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Steam Cracking For Olefins Production

Process Economics Program Report 248

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Published July 2003

The technology for producing olefins by thermal steam cracking appears to have reached a stage of maturity in which improvements in yield and product selectivity are becoming increasingly difficult. For the conventional steam cracking process, ethylene yields are improved by raising the cracking temperature and reducing residence time, i.e., increasing the cracking severity. These severe conditions, however, are constrained by the metallurgy of the cracking tubes and rapid coking tendency in the cracking coils. At present, the maximum skin temperature for cracking tubes made of Cr-Ni alloys is about 1100°C (2010°F).

In this report, we evaluate recent developments in cracking furnace design, including the use of ceramic materials for ultra-high temperature cracking. Silicon carbide ceramics can withstand temperatures up to 1400°C (2550°F), have high conductivity and low surface catalytic activity towards coke formation. We have developed a conceptual design and preliminary economics for a steam cracking process using ceramic furnaces, based on technology patented by IFP (Institut Français du Pétrole). Although the process is still in development stage, our analysis shows that the technology offers competitive economics when compared to conventional cracking in metal tubes.

An alternative route to improving the performance of steam cracking is to carry out the reaction in the presence of a catalyst. Catalytic cracking, particularly of liquid feeds such as naphtha and gasoil, can achieve higher olefin yields at moderate reaction conditions coupled with reduced energy consumption. This report evaluates the main technology developments in catalytic steam cracking using metal oxide and zeolite-based catalysts. A promising technology, although still in laboratory research stage, is Japan's AIST process using a lanthanum-modified ZSM-5 catalyst. When cracking light naphtha at 650°C (1200°F), the process achieves an overall ethylene-plus-propylene yield of about 70 wt% and provides significant potential savings in both investment and production costs.

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Table of Contents

Section Page Number

INTRODUCTION 1-1
SUMMARY 2-1
GENERAL ASPECTS 2-1
TECHNICAL ASPECTS 2-1
Advances in Furnace Design for Thermal Cracking 2-1
Advances in Catalytic Steam Cracking 2-3
Processes Using Metal Oxide Catalysts 2-3
Processes Using Zeolite-Based Catalysts 2-3
RIPP/Sinopec's Catalytic Pyrolysis Process (CPP) 2-3
Asahi Chemical's Process 2-4
AIST's Process 2-4
PROCESS ECONOMICS 2-4
Ethylene from Ethane by Steam Cracking in Ceramic Furnace 2-4
Ethylene from Light Naphtha by Catalytic Steam Cracking 2-5
INDUSTRIAL STATUS 3-1
OLEFINS FEEDSTOCKS 3-1
ETHYLENE SUPPLY AND DEMAND 3-3
U.S. Ethylene Outlook 3-7
Western European Ethylene Outlook 3-7
Asian Ethylene Outlook 3-8
Middle Eastern Ethylene Outlook 3-8
PROPYLENE MARKET 3-9
C4 OLEFINS MARKET 3-10
PRODUCERS AND PLANT CAPACITIES 3-10
THERMAL STEAM CRACKING TECHNOLOGY 4-1
REACTION MECHANISM 4-1
CONVENTIONAL STEAM CRACKING TECHNOLOGY 4-2
STEAM CRACKING YIELDS 4-4
COMMERCIAL STEAM CRACKING PROCESSES 4-5
Linde AG 4-5
Kellogg Brown & Root 4-7
ABB Lummus Global 4-8
Stone & Webster 4-9
Technip 4-10
NONCONVENTIONAL THERMAL CRACKING PROCESSES 4-11
Thermal Cracking with Partial Combustion 4-11
The Advanced Cracking Reactor Process 4-11
Ethylene from Light Crude by Dow's Partial Combustion Process 4-12
Fluidized or Circulating Bed Cracking 4-12
The Lurgi Sand Cracker 4-12
BASF's Fluidized Coke/Flow Cracking 4-12
The KK Process 4-13
The Ube Process 4-13
Quick Contact Reaction System/Thermal Regenerative Cracking 4-13
Shock Wave Reactor (SWR) 4-14
TRANSFORMATION TECHNOLOGIES 4-14
Methathesis of Ethylene and Butylenes 4-14
SUPERFLEX Process 4-15
Olefins Interconversion 4-16
Propylur Process 4-16
ADVANCES IN FURNACE DESIGN FOR THERMAL CRACKING 5-1
FIREBOX DESIGN 5-1
Burner Arrangement 5-2
Low NOx Burners 5-3
Refractory Coating 5-3
Modeling Applications 5-4
COIL DESIGN 5-4
TUBE METALLURGY 5-6
COKE REDUCTION 5-7
Mechanisms of Coke Formation 5-8
Catalytic Coking 5-8
Pyrolytic (Thermal) Coking 5-9
Aerosol Coking (Polyaromatic Condensation) 5-9
Antifoulant Additives 5-9
Permanent Surface Coatings 5-11
Other Surface Treatments 5-13
TRANSFER LINE EXCHANGERS 5-13
CERAMIC FURNACES 5-14
ECONOMICS OF STEAM CRACKING IN CERAMIC FURNACE 6-1
PROCESS DESCRIPTION 6-1
Section 100-Cracking and Quenching 6-1
Section 200-Compression and Deacidification 6-2
Section 300-C2 Recovery 6-3
Section 400-Ethylene Separation and Autorefrigeration 6-3
Section 500-Propylene Refrigeration 6-4
Section 600-Methane Refrigeration 6-4
PROCESS DISCUSSION 6-23
COST ESTIMATES 6-24
Capital Costs 6-24
Production Costs 6-25
ECONOMICS COMPARISON 6-35
CATALYTIC STEAM CRACKING TECHNOLOGY 7-1
PROCESSES USING METAL OXIDE CATALYSTS 7-1
The VNIIOS Process 7-2
The Linde/Veba Thermocatalytic Process 7-3
Toyo Engineering's Process 7-3
LG Petrochemical's Process 7-3
PROCESSES USING ZEOLITE-BASED CATALYSTS 7-4
Chemistry 7-4
Zeolite Catalysts 7-5
Fluid Catalytic Cracking (FCC) Processes 7-6
RIPP/Sinopec's Catalytic Pyrolysis Process (CPP) 7-7
Asahi Chemical's Process 7-11
AIST's Process 7-12
Feasibility Study - AIST's Process 7-12
Process Economics 7-18
Process Status 7-18
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

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