.I

Report No. 9

TEREPHTHALIC ACID AND

DIMETHYL TEREPHTHALATE

by LLOYD M. ELKIN

contributions by SHIGEYOSHI TAKAOKA

February 19 6 6

A private report by the

PROCESS ECONOMICS PROGRAM

STANFORD RESEARCH INSTITUTE MENLO PARK. CALIFORNIA

CONTENTS

I INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1

II SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . 3

III INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . 11

IV CHEMISTRY . . . . . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene . . . . . . . . . . . . . . . .

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator . .

Terephthalic Acid from Phthalic Anhydride . . . . . . Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications . . . . . . . . . . . First Oxidation . . . . . . . . . . . . . . . . . . First Esterification . . . . . . . . . . . . . . . . Second Oxidation . . . . . . . . . . . . . . . . . . Second Esterification . . . . . . . . . . . . . . .

. . . 21

. . . 21

. . . 24

. . . 26

. . . 28

. . . 29

. . . 29

. . . 32

. . . 33

. . . 35

V PROCESSES FOR THE PRODUCTION OF TEREPHTHALIC ACID ..... 37

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene ................... 37

Review of Processes ................... 37 Basic Patents ..................... 37 Raw Materials ..................... 37 Catalysts ....................... 37 Promotors ....................... 38 Solvents ........................ 30 Reactor Design and Reaction Conditions ......... 39 Separation of Products ................. 40 Purification ...................... 40 Catalyst Recovery ................... 42

iii

CONTENTS

V (continued)

Process Description for Crude Acid Production ...... Process Discussion for Crude Acid Production .......

Process Description and Discussion for Purification of Crude Acid .......................

Cost Estimates ......................

Capital Costs .....................

Production Costs ....................

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl-Ethyl Ketone Activator ....... Review of Processes ...................

Production of Crude Terephthalic Acid .........

Purification of Crude Terephthalic Acid ........

Process Description ...................

Process Discussion ....................

Capital Costs ......................

Production Costs ......... '. ........... Terephthalic Acid from Phthalic Anhydride .........

Review of Processes ...................

Raw Materials .....................

Catalysts .......................

Reactor Conditions and Design .............

Work-Up of Reactor Products ..............

Other Process Details .................

Process Description ...................

Process Discussion ....................

Capital Costs ......................

Production Costs .....................

Terephthalic Acid by Nitric Acid Oxidation of p-Xylene ... Review of Processes ...................

Process Description ...................

Process Discussion ....................

Capital Costs ......................

Production Costs .....................

42 48

49 55 55 59

59 59 59 65 65 73 75 75 79 79 79 79 85 85 85 86 93 94 94 98 98

103 110 110 110

iv

CONTENTS

V (continued)

Dimethyl Terephthalate by Esterification of Terephthalic Acid ........................... 114 Review of Processes ................... 114 Process Description ................... 117 Process Discussion .................... 125

Feed Treatment Section ................. 125 Reactor Section .................... 125 Methanol Recovery Section ............... 126 Product Distillation Section .............. 126

Capital Costs ...................... 126

. Production Costs ..................... 129 Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications .............. 129

Review of Processes ................... 129 Production of Crude Dimethyl Terephthalate ....... 129 Purification of Dimethyl Terephthalate ......... 134

Process Description .................... 134 Process Discussion .................... 145 Capital Costs ...................... 146 Production Costs ..................... 149

Other Processes ...................... 149 Oxidation with Nitrogen Dioxide ............. 149 Oxidation with Sulfur Dioxide .............. 149 Decarboxylation of Trimellitic Acid ........... 151 Reaction with Sodium Metal and Carbon Dioxide ...... 151 Reaction with Alkali Metal Alkyl Carbonate ........ 152 Oxidation in Alkaline Solution .............. 152 Oxidation in Alkaline Solution in Presence of Catalyst . . 152 Oxidation with Sodium Hypochlorite ............ 153 Oxidation with Sulfur Compounds ............. 153

V

CONTENTS

APPENDIX A Design and Cost Basis ............... 155

APPENDIX B Physical Data ................... 159

APPENDIX C Raw Material and Product Specifications ...... 163

APPENDIX D Handling and Safety ................ 167

Cited References ......................... 169

Supplementary References .. ; .................. 183

vi

Crude Terephthalic Acid by Bromine-Promoted Air Oxidation of p-Xylene . . . . . . . . . . . . . . . . . . . . . . . . . 43

Purification of Crude Terephthalic Acid . . . . . . . . . . . 51

Crude Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator . . . . . . . . 67

Crude Terephthalic Acid from Phthalic Anhydride . . . . . . . 87

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene . 105

Dimethyl Terephthalate by Esterification of Terephthalic Acid.... , . . . . . . . . . . . . . . . . . . . . . . . . 119

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications . . . . . . . . . . . . . . . . . . . . . 137

Vii

TABLES

7

8

9

10

11

12

13

14

Summary of Economics of Evaluated Processes . . . . . . . . .

Summary of Processes Evaluated . . . . . . . . . . . . . . .

Plant Capacities, Americas . . . . . . . . . . . . . . . . .

Plant Capacities, Western Europe . . . . . . . . . . . . . .

Plant Capacities, Asia . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene Major Process Equipment List . . . . . . . . . . . . . . . .

Crude Terephthalic Acid 'by Bromine-Promoted Catalytic Air Oxidation of p-Xylene

4

7

13

15

17

43

Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . 45

Purification of Crude Terephthalic Acid Major Process Equipment List . . . . . . . . . . . . . . . . 51

Purification of Crude Terephthalic Acid Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

Terephthalic. Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

'Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene

53

56

Process Unit and Utilities Investment . . . . . . . . . . . . 57

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene Total Capital Investment . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation of p-Xylene Production Costs . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Summary of Processes . . . . . . . . . . . . . . . . . . . .

58

60

63

viii

TABLES

15

16

. 17

18

19

20

21

22

23

24

25

26

Crude Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Major Process Equipment List . . . . . . . . . . . . . . . .

Crude Terephthalic &id by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Process Unit and Utilities Investment . . . . . . . . . . . .

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Total Capital Investment . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone Activator Production Costs . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid from Phthalic Anhydride Summary of Processes . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid from Phthalic Anhydride Major Process Equipment List . . . . . . . . . . . . . . . .

Crude Terephthalic Acid from Phthalic Anhydride Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid from Phthalic Anhydride Utilities Summary......................

Crude Terephthalic Acid from Phthalic Anhydride Process Unit and Utilities Investment . . . . . . . . . . . .

Crude Terephthalic Acid from Phthalic Anhydride Total Capital Investment . . . . . . . . . . . . . . . . . .

IX

67

69

71

76

77

78

81

87

89

91

95

96

TABLES

27

28

29

30

31

32

33

34

35

36

37

38

39

40

Crude Terephthalic Acid from Phthalic Anhydride Production Costs . . . . . . . . . . . . . . . . . . . . . .

Terephthalic Acid from Phthalic Anhydride Production Costs . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Summary of Processes . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Major Process Equipment List . . . . . . . . . . . . . . . .

Crude Terephthalic Acid' by Nitric Acid Oxidation of p-Xylene Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Process Unit and Utilities Investment . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Total Capital Investment . . . . . . . . . . . . . . . . . .

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Production Costs . . . . . . . . . . . . . . . . . . . . . .

Terephthalic Acid by Nitric Acid Oxidation of p-Xylene Production Costs . . . . . . . . . . . . . . . . . . . . . .

Dimethyl Terephthalate by Esterification of Terephthalic Acid Major Process Equipment List . . . . ; . . . . . . . . . . .

Dimethyl Terephthalate by Esterification of Terephthalic Acid Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .

Dimethyl Terephthalate by Esterification of Terephthalic Acid Utilities Summary......................

Dimethyl Terephthalate by Esterification of Terephthalic Acid Process Unit and Utilities Investment . . . . . . . . . . . .

97

99

101

105

107

109

111

112

113

115

118

121

123

127

X

TABLES

41

42

43

44

45

46

47

48

49

Dimethyl Terephthalate by Esterification of Terephthalic Acid Total Capital Investment . . . . . . . . . . . . . . . . . .

Dimethyl Terephthalate by Esterification of Terephthalic Acid Production Costs . . . . . . . . . . . . . . . . . . . . . .

Purification of Dimethyl Terephthalate Summary of Processes . . . . . . . . . . . . . . . . . . . .

130

131

135

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Major Process Equipment List . . . . . . . . . . . . . . . . 136

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . 139

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Utilities Summary . . . . . . . . . . . . . . . . . . . . . . 143

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Process Unit and Utilities Investment . . . . . . . . . . . . 147

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Total Capital Investment . . . . . . . . . . . . . . . . . , 148

Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications Production Costs . . . . . . . . . . . . . . . . . . . . . . 150

xi

DATE: Terephthalic Acid and Dimethyl Terephthalate, February 1966