7 Report No. 34 PHTHALIC ANHYDRIDE by LLOYD M. ELKIN contributions by Kenneth E. Lunde March 1968 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION... 1 2 SUMMARY... 3 3 INDUSTRY STATUS... 13 4 CHEMISTRY... 23 5 PHTHALIC ANHYDRIDE FROM o-xylene: FIXED-BED LOW-TEMPERATURE HIGH-SPACE-VELOCITY PROCESS... Review of Processes... Process Description... Process Discussion... Capital Costs....'.. Production Cost... 35 35 35 46 46 47 6 PHTHALIC ANHYDRIDE FROM o-xylene: FIXED-BED LOW-TEMPERATURE LOW-SPACE-VELOCITY PROCESS... Review of Processes... 53 Process Description... 53 Process Discussion... 66 Capital Costs... 67 Production Cost 1'... 67 53 PHTHALIC ANHYDRIDE FROM NAPHTHALENE: FIXED-BED LOW-TEMPERATURE LOW-SPACE-VELOCITY PROCESS... Review of Processes... Process Description... Process Discussion... Capital Costs... Production Cost... 73 73 90 97 97 100 PHTHALIC ANHYDRIDE FROM o-xylene: FIXED-BED HIGH-TEMPERATURE HIGH-SPACE-VELOCITY PROCESS... Review of Processes... 103 Process Description..................... 103 103 Iii
CONTENTS 9 10 11 12 13 PHTHALIC ANHYDRIDE FROM NAPHTHALENE: FIXED-BED HIGH-TEMPERATURE HIGH-SPACE-VELOCITY PROCESS...... Review of Processes... Process Description... Process Discussion... Capital Costs... Production Cost... PHTHALIC ANHYDRIDE FROM o-xylene: FLUID BED PROCESS..... 127 Review of Processes...... 127 Process Description...... 127 Process Discussion...... 140 Capital Costs...... 140 Production Cost..... a 140 PHTHALIC ANHYDRIDE FROM NAPHTHALENE: FLUID BED PROCESS... 147 Review of Processes...... 147 Process Description...... 147 Process Discussion...... 156 Capital Costs...... 157 Production Cost... v...... 157 RECOVERY AND PURIFICATION OF PHTHALIC ANHYDRIDE.... Review of Processes..........,....... Recovery of Phthalic Anhydride as a Dust or Slurry... Process Description--Condensation as Dust...... Process Discussion--Condensation as Dust.,..... Capital Costs--Condensation as Dust............ 109... 109... 109... 120... 121. -. 122... 167... 167... 167,.. 178... 185... 187 OTHER PROCESSES....................... 189 APPENDIX A DESIGN AND COST BASIS...,............ 195 APPENDIX B PHYSICAL DATA.............,...... 201 APPENDIX C PRODUCT, RAW MATERIAL, AND CATALYST SPECIFICATIONS.. 205 iv
CONTENTS APPENDIX D HANDLING AND SAFETY.... 209 CITED REFERENCES... 211 SUPPLEMENTAL REFERENCES... 235 V
ILLUSTRATIONS 4.1 4.2 5.1 5.2 6.1 6.2 7.1 9.1 9.2 10.1 10.2 11.1 Sequence of Reactions in the Catalytic Oxidation of Naphthalene or o-xylene..........,..,..... Detailed Reaction Mechanism (Speculative) for the Catalytic Oxidation of o-xylene................... Production Cost Variation..................... Production Cost Variation..,...,.....,............ Production Cost Variation........................,........,.... Production Cost Variation...................,.................... 25 29 41 51 61 71 91 115 126 135 145 151 Vii
ILLUSTRATIONS 11.2 Production Cost Variation.................. 165 12.1 Recovery of Phthalic Anhydride by Condensation as Dust... 181 viii
TABLES 2.1 2.2 2.3 Summary of Processes Evaluated............... 5 Summary of Costs of Evaluated Processes........., 7 Comparison of Processes with Fixed Capital Amortized in a Two-Year Period...................... 9 3.1 Plant Capacity United States....................... 15 3.2 Plant Capacity The Americas Outside the United States........... 16 3.3 3.4 5.1 5.2 5.3 5.4 5.5 Plant Capacity Europe... 17 Plant Capacity Asia, Australia, and South Africa............. 21 Major Process Equipment List.....,.......... 39 Stream Flows........................ 43 Utilities Summary..................... 45 Process Unit and Utilities Investment........... 48 Total Capital Investment.................. 49 ix
TABLES 5.6 6.1 6.2 6.3 6.4 6.5 6.6 6.7 7.1 7.2 Production Costs...........,........., 50 Summary of Processes.................... 55 Major Process Equipment List..............., 61 Stream Flows........................ 63 Utilities Summary..................... 65 Process Unit and Utilities Investment....,...... 68 Total Capital Investment.................. 69 Production Costs...................... 70 Fixed-Bed Processes Summary of Patents..................... 75 es Summary of Processes..........,......... 83 X
TABLES 7.3 7.4 7.5 7.6 8.1 9.1 9.2 9.3 9.4 9.5 Stream Flows........................ 93 Process Unit and Utilities Investment........... 98 Total Capital Investment.................. 99 Production Cost of Phthalic Anhydride.... 100 Summary of Processes.................... 105 Major Process Equipment List................ 113 Stream Flows.,...................... 117 Utilities Summary..................... 119 Process Unit and Utilities Investment........... 123 Total Capital Investment.................. 124 Xi
TABLES 9.6 10.1 10.2 10.3 10.4 10.5 10.6 10.7 11.1 11.2 Production Costs............... 125 Summary of Processes............. 129 Major Process Equipment List......... 135 Stream Flows................. 137 Utilities Summary.............. 139 Process Unit and Utilities Investment.... 142 Total Capital Investment........ Production Costs............ Major Process Equipment List...... Stream Flows................. 143... 144... 150... 153 xii
TABLES 11.3 11.4 11.5 11.6 12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 Utilities Summary..................... 155 Process Unit and Utilities Investment........... 160 Total Capital Investment................. 161 Production Costs..................... 163 Condensation of Phthalic Anhydride Summary of Processes................... 168 Thermal or Chemical Treatment of Crude Phthalic Anhydride Summary of Processes.................,. 170 Distillation of Phthalic Anhydride Summary of Processes................... 173 Recovery of Phthalic Anhydride from Still Residue Summary of Processes................... 174 Recovery of Phthalic Anhydride as a Dust or Slurry Summary of Patents.................... 177 Recovery of Phthalic Anhydride by Condensation as Bust Major Process Equipment List........ -...... 181 Recovery of Phthalic Anhydride by Condensation as Dust Utilities Summary..................... 183 Recovery of Phthalic Anhydride by Condensation as Dust Stream Flows....................... 184 Recovery of Phthalic Anhydride by Condensation as Dust Process Unit and Utilities Investment........... 188 xiii