.

Terephthalic Acid and Dimethyl Terephthalate, February 1966

Report

No. 9

TEREPHTHALIC
ACID AND
DIMETHYL
TEREPHTHALATE

by LLOYD
contributions

by SHIGEYOSHI

M. ELKIN
TAKAOKA

February

19 6 6

A private report by the

PROCESS
STANFORD

ECONOMICS

RESEARCH

INSTITUTE

PROGRAM
MENLO

PARK.

CALIFORNIA

Terephthalic Acid and Dimethyl Terephthalate, February 1966

CONTENTS

I
II
III
IV

INTRODUCTION
SUMMARY

. . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . .

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
. . . . . . . . . . . . . . .
V

. . . . . . . . . . . . . . . . . . . . . . . . . .

INDUSTRY STATUS
CHEMISTRY

PROCESSES FOR THE PRODUCTION OF TEREPHTHALIC ACID

iii

3
11
21

. . .

21

. . .
. . .

24
26
28

.
.
.
.
.

29
29
32
33
35

.....

Terephthalic Acid by Bromine-Promoted Catalytic Air

Oxidation of p-Xylene ...................
Review of Processes
...................
Basic Patents
.....................
Raw Materials
.....................
Catalysts
.......................
Promotors
.......................
Solvents ........................
Reactor Design and Reaction Conditions .........
Separation of Products .................
Purification ......................
Catalyst Recovery
...................

.
.
.
.
.

.
.
.
.
.

37
37
37
37
37
37
38
30
39
40
40
42

Terephthalic Acid and Dimethyl Terephthalate, February 1966

CONTENTS

(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 .....................

iv

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

Terephthalic Acid and Dimethyl Terephthalate, February 1966

CONTENTS

(continued)
Dimethyl Terephthalate by Esterification of Terephthalic
Acid
...........................
...................
Review of Processes
...................
Process Description
Process Discussion ....................
Feed Treatment Section .................
....................
Reactor Section
...............
Methanol Recovery Section
Product Distillation Section ..............
Capital Costs
......................
Production Costs .....................
Dimethyl Terephthalate from p-Xylene by Successive
..............
Oxidations and Esterifications
...................
Review of Processes
Production of Crude Dimethyl Terephthalate .......
Purification of Dimethyl Terephthalate .........
....................
Process Description
Process Discussion ....................
Capital Costs
......................
Production Costs .....................
Other Processes
......................
.............
Oxidation with Nitrogen Dioxide
..............
Oxidation with Sulfur Dioxide
...........
Decarboxylation of Trimellitic Acid
......
Reaction with Sodium Metal and Carbon Dioxide
Reaction with Alkali Metal Alkyl Carbonate ........
Oxidation in Alkaline Solution ..............
Oxidation in Alkaline Solution in Presence of Catalyst
Oxidation with Sodium Hypochlorite ............
.............
Oxidation with Sulfur Compounds

114
114
117
125
125
125
126
126
126
129

. .

129
129
129
134
134
145
146
149
149
149
149
151
151
152
152
152
153
153

Terephthalic Acid and Dimethyl Terephthalate, February 1966

CONTENTS

Design and Cost Basis

APPENDIX B

Physical Data

APPENDIX C

Raw Material and Product Specifications

APPENDIX D

Handling and Safety

Cited References

..

159

...................

................

.........................

Supplementary References

155

...............

APPENDIX A

; ..................

vi

......

163
167
169
183

Terephthalic Acid and Dimethyl Terephthalate, February 1966

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

Terephthalic Acid and Dimethyl Terephthalate, February 1966

TABLES

. . . . . . . . .

. . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . .

13

Summary of Economics of Evaluated Processes

Summary of Processes Evaluated
Plant Capacities, Americas

. . . . . . . . . . . . . .

15

. . . . . . . . . . . . . . . . . . .

17

Crude Terephthalic Acid by Bromine-Promoted Catalytic Air

Oxidation of p-Xylene
Major Process Equipment List
. . . . . . . . . . . . . . . .

43

Crude Terephthalic Acid 'by Bromine-Promoted Catalytic Air

Oxidation of p-Xylene
Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

45

Purification of Crude Terephthalic Acid

Major Process Equipment List
. . . . . . . . . . . . . . . .

51

Purification of Crude Terephthalic Acid

Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

53

Terephthalic. Acid by Bromine-Promoted Catalytic Air Oxidation

of p-Xylene
Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

56

'Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation

of p-Xylene
Process Unit and Utilities Investment . . . . . . . . . . . .

57

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation

of p-Xylene
Total Capital Investment
. . . . . . . . . . . . . . . . . .

58

Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation

of p-Xylene
Production Costs
. . . . . . . . . . . . . . . . . . . . . .

60

Crude Terephthalic Acid by Catalytic Oxidation of p-Xylene in

the Presence of Methyl Ethyl Ketone Activator
Summary of Processes
. . . . . . . . . . . . . . . . . . . .

63

Plant Capacities, Western Europe

Plant Capacities, Asia

8
9
10

11

12

13

14

viii

Terephthalic Acid and Dimethyl Terephthalate, February 1966

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
. . . . . . . . . . . . . . . .

67

Crude Terephthalic &id by Catalytic Oxidation of p-Xylene in

the Presence of Methyl Ethyl Ketone Activator
Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

69

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the

Presence of Methyl Ethyl Ketone Activator
Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

71

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the

Presence of Methyl Ethyl Ketone Activator
Process Unit and Utilities Investment . . . . . . . . . . . .

76

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the

Presence of Methyl Ethyl Ketone Activator
Total Capital Investment
. . . . . . . . . . . . . . . . . .

77

Terephthalic Acid by Catalytic Oxidation of p-Xylene in the

Presence of Methyl Ethyl Ketone Activator
Production Costs
. . . . . . . . . . . . . . . . . . . . . .

78

Crude Terephthalic Acid from Phthalic Anhydride

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

81

Crude Terephthalic Acid from Phthalic Anhydride

Major Process Equipment List
. . . . . . . . . . . . . . . .

87

Crude Terephthalic Acid from Phthalic Anhydride

Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

89

Crude Terephthalic Acid from Phthalic Anhydride

Utilities Summary......................

91

Crude Terephthalic Acid from Phthalic Anhydride

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

95

Crude Terephthalic Acid from Phthalic Anhydride

Total Capital Investment
. . . . . . . . . . . . . . . . . .

96

IX

Terephthalic Acid and Dimethyl Terephthalate, February 1966

TABLES

27
28
29
30
31
32
33
34
35
36
37
38
39
40

Crude Terephthalic Acid from Phthalic Anhydride

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

97

Terephthalic Acid from Phthalic Anhydride

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

99

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

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

101

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

Major Process Equipment List
. . . . . . . . . . . . . . . .

105

Crude Terephthalic Acid' by Nitric Acid Oxidation of p-Xylene

Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

107

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

Utilities Summary . . . . . . . . . . . . . . . . . . . . . .

109

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

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

111

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

Total Capital Investment
. . . . . . . . . . . . . . . . . .

112

Crude Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

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

113

Terephthalic Acid by Nitric Acid Oxidation of p-Xylene

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

115

Dimethyl Terephthalate by Esterification of Terephthalic Acid

Major Process Equipment List
. . . . ; . . . . . . . . . . .

118

Dimethyl Terephthalate by Esterification of Terephthalic Acid

Stream Flows
. . . . . . . . . . . . . . . . . . . . . . . .

121

Dimethyl Terephthalate by Esterification of Terephthalic Acid

Utilities Summary......................

123

Dimethyl Terephthalate by Esterification of Terephthalic Acid

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

127

Terephthalic Acid and Dimethyl Terephthalate, February 1966

TABLES

41
42
43
44

45

46

47

48

49

Dimethyl Terephthalate by Esterification of Terephthalic Acid

Total Capital Investment
. . . . . . . . . . . . . . . . . .

130

Dimethyl Terephthalate by Esterification of Terephthalic Acid

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

131

Purification of Dimethyl Terephthalate

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

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

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

Dimethyl

xi