.
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