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Report No. 10.1
COAL TAR CHEMICALS
JAMES J. L. MA
December 1976
A private report by the
a
PROCESS ECONOMICS PROGRAM
STANFORD RESEARCH INSTITUTE 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.
CONTENTS
INTRODUCTION .........................
SUMMARY ...........................
General Aspects .......................
Economics Coal Tar Fractionation ......................................
Light Oil Refining ..................... Hydrorefining Coal Tar Naphthalene .............
Tar Acids from Coal Carbonization .............
Tar Acids from Coal Gasification ..............
Technical Aspects Coal Carbonization'
.....................
Coal Tar Fractionation
......................................
Light Oil Refining .....................
Hydrorefining Coal Tar Naphthalene .............
Tar Acids from Coal Carbonization .............
Tar Acids from Coal Gasification ..............
Tar Bases Anthracene and Carbazole ....................................
INDUSTRY STATUS .......................
Coke Oven Plants and Chemical By-Products ..........
Coal Tar and Other By-Products ................
BTX and Naphthalene .....................
Tar Acids ..........................
Tar Bases ..........................
COAL CARBONIZATION AND GASIFICATION BY-PRODUCTS .......
Coal Carbonization ......................
Review of Carbonization Processes .............
By-Products Recovery System ..... .......
Effect of Operating Conditions on By-Product Yields
. ....
By-Products from Coal Gasification ..............
COAL TAR FRACTIONATION ....................
Review of Processes ..................... Patents Commercial Processes .....................................
Process Description ..................... Process Discussion ......................
Cost Estimates ........................
Capital Costs Production Costs' ............................................
1
3
3 5 7 7 8 8 9 10 10 10 11 12 13 13 14 14
15
15
18 21 21 26
29
29 29 30 31 32
39
39 39 42 49 55 56 56 57
vii
CONTENTS
6 LIGHT OIL REFINING . . . . . . . . . . . . . . . . . . . . . . 63
Chemistry Review of Processes
. . . . . . . . .
Patents . . .
Commercial Processes . . l
Definitions . . . . . .
Acid Wash . . . . . . . Catalytic Hydrorefining
Process Description . . . . Hydrorefining . . . . . . Fractionation Recycled Gases Purification
Process Discussion . . . . . Cost Estimates . . . . . . .
Capital Costs . . . . . Production Costs' . . . . .
................. 63
................. 66
................. 66
................. 70
................. 70
................. 72
................. 74
................. 75
................. 76
................. 77
................ 78
................. 86
................. 88
................. 88
................. 88
7 HYDROREFINING COAL TAR NAPHTHALENE . . . . . . . . . . . . . . 97
Chemistry . . . Review of Processes . .
Patents .
Commercial Processes. Prepurification . . Refining by Acid Wash Hydrorefining . . .
Process Description . .
Process Discussion . . . Cost Estimates . . . . .
Capital Costs . . . . Production Costs . . .
................... 99
................... 100
................... 100
................... 100
................... 100
.................. 108
................... 108
................... 111
................... 120
................... 121
................... 121
................... 121
8 TAR ACIDS .......................... 129
Review of Processes ............... 130
Tar Acids from Coal Carbonization .............. 142
Process Description .................... 142
Process Discussion ..................... 149
Cost Estimates ....................... 150
Capital Costs Production Costs'
..................... 150
..................... 150
Tar Acids from Coal Gasification ............... 158
Process Description .................... 158
Process Discussion ..................... 165
Cost Estimates ....................... 166
Capital Costs ...................... 166
Production Costs ..................... 167
... Vlll
CONTENTS
9 OTHER PRODUCTS ........................
Tar Bases Review of Processes
............................................
Patents Commercial Processes
......................................
Anthracene and Carbazole ................... Review of Processes ....................
Patents Commercial Processes ......................................
APPENDIX A DESIGN AND COST BASES ................
APPENDIX B PHYSICAL PROPERTIES .................
APPENDIX C TYPICAL SPECIFICATIONS FOR COAL TAR CHEMICALS ....
APPENDIX D PRODUCT TOXICITY AND HANDLING ............
CITED REFERENCES ........................
PATENT REFERENCES BY COMPANY ..................
175
175 177 177 180 187 188 188 190
195
199
201
207
209
217
ix
4.1
4.2
4.3
4.4
5.1 Coal Tar Fractionation
5.2
0 5.3
5.4
5.5
5.6 Coal Tar Fractionation
5.7 Coal Tar Fractionation
6.1 Light Oil Separation Before Refining . . . . . . . . . . . .
6.2
6.3
ILLUSTRATIONS
Coke Oven Gas By-Products Recovery System Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . 22 1
Relationship of Coal Tar and Light Oil Yields to Volatile Matter Content of Coal at 600’ and 900°C Carbonization Temperatures . . . . . . . . . . . . . . . . . . . . . . .
Effect of Coking Temperature on Gas Yields . . . . . . . . .
34
35
Effect of Coking Temperature on Aromatic Hydrocarbon Yields from Pittsburgh Seam Coal . . . . . . . . . . . . . . . . . 36
Coke and Chemical Yields from Coal Carbonization and Coal
Tar Distillation Block Diagram . . . . . . . . . . . . . . . . . . . . . . . 223
Coal Tar Fractionation Type l System . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation Type 2 System . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation Type 3 System . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation
46
47
48
Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . 2 25
Effect of Plant Capacity on Total Fixed Capital . . . . . . . 59
Effect of Operating Level and Plant Capacity on Net Production Cost . . . . . . . . . . . . . . . . . . . . . .
Light Oil Refining by Acid Wash . . . . . . . . . . . . . .
Light Oil Refining
61
71
73
Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . 227
Xi
6.4 Light Oil Refining Effect of Plant Capacity on Total Fixed Capital . . . . . . 91
6.5 Light Oil Refining
Effect of Operating Level and Plant Capacity on Net Production Cost . . . . . . . . . . . . . . . . . . . . .
Light Oil Refining Effect of Crude Light Oil Price on Net Production Cost . .
Naphthalene Relationship of Naphthalene Purity to Freezing Temperature .
Hydrorefining Coal Tar Naphthalene Purification of Naphthalene before Refining . . . . . . . .
94
6.6 95
7.1 98
7.2
7.3
7.4
7.5
Refining Coal Tar Naphthalene by Acid Wash . . . . . . . .
Hydrorefining Coal Tar Naphthalene . . . . . . . . . . . .
Hydroref ining Coal Tar Naphthalene Flow Diagram . . . . . . . . . . . . . . . . . . . . . . .
Hydrorefining Coal Tar Naphthalene Effect of Plant Capacity on Total Fixed Capital . . . . . .
Hydrorefining Coal Tar Naphthalene Effect of Operating Level and Plant Capacity on Net Production Cost . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Middle Oil by Caustic Wash and Carbonation . . . . . . . . . . . . . . . . . . . . . . . .
106
109
110
231
7.6 124
7.7
128
8.1
8.2
8.3
8.4
8.5
Tar Acids from Middle Oil by Acid and Caustic Extractions .
Tar Acids from Middle Oil by Methanol-Water Extraction . .
Tar Acids from Middle Oil by Double Extractions . . . . . .
Tar Acids from Aqueous Effluent of Coal Gasification by Solvent Extraction . . . . . . . . . . . . . . . . . . . .
Tar Acids from Middle Oil by Pressurized Hot Water Extraction . . . . . . . . . . . . . . . . . . . . . ‘. . .
133
135
137
138
8.6
140
141
ILLUSTRATIONS
xii
l
0
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14
9.1
9.2
l 9.3
9.4
0 9.5
9.6
ILLUSTRATIONS
Tar Acids from Coal Carbonization Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization Effect of Plant Capacity on Total Fixed Capital . . . . . .
Tar Acids from Coal Carbonization
Effect of Operating Level and Plant Capacity on Net Production Cost . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization Effect of Crude Tar Acids Price on Net Production Cost . . .
Tar Acids from Coal Gasification Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Gasification Effect of Plant Capacity on Total Fixed Capital . . . . . .
Tar Acids from Coal Gasification Effect of Operating Level and Plant Capacity on Net Production Cost . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Gasification Effect of Crude Tar Acids Price on Net Production Cost . . .
Tar Bases from Coal Carbonization Recovery Schemes . . . . . . . . . . . . . . . . . . . . . .
Tar Bases from Coal Carbonization Scheme A of Figure 9.1 . . . . . . . . . . . . . . . . . . .
Scheme B--Continuous Recovery of Tar Bases from Ammonia Saturator Liquor . . . . . . . . . . . . . . . . . . . . . .
Scheme C--Recovery of Tar Bases from Ammonia Saturator Liquor--An Alternative Procedure to Scheme B . . . . . . . .
Recovery of Anthracene from Anthracene Oil . . . . . . . . .
Recovery of Carbazole from Anthracene Cake or Recrystallization Residues . . . . . . . . . . . . . . . .
235
152
156
157
2 39
169
172
173
181
183
184
186
191
193
l xiii
-
l
2.1 Coal Tar Chemicals Summary of Costs . . . . . . . . . . . . . . . . . . . . . .
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
By-Product Coke Oven Plants in the United States . . . . . . 16
U.S. and World Production of Coke . . . . . . . . . . . . .
U.S. Production of Coal Tar and Other By-Products . . . . .
U.S. Coke Oven BTX Production Capacities . . . . . . . . . .
U.S. Production of BTX and Naphthalene . . . . . . . . . . .
U.S. Coke Oven Naphthalene Production Capacity . . . . . . .
U.S. Production of Phenol, Cresols, and Cresylic Acids . . .
U.S. Producers of Coal Tar Phenols, Cresols, and Cresylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1
5.1
Coal Carbonization By-Product Yields . . . . . . . . . . . .
Coal Tar Fractionation
5.2
Crude Coal Tar Fractions and Some of the Major Chemical Components . . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation Major Chemical Components Present In Significant Quantities in Coal Tar . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Coal Tar Fractionation
5.4
Patent Summary . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation
5.5
Design Bases and Assumptions . . . . . . . . . . . . . . . .
Coal Tar Fractionation
5.6
Major Equipment and Utilities Summary . . . . . . . . . . .
Coal Tar Fractionation
5.7
Stream Flows . . . . . . . . . . . . . . . . . . . . . . . .
Coal Tar Fractionation Total Capital Investment . . . . . . . . . . . . . . . . . .
TABLES
xv
6
19
20
22
23
24
25
28
37
40
41
43
51
52
54
58
TABLES
5.8
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
7.1
7.2
7.3
7.4
7.5
Coal Tar Fractionation Production Costs . . . . . . . . . . . . . . . . . . . . . . 60
Light Oil Refining
Analysis of a Typical Crude Coke Oven Light Oil . . . . . . 65
Light Oil Refining
Patent Summary . . . . . . . . . . . . . . . . . . . . . . . 67
Light Oil Refining
Design Bases and Assumptions . . . . . . . . . . . . . . . . 80
Light Oil Refining Major Equipment and Utilities Summary . . . . . . . . . . . 81
Light Oil Refining Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . 83
Light Oil Refining Summary of Waste Streams . . . . . . . . . . . . . . . . . . 85
Light Oil Refining Total Capital Investment . . . . . . . . . . . . . . . . . . 90
Light Oil Refining Production Costs . . . . . . . . . . . . . . . . . . . . . . 92
Substances Associated With Naphthalene in the 210 to 230°C Fraction of Coal Tar . . . . . . . . . . . . . . . . . . . 101
Recovery and Refining of Naphthalene from Coke Oven Gas, Light Oil, and Coal Tar
Patent Summary . . . . . . . . . . . . . . . . . . . . . . . 103
Hydrorefining Coal Tar Naphthalene Design Bases and Assumptions . . . . . . . . . . . . . . . . 114
Hydrorefining Coal Tar Naphthalene
Major Equipment and Utilities Summary . . . . . . . . . . . 115
Hydrorefining Coal Tar Naphthalene Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . 117
xvi
7.6
7.7
7.8
8.1
8.2
8.3
8.4
l 8.5
8.6
8.7
8.8
8.9
8.10
8.11
TABLES
Hydrorefining Coal Tar Naphthalene
Summary of Waste Streams . . . . . . . . . . . . . . . . .
Hydrorefining Coal Tar Naphthalene Total Capital Investment . . . . . . . . . . . . . . . . .
Hydrorefining Coal Tar Naphthalene Production Costs . . . . . . . . . . . . . . . . . . . . .
Tar Acids Patent Summary . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization Design Bases and Assumptions . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization Major Equipment and Utilities Summary . . . . . . . . . .
Tar Acids from Coal Carbonization Stream Flows . . . . . . . . . . . . . . . . . . . , . . .
Tar Acids from Coal Carbonization Summary of Waste Streams . . . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization
Total Capital Investment . . . . . . . . . . . . . . . . .
Tar Acids from Coal Carbonization
Production Costs . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Gasification Design Bases and Assumptions . . . . . . . . . . . . . . .
Tar Acids from Coal Gasification Major Equipment and Utilities Summary . . . . . . , . . .
Tar Acids from Coal Gasification Stream Flows . . . . . . . . . . . . . . . . . . . . . . .
Tar Acids from Coal Gasification Summary of Waste Streams . . . . . . . . . . . . . . . . .
119
123
126
131
144
145
147
148
151
154
160
161
163
164
xvii
TABLES
8.12 Tar Acids from Coal Gasification Total Capital Investment . . . . . . . . . . . . . . . . . 168
8.13 Tar Acids from Coal Gasification
Production Costs . . . . . . . . . . . . . . . . . . . . . 170
9.1 Tar Bases
Patent Summary . . . . . . . . . . . . . . . . . . . . . . 178
9.2 Anthracene and Carbazole Patent Summary . . . . . . . . . . . . . . . . . . . . . . 189
B.l Physical Properties of Selected Coal Tar Compounds . . . . 200
c.1 Typical Specifications for Benzene . . . . . . . . . . . . 202
c.2 Typical Specifications for Toluene . . . . . . . . . . . . 203
C.3 Typical Specifications for Coal Tar Naphthalene . . . . . 204
C.4 Typical Specifications for Coal Tar Cresols and Cresylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 205
xviii
