Report No. 34A PHTHALIC ANHYDRIDE Supplement A by LLOYD M. ELKIN June 1974 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION........................ 1 2 SUMMARY... 3 General Aspects.... 3 Economic Aspects... 4 Technical Aspects... 10 3 INDUSTRY STATUS....................... 13 4 CHEMISTRY.......................... Phthalic Anhydride from o-xylene by Vapor........................ Phthalic Anhydride from Naphthalene by Vapor.............................................. 5 PHTHALIC ANHYDRIDE FROM o-xylene BY AIR OXIDATION IN FIXED BED REACTORS... Review of Patents... Process Description... Process Discussion... Air Compressor... Xylene Injection... Air Preheater... Reactor Design... Steam Pressures... Switch Condensers... Beat Balance... Off-Gas Treatment... Heat Treatment... Distillation System... Maleic Anhydride... Storage... F... Cost Estimates... Capital Costs... Production Costs... SRI Versions of the BASF, Von Heyden, and Rhone-Progil Processes... High Temperature Process... 29 29 30 31 33 33 51 62 62 62 63 63 63 64 64 65 65 65 72 79 Vii
CONTENTS 6 PHTHALIC ANHYDRIDE FROM o-xylene BY LIQUID PHASE OXIDATION...................... 85 Review of Patents... Process Description... Process Discussion... Material and Heat Balances... Conversions, Yields, and Yield Structures in Oxidation Reactors... Overall Yield... Water Removal Column and Benzene Adsorber Hydrolyzer... Crystallizer... Acetic Acid Wash Stream... Bleed Stream... Distillation Columns... Material of Construction... Cost Estimates... Capital Costs... Production Costs...... 85... 91... 101 101... 101... 101... 102... 102... 102... 102... 102 7 PHTHALIC ANHYDRIDE FROM NAPHTHALENE BY AIR OXIDATION IN FIXED BED REACTORS... 109 Explosive Limits... 109 Capital and Production Costs... 109 Low-Temperature Oxidation... 109 _ High-Temperature Oxidation... 113 (3 PHTHALIC ANHYDRIDE FROM o-xylene OR NAPHTHALENE IN FLUID BED REACTORS... 115 Review of Patents... 115 Capital and Production Costs... 115 9 RECOVERY AND PURIFICATION OF CRUDE PHTHALIC ANHYDRIDE... 133 Review of Patents..................... 133 APPENDIX DESIGN AND COST BASIS... 145 CITED REFERENCES... 149 PATENT REFERENCES BY COMPANY... 1 viii
ILLUSTRATIONS 5.1 in Fixed Red Reactors: Low-Temperature Process.... 57 5.2 in Fixed Red Reactors: Low-Temperature Process Effect of Operating Level and on Production Cost................... 71 6.1.................... 95 6.2 Effect of Operating Level and on Production Cost................... 107 ix
TABLES 2.1 2.2 2.3 3.1 3.2 3.3 3.4 3.5 3.6 5.1 5.2 5.3 5.4 5.5 5.6 Cost Comparison..................... 5 Summary of Process Conditions for Vapor Phase Processes..................... 7 Summary of Process Conditions for a Liquid Phase Process...................... 9 United States.......,.....,...,.... 15 The Americas Other than the United States...,.... 17 Western Europe............,......... 19 Eastern Europe...................... 23 Japan.......................... 25 Asia, Australia, and South Africa............ 26 in Fixed Bed Reactors Patent Summary (Catalysts)................ 35 in Fixed Bed Reactors Patent Summary (Reactor Design)............. 49 Major Process Equipment and Utilities Summary...... 55 Stream Flows,...................... 59 Total Capital Investment................. 67 Production Costs..................... 69 xi
TABLES 5.7 5.8 5.9 5.10 5.11 5.12 6.1 6.2 6.3 6.4 6.5 6.6 Process Information................... 73 Process Summary..,.................. 74 Cost Comparison..................... 77 in Fixed Bed Reactors: High-Temperature Process Major Process Equipment and Utilities Summary...... 80 in Fixed Bed Reactors: High-Temperature Process Total Capital Investment................. 81 in Fixed Bed Reactors: High-Temperature Process Production Costs..................... 83 Patent Summary,..................... 87 Major Process Equipment and Utilities Summary...... 94 Stream Flows....................... 97 Process Conditions in Oxidation Reactors......... 99 Total Capital Investment....,............ 103 Production Costs..,.................. 105 xii
TABLES 7.1 7.2 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 9.1 9.2 Phthalic Anhydride from Naphthalene by Air Oxidation in Fixed Bed Reactors Patent Summary (Catalysts)................ 111 Phthalic Anhydride from Naphthalene by Low-Temperature Oxidation in Fixed Bed Reactors Capital and Production Costs............... 114 Phthalic Anhydride from o-xylene or Naphthalene in Fluid Bed Reactors Patent Summary (o-xylene Feed).............. 117 Phthalic Anhydride from o-xylene or Naphthalene in Fluid Bed Reactors Patent Summary (Naphthalene Feed)............ 119 Phthalic Anhydride from o-xylene or Naphthalene in Fluid Bed Reactors Patent Summary (Reactor Design or Related Subjects)... 121 Phthalic Anhydride from Petroleum Naphthalene by a Fluid Bed Process Major Process Equipment................. 124 Phthalic Anhydride from Petroleum Naphthalene by a Fluid Bed Process Total Capital Investment................. 125 Phthalic Anhydride from Petroleum Naphthalene by a Fluid Red Process Production Costs..................... 127 Phthalic Anhydride from Coal-Tar Naphthalene by a Fluid Bed Process Production Costs..................... 129 Phthalic Anhydride from o-xylene by a Fluid Bed Process Production Costs..................... 131 Condensation of Phthalic Anhydride Patent Summary...................... 134 Thermal or Chemical Treatment of Crude Phthalic Anhydride Patent Summary...................... 135 xiii
TABLES 9.3 Distillation of Phthalic Anhydride Patent Summary.... i................. 137 9.4 Recovery of Phthalic Anhydride from Still Residue Patent Summary...................... 140 9.5 Treatment of Off-Gas Patent Summary...................... 141 9.6 Miscellaneous Patent Summary...................... 143 xiv