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 3 + 1.5 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 3 + 2 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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TABLE OF CONTENTS REPORT 17C PROPANE-BASED ACRYLONITRILE TABLE OF CONTENTS...I TABLE OF TABLES... V TABLE OF FIGURES... VII 1 INTRODUCTION... 1-1 INTRODUCTION... 1-1 CONCISE SUMMARY OF FINDINGS... 1-1 REPORT CONTENTS... 1-1 2 SUMMARY... 2-1 INTRODUCTION... 2-1 MANUFACTURING TECHNOLOGY... 2-1 REPORT STRUCTURE... 2-1 REFERENCES TO PREVIOUS PEP REPORTS... 2-2 SUMMARY OF PROCESSES REVIEWED... 2-2 Generic Description of Ammoxidation Processes... 2-2 Ammoxidation Reaction... 2-2 Separation Process... 2-3 ENVIRONMENTAL CONCERNS... 2-3 SUMMARY OF RESULTS... 2-4 CONCLUSIONS... 2-5 Strategic Considerations... 2-5 3 INDUSTRY STATUS... 3-1 INTRODUCTION... 3-1 RECENT DEVELOPMENTS... 3-1 CONSUMPTION AND DEMAND... 3-1 PRICE HISTORY... 3-2 GLOBAL PRODUCTION & CAPACITY... 3-6 Current Production Capacity... 3-6 i
4 TECHNICAL REVIEW - ACRYLONITRILE FROM PROPANE... 4-1 INTRODUCTION... 4-1 CHEMISTRY OF ACRYLONITRILE PRODUCTION... 4-1 Reaction cycle... 4-2 Reactor Configuration... 4-4 Catalyst Structure... 4-4 Propane Ammoxidation Catalysts... 4-4 Vanadium-Antimony Catalysts... 4-5 Vanadium-Antimony-Tin Catalysts... 4-6 Vanadium-Phosphorous Catalysts... 4-6 Vanadium-Antimony-Tungsten Catalysts... 4-7 Vanadium-Molybdenum Catalysts... 4-8 Mo-V-Te Catalysts... 4-11 Halide promoters... 4-12 Non-Vanadium Containing Catalysts... 4-12 Reactor Configuration... 4-12 Reactor Startup... 4-13 Increasing Attrition Resistance... 4-14 5 PROPANE-BASED ACRYLONITRILE (SOHIO CATALYST)... 5-1 PROCESS REVIEW... 5-1 Ammoxidation Catalysts... 5-1 Acrylonitrile Recovery... 5-1 Ammonia Recovery and Recycle... 5-2 Recovery Section... 5-2 Treatment of Wastewaters... 5-2 PROCESS DESCRIPTION... 5-2 Section 100 Reaction... 5-3 Gaseous Recycle... 5-3 Quench Tower and Ammonia Neutralization... 5-3 Organic Product Separation from Waste Gases... 5-3 Section 200 Acrylonitrile Recovery and Purification... 5-4 Section 300 HCN Recovery and Purification... 5-4 PROCESS DISCUSSION... 5-14 Materials of Construction... 5-14 Waste Streams... 5-14 Uncertainties... 5-14 ii
CAPITAL AND OPERATING COSTS... 5-15 6 PROPANE-BASED ACRYLONITRILE (ASAHI PROCESS)... 6-1 PROCESS REVIEW... 6-1 PROCESS DESCRIPTION... 6-1 Section 100 Reaction... 6-1 Ammonia Separation from Reactor Effluent... 6-3 Organics Separation from Reactor Effluent... 6-3 Section 200 Acrylonitrile Recovery and Purification... 6-3 Section 300 HCN Recovery and Purification... 6-3 PROCESS DISCUSSION... 6-12 Materials of Construction... 6-12 Waste Streams... 6-12 CAPITAL AND OPERATING COSTS... 6-12 7 PROPANE-BASED ACRYLONITRILE (MITSUBISHI PROCESS)... 7-1 PROCESS REVIEW... 7-1 PROCESS DESCRIPTION... 7-1 Section 100 Reaction... 7-3 Ammonia Separation from Reactor Effluent... 7-3 Organics Separation from Reactor Effluent... 7-3 Section 200 Acrylonitrile Recovery and Purification... 7-3 Section 300 HCN Recovery and Purification... 7-4 PROCESS DISCUSSION... 7-11 Materials of Construction... 7-11 Waste Streams... 7-11 Uncertainties... 7-11 CAPITAL AND OPERATING COSTS... 7-11 8 PROPYLENE-BASED ACRYLONITRILE (SOHIO PROCESS)... 8-1 PROCESS REVIEW... 8-1 PROCESS DESCRIPTION... 8-1 Section 100 Reaction... 8-1 Ammonia Separation from Reactor Effluent... 8-3 Organics Separation from Reactor Effluent... 8-3 Section 200 Acrylonitrile Recovery and Purification... 8-3 Section 300 HCN Recovery and Purification... 8-3 PROCESS DISCUSSION... 8-10 Materials of Construction... 8-10 iii
Waste Streams... 8-10 Uncertainties... 8-10 CAPITAL AND OPERATING COSTS... 8-11 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
TABLE OF TABLES Table 2.1 PROPANE AND PROPYLENE-BASED ACRYLONITRILE ECONOMICS... 2-4 Table 3.1 US, W. EUROPEAN, AND JAPANESE CONSUMPTION BY END-USE... 3-2 Table 3.2 ACRYLONITRILE U.S. PRICE HISTORY... 3-3 Table 3.3 ACRYLONITRILE EUROPEAN PRICE HISTORY... 3-4 Table 3.4 ACRYLONITRILE JAPANESE UNIT SALES HISTORY... 3-5 Table 3.5 GLOBAL ACRYLONITRILE CAPACITY... 3-6 Table 3.6 GLOBAL ACN CAPACITY BY COMPANY... 3-7 Table 3.7 U.S. PRODUCERS OF ACRYLONITRILE... 3-8 Table 3.8 WESTERN EUROPEAN PRODUCERS OF ACRYLONITRILE... 3-9 Table 3.9 JAPANESE PRODUCERS OF ACN... 3-10 Table 3.10 PRODUCERS OF ACRYLONITRILE IN PEOPLE'S REPUBLIC OF CHINA... 3-11 Table 3.11 PRODUCERS OF ACRYLONITRILE IN OTHER WORLD REGIONS... 3-12 Table 4.2 PERFORMANCE OF SELECTED CATALYSTS... 4-8 Table 4.3 CATALYTIC PROPERTIES OF MO-V-X-Y OXIDES... 4-9 Table 4.4 CATALYTIC PROPERTIES OF Mo 1 V 0.3 Te 0.23 Nb 0.12 O x, / ANTIMONY OXIDES... 4-10 Table 4.5 EFFECT OF HALIDE PROMOTERS ON AMMOXIDATION OF PROPANE... 4-12 Table 4.6 EFFECT OF ADDITION OF AMMONIA IN SIDE STREAM... 4-13 Table 5.2 PROPANE-BASED ACRYLONITRILE (SOHIO) DESIGN BASES... 5-5 Table 5.3 PROPANE-BASED ACRYLONITRILE (SOHIO) STREAM FLOWS... 5-6 Table 5.4 PROPANE-BASED ACRYLONITRILE (SOHIO) MAJOR EQUIPMENT... 5-16 Table 5.5 PROPANE-BASED ACRYLONITRILE (SOHIO) CAPITAL INVESTMENT... 5-19 Table 5.6 PROPANE-BASED ACRYLONITRILE (SOHIO) CAPITAL INV BY SECTION... 5-20 Table 5.7 PROPANE-BASED ACRYLONITRILE (SOHIO) UTILITIES SUMMARY... 5-22 Table 5.8 PROPANE-BASED ACRYLONITRILE (SOHIO) VARIABLE COST SUMMARY... 5-23 Table 5.9 PROPANE-BASED ACRYLONITRILE (SOHIO) PRODUCTION COSTS... 5-24 Table 6.2 PROPANE-BASED ACRYLONITRILE (ASAHI) DESIGN BASES... 6-2 Table 6.3 PROPANE-BASED ACRYLONITRILE (ASAHI) STREAM FLOWS... 6-5 Table 6.4 PROPANE-BASED ACRYLONITRILE (ASAHI) MAJOR EQUIPMENT... 6-14 Table 6.5 PROPANE-BASED ACRYLONITRILE (ASAHI) UTILITIES SUMMARY... 6-17 v
Table 6.6 PROPANE-BASED ACRYLONITRILE (ASAHI) CAPITAL INVESTMENT... 6-18 Table 6.7 PROPANE-BASED ACRYLONITRILE (ASAHI) CAPITAL INV BY SECTION... 6-19 Table 6.8 PROPANE-BASED ACRYLONITRILE (ASAHI) PRODUCTION COSTS... 6-21 Table 7.2 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) DESIGN BASES... 7-2 Table 7.3 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) STREAM FLOWS... 7-5 Table 7.4 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) MAJOR EQUIPMENT... 7-13 Table 7.5 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) UTILITIES SUMMARY... 7-16 Table 7.6 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) CAPITAL INVESTMENT... 7-17 Table 7.7 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) INV. BY SECTION... 7-18 Table 7.8 PROPANE-BASED ACRYLONITRILE (MITSUBISHI) PRODUCTION COSTS... 7-20 Table 8.2 PROPYLENE-BASED ACRYLONITRILE (SOHIO) DESIGN BASES... 8-2 Table 8.3 PROPYLENE-BASED ACRYLONITRILE (SOHIO) STREAM FLOWS... 8-4 Table 8.4 PROPYLENE-BASED ACRYLONITRILE (SOHIO) MAJOR EQUIPMENT... 8-12 Table 8.5 PROPYLENE-BASED ACRYLONITRILE (SOHIO) UTILITIES SUMMARY... 8-15 Table 8.6 PROPYLENE-BASED ACRYLONITRILE (SOHIO) CAPITAL INVESTMENT... 8-16 Table 8.7 PROPYLENE-BASED ACRYLONITRILE (SOHIO) CAPITAL INV BY SECTION... 8-17 Table 8.8 PROPYLENE-BASED ACRYLONITRILE (SOHIO) PRODUCTION COSTS... 8-19 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
TABLE OF FIGURES Figure 4.1 Reaction Cycle for Ammoxidation of Propane... 4-3 Figure 4.2 Reaction Cycle for V-Sb-Al-W Oxide Catalsyt... 4-4 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