a

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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

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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

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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

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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

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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

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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