LINEAR ALPHA OLEFINS (December 2008)

Abstract Process Economics Program Report 12E LINEAR ALPHA OLEFINS (December 2008)

This report updates the Process Economics Program technical and economic appraisal of linear alpha olefin technologies for Shell, Chevron, Ineos, IFP (Institut Francais du Patrole) and UOP that were last examined in PEP Report 12D (June 2001). In addition, the following new technologies are evaluated in detailed fashion as customary in the PEP: • SABIC/Linde LAO technology (alpha-SABLINTM) • DuPont LAO technology (VersipolTM) Shell uses a liganded nickel catalyst system for ethylene oligomerization compared with Chevron and Ineos, which employ a Ziegler catalyst. IFP’s AlphaSelectTM targets the maximizing of alpha olefin production in the C4–C10 range using zirconium-based catalysts. The UOP/Union Carbide’s Linear-1TM technology, like Shell, is founded on liganded nickel compounds and, although focusing on producing C4–C10 alpha olefins, can produce the detergent-grade alpha olefins as well. SABIC (Saudi Arabia Basic Industries Corporation) is a new entrant in the field of LAO production business. It recently commercialized a technology jointly with Linde by commissioning a 150,000 TPA LAO plant In Saudi Arabia. The SABIC/Linde technology is commercially branded as alpha-SABLIN technology. Like other three main licensors, the SABIC/Linde technology can also produce all types of LAO products. Additionally, the technology can be operated under specific catalytic conditions to produce specific ranges (including narrow-range) of the LAO product also. The technology is based upon a proprietary zirconium based catalyst used in conjunction with an aluminium alkyl cocatalyst. The current report presents a detailed techno- economic evaluation of the alpha-SABLIN technology. DuPont’s LAO technology (offered for licensing) is commercially known as Versipol™. The technology has not yet found an application in the form of a plant. DuPont catalyst is comprised of an iron complex of a selected diimine of a 2,6-diacylpyridine or 2,6-pyridinedicarboxaldehyde. The catalyst, which is inert at the ambient conditions of reaction, is activated for oligomerization by an alkylaluminum compound. This technology has also been analyzed in detail. This report also presents a detailed technical review of the major LAO technologies (Shell, Chevron-Phillip, Ineos, IFP, UOP, SABIC/Linde, DuPont and Exxon) based upon their patents issued in the last seven or eight years.

by SYEDNAQVI OLEFINS December 2008 Report No.12E

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For detailed marketing data and information, the reader is referred to one of the SRI Consulting 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 SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

CONTENTS

1 INTRODUCTION ...... 1-1

2 SUMMARY ...... 2-1

COMMERCIAL STATUS ...... 2-1

INDUSTRIAL PRODUCERS/LICENSORS ...... 2-2

LINEAR ALPHA OLEFINS TECHNOLOGIES...... 2-2

Shell Higher Olefins Process for Linear Alpha and Internal Olefins...... 2-3

Chevron Linear Alpha Olefins Process ...... 2-4

Ineos Linear Alpha Olefins Process ...... 2-5

SABIC/Linear Alpha Olefins Technology (alpha-SABLIN) ...... 2-6

DuPont Linear Alpha Olefins Technology (Versipol)...... 2-7

Institut Francais du Petrole (IFP) LAO Technology (AlphaSelect)...... 2-7

UOP/UCC Linear Alpha Olefins Technology (Linear-1)...... 2-9

Exxon Linear Alpha Olefins Technology ...... 2-10

PROCESS ECONOMICS...... 2-11

3 INDUSTRY STATUS...... 3-1

CAPACITY, PRODUCTION, AND CONSUMPTION ...... 3-2

4 TECHNICAL REVIEW...... 4-1

TECHNICAL REVIEW ...... 4-2

Shell Higher Olefins Process for Linear Alpha and Internal Olefins...... 4-2 Shell Current Research on Oligomerization Catalysts & Process ...... 4-3

Chevron Linear Alpha Olefins Process ...... 4-7 Chevron Current Research on Oligomerization Catalysts & Process...... 4-9

Ineos Linear Alpha Olefins Process ...... 4-11 Ineos Current Research on Oligomerization Catalysts & Process ...... 4-14

Institut Francais du Petrole (IFP) LAOs Technology (AlphaSelectTM)...... 4-16 IFP Current Research on Oligomerization Catalysts & Process...... 4-18

UOP/UCC Linear Alpha Olefins Technology (Linear-1)...... 4-21 UOP/UCC Current Research on Oligomerization Catalysts & Process...... 4-22

SABIC/Linde Linear Alpha Olefins Technology (alpha-Sablin) ...... 4-25 SABIC/Linde Current Research on Oligomerization Catalysts & Process...... 4-25

DuPont Linear Alpha Olefins Technology (Versipol)...... 4-27

Exxon Linear Alpha Olefins Technology ...... 4-28 Exxon Current Research on Oligomerization Catalysts & Process ...... 4-29

5 SABIC-LINDE LINEAR ALPHA OLEFINS PROCESS ...... 5-1

PROCESS DESCRIPTION ...... 5-2

Section 100 - Ethylene Oligomerization ...... 5-2

Section 200 - Alpha Olefins Separation ...... 5-4

PROCESS DISCUSSION...... 5-15

Materials of Construction...... 5-16

Process Waste Effluents ...... 5-16

COST ESTIMATES ...... 5-17

Fixed-Capital Costs ...... 5-17

Production Costs ...... 5-18

6 DUPONT LINEAR ALPHA OLEFINS PROCESS ...... 6-1

PROCESS DESCRIPTION ...... 6-2

Section 100 - Ethylene Oligomerization ...... 6-2

Section 200 - Alpha Olefins Separation ...... 6-3

PROCESS DISCUSSION...... 6-15

Materials of Construction...... 6-15

Process Waste Effluents ...... 6-16

COST ESTIMATES ...... 6-16

Fixed-Capital Costs ...... 6-16

Production Costs ...... 6-17

7 IFP & UOP LINEAR ALPHA OLEFINS PROCESSES ...... 7-1

COST ESTIMATES ...... 7-8

Fixed-Capital Costs ...... 7-8

Production Costs ...... 7-8

COST ESTIMATES ...... 7-21

Fixed-Capital Costs ...... 7-21

Production Costs ...... 7-21

8 PROCESS ECONOMICS OF SHELL, CHEVRON AND INEOS LINEAR ALPHA OLEFINS TECHNOLOGIES ...... 8-1

APPENDIX A: PATENT SUMMARY TABLES...... A-1

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 DIAGRAM...... E-1

4.1 Ineos Linear Alpha Olefins Process Poisson Product Distribution for Various Values of X ...... 4-13

5.1 SABIC-Linde Linear Alpha-Olefins Process Flow Diagram ...... E-3

5.2 SABIC-Linde Linear Alpha Olefins Process Net Production Cost and Product Value as a Function of Ethylene Price ...... 5-23

5.3 SABIC-Linde Linear Alpha Olefins Process Product Operating Level and Plant Capacity ...... 5-24

6.1 DuPont Linear Alpha-Olefins Process Flow Diagram ...... E-7

6.2 DuPont Linear Alpha Olefins Process Net Production Cost and Product Value as a Function of Ethylene Price ...... 6-22

6.3 DuPont Linear Alpha Olefins Process Product Value as a Function of Plant Operating Level and Plant Capacity...... 6-23

7.1-A IFP Linear Alpha Olefins Process Net Production Cost and Product Value as a Function of Ethylene Price ...... 7-14

7.1-B UOP Linear Alpha Olefins Process Net Production Cost and Product Value as a Function of Ethylene Price ...... 7-27

2.1 Major World Producers of Linear Alpha Olefins ...... 2-2

2.2 Commercial Linear Alpha Olefins Technologies Total Capital Investment...... 2-12

2.3 Linear Alpha Olefins Technologies (In Ready-State for Commercialization) Total Capital Investment...... 2-13

2.4 Commerical Linear Alpha Olefins Technologies Production Costs ...... 2-15

2.5 Linear Alpha Olefins Technologies (In Ready-State for Commercialization) Production Costs ...... 2-16

3.1 World Supply/Demand for Linear Alpha Olefins by Region ...... 3-2

3.2 World Producers of Linear Alpha Olefins ...... 3-3

3.3 Major World Producers of Linear Alpha Olefins ...... 3-4

3.4 Linear Alpha Olefins Consumption Breakdown in Major Areas ...... 3-4

5.1 SABIC-Linde Linear Alpha Olefins Process Design Bases ...... 5-5

5.2 SABIC-Linde Linear Alpha Olefins Process Stream Flows...... 5-7

5.3 SABIC-Linde Linear Alpha Olefins Process Major Equipment ...... 5-11

5.4 SABIC-Linde Linear Alpha Olefins Process Utilities Summary...... 5-14

5.5 SABIC-Linde Linear Alpha Olefins Process Total Capital Investment...... 5-19

5.6 SABIC-Linde Linear Alpha Olefins Process Capital Investment by Section...... 5-20

5.7 SABIC-Linde Linear Alpha Olefins Process Production Costs ...... 5-21

6.1 DuPont Linear Alpha Olefins Process Design Bases ...... 6-5

6.2 DuPont Linear Alpha Olefins Process Stream Flows...... 6-7

6.3 DuPont Linear Alpha Olefins Process Major Equipment ...... 6-11

6.4 DuPont Linear Alpha Olefins Process Utilities Summary...... 6-14

6.5 DuPont Linear Alpha Olefins Process Total Captial Investment...... 6-18

6.6 DuPont Linear Alpha Olefins Process Capital Investment by Section...... 6-19

6.7 DuPont Linear Alpha Olefins Process Production Costs ...... 6-20

7.1-A IFP Linear Alpha Olefins Process Design Bases ...... 7-2

7.2-A IFP Linear Alpha Olefins Process Major Equipment ...... 7-4

7.3-A IFP Linear Alpha Olefins Process Utilities Summary...... 7-7

7.4-A IFP Linear Alpha Olefins Process Total Capital Investment...... 7-10

7.5-A IFP Linear Alpha Olefins Process Capital Investment by Section...... 7-11

7.6-A IFP Linear Alpha Olefins Process Production Costs ...... 7-12

7.1-B UOP Linear Alpha Olefins Process Design Bases ...... 7-15

7.2-B UOP Linear Alpha Olefins Process Major Equipment ...... 7-17

7.3-B UOP Linear Alpha Olefins Process Utilities Summary...... 7-20

7.4-B UOP Linear Alpha Olefins Process Total Capital Investment...... 7-23

7.5-B UOP Linear Alpha Olefins Process Capital Investment by Section...... 7-24

7.6-B UOP Linear Alpha Olefins Process Production Costs ...... 7-25

8.1 Commercial Linear Alpha Olefins Technologies Total Capital Investment...... 8-2

8.2 Linear Alpha Olefins Technologies (In Ready-State for Commercialization) Total Capital Investment...... 8-3

8.3 Commercial Linear Alpha Olefins Technologies Production Costs ...... 8-4

8.4 Linear Alpha Olefins Technologies (In Ready-State for Commercialization) Production Costs ...... 8-5