PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Menlo Park, California 94025 Abstracl Process Economics Program Report No. 668 PEROXIDE (March 1662)

This report, our third on the subject, presents an update of technological developments for the production of since 1976 when PEP Report 68Al was issued. We evaluate the following three processes:

l Conventional anthraquinone process, producing hydrogen peroxide via cyclic oxidation and operation

a Huron-Dow process, generating hydrogen peroxide in alkaline solution by cathodic reduc- tion of

l Du Pont process, producing hydrogen peroxide by direct combination of oxygen and hy- drogen.

We also present the economics of an ARC0 process for comparison. This process, previously evaluated in PEP Review 90-l -2, produces hydrogen peroxide by oxidation of methyl benzyl alco- hol.

Dioxin generated during pulp bleaching with chlorine has always created a waste disposal problem for the pulp and paper industry. For years, the industry has tried various alternative chemi- cals such as chlorine dioxide, hypochlorite, and , to reduce or minimize pollution. Recently, a new technique that replaces chlorine with hydrogen peroxide as the principal oxidant in pulp bleach- ing has proven commercially successful. Environmentally sound chemi-thermal mechanical pulp (CTMP) mills in Canada and elsewhere have attracted attention in the hydrogen peroxide industry; they also have created great concerns in the chlorine industry.

Other potential applications for hydrogen peroxide include waste treatment, bio-reclamation, geothermal energy, and aseptic packaging.

PEP’88 YRC P B B 0 a x x For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMlCAL ECONOMCS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMlcAlS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI D/RECTORY OF C/-EM/CAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia.

ii 1 INlRODUCTlON ...... l-l

2 SUMMARY ...... 2-l

GENERAL ASPECTS ...... ,...... 2-l

TECHNICAL ASPECTS ...... 2-l Technology...... 2-2 Anthraquinone Process ...... 2-2 Huron-DowProcess ...... 2-2 DuPont Direct H&I2 Process...... 2-2 ARCOH202Process ...... 2-3 Economics ...... 2-3

3 INDUSTRY STATUS ...... 3-l

HYDROGEN PEROXIDE DEMAND ...... 3-l NorthAmerica ...... 3-l WesternEurope ...... 3-2 Japan ...... 3-3 OtherRegions ...... 3-3

HYDROGEN PEROXIDE PRODUCERS ...... 3-5

4 HYDROGEN PEROXIDE PRODUCTlON BY ANTHRAQUINONE PROCESSES ...... 4-l

PROCESS GENERAL AND CHEMISTRY ...... 4-l

REVIEWOF PROCESSES ...... 4-5 Working Solutions ...... 4-5 Working Compounds ...... 4-6 Solvent Systems ...... 4-7 Catalytic Hydrogenation ...... 4-8 Oxidation ...... 4-11 Hydrogen Peroxide Recovery and Purification ...... 4-l 2 Regeneration of Working Solution and Catalyst ...... 4-l 3 Stabilization of Hydrogen Peroxide ...... 4-l 5 Concentration of Hydrogen Peroxide Solution ...... 4-l 6

- iii - CONTENTS (Concluded)

5 HYDROGEN PEROXIDE PRODUCTION BY OTHER PROCESSES ...... 5-l HYDROGEN PEROXIDE BY DIRECT COMBlNATlON OF OXYGEN AND HYDROGEN ...... 5-l Homogeneous Catalysts ...... 5-l Heterogeneous Catalysts ...... 5-2 Processes With Organic Solvents ...... 5-2 Processes Without Organic Solvents ...... 5-3 HYDROGEN PEROXIDE BY CATHODIC REDUCTtON OF OXYGEN ...... 5-5

6 ECONOMICS OF HYDROGEN PEROXIDE PRODUCTION BYANTHRAQUINONEPROCESS ...... 6-l PROCESS DESCRIPTION ...... 6-l Reduction and Oxidation of Working Solution ...... 6-2 Recovery of Hz02 and Working Solution ...... 6-3 Concentration of H&I2 Solution ...... 6-4 Regeneration of Working Solution ...... 6-4 PROCESS DISCUSSION ...... 6-l 2 COST ESTIMATES ...... 6-13

7 HYDROGEN PEROXIDE PRODUCTlON BY OTHER PROCESSES ...... 7-l HYDROGEN PEROXIDE BY CATHODIC REDUCTtON OF OXYGEN ...... 7-l PIocessDescription ...... 7-l ProcessDiscussion ...... 7-6 Cost Estimates ...... 7-6 EconomicComparison ...... 7-8 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN ...... 7-17 ProcessDescription ...... 7-17 ProcessDiscussion ...... 7-24 Cost Estimates ...... 7-24 HYDROGEN PEROXIDE BY OXIDATION OF METHYL BENZYL ALCOHOL...... 7-25

APPENDIX A: PATENT SUMMARY TABLES ...... A-l

APPENDIX B: DESIGN AND COST BASES ...... B-l

APPENDIX C: CITED REFERENCES ...... C-l

APPENDIX D: PATENT REFERENCES BY COMPANY ...... D-l

APPENDIX E: PROCESS FLOW DIAGRAMS ...... E-l

- iv - ILLUSTRATIONS

4.1 BLOCK DIAGRAM OF ANTHRAQUINONE PROCESS , ...... 4-2

4.2 SKETCH OF HYDROGENATiON REACTORS ...... 4-9

5.1 HYDROGEN PEROXIDE BY CATHODIC REDUCTlON OF OXYGEN SKETCH OF DOW CHEMICAL ELECTROLYTICCELL ...... 5-7

5.2 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN SKETCH OF H-D TECH ELECTROLYTICCELL ...... 5-10

5.3 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN SKETCH OF FMC ELECTROLYTICCELL ...... 5-l 1

8.1 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS PROCESS FLOW DIAGRAM ...... , ...... E-3

8.2 HYDROGEN PEROXIDE BY ANTHRAQINONE PROCESS EFFECT OF OPERATiNG LEVEL AND PLANT CAPACllY ON PRODUCT VALUE ...... 8-28

7.1 HYDROGEN PEROXIDE BY CATHODIC REDUCTlON OF OXYGEN BY HURON-DOW TECHNOLOGY PROCESS FLOW DIAGRAM ...... E-11

7.2 SKETCH OF DOUBLE-SIDED H-D ELECTROLMC CELL ...... 7-7

7.3 HYDROGEN PEROXIDE BY ELECTROLYTICAND MIXING PROCESSES BREAK-EVEN PRODUCTION CAPACITY ...... 7-18

7.4 HYDROGEN PEROXIDE DIRECTLYFROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY PROCESS FLOW DIAGRAM ...... E-13

7.5 HYDROGEN PEROXIDE BY DIRECT AND ANTHRAQUINONE PROCESSES BREAK-EVEN PRODUCTION CAPACilY ...... 7-35

-V- TABLES

2.1 HYDROGEN PEROXIDE PROCESSES l SUMMARY OF ECONOMICS ...... 2-5 2.2 HYDROGEN PEROXIDE ON-SlTE PRODUCTION SUMMARY OF ECONOMICS ...... , ...... 2-8

3.1 CONSUMPTION OF HYDROGEN PEROXIDE IN NORTH AMERICA ...... 3-3

3.2 CONSUMPTION OF HYDROGEN PEROXIDE IN WESTERN EUROPE . . . . . 3-4

3.3 CONSUMPTION OF HYDROGEN PEROXIDE IN JAPAN ...... 3-4

3.4 U.S. PRODUCERS OF HYDROGEN PEROXIDE ...... 3-5

3.5 CANADIAN PRODUCERS OF HYDROGEN PEROXIDE ...... 3-8

3.8 WESTERN EUROPEAN PRODUCERS OF HYDROGEN PEROXIDE ...... 3-7

3.7 JAPANESE PRODUCERS OF HYDROGEN PEROXIDE ...... 3-10

3.8 HYDROGEN PEROXIDE PRODUCERS OF OTHER COUNTRIES ...... 3-l 1

3.9 PRODUCTION CAPACITIES BY MAJOR HYDROGEN PEROXIDE PROCESSES IN MAJOR PRODUCING REGIONS AND THE WORLD ...... 3-15

4.1 WORKING SOLUTIONS FOR ANTHRAQUINONE PROCESSES PATENTSUMMARY ...... , ...... A-3

4.2 CATALYTICHYDROGENATION PATENTSUMMARY ...... A-9

4.3 OXIDATION OF ANTHRAHYDROQUINONE PATENTSUMMARY...... A-15

4.4 HYDROGEN PEROXIDE PURIFICATION l PATENTSUMMARY...... A-17 4.5 REGENERATIONOF WORKING SOLUTiON AND CATALYST PATENT SUMMARY ...... A-21

4.8 STABILIZATION OF HYDROGEN PEROXIDE PATENTSUMMARY...... A-25

5.1 HYDROGEN PEROXIDE DIRECILY FROM OXYGEN AND HYDROGEN PATENTSUMMARY ...... A-29

5.2 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN PATENTSUMMARY...... A-33

- vii - TABLES (Continued)

5.3 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN CHARACTERlSTlCS OF ELECTROLYTICCELLS ...... A-38

6.1 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS DESIGN BASES AND ASSUMPTlONS ...... 6-2

8.2 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS STREAM FLOWS ...... 6-6

6.3 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS MAJOR EQUIPMENT ...... 8-6

6.4 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS UTIUTIESSUMMARY ...... 8-l 1

6.5 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS TOTAL CAPlTAL INVESTMENT ...... 8-15

6.6 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS CAPITAL INVESTMENT BY SECTlON ...... 8-l 8

8.7 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS PRODUCTIONCOSTS ...... 8-16

6.6 HYDROGEN PEROXiDE BY ANTHRAQUINONE PROCESS (W.S. PRODUCTION CAPACITY = 9 G H202/L) TOTAL CAPITAL INVESTMENT ...... 6-20

6.9 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS (WS. PRODUCTlON CAPACITY = 9 G H&)2/L) CAPITAL INVESTMENT BY SECTION ...... , . . 8-21

8.10 HYDROGEN PEROXIDE BY ANTHRAQUINONE PROCESS (W.S. PRODUCTlON CAPACITY = 9 G H202/L) PRODUCTION COSTS ...... 8-23

6.11 ECONOMIC COMPARISON BElWEEN ANTHRAQUINONE PROCESSES WITH HIGH AND LOW WORKING SOLUTION PRODUCTION CAPACllY . . . 8-25

7.1 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN By HURON-DOW TECHNOLOGY DESIGN BASES AND ASSUMPTIONS ...... 7-2

7.2 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN BY HURON-DOW TECHNOLOGY STREAM FLOWS ...... , ...... 7-2

- viii - TABLES (Continued)

7.3 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN BY HURON-DOW TECHNOLOGY MAJOR EQUIPMENT ...... 7-4

7.4 HYDROGEN PEROXIDE BY CATHODIC REDUCTlON OF OXYGEN BY HURON-DOW TECHNOLOGY UTlUTiES SUMMARY ...... 7-5

7.5 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN BY HURON-DOW TECHNOLOGY TOTAL CAPITAL INVESTMENT ...... , ...... , 7-9

7.8 HYDROGEN PEROXIDE BY CATHODIC REDUCTION OF OXYGEN BY HURON-DOW TECHNOLOGY PRODUCTION COSTS ...... 7-10

7.7 HYDROGEN PEROXIDE BY MIXING Hf12 AND CAUSTIC SODA MAJOR EQUIPMIENT ...... 7-12

7.8 HYDROGEN PEROXIDE BY MIXING HA AND CAUSTlC SODA TOTAL CAPlTAL INVESTMENT ...... , ...... 7-13

7.9 HYDROGEN PEROXIDE BY MIXING H& AND CAUSTIC SODA PRODUCTION COSTS ...... , ...... 7-14

7.10 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY DESIGN BASES AND ASSUMPTIONS ...... , ...... 7-18

7.11 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY STREAM FLOWS ...... , . . . . . , . . , ...... 7-19

7.12 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY MAJOREQUIPMENT...... 7-21

7.13 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY UTILITIES SUMMARY ...... 7-23

7.14 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY TOTAL CAPITAL INVESTMENT ...... 7-27

7.15 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY PRODUCTlON COSTS ...... 7-28

- ix - TABLES (Concluded)

7.16 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN BY DU PONT TECHNOLOGY (WITHOUT RECYCLING FLASHED GAS) PRODUCTIONCOSTS ...... 7-30

7.17 HYDROGEN PEROXIDE BY THE ARC0 PROCESS PRODUCTIONCOSTS ...... a..... 7-32

7.18 ECONOMIC COMPARISON OF HYDROGEN PEROXIDE PROCESSES . . . . 7-34

7.19 HYDROGEN PEROXIDE DIRECT FROM HYDROGEN AND OXYGEN (HYPOTHETICAL CASE) PRODUCTION COSTS ...... 7-38

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