ABSTRACT Process Economics Program Report 17C PROPANE-BASED ACRYLONITRILE (June 2001)

Transcription

1 ABSTRACT Process Economics Program Report 17C PROPANE-BASED ACRYLONITRILE (June 2001) Acrylonitrile currently is commercially produced by the ammoxidation of propylene: CH 3 CH=CH 2 + NH O 2 CH 2 =CHCN + 3 H 2 O Acrylonitrile can also be produced by ammoxidation of propane: CH 3 CH 2 CH 3 + NH O 2 CH 2 =CHCN + 4 H 2 O Given the lower cost of propane relative to propylene, manufacturers have tried to develop catalysts for ammoxidation of propane directly to acrylonitrile. However, the lower conversion rates for propane ammoxidation have meant that the capital costs are higher than the costs for propylene-based processes. Lower conversions also meant lower yields and higher waste volumes, further reducing the potential cost advantage. At the time of writing of this report, three companies (BP Nitriles Group [Sohio], Asahi Chemicals and Mitsubishi Chemicals) are in the process of commercializing propane-based processes for acrylonitrile. Of the three propane-based processes considered in this reports, the one based on BP/Sohio patents had the most attractive economics, followed by the process based Mitsubishi patents and then the process based on Asahi patents. Inclusion of a recycle into the processes based on Asahi or Mitsubishi patents (as is being developed by Mitsubishi and BOC), would improve their economics relative to the BP/Sohio propane-based process. With a propane price of 9 /lb., and a propylene price of 18 /lb., the propane-based process based on BP/Sohio patents had a lower product value, i.e. had better economics taking return on investment into account, than the process based on propylene ammoxidation. The propanebased process based on Mitsubishi patents had approximately the same product value as the propylene-based process, and the propane-based process based on Asahi patents had a less attractive product value than the propylene-based process. PEP 99 17C TFM

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3 TABLE OF CONTENTS REPORT 17C PROPANE-BASED ACRYLONITRILE TABLE OF CONTENTS...I TABLE OF TABLES... V TABLE OF FIGURES... VII 1 INTRODUCTION INTRODUCTION CONCISE SUMMARY OF FINDINGS REPORT CONTENTS SUMMARY INTRODUCTION MANUFACTURING TECHNOLOGY REPORT STRUCTURE REFERENCES TO PREVIOUS PEP REPORTS SUMMARY OF PROCESSES REVIEWED Generic Description of Ammoxidation Processes Ammoxidation Reaction Separation Process ENVIRONMENTAL CONCERNS SUMMARY OF RESULTS CONCLUSIONS Strategic Considerations INDUSTRY STATUS INTRODUCTION RECENT DEVELOPMENTS CONSUMPTION AND DEMAND PRICE HISTORY GLOBAL PRODUCTION & CAPACITY Current Production Capacity i

4 4 TECHNICAL REVIEW - ACRYLONITRILE FROM PROPANE INTRODUCTION CHEMISTRY OF ACRYLONITRILE PRODUCTION Reaction cycle Reactor Configuration Catalyst Structure Propane Ammoxidation Catalysts Vanadium-Antimony Catalysts Vanadium-Antimony-Tin Catalysts Vanadium-Phosphorous Catalysts Vanadium-Antimony-Tungsten Catalysts Vanadium-Molybdenum Catalysts Mo-V-Te Catalysts Halide promoters Non-Vanadium Containing Catalysts Reactor Configuration Reactor Startup Increasing Attrition Resistance PROPANE-BASED ACRYLONITRILE (SOHIO CATALYST) PROCESS REVIEW Ammoxidation Catalysts Acrylonitrile Recovery Ammonia Recovery and Recycle Recovery Section Treatment of Wastewaters PROCESS DESCRIPTION Section 100 Reaction Gaseous Recycle Quench Tower and Ammonia Neutralization Organic Product Separation from Waste Gases Section 200 Acrylonitrile Recovery and Purification Section 300 HCN Recovery and Purification PROCESS DISCUSSION Materials of Construction Waste Streams Uncertainties ii

5 CAPITAL AND OPERATING COSTS PROPANE-BASED ACRYLONITRILE (ASAHI PROCESS) PROCESS REVIEW PROCESS DESCRIPTION Section 100 Reaction Ammonia Separation from Reactor Effluent Organics Separation from Reactor Effluent Section 200 Acrylonitrile Recovery and Purification Section 300 HCN Recovery and Purification PROCESS DISCUSSION Materials of Construction Waste Streams CAPITAL AND OPERATING COSTS PROPANE-BASED ACRYLONITRILE (MITSUBISHI PROCESS) PROCESS REVIEW PROCESS DESCRIPTION Section 100 Reaction Ammonia Separation from Reactor Effluent Organics Separation from Reactor Effluent Section 200 Acrylonitrile Recovery and Purification Section 300 HCN Recovery and Purification PROCESS DISCUSSION Materials of Construction Waste Streams Uncertainties CAPITAL AND OPERATING COSTS PROPYLENE-BASED ACRYLONITRILE (SOHIO PROCESS) PROCESS REVIEW PROCESS DESCRIPTION Section 100 Reaction Ammonia Separation from Reactor Effluent Organics Separation from Reactor Effluent Section 200 Acrylonitrile Recovery and Purification Section 300 HCN Recovery and Purification PROCESS DISCUSSION Materials of Construction iii

6 Waste Streams Uncertainties CAPITAL AND OPERATING COSTS APPENDIX A - PATENT SUMMARIES... A-1 APPENDIX B - DESIGN COST BASIS... B-1 DESIGN CONDITIONS... B-3 COST BASES... B-3 Capital Investment... B-3 Production Costs... B-4 Effect of Operating Level on Production Costs... B-4 APPENDIX C - CITED REFERENCES...C-1 APPENDIX D - PROCESS FLOW DIAGRAMS...D-1 APPENDIX E - CITED REFERENCES... E-1 iv

7 TABLE OF TABLES Table 2.1 PROPANE AND PROPYLENE-BASED ACRYLONITRILE ECONOMICS Table 3.1 US, W. EUROPEAN, AND JAPANESE CONSUMPTION BY END-USE Table 3.2 ACRYLONITRILE U.S. PRICE HISTORY Table 3.3 ACRYLONITRILE EUROPEAN PRICE HISTORY Table 3.4 ACRYLONITRILE JAPANESE UNIT SALES HISTORY Table 3.5 GLOBAL ACRYLONITRILE CAPACITY Table 3.6 GLOBAL ACN CAPACITY BY COMPANY Table 3.7 U.S. PRODUCERS OF ACRYLONITRILE Table 3.8 WESTERN EUROPEAN PRODUCERS OF ACRYLONITRILE Table 3.9 JAPANESE PRODUCERS OF ACN Table 3.10 PRODUCERS OF ACRYLONITRILE IN PEOPLE'S REPUBLIC OF CHINA Table 3.11 PRODUCERS OF ACRYLONITRILE IN OTHER WORLD REGIONS Table 4.2 PERFORMANCE OF SELECTED CATALYSTS Table 4.3 CATALYTIC PROPERTIES OF MO-V-X-Y OXIDES Table 4.4 CATALYTIC PROPERTIES OF Mo 1 V 0.3 Te 0.23 Nb 0.12 O x, / ANTIMONY OXIDES Table 4.5 EFFECT OF HALIDE PROMOTERS ON AMMOXIDATION OF PROPANE Table 4.6 EFFECT OF ADDITION OF AMMONIA IN SIDE STREAM Table 5.2 PROPANE-BASED ACRYLONITRILE (SOHIO) DESIGN BASES Table 5.3 PROPANE-BASED ACRYLONITRILE (SOHIO) STREAM FLOWS Table 5.4 PROPANE-BASED ACRYLONITRILE (SOHIO) MAJOR EQUIPMENT Table 5.5 PROPANE-BASED ACRYLONITRILE (SOHIO) CAPITAL INVESTMENT Table 5.6 PROPANE-BASED ACRYLONITRILE (SOHIO) CAPITAL INV BY SECTION Table 5.7 PROPANE-BASED ACRYLONITRILE (SOHIO) UTILITIES SUMMARY Table 5.8 PROPANE-BASED ACRYLONITRILE (SOHIO) VARIABLE COST SUMMARY Table 5.9 PROPANE-BASED ACRYLONITRILE (SOHIO) PRODUCTION COSTS Table 6.2 PROPANE-BASED ACRYLONITRILE (ASAHI) DESIGN BASES Table 6.3 PROPANE-BASED ACRYLONITRILE (ASAHI) STREAM FLOWS Table 6.4 PROPANE-BASED ACRYLONITRILE (ASAHI) MAJOR EQUIPMENT Table 6.5 PROPANE-BASED ACRYLONITRILE (ASAHI) UTILITIES SUMMARY v

8 Table 6.6 PROPANE-BASED ACRYLONITRILE (ASAHI) CAPITAL INVESTMENT Table 6.7 PROPANE-BASED ACRYLONITRILE (ASAHI) CAPITAL INV BY SECTION Table 6.8 PROPANE-BASED ACRYLONITRILE (ASAHI) PRODUCTION COSTS Table 7.2 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) DESIGN BASES Table 7.3 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) STREAM FLOWS Table 7.4 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) MAJOR EQUIPMENT Table 7.5 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) UTILITIES SUMMARY Table 7.6 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) CAPITAL INVESTMENT Table 7.7 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) INV. BY SECTION Table 7.8 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) PRODUCTION COSTS Table 8.2 PROPYLENE-BASED ACRYLONITRILE (SOHIO) DESIGN BASES Table 8.3 PROPYLENE-BASED ACRYLONITRILE (SOHIO) STREAM FLOWS Table 8.4 PROPYLENE-BASED ACRYLONITRILE (SOHIO) MAJOR EQUIPMENT Table 8.5 PROPYLENE-BASED ACRYLONITRILE (SOHIO) UTILITIES SUMMARY Table 8.6 PROPYLENE-BASED ACRYLONITRILE (SOHIO) CAPITAL INVESTMENT Table 8.7 PROPYLENE-BASED ACRYLONITRILE (SOHIO) CAPITAL INV BY SECTION Table 8.8 PROPYLENE-BASED ACRYLONITRILE (SOHIO) PRODUCTION COSTS Table 4.1 ACRYLONITRILE FROM PROPANE - TECHNICAL REVIEW...A-2 Table 5.1 ACRYLONITRILE FROM PROPANE (SOHIO CATALYST)...A-16 Table 6.1 ACRYLONITRILE FROM PROPANE (ASAHI CATALYST)...A-19 Table 7.1 ACRYLONITRILE FROM PROPANE (MITSUBISHI CATALYST)...A-20 Table 8.1 PROPYLENE-BASED ACRYLONITRILE (SOHIO CATALYST)...A-21 vi

9 TABLE OF FIGURES Figure 4.1 Reaction Cycle for Ammoxidation of Propane Figure 4.2 Reaction Cycle for V-Sb-Al-W Oxide Catalsyt Figure 5.1 Acrylonitrile From Propane (Sohio Process) PFD... D-Error! Bookmark not defined. Figure 6.1 Acrylonitrile From Propane (Asahi Process) PFD... D-Error! Bookmark not defined. Figure 7.1 Acrylonitrile From Propane (Mitsubishi Process) PFDD-Error! Bookmark not defined. Figure 8.1 Propylene-Based Acrylonitrile (Sohio Process) PFD. D-Error! Bookmark not defined. vii