Report No. 9C Supplement TEREPHTHALIC ACID AND DIMETHYL TEREPHTHALATE and FUMIHIKO by LLOYD M. ELKIN YAMAGUCHI August 1976 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD HYDROCARBONS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe. ii
CONTENTS 1 INTRODUCTION......................... 1 2 SUMMARY........................... 3 Industry Status... 3 Description of Processes Evaluated... 4 Capital and Production Costs... 7 Future Developments... 10 3 INDUSTRYSTATUS....................... 11 4 CHEMISTRY.......................... 17 TPA from p-xylene by Bromine-Promoted Catalytic Air Oxidation. 17 DMT from p-xylene by Successive Oxidations. 19 Ammoxidation of p-xylene.................. 20 TPA from Phthalic Anhydride (or Benzoic Acid).. 21 TPA from p-xylene by Catalytic Oxidation in the presence of Activators.......................... 22 TPA from p-xylene by Liquid Phase Oxidation in the Presence of Large Amounts of Catalyst.................. 22 5 REVIEW OF PATENTS...................... 25 TPA from p-xylene by Bromine-Promoted Catalytic Air Oxidation TPA from p-xylene by Catalytic Oxidation in the Presence of Activators... TPA from Phthalic Anhydride or Benzoic Acid... TPA from p-xylene by Nitric Acid Oxidation... TPA Purification... DMT from Crude TPA by Esterification with Methanol... DMT Purification... Stabilizers for Molten DMT... Catalyst. Recovery Other Oxidation Processes......, 25. 3l.. 31. 40. 40. 51. 55. 55. 55 55 6 TEREPHTHALIC ACID FROM p-xylene BY BROMINE-PROMOTED CATALYTIC AIR OXIDATION, CONVENTIONAL PROCESS... 63 Updated Capital Costs... 63 Updated Production Costs... 63 Discussion of Factors Affecting Costs... 63 Vii
CONTENTS 7 DIMETHYL TEREPHTHALATE FROM p-xylene BY SUCCESSIVE OXIDATIONS AND ESTERIFICATIONS... Review of Patents... Oxidation Step... Esterification Step... Purification of DMT... Treatment of Distillation Residues... Recovery of Oxidation Catalyst... Process Description... Process Discussion... Material Balance... Oxidation Reactor Design... Oxygen Consumption... Esterification Reaction Time... Heat of Esterification... Methanol Distillation... DMT Distillation Columns... Column Design... Air Cooled Heat Exchangers... Two-Stage Crystallization... Balance on Generated and Consumed Low Pressure Steam... Stabilizers for Molten DMT... Utility Consumptions... Cost Estimates....... Capital Costs... Production Costs... 69 69 69 73 73 74 74 75 87 87 87 88 88 88 88 89 89 89 90 90 90 91 91 91 93 8 TEREPHTHALIC ACID FROM p-xylene; COPRODUCTION WITH DIMETHYL TEREPHTHALATE... Introduction 97 Process Description......... 98 Process Discussion.... 102 Material Balance Reactions and Physical Changes Occuring in 102 the Heat Treatment Vessels 102 Purification Method... 103 Cost Estimates... 103 Capital Costs... 103 Production Costs... 103 Cost Comparison... 103 97 Viii
CONTENTS 9 DIMETHYL TEREPHTHALATE FROM CRUDE TEREPHTHALIC ACID BY ESTERIFICATION WITH METHANOL................. 111 Updated Capital Costs... 111 Updated Production Costs... 111 Discussion of Factors Affecting Costs... 111 10 TEREPHTHALIC ACID FROM p-xylene BY BROMINE-PROMOTED CATALYTIC AIR OXIDATION, MODIFIED PROCESS... 119 Process Description Process Discussion, Purification Section, Batch versus... 119 127 Continuous Operation... 127 Process Discussion, Catalyst Recovery Section... 127 Batch versus Continuous Operation 127 Chemical Treatment Reactor R-301.,:... 127 Water Type..... 127 Carbon Dioxide Contamination... 128 Cost Estimates... 128 Capital Costs 128 Production Costs'... 128 11 TEREPHTHALIC ACID FROM p-xylene BY AMMOXIDATION AND HYDROLYSIS. 133 Review of Patents... 133 Process Description... 140 Process Discussion... 161 By-Products in Ammoxidation of p-xylene... 161 Overall Yield... 162 Utilities Comparison... 162 Materials of Construction... 162 Cost Estimates... 163 Capital Costs 163 Production Costs'... 163 CITED REFERENCES.......................... 169 PATENT REFERENCES BY COMPANY.................... 187 ix
ILLUSTRATIONS 6.1 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Air Oxidation, Conventional Process Production Costs.................... 66 7.1 Dimethyl from p-xylene by Successive Oxidations Flow Sheet........................, 195 7.2 Dimethyl from p-xylene by Successive Oxidations Production Cost..............,........ 96 8.1 Terephthalic Acid from p-xylene; Coproduction with Dimethyl Flow Sheet................... W...... 199 8.2 Terephthalic Acid from p-xylene; Coproduction with Dimethyl Production Cost.................... 109 9.1 Dimethyl from Crude Terephthalic Acid by Esterification with Methanol Production Cost...................... 117 10.1 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Flow Sheet..........................201 10.2 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Production Cost..................... 132 11.1 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Flow Sheet..........................203 11.2 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Production Cost........................ 168 Xi
TABLES 2.1 3.1 Summary of Capital and Production Costs........... Dimethyl and Terephthalic Acid Plant Capacities in the Americas.............. 8 13 3.2 Dimethyl and Terephthalic Acid Plant Capacities in Western Europe. 14 3.3 3.4 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 Dimethyl and Terephthalic Acid Plant Capacities in the Eastern Bloc Countries....... Dimethyl and Terephthalic Acid Plant Capacities in the Middle and Far East......... Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Air Oxidation Terephthalic Acid from p-xylene by Catalytic Oxidation in the Presence of Activators Terephthalic Acid from Phthalic Anhydride or Benzoic Acid Terephthalic Acid from p-xylene by Nitric Acid Oxidation Terephthalic Acid Purification Dimethyl from Crude Terephthalic Acid by Esterification with Methanol Dimethyl Purification Stabilizers for Molten Dimethyl Patent Summary......... ~~~o...~~~~. Catalyst Recovery Other Oxidation Processes xiii 15 16 26 32 36 41 42 52 56 58 59 62
TABLES 6.1 6.2 7.1 7.2 7.3 7.4 7.5 7.6 8.1 8.2 8.3 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Air Oxidation, Conventional Process Total Capital Investment.................. Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Air Oxidation, Conventional Process Production Costs...................... Dimethyl from p-xylene by Successive Oxidations Patent Summary: Oxidation Reaction............ Dimethyl from p-xylene by Successive Oxidations Major Equipment and Utilities Summary........... Dimethyl from p-xylene by Successive Oxidations Stream Flows........................ Dimethyl from p-xylene by Successive Oxidations Sumnary of Reactor Conditions............... Dimethyl from p-xylene by Successive Oxidations Total Capital Investment.................. Dimethyl from p-xylene by Successive Oxidations Production Costs...................... Terephthalic Acid from p-xylene; Coproduction with Dimethyl Major Equipment and Utilities Summary........... Terephthalic Acid from p-xylene; Coproduction with Dimethyl Stream Flows......,.................. Terephthalic Acid from p-xylene; Coproduction with Dimethyl Total Capital Investment.................. 64 65 70 81 84 86 92 94 100 101 106 xiv
TABLES 8.4 Terephthalic Acid from p-xylene; Coproduction with Dimethyl Production Costs...................... 9.1 Dimethyl from Crude Terephthalic Acid by Esterification with Methanol Total Capital Investment.................. 9.2 Dimethyl from Crude Terephthalic Acid by Esterification with Methanol Production Costs...................... 10.1 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Major Equipment and Utilities Summary........... 10.2 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Stream Flows........................ 10.3 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Total Capital Investment.................. 10.4 Terephthalic Acid from p-xylene by Bromine-Promoted Catalytic Production Costs...................... 11.1 Terephthalonitrile from p-xylene by Ammoxidation, Reactor Conditions 11.2 Terephthalonitrile from p-xylene by Ammoxidation, Process Design Features 11.3 Terephthalic Acid from Terephthalonitrile 11.4 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Major Equipment and Utilities Summary........... 11.5 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Stream Flows........................ 107 114 116 122 125 129 130 134 137 138 148 152 xv
TABLES 11.6 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Summary of Reactor Conditions................ 159 11.7 Terephthalic Acid from p-xylene by Ammoxidation and Hydrolysis Total Capital Investment.................. 164 11.8 Terephthalic Acid from @-Xylene by Ammoxidation and Hydrolysis Production Costs...................... 166 xvi