluents iii

3 CONTENTS (Continued) 4 SHELL HIGHER OLEFINS PROCESS FOR LINEAR ALPHA AND INTERNAL OLEFINS (Concluded) Materials of Construction COST ESTIMATES Fixed-Capital Costs Production Costs CHEVRON LINEAR ALPHA OLEFINS PROCESS PROCESS REVIEW Reactors and Reaction Conditions Catalyst System Product Separation PROCESS DESCRIPTION Section 100 Ethylene Oligomerization Section 200 Alpha Olefins Separation PROCESS DISCUSSION Materials of Construction Process Waste Effluents COST ESTIMATES Fixed-Capital Costs PRODUCTION COSTS BP AMOCO LINEAR ALPHA OLEFINS PROCESS PROCESS REVIEW Reactors and Reaction Conditions Catalyst Product Separation PROCESS DESCRIPTION Section 100 Ethylene Growth Section 200 Aluminumalkyls Displacement iv

4 CONTENTS (Continued) 6 BP AMOCO LINEAR ALPHA OLEFINS PROCESS (Concluded) Section 300 Alpha Olefins Separation PROCESS DISCUSSION Materials of Construction Process Waste Effluents COST ESTIMATES Fixed-Capital Costs Production Costs IFP LINEAR ALPHA OLEFINS PROCESS PROCESS REVIEW Catalyst System Reactor and Reaction Conditions Product Separation PROCESS DESCRIPTION Section 100 Ethylene Oligomerization Section 200 Alpha Olefins Separation PROCESS DISCUSSION Materials of Construction Process Waste Effluents COST ESTIMATES Fixed-Capital Costs Production Costs UOP/UNION CARBIDE LINEAR ALPHA OLEFINS PROCESS PROCESS REVIEW Catalyst System Reactor and Reaction Conditions Products Separation v

5 CONTENTS (Continued) 8 UOP/UNION CARBIDE LINEAR ALPHA OLEFINS PROCESS (Concluded) PROCESS DESCRIPTION Section 100 Ethylene Oligomerization Section 200 Alpha Olefins Separation PROCESS DISCUSSION Materials of Construction Process Waste Effluents COST ESTIMATES Fixed-Capital Costs Production Costs PHILLIPS ETHYLENE TRIMERIZATION TECHNOLOGY PROCESS REVIEW Catalyst System Reactor and Reaction Conditions Products Separation PROCESS DESCRIPTION Section 100 Catalyst Preparation Section 200 Trimerization Section 300 Products Separation PROCESS DISCUSSION Materials of Construction Waste Effluents COST ESTIMATES Fixed-Capital Costs Production Costs SASOL 1-HEXENE RECOVERY TECHNOLOGY SASOL S 1-HEXENE IS A GASOLINE FUEL ALTERNATIVE PEP S ECONOMIC MODULE FOR THE SASOL PROCESS vi

6 CONTENTS (Concluded) APPENDIX A: PATENT SUMMARY TABLES...A Shell Higher Olefins Process for Linear Alpha and Internal Olefins...A Chevron Linear Alpha Olefins Process...A BP Amoco Linear Alpha Olefins Process...A IFP Linear Alpha Olefins Process... A UOP/UCC Linear Alpha Olefins Process...A Phillips Ethylene Trimerization Technology...A-20 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAMS...E Shell Higher Olefins Process for Linear Alpha and Internal Olefins... E Chevron Linear Alpha Olefins Process...E BP Amoco Linear Alpha Olefins Process...E IFP Linear Alpha Olefins Process... E UOP/UCC Linear Alpha Olefins Process...E Phillips Ethylene Trimerization Technology...E-25 vii

7 ILLUSTRATIONS 2.1 Effect of 1-Butene Content of LAO Products on Profit Margin for the Shell Process Process Flow Diagram: Shell Higher Olefins Process for Linear Alpha and Internal Olefins...E Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Oligomer Product Distribution as a Function of the Growth Factor, K Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Net Production Cost and Product Value as a Function of Ethylene Price Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Product Value as a Function of Plant Operating Level and Plant Capacity Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Effect of 1-Butene Content on Process Profitability Process Flow Diagram: Chevron Linear Alpha Olefins Process... E Chevron Linear Alpha Olefins Process: Net Production Cost and Product Value as a Function of Ethylene Price Chevron Linear Alpha Olefins Process: Product Value as a Function of Plant Operating Level and Plant Capacity Chevron Linear Alpha Olefins Process: Effect of 1-Butene Content on Process Profit Margin Process Flow Diagram: BP Amoco Linear Alpha Olefins Process...E BP Amoco Linear Alpha Olefins Process: Poisson Product Distribution for Various Values of X BP Amoco Linear Alpha Olefins Process: Net Production Cost and Product Value as a Function of Ethylene Price BP Amoco Linear Alpha Olefins Process: Product Value as a Function of Plant Operating Level and Plant Capacity Process Flow Diagram: IFP Linear Alpha Olefins Process... E IFP Linear Alpha Olefins Process: Net Production Cost and Product Value as a Function of Ethylene Price IFP Linear Alpha Olefins Process: Product Value as a Function of Plant Operating Level and Plant Capacity IFP Linear Alpha Olefins Process: Effect of 1-Butene Content on Process Profit Margin viii

8 ILLUSTRATIONS (Concluded) 8.1 Process Flow Diagram: UOP/UCC Linear Alpha Olefins Process...E UOP/UCC Linear Alpha Olefins Process: Net Production Cost and Product Value as a Function of Ethylene Price UOP/UCC Linear Alpha Olefins Process: Product Value as a Function of Plant Operating Level and Plant Capacity UOP/UCC Linear Alpha Olefins Process: Effect of 1-Butene Content on Process Profit Margin Process Flow Diagram: Phillips Ethylene Trimerization Technology...E Phillips Ethylene Trimerization Technology: Net Production Cost and Product Value as a Function of Ethylene Price Phillips Ethylene Trimerization Technology: Product Value as a Function of Plant Operating Level and Plant Capacity Block Diagram for Sasol 1-Hexene Recovery Technology Hexene Upgrading Scheme ix

9 TABLES 2.1 Leading Linear Alpha Olefins Processes: Total Capital Investment Leading Linear Alpha Olefins Processes: Production Costs C 4 C 10 Linear Alpha Olefins Processes: Total Capital Investment C 4 C 10 Linear Alpha Olefins Processes: Production Costs Hexene Technologies: Production Costs World Producers of Linear Alpha Olefins Supply/Demand for LAOs by LAO-Producing Region Consumption of LAOs by Major Region Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Patent Summary... A Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Design Bases Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Stream Flows Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Major Equipment Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Utilities Summary Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Total Capital Investment Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Capital Investment by Section Shell Higher Olefins Process for Linear Alpha and Internal Olefins: Production Costs Chevron Linear Alpha Olefins Process: Patent Summary... A Chevron Linear Alpha Olefins Process: Design Bases Chevron Linear Alpha Olefins Process: Stream Flows Chevron Linear Alpha Olefins Process: Major Equipment Chevron Linear Alpha Olefins Process: Utilities Summary Chevron Linear Alpha Olefins Process: Total Capital Investment Chevron Linear Alpha Olefins Process: Capital Investment by Section x

10 TABLES (Continued) 5.8 Chevron Linear Alpha Olefins Process: Production Costs BP Amoco Linear Alpha Olefins Process: Patent Summary... A BP Amoco Linear Alpha Olefins Process: Design Bases BP Amoco Linear Alpha Olefins Process: Stream Flows BP Amoco Linear Alpha Olefins Process: Major Equipment BP Amoco Linear Alpha Olefins Process: Utilities Summary BP Amoco Linear Alpha Olefins Process: Total Capital Investment BP Amoco Linear Alpha Olefins Process: Capital Investment by Section BP Amoco Linear Alpha Olefins Process: Production Costs IFP Linear Alpha Olefins Process: Patent Summary... A IFP Linear Alpha Olefins Process: Design Bases IFP Linear Alpha Olefins Process: Stream Flows IFP Linear Alpha Olefins Process: Major Equipment IFP Linear Alpha Olefins Process: Utilities Summary IFP Linear Alpha Olefins Process: Total Capital Investment IFP Linear Alpha Olefins Process: Capital Investment by Section IFP Linear Alpha Olefins Process: Production Costs UOP/UCC Linear Alpha Olefins Process: Patent Summary... A UOP/UCC Linear Alpha Olefins Process: Design Bases UOP/UCC Linear Alpha Olefins Process: Stream Flows UOP/UCC Linear Alpha Olefins Process: Major Equipment UOP/UCC Linear Alpha Olefins Process: Utilities Summary UOP/UCC Linear Alpha Olefins Process: Total Capital Investment UOP/UCC Linear Alpha Olefins Process: Capital Investment by Section UOP/UCC Linear Alpha Olefins Process: Production Costs Phillips Ethylene Trimerization Technology: Patent Summary... A-20 xi

11 TABLES (Concluded) 9.2 Phillips Ethylene Trimerization Technology: Design Bases Phillips Ethylene Trimerization Technology: Stream Flows Phillips Ethylene Trimerization Technology: Major Equipment Phillips Ethylene Trimerization Technology: Utilities Summary Phillips Ethylene Trimerization Technology: Total Capital Investment Phillips Ethylene Trimerization Technology: Capital Investment by Section Phillips Ethylene Trimerization Technology: Production Costs Product Selectivity In the Sasol Process Category Distribution of Components Fischer-Tropsch Products Raw Materials and Products for the Sasol Process Sasol 1-Hexene Recovery Technology: Total Capital Investment Sasol 1-Hexene Recovery Technology: Production Costs xii

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