WO1997005300B1 - Method for starting a chlor-alkali diaphragm cell - Google Patents
Method for starting a chlor-alkali diaphragm cellInfo
- Publication number
- WO1997005300B1 WO1997005300B1 PCT/US1996/012096 US9612096W WO9705300B1 WO 1997005300 B1 WO1997005300 B1 WO 1997005300B1 US 9612096 W US9612096 W US 9612096W WO 9705300 B1 WO9705300 B1 WO 9705300B1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amphoteric
- aluminum
- anolyte
- added
- original
- Prior art date
Links
- 239000003513 alkali Substances 0.000 title claims abstract 6
- 239000000463 material Substances 0.000 claims abstract 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 8
- -1 aluminum compound Chemical class 0.000 claims abstract 6
- 230000035699 permeability Effects 0.000 claims abstract 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 239000011777 magnesium Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims 18
- 229910010272 inorganic material Inorganic materials 0.000 claims 11
- 239000011147 inorganic material Substances 0.000 claims 11
- 210000000188 Diaphragm Anatomy 0.000 claims 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- 239000000203 mixture Substances 0.000 claims 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 239000007788 liquid Substances 0.000 claims 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 4
- 229960000892 attapulgite Drugs 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 150000004677 hydrates Chemical class 0.000 claims 3
- 150000002681 magnesium compounds Chemical class 0.000 claims 3
- 229910052625 palygorskite Inorganic materials 0.000 claims 3
- 239000004113 Sepiolite Substances 0.000 claims 2
- 229940077744 antacids containing magnesium compounds Drugs 0.000 claims 2
- 239000012267 brine Substances 0.000 claims 2
- 239000004927 clay Substances 0.000 claims 2
- 229910052570 clay Inorganic materials 0.000 claims 2
- TUKQLEWOUPCTOS-UHFFFAOYSA-N dimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane;hydrate Chemical compound O.[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O TUKQLEWOUPCTOS-UHFFFAOYSA-N 0.000 claims 2
- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 claims 2
- 229910000271 hectorite Inorganic materials 0.000 claims 2
- MJMDTFNVECGTEM-UHFFFAOYSA-L magnesium dichloride monohydrate Chemical class O.[Mg+2].[Cl-].[Cl-] MJMDTFNVECGTEM-UHFFFAOYSA-L 0.000 claims 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- 229910000275 saponite Inorganic materials 0.000 claims 2
- 229910052624 sepiolite Inorganic materials 0.000 claims 2
- 235000019355 sepiolite Nutrition 0.000 claims 2
- 239000011780 sodium chloride Substances 0.000 claims 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N Aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H Aluminium sulfate Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 229910052612 amphibole Inorganic materials 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 230000000875 corresponding Effects 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 230000000295 complement Effects 0.000 abstract 1
Abstract
Describes adding an anolyte soluble amphoteric material, e.g., an aluminum compound, to the anolyte of a chlor-alkali diaphragm cell having a synthetic diaphragm during the start-up period of the cell to reduce the permeability of the diaphragm. Complementary inorganic porosity modifying materials, e.g., magnesium materials such as magnesium chloride, and clays are also added to the anolyte during the start-up period of the cell.
Claims
AMENDED CLAIMS
[received by the International Bureau on 24 February 1997 (24.02.97); original claims 4-6 and 13-17 cancelled; original claims 1 and 9 amended; new claims 18-26 added; remaining claims unchanged (3 pages)]
1. In the process of operating a chlor-alkali electrolytic cell having a synthetic liquid permeable diaphragm separating the anolyte compartment from the catholyte compartment, the improvement which comprises introducing into the anolyte compartment during the cell start-up period a permeability moderating amount of inorganic amphoteric material that is soluble in the anolyte, that has an insoluble form under the conditions existing within the diaphragm, and that is dissolved by product catholyte liquor.
2. The process of claim 1 wherein the chlor- alkali cell electrolyzes sodium chloride brine and the product catholyte liquor is sodium hydroxide.
3. The process of claim 2 wherein the amphoteric material is selected from compounds of aluminum, zinc and mixtures of such compounds.
7. The process of claim 3 wherein the amphoteric compound is added at cell start-up.
8. The process of claim 3 wherein the product catholyte liquor has a concentration of from 9.5 to 11.5 weight percent sodium hydroxide.
9. The process of claim 3 wherein a permeability moderating amount of non-amphoteric inorganic material is added also to the anolyte during the cell start-up period.
33
10. The process of claim 9 wherein the non- amphoteric inorganic material is selected from magnesium compounds, zirconium compounds, amphibole clays, smectite clays and mixtures of such inorganic materials.
11. The process of claim 10 wherein the non- amphoteric inorganic material is magnesium chloride, magnesium chloride hydrates, clays selected from attapulgite, sepiolite, montmorillonite, saponite and hectorite clays, and mixtures of such inorganic materials.
12. The process of claim 9 wherein the non- amphoteric inorganic material is added to the anolyte contemporaneously with the amphoteric material.
18. In the process of operating a chlor-alkali electrolytic cell for the electrolysis of sodium chloride brine, said cell having a synthetic liquid permeable diaphragm separating the anolyte compartment from the catholyte compartment, the improvement which comprises introducing into the anolyte compartment during the cell start-up period a permeability moderating amount of an amphoteric aluminum compound selected from aluminum chloride, aluminum sulfate, aluminum nitrate, hydrates of said aluminum compounds and readily soluble forms of aluminum hydroxide.
19. The process of claim 18 wherein from 8 to 50 grams of the aluminum compound, calculated as elemental aluminum, per square meter of diaphragm surface area is used.
20 . The process of claim 19 wherein from 15 to 35 grams of the aluminum compound are used.
21. The process of claim 18 wherein a permeability moderating amount of non-amphoteric inorganic material selected from magnesium compounds and clays are added also to the anolyte during the start-up period.
22. The process of claim 21 wherein the non- amphoteric inorganic material is selected from magnesium chloride, magnesium chloride hydrates, clays selected from attapulgite, sepiolite, montmorillonite, saponite and hectorite clays, and mixtures of such inorganic materials.
23. The process of claim 22 wherein from 15 to 35 grams of the aluminum compound, calculated as aluminum, per square meter of diaphragm surface,* from 2 to 40 grams of the magnesium compound, calculated as magnesium, per square meter of diaphragm surface, and from 20 to 200 grams of clay per square meter of diaphragm surface, are added to the anolyte.
24. The process of claim 21 wherein the amphoteric material is aluminum chloride or hydrates of aluminum chloride; and the non-amphoteric material is magnesium chloride, hydrates of magnesium chloride, attapulgite clay and mixtures of said non-amphoteric materials.
25. The process of claim 24 wherein the amphoteric material is added at cell start-up.
26. The process of claim 22 wherein the non- amphoteric inorganic material is added to the anolyte contemporaneously with the amphoteric material.
35
Statement Under Article 19
Claim 1 has been amended to specify that the diaphragm is "liquid permeable". Basis for this amendment may be found on page 1, line 20 of the specification. This amendment makes more explicit what waε implicit in the claim,* namely, that diaphragms used in chlor-alkali electrolytic cells are permeable to liquid, e.g., the alkali metal halide aqueous solution, introduced into the anolyte compartment.
Claim 9 has been amended to state that the non-amphoteric inorganic material is "also" added to the anolyte during the cell start-up period, i.e., the non-amphoteric material is added in addition to the permeability moderating amount of inorganic amphoteric material.
Claim 18 is based on original claims 1, 2 and 4. Claims 19 and 20 are based respectively on original claims 5 and 6. Claim 21 is based on original claim 13; claim 22 is based on original claim 11; and claim 23 is based on original claim 14. Claim 24 is based on original claim 4, and claim 25 is based on original claim 7. Finally, claim 26 is based on original claim 12.
The foregoing amendments to the claims conform the pending claims to the corresponding priority U.S. application, which claims have been allowed.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002223854A CA2223854C (en) | 1995-07-26 | 1996-07-23 | Method for starting a chlor-alkali diaphragm cell |
| DE69622188T DE69622188T2 (en) | 1995-07-26 | 1996-07-23 | METHOD FOR STARTING A CHLORINE ALKALI DIAPHRAGIC CELL |
| EP96926757A EP0865517B1 (en) | 1995-07-26 | 1996-07-23 | Method for starting a chlor-alkali diaphragm cell |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/507,173 US5630930A (en) | 1995-07-26 | 1995-07-26 | Method for starting a chlor-alkali diaphragm cell |
| US08/507,173 | 1995-07-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1997005300A1 WO1997005300A1 (en) | 1997-02-13 |
| WO1997005300B1 true WO1997005300B1 (en) | 1997-03-27 |
Family
ID=24017544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1996/012096 WO1997005300A1 (en) | 1995-07-26 | 1996-07-23 | Method for starting a chlor-alkali diaphragm cell |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5630930A (en) |
| EP (1) | EP0865517B1 (en) |
| CA (1) | CA2223854C (en) |
| DE (1) | DE69622188T2 (en) |
| WO (1) | WO1997005300A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19650316A1 (en) * | 1996-12-04 | 1998-06-10 | Basf Ag | Process for modifying the flow resistance of diaphragms |
| US6296745B1 (en) | 2000-04-28 | 2001-10-02 | Ppg Industries Ohio, Inc. | Method of operating chlor-alkali electrolytic cells |
| US7329332B2 (en) * | 2004-08-25 | 2008-02-12 | Ppg Industries Ohio, Inc. | Diaphragm for electrolytic cell |
| US7618527B2 (en) * | 2005-08-31 | 2009-11-17 | Ppg Industries Ohio, Inc. | Method of operating a diaphragm electrolytic cell |
| US8460536B2 (en) * | 2006-01-19 | 2013-06-11 | Eagle Controlled 2 Ohio Spinco, Inc. | Diaphragm for electrolytic cell |
| US8784620B2 (en) | 2010-05-13 | 2014-07-22 | Axiall Ohio, Inc. | Method of operating a diaphragm electrolytic cell |
| WO2019055815A1 (en) * | 2017-09-15 | 2019-03-21 | Dow Global Technologies Llc | Electrolyte permeable diaphragm |
| WO2019055801A1 (en) * | 2017-09-15 | 2019-03-21 | Dow Global Technologies Llc | Temporarily modifying the permeability of an electrolyte permeable diaphragm |
| EP3670706B1 (en) * | 2018-12-18 | 2024-02-21 | Covestro Deutschland AG | Method for the membrane electrolysis of alkali chloride solutions with gas diffusion electrode |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE795460A (en) * | 1972-02-16 | 1973-08-16 | Diamond Shamrock Corp | PERFECTIONS RELATING TO ELECTROLYTIC TANKS |
| US3991251A (en) * | 1973-10-03 | 1976-11-09 | Ppg Industries, Inc. | Treatment of asbestos diaphragms and resulting diaphragm |
| US4210515A (en) * | 1975-02-10 | 1980-07-01 | Basf Wyandotte Corporation | Thermoplastic fibers as separator or diaphragm in electrochemical cells |
| US4184939A (en) * | 1977-09-26 | 1980-01-22 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4207163A (en) * | 1977-09-26 | 1980-06-10 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4278524A (en) * | 1977-09-26 | 1981-07-14 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4216072A (en) * | 1977-11-10 | 1980-08-05 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4170537A (en) * | 1978-10-20 | 1979-10-09 | Ppg Industries, Inc. | Method of preparing a diaphragm having a gel of a hydrous oxide of zirconium in a porous matrix |
| US4170539A (en) * | 1978-10-20 | 1979-10-09 | Ppg Industries, Inc. | Diaphragm having zirconium oxide and a hydrophilic fluorocarbon resin in a hydrophobic matrix |
| US4170538A (en) * | 1978-10-20 | 1979-10-09 | Ppg Industries, Inc. | Diaphragm having zirconium and magnesium compounds in a porous matrix |
| US4173526A (en) * | 1978-11-21 | 1979-11-06 | E. I. Du Pont De Nemours And Company | Chlor-alkali cell diaphragm and its treatment |
| US4416757A (en) * | 1978-12-22 | 1983-11-22 | Olin Corporation | Coated thermoplastic polymer diaphragms and a method for their preparation |
| US4253935A (en) * | 1979-09-19 | 1981-03-03 | Ppg Industries, Inc. | Method of preparing a diaphragm having a gel of a hydrous oxide or zirconium in a porous matrix |
| US4606805A (en) * | 1982-09-03 | 1986-08-19 | The Dow Chemical Company | Electrolyte permeable diaphragm and method of making same |
| US4665120A (en) * | 1983-01-27 | 1987-05-12 | Eltech Systems Corporation | Modified liquid permeable asbestos diaphragms with improved dimensional stability |
| US4853101A (en) * | 1984-09-17 | 1989-08-01 | Eltech Systems Corporation | Porous separator comprising inorganic/polymer composite fiber and method of making same |
| US4666573A (en) * | 1985-09-05 | 1987-05-19 | Ppg Industries, Inc. | Synthetic diaphragm and process of use thereof |
| US4680101A (en) * | 1986-11-04 | 1987-07-14 | Ppg Industries, Inc. | Electrolyte permeable diaphragm including a polymeric metal oxide |
| US4720334A (en) * | 1986-11-04 | 1988-01-19 | Ppg Industries, Inc. | Diaphragm for electrolytic cell |
| US5192401A (en) * | 1988-12-14 | 1993-03-09 | Ppg Industries, Inc. | Diaphragm for use in chlor-alkali cells |
| US5188712A (en) * | 1991-01-03 | 1993-02-23 | Ppg Industries, Inc. | Diaphragm for use in chlor-alkali cells |
-
1995
- 1995-07-26 US US08/507,173 patent/US5630930A/en not_active Expired - Lifetime
-
1996
- 1996-07-23 CA CA002223854A patent/CA2223854C/en not_active Expired - Fee Related
- 1996-07-23 DE DE69622188T patent/DE69622188T2/en not_active Expired - Lifetime
- 1996-07-23 WO PCT/US1996/012096 patent/WO1997005300A1/en active Search and Examination
- 1996-07-23 EP EP96926757A patent/EP0865517B1/en not_active Expired - Lifetime
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