a
-
a
Report No. 61
CHLORINE
by YEN-CHEN YEN
April 1970
A private report by the
PROCESS ECONOMICS PROGRAM
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
CONTENTS
1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 1
2 SUMMARY........................... 3
3 INDUSTRIAL STATUS ...................... 19
In the United States .................... 19 Production ........................ 19 Market .......................... 22 Trends .......................... 22
InCanada .......................... 23 InEurope .......................... 25 InJapan .......................... 32 In Other Countries ..................... 32-a
4 CHLORINE BY ELECTROLYSIS OF AQUEOUS SODIUM CHLORIDE . . . . . 33
Chemistry ....................... Review of Processes ...................
Diaphragm Cells .................... Mercury Cells ..................... Dimensionally Stable Anode .............. Chlorine Treatment .................. Processes Using Unconventional Raw Materials or Making Unconventional Products ...............
Chlorine by Salt Electrolysis Using a Diaphragm Cell . . Process Description .................. Process Discussion .................. Cost Estimates ....................
Chlorine by Salt Electrolysis Using a Mercury Cell . , . Process Description .................. Process Discussion .................. Cost Estimates ....................
Comparison of Costs of Diaphragm Cell Process and Mercury Cell Process ......................
. . 33
. . 36
. . 36
. . 42
. . 52
. . 53
. . 55
. . 61
. . 61
. . 71
. . 72
. . 79
. . 79
. . 89
. . 91
. . 98
5 CHLORINE BY ELECTROLYSIS OF HYDROGEN CHLORIDE ........ 101
Cells for Electrolysis of Hydrochloric Acid ......... 101 Process Description ..................... 103 Process Discussion ..................... 110 Cost Estimates ....................... 112 Improvements in the Electrolysis of Hydrochloric Acid .... 119 Other Processes for Electrolysis of Hydrogen Chloride .... 121
V
CONTENTS
5 (continued)
Westvaco Copper Chloride Process .............. 122
Schroeder Process ...................... 124
Mercury Chloride Process .................. 125
6 CHLORINE BY OXIDATION OF HYDROGEN CHLORIDE USING A HETER- OGENEOUS CATALYST ......................
Chemistry .......................... Review of Processes .....................
Process Description .....................
Process Discussion .....................
Cost Estimates .......................
7 CHLORINE BY OXIDATION OF HYDROGEN CHLORIDE USING NITRIC ACID ............................
Chemistry .......................... Review of Processes .....................
Process Description .....................
Process Discussion .....................
Cost Estimates .......................
8 CHIQRINE FROM AMMONIUM CHLORIDE COPRODUCED IN A MODIFIED SOLVAY PROCESS .......................
Process Review .......................
Coproduction of Ammonium Chloride in Soda Manufacture ...
Ammonia and Hydrogen Chloride from Ammonium Chloride ...
Chlorine Directly from Ammonium Chloride .........
A Modified Solvay Process for Production of Soda Ash with Coproduction of Ammonium Chloride .............
Process Description ....................
Process Discussion ....................
Main Procedures .....................
Crystallizer ......................
Materials of Construction ................
Ammoniation .......................
Calcination .......................
Ammonia Still ......................
Separation of Products .................
Purity of the Products .................
Cost Estimates ........................
Use of Brine as a Raw Material ...............
127
127 130 140 146 151
161
161 163 164 175 176
181
181 181 188 190
196 196 207 207 207 207 208 208 208 208 209 209 209
vi
.-
CONTENTS
8 (continued)
A Process for the Manufacture of Chlorine from Ammonium
Chloride.......................... Process Description . . . . . . . . , . . . . . . . . . . . Process Discussion . . . . . . . . . . . . . . . . . . . . Cost Estimates . . . . . . . . . . . . . . . . . . . . . .
Integration of Modified Solvay Process and Chlorine Pro- duction from Ammonium Chloride . . . . . . . . . . . . . . .
Conversion of a Soda Ash Plant from the Conventional Solvay Process to the Modified Solvay Process . . . . . . . . . . .
9 CHLORINE AND SODA ASH BY ELECTROLYSIS ............
Carbonation of Cell Liquor ................. Integration of Electrolysis and Solvay Process ....... A Process for the Manufacture of Soda Ash and Chlorine by Electrolysis and Carbonation ................ Process Description .................... Process Discussion .................... Cost Estimates ......................
A Process for Manufacture of Soda Ash and Chlorine by Solvay Process and Salt Electrolysis ...............
Comparison of Various Processes for Production of Chlorine andSoda ..........................
10 OTHER PROCESSES FOR CHLORINE MANUFACTURE . . . . . . . . . .
Chlorine as a By-Product of Sodium Manufacture . . . . . . . Chlorine as a By-Product of Magnesium Production . . . . . . Chlorine from Sodium Chloride Using Sulfur Trioxide . . . . . Chlorine from Metallic Chlorides by Electrolysis . . . . . . Chlorine from Iron Chloride by Oxidation . . . . . . . . . . Chlorine from the Waste Liquor of a Solvay Soda Plant . . , . Chlorine from Sodium Chloride Using Manganese Dioxide . . , . Chlorine from Sodium Chloride Using Siliceous Materials . . . Chlorine from Sodium Chlorate . . . . . . . . . . . . . . . . Chlorine by Oxidation of Hydrogen Chloride in a Plasma . . . Chlorine by Thermal Dissociation of Hydrogen Chloride . . . .
215 215 225 227
233
234
243
243 244
253 253 258 258
263
263
273
273 274 275 276 276 277 277 278 278 278 279
vii
CONTENTS
APPENDIX A DESIGN AND COST BASIS ................ 281
APPENDIX B PHYSICAL DATA .................... 285
APPENDIX C HAZARDS AND SAFETY ................. 287
APPENDIX D SOURCES OF HYDROGEN CHLORIDE AS A RAW MATERIAL FOR
CHLORINE PRODUCTION ................ 289
CITED REFERENCES ........................ 291
PATENT REFERENCES BY COMPANY .................. 343
viii
ILLUSTRATIONS
4.1
4.2
4.3
4.4
5.1
5.2
6.1
6.2
6.3
7.1
7.2
8.1
8.2
8.3
8.4
9.1
9.2
9.3
Chlorine from Salt by Electrolysis, Diaphram Cell Process.......................... 65
Chlorine from Salt by Electrolysis, Diaphram Cell Process Production Costs at Different Production Levels , . . . . . 77
Chlorine from Salt by Electrolysis, Mercury Cell Process . 83
Chlorine from Salt by Electrolysis, hfercury Cell Process Production Costs at Different Production Levels . . . . . . 97
Chlorine from Hydrochloric Acid by Electrolysis . . . . . . 107
Chlorine from Hydrochloric Acid by Electrolysis Production Costs at Different Production Levels . . . . . . 117
Chlorine from Hydorgen Chloride by Oxidation . . . . . . . 143
Chlorine from Hydrogen Chloride by Oxidation Comparison of Investment Estimates . . . . . . . . . . . . 157
Chlorine from Hydrogen Chloride by Oxidation Using a Heter- ogeneous Catalyst Production Costs at Different Production Levels . . . . . . 158
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid Production Costs at Different Production Levels . . . . . . 180
Soda Ash by Modified Solvay Process . . . . . . . . . . . . 201
Chlorine from Ammonium Chloride . . . . . . . . . . . . . . 221
Chlorine by Modified Solvay Process and Ammonium Chloride Oxidation Production Costs at Different Production Levels . . . , , . 235
Conventional Solvay Process and Modified Solvay Process , . 237
Electrolysis of the Mother Liquor from Bicarbonate Sepa- ration in the Solvay Process . . . . . . . . . . . . . . . 252
Chlorine and Soda Ash by Electrolysis and Carbonation , . . 255
Chlorine and Soda Ash by Solvay Process and Salt Elec- trolysis . . . . . . . . . . . . . . . . . . . . . . . . . 264
ix
ILLUSTRATIONS
9.4 Total Capital Investment for Different Processes for
Producing Chlorine and Soda . . . . . . , , . . . . . . . . 268
9.5 Production Cost of Chlorine with Coproduction of Soda by Different Processes . . , . . . . . . , . . . . . . . . 296
TABLES
2.1
2.2
2.3
3.1
3.2
3.3
3.4
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
Comparison of Various Processes for Producing Chlorine with Coproduction of Soda . . . . . . . . . . . . 5
Comparison of Processes for Producing Chlorine from
Hydrogen Chloride . . . . . . . . . . . . . . . . . . . . . 8
Comparison of Diaphragm Cell and Mercury Cell for Chlorine-Alkali Production . . . . . . . . . . . . . . . . 10
Chlorine Producers in the United States . . . . . . . . . . 20
Chlorine Producers in Canada . . . . . . . . . . . . . . . 24
Chlorine Producers in Europe . . . . . . . . . . . . . . . 26
Chlorine Producers in Japan . . . . . . . . . . . . . . . 31
Characteristics of Diaphragm Cells Available for License . 37
Diaphragm Cell Process Patent Summary . . . . . . . . . . . . . . . . . . . . . . 40
Characteristics of Mercury Cells Available for License . . 43
Mercury Cell Process Patent Summary . . . . . . . . . . . . . . . . . . . . . . 48
Dimensionally Stable Anodes Patent Summary . . . . . . . . . . . . . . . . . . . . . . 54
Liquefaction of Chlorine Patent Summary . . . . . . . . . . . . . . . . . . . . . . 56
Recovery or Removal of Chlorine from a Dilute Chlorine Stream Patent Summary . . . . . . . . . . . . . . . . . . . . . . 57
Treatment of Chlorine-Containing Gases Patent Summary . . . . . . . . . . . . . . . . . . . . . . 58
Chlorine from Seawater by Electrolysis Patent Summary . . . . . . . . . . . . . . . . . . . . . . 59
Chlorine by Salt Electrolysis, Diaphragm Cell Process
Major Process Equipment . . . . . . . . . . . . . . . . . . 65
Chlorine by Salt Electrolysis, Diaphragm Cell Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 69
Chlorine by Salt Electrolysis, Diaphragm Cell Process Total Capital Investment . . . . . . . . . . . . . . . . . 73
xi
TABLES
4.13
4.14
4.15
4.16
4.17
5.1
5.2
5.3
5.4
5.5
5.6
6.1
6.2
6.3
6.4
Chlorine by Salt Electrolysis, Diaphragm Cell Process Production Costs . . , . . . . . . . . . . . . . . . . . . 75
Chlorine by Salt Electrolysis, Mercury Cell Process
Major Process Equipment and Utilities Summary . . . , . . . 81
Chlorine by Salt Electrolysis, Mercury Cell Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 87
Chlorine by Salt Electrolysis, Mercury Cell Process Total Capital Investment . . . . . . . . . . . . . . . . . 93
Chlorine by Salt Electrolysis, Mercury Cell Process Production Costs . . , . . . . . . . . . . . . . . . . . . 95
Cells for Electrolysis of Hydrochloric Acid
Patent Summary . . . , . . . . . . . . . . . . . . . . . . 102
Chlorine by Electrolysis of Hydrochloric Acid Major Process Equipment and Utilities Summary . . . . . . . 107
Chlorine by Electrolysis of Hydrochloric Acid Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 109
Chlorine by Electrolysis of Hydrochloric Acid Total Capital Investment . . . . . . . . . . . . . . . . . 113
Chlorine by Electrolysis of Hydrochloric Acid Production Costs . . . . . . . . . , . . . . . . . . . . . 115
Devices for Reducing Voltage for Hydrochloric Acid Electrolysis Patent Summary . . . , . . . . . . . . . . . . . . . . . . 120
Chlorine by Hydrogen Chloride Oxidation Using a Heter- ogeneous Catalyst Patent Summary . . . , . . . . . . . . . . . . . . . . . . 131
Chlorine by Hydrogen Chloride Oxidation Using a Heter- ogeneous Catalyst Major Process Equipment and Utilities Summary . , , . . . . 143
Chlorine by Hydrogen Chloride Oxidation Using a Heter- ogeneous Catalyst Stream Flows . : . . . . . . . . . . . . . . . . . . . . . 145
Comparison of Processes Using Air and Oxygen for Oxidation of Hydrogen Chloride Major Process Equipment and Utilities Summary . . . . . . . 150
xii
TABLES
6.5
6.6
6.7
7.1
7.2
7.3
7.4
7.5
7.6
8.1
8.2
8.3
8.4
Chlorine by Hydrogen Chloride Oxidation Using a Heter-
ogeneous Catalyst
Total Capital Investment . . . . . . . . . . . . . . . . . 153
Chlorine by Hydrogen Chloride Oxidation Using a Heter-
ogeneous Catalyst Production Costs . . . . . . . . . . . . . . . . . . . . . 155
Chlorine by Hydrogen Chloride Oxidation Using Oxygen
Production Costs . . . . . . . . . . . . . . . . . . . . . 159
Chlorine from Hydrogen Chloride or Alkali Chloride by Oxidation with Nitric Acid or Related Compounds Patent Summary . . . . . . . . . . . . . . . . . . . . . . 165
Chlorine from Nitrosyl Chloride Patent Summary . . . . . . . . . . . . . . . . . . . . . . 167
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid Major Process Equipment and Utilities Summary . . . . . . . 171
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 173
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid Total Capital Investment . . . . . . . . . . . . . . . . . 178
Chlorine from Hydrogen Chloride by Oxidation with Nitric Acid Production Costs . . . . . . . . . . . . . . . . . . . . . 179
Production of Ammonium Chloride as a Coproduction of Soda Ash Manufacture by the Solvay Process Patent Summary . . . . . . . . . . . . . . . . . . . . . . 183
Ammonia and Hydrochloric Acid from Ammonium Chloride
Patent Summary . . . . . . . . . . . . . . . . . . . . . . 189
Chlorine from Ammonium Chloride Patent Summary . . . . . . . . . . . . . . . . . . . . . . 191
Soda Ash by Modified Solvay Process with Coproduction of Ammonium Chloride Major Process Equipment and Utilities Summary . . . . . . . 201
xiii
TABLES
8.5
8.6
8.7
8.8
8.9
8.10
8.11
8.12
8.13
9.1
9.2
9.3
9.4
9.5
9.6
Soda Ash by Modified Solvay Process with Coproduction of Ammonium Chloride Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 205
Soda Ash by Modified Solvay Process
Total Capital Investment . , . . . . . . . . . . . . . . .
Soda Ash by Modified Solvay Process Production Costs . . . . . . . . . . . . . . . . . . . . .
211
213
Chlorine from Ammonium Chloride Major Process Equipment and Utilities Summary . . . . . . .
Chlorine from Ammonium Chloride Stream Flows . . . . . . . . . . . . . . . . . . . . . . .
219
223
Chlorine from Ammonium Chloride Total Capital Investment . . . . . . . . . . . . . . . . .
Chlorine from Ammonium Chloride Production Costs . . . . . . . . . . . . . . . . . . . . .
229
231
Soda Ash Production Cost Changes by Converting an Existing Conventional Solvay Process to a Modified Process . . . . .
Payout in Converting a Conventional Solvay Soda Ash Process to a Modified Solvay Process . . , . . . . . . . .
240
241
Sodium Carbonate from Electrolytic Cell Liquor Patent Summary . . . . . . . . . . . . . . . . . . . . . . 245
Integration of Salt Electrolysis and Solvay Process Patent Summary . . . . . . . . . . . . . . . . . . . . . . 249
Chlorine with Coproduction of Soda Ash by Electrolysis and Carbonation Major Process Equipment and Utilities Summary . . . . . . . 255
Chlorine with Coproduction of Soda Ash by Electrolysis and Carbonation Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 257
Chlorine with Coproduction of Soda Ash by Electrolysis and Carbonation Battery Limits and Utilities Cost of Carbonation Section . 259
Chlorine with Coproduction of Soda Ash by Electrolysis and Carbonation Total Capital Investment . . . . . . . . . . . . . . . . . 260
xiv
TABLES
9.7 Chlorine with Coproduction of Soda Ash by Electrolysis and Carbonation Production Costs . . . . . . . . . . . . . . . . . . . . . 261
9.8 Chlorine by Integrated Solvay Process and Salt Electrolysis Total Capital Investment . . . . . . . . . . . . . . . . . 265
9.9 Chlorine by Integrated Solvay Process and Salt Electrolysis Production Cost . . . . . . . . . . . . . . , . . . . . . . 266
9.10 Comparison of Payoff Period of Different Processes at Various Rates of Chlorine Production . . . . . . . . . . . 270
xv