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