Report No. 6A ACRYLICACID AND ACRYLIC ESTERS Supplement A by RICHARD G. DENNEY April 1967 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS I II III IV V INTRODUCTION... 1 SUMMARY... 3 General Aspects... 3 Technical Aspects... 5 INDUSTRY STATUS... 9 CHEMISTRY OF ACRYLIC ACID PRODUCTION... 19 CHEMISTRY OF ACRYLIC ESTERS PRODUCTION... 21 VI VII w PROCESSES FOR ACRYLIC ACID MANUFACTURE... Propylene Oxidation es... Basic Low Conversion... Revisions... Revised Description... Revised Capital Cost Estimates... Revised Production Costs... Review of New es... Oxidation Reaction... Purification... Description... Discussion... Capital Cost Estimate... Production Costs... Other Acid es... PROCESSES FOR LOWER ACRYLIC ESTER PRODUCTION... Acetylene... Review of New es... Revised Capital Cost Estimates... Revised Production Costs... B-Propiolactone... Acrylonitrile... Revised Description... Discussion... Revised Capital Cost Estimates... Revised Production Costs... 23 23 23 23 24 33 38 38 38 50 50 60 63 70 70 85 85 85 86 86 86 93 94 102 102 103 iii
CONTENTS VII (continued) Direct Esterification... 109 Review of New es... 109 Capital Cost Estimates... 112 Production Costs... 114 VIII PROCESSES FOR HIGHER ACRYLIC ESTER MANUFACTURE....... 121 IX INTEGRATED PROCESSES.................... 123 APPENDIX A DESIGN AND COST BASIS................ 141 CITED REFERENCES......................... 151 SUPPLEMENTARY REFERENCES..................... 157 iv
ILLUSTRATIONS 3.1 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 6.13 6.14 History of Acid and Ester Industry in the United States--1960 to Present............... 10 Acid by Low Conversion Propylene Oxidation--Revised Flowsheet......................... 27 Acid by Low Conversion Propylene Oxidation Total Production Cost................... 41 Acid by Low Conversion Propylene Oxidation Effect of Plant Capacity and Production Rate on Net Total Production Cost...................... 42 Vapor Phase Propylene Oxidation Effect of Conversion on Selectivity to Acid.... 48.... 53 Acid by Propylene Oxidation Effect of Reactor Space Velocity on Propylene Conversion.. 61 Effect of Reactor Space Velocity on Total Fixed Capital.. 68 Effect of Plant Capacity on Capital Investment....... 69 Total Production Cost................... 73 Effect of Reactor Space Velocity on Net Total Production Cost................... 74 Effect of Plant Capacity and Production Rate on Net Total Production Cost................... 75 Effect of Plant Capacity on Acid Plant Fixed Capital Investment.................. 77 Acid by Catalytic Acetylene Effect of Raw Material Costs on Total Production Cost... 78 Acid by 8-Propiolactone Effect of Raw Material Costs on Total Production Cost... 79 V
ILLUSTRATIONS 6.15 6.16 6.17 6.18 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 Acid by Acrylonitrile Total Production Cost.................... 80 Acid by Catalytic Acetylene Effect of Plant Capacity and Production Rate on Total Production Cost.................... 81 Acid by B-Propiolactone Effect of Plant Capacity and Production Rate on Total Production Cost.................... 82 Acid by Acrylonitrile Effect of Plant Capacity and Production Rate on Net Total Production Cost.................. 83 Lower Esters by Stoichiometric-Catalytic Acetylene Effect of Raw Material Costs on Net Total Production Cost.. 88 Lower Esters by Stoichiometric-Catalytic Acetylene Effect of Plant Capacity and Production Rate on Total Production Cost.................... 89 Lower Esters by &Propiolactone Total Production Cost.................... 91 Lower Esters by 5-Propiolactone Effect of Plant Capacity and Production Rate on Net Total Production Cost....................... 92 Revised Flowsheet...................... 97 Effect of Plant Capacity on Capital Investment....... 106 Total Production Cost.,.................. 110 Effect of Plant Capacity and Production Rate on Net Total Production Cost....................... 111 vi
ILLUSTRATIONS 7.9 Lower Esters Effect of Plant Capacity on Fixed Capital Investment.... 115 7.10 Lower Esters by Dilute Acid Direct Esterification Effect of Raw Material Costs and By-product Credit on Net Total Production Cost................. 118 7.11 Lower Esters by Dilute Acid Direct Esterification Effect of Plant Capacity and Production Rate on Net Total Production Cost...............,...... 119 9.1 Integrated Ester Plant by Acrylonitrile Effect of Acrylonitrile Unit Cost on Total Production Costs........................... 140
TABLES i2.1 Summary of Costs of Evaluated es........... 2.2 Summary of Costs of Typical Integrated Ester Plants. 2.3 Summary of Technical Aspects of Evaluated es..... 3.1 Plant Capacities Americas.......................... 3.2 3.3 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 6.11 6.12 Plant Capacities Asia............................ Plant Capacities Europe........................... Revised Revised Acid by Low Conversion Propylene Oxidation Major Equipment and Utilities Summary.... Acid by Low Conversion Propylene Oxidation Stream Flows.................... Acid by Low Conversion Propylene Oxidation Revised Unit and Utilities Investment........ Revised Revised Summary Summary Acid by Low Conversion Propylene Oxidation Total Capital Investment.............. Acid by Low Conversion Propylene Oxidation Production Costs.................. Acid by Acrolein Oxidation of New es. 0................. Acid by Propylene Oxidation of New es.................. Major! Equipment and Utilities Summary........ Stream Flows........................ Unit and Utilities Investment............ Total Capital Investment.................. Production Costs...................... 11 15 17 26 29 35 37 39 43 45 51 55 65 67 71 ix
TABLES 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 9.1 9.2 9.3 9.4 Lower Esters by Stoichiometric-Catalytic Acetylene Revised Total Capital Investment.............. 87 Lower Esters by g-propiolactone Revised Total Capital Investment.............. 90 Revised Major Equipment and Utilities Summary... 95 Revised Stream Flows.................... 99 Revised Unit and Utilities Investment....... 104 Revised Total Capital Investment.............. 105 Revised Production Costs.................. 107 Lower Esters by Dilute Acid Direct Esterification Total Capital Investment.................. 113 Lower Esters by Dilute Acid Direct Esterification Production Costs...................... 116 Integrated Ester Plant by Low Conversion Propylene Oxidation and Concentrated Acid Esterification Total Capital Investment.................. 124 Integrated Ester Plant by Low Conversion Propylene Oxidation and Concentrated Acid Esterification Allocated Production Costs................. 127 Integrated Ester Plant by High Conversion Propylene Oxidation and Concentrated Acid Esterification Total Capital Investment.................. 129 Integrated Ester Plant by High Conversion Propylene Oxidation and Concentrated Acid Esterification Allocated Production Costs................ 131
TABLES 9.5 Integrated Ester Plant by High Conversion Propylene Oxidation and Dilute Acid Esterification Total Capital Investment.................. 133 9.6 Integrated Ester Plant by High Conversion Propylene Oxidation and Dilute Acid Esterification Allocated Production Costs......,.......... 135 9.7 Integrated Ester Plant by Acrylonitrile Total Capital Investment.................. 137 9.8 Integrated Ester Plant by Acrylonitrile Allocated Production Costs................. 139 xi