EP0903425A1 - Procédé d'éléctrolyse d'une saumure - Google Patents
Procédé d'éléctrolyse d'une saumure Download PDFInfo
- Publication number
- EP0903425A1 EP0903425A1 EP98402268A EP98402268A EP0903425A1 EP 0903425 A1 EP0903425 A1 EP 0903425A1 EP 98402268 A EP98402268 A EP 98402268A EP 98402268 A EP98402268 A EP 98402268A EP 0903425 A1 EP0903425 A1 EP 0903425A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- membrane
- compartment
- oxygen
- soda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 title claims description 22
- 239000012267 brine Substances 0.000 title description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title description 7
- 239000012528 membrane Substances 0.000 claims abstract description 51
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000011780 sodium chloride Substances 0.000 claims abstract description 20
- 238000005341 cation exchange Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 27
- 239000000243 solution Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 208000031968 Cadaver Diseases 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010349 cathodic reaction Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Definitions
- the present invention relates to a process for the electrolysis of a brine, and more specifically an aqueous solution of chloride sodium by means of a membrane electrolysis cell and a gas electrode, said electrode being placed directly against the membrane and in a cathode compartment supplied only by some gas.
- the present invention relates to a method for producing an aqueous solution of sodium hydroxide by electrolysis of an aqueous sodium chloride solution using a "oxygen reduction cathode” having a soda yield (yield current) and improved membrane life.
- a conventional membrane electrolysis cell includes a gas electrode placed in the cathode compartment of the electrolysis cell to split this compartment in a solution compartment on the membrane side ion exchanger and in a gas compartment on the opposite side,
- the gas electrode is usually obtained by molding a mixture a hydrophobic substance such as a polytetrafluoroethylene resin (hereinafter called PTFE) and a catalyst or a catalyst on support, so that it has hydrophobic properties preventing the passage of liquids.
- PTFE polytetrafluoroethylene resin
- a catalyst or a catalyst on support so that it has hydrophobic properties preventing the passage of liquids.
- PTFE polytetrafluoroethylene resin
- a catalyst or a catalyst on support so that it has hydrophobic properties preventing the passage of liquids.
- such a gas electrode gradually loses its hydrophobic properties when exposed at a high temperature of the order of 90 ° C and an aqueous solution sodium hydroxide of high concentration of about 32% see more
- the liquid present in the solution compartment tends to enter the gas compartment.
- the gas electrode is made up by a mixture mainly comprising a carbonaceous material and a resin, it has mechanical fragility and tends to crack.
- the soda produced must have a titer between 30 and 35% under penalty of reducing the current efficiency by increasing the back-migration hydroxyl ions in the membrane, and degrade physically the membrane. These specifications are given by chlorine-soda membrane manufacturers, and are valid for all types membranes. This involves adding water to dilute the soda produced, 4.5 moles of water per mole of soda (to have a soda 33%).
- the electro-osmotic flow through the membrane brings into the cathode compartment 3.5 moles of water per mole of Na +, when the NaCl concentration in the anode compartment is 220 g / l.
- an electrolysis cell membrane and oxygen reduction cathode comprising a membrane cation exchanger which divides the cell into an anode compartment and a cathode compartment in which said cathode is placed directly against the cation exchange membrane, said cathode compartment being supplied by a humidified gas containing oxygen, characterized in that, to obtain a concentration by weight in sodium hydroxide between the cation exchange membrane and the cathode less than 38.8%, an aqueous chloride solution is used sodium (anolyte) having a concentration of sodium chloride less than 200 g / l and, preferably between 160 g / l and 190 g / l and in that the water humidifying the oxygen-containing gas is in the form water vapor.
- the temperature of the cathode compartment may be higher than the temperature of the anode compartment.
- the temperature of the compartment cathode may be 5 ° C to 20 ° C higher than the temperature of the anode compartment, preferably 10 ° C to 15 ° C higher.
- the cathode compartment is supplied with a gas containing oxygen, previously moistened by bubbling in water heated to a temperature ranging from 50 ° C to 100 ° C and preferably at a temperature between 80 ° C and 100 ° C.
- humidified oxygen will be introduced in the cathode compartment so that the humidifying water oxygen is in the form of water vapor. This can be achieved by keeping the temperature of the bubbler lower or equal to that of the cathode compartment.
- the water vapor content of the humidified gas containing oxygen is between 10% and 80% and, preferably between 20% and 60%.
- the oxygen-containing gas can be air, air enriched in oxygen or even oxygen. Preferably, we will use oxygen.
- the volume concentration of oxygen in the gas is less equal to 20%, and preferably at least equal to 50%.
- the oxygen-enriched gases are preferably decarbonated.
- the weight concentration of soda between the cation exchange membrane and the cathode is less than 38.8%, preferably less than 37%.
- the process of the invention has the advantage of leading to a high soda yield (current efficiency), improve the service life of the membranes cation exchangers and not to significantly disturb the cell voltage.
- the soda obtained by the process according to the present invention has a purity equivalent to the soda obtained according to the conventional hydrogen cathode processes.
- the invention can be implemented with a device such as described below.
- a capillary placed between the cathode joint and the membrane (not shown in Figure 1 allows to draw soda between the membrane and cathode to measure its concentration. Chlorine comes out in (15).
- An aqueous NaCl solution is introduced into the compartment anodic (1) by (3) at a weight concentration of NaCl such that defined above and humidified gas containing oxygen in the cathode compartment (11) by (12); water humidifying gas containing oxygen being in the form of water vapor.
- the temperature of the electrolysis is set at around 80-90 ° C, the temperature of the cathode compartment can be higher than the temperature of the anode compartment.
- the present invention it is advantageous to operate with a oxygen flow which is greater than the consumption of the cathode.
- the temperature of the water in which the oxygen-containing gas is bubbling can be increased or decreased, as can the flow rate of humidified gas containing oxygen to adjust the titer of the soda at the outlet (14) of the cell.
- the electrolysis cell of aqueous chloride solution is used sodium as shown in Figure 1.
- the electrolysis is carried out with an energy source which is connected to the anode (+) and to the cathode (-) of the cell so as to apply to the cell a current density i of 3 to 4 k A / m 2 .
- the anode (8) consists of a titanium substrate coated with ruthenium oxide RuO 2 .
- the cathode (10) consists of platinized carbon shaped with PTFE on a grid of silver nickel. (10% platinum on carbon; 0.56 mg Pt per cm 2 ).
- This cathode is sold by E-TEK, Inc.
- the cation exchange membrane (9) is a Nafion membrane N966, produced by the departments du Pont de Nemours.
- the gas used is pure oxygen.
- Nafion® N966 membrane titanium substrate anode coated with RuO 2 .
- Oxygen is humidified by bubbling in water at 80 ° C before his entry into the cell. Its flow is 5 l / h.
- the water vapor content of humidified oxygen is about 55%.
- Weight concentration of NaCl in the anolyte 220 g / l.
- Weight concentration of soda between the membrane and the cathode 40%.
- Soda yield 93% (24-hour assessment of continuous operation).
- Nafion® N966 membrane titanium substrate anode coated with RuO 2 .
- Oxygen is humidified by bubbling in water at 80 ° C before its entry into the cell, its flow rate is doubled compared to Example 1.
- Weight concentration of NaCl in the anolyte 220 g / l.
- Ecell cell voltage 2.2 V.
- Soda yield 93.4% (24-hour assessment of continuous operation).
- Nafion® N966 membrane titanium substrate anode coated with RuO 2 .
- Oxygen is humidified by bubbling in water at 80 ° C before upon entering the cell, the oxygen flow rate is identical to that of Example 1.
- Weight concentration of NaCl in the anolyte 190 g / l.
- Weight concentration of soda between the membrane and the cathode 37.5%.
- Soda yield 95.9% (24-hour assessment of continuous operation).
- the operating conditions are identical to those of Example 3, except that the concentration by weight of NaCl in the anolyte is 170 g / l.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
- un compartiment anodique constitué d'un corps de cellule (1), d'un dégazeur (2). La solution de chlorure de sodium (saumure) est introduite par (3) et circule par gaz lift entre le corps de la cellule et le dégazeur (conduites (4) et (5)). Un trop plein (6) permet d'éliminer par (7) une partie de la saumure appauvrie. Des ajouts de saumure concentrée permettent de maintenir la concentration en NaCl dans l'anolyte à la valeur choisie ;
- une anode (8) qui peut être constituée par substrat en titane revêtu de RuO2,
- une membrane échangeuse de cations (9),
- une cathode (10) placée directement contre la membrane (9), qui peut être constituée d'une grille de nickel argenté recouverte de carbone platiné,
- un compartiment cathodique (11) constitué d'un corps de cellule. Le gaz humidifié contenant de l'oxygène est alimenté par le bas de la cellule (12) et ressort en partie haute (13) dans une colonne d'eau non représentée sur la figure 1 qui fixe la pression de travail. La soude est soutirée en (14) directement au titre voulue dans le bas de la cellule.
- concentration pondérale de la soude sortie cellule : 32 %,
- concentration pondérale de la soude entre la membrane et la cathode : 35 %,
- rendement en soude : 96 %.
Claims (8)
- Procédé d'électrolyse d'une solution aqueuse de chlorure de sodium au moyen d'une cellule d'électrolyse à membrane et à cathode à réduction d'oxygène comprenant une membrane échangeuse de cations qui divise la cellule en un compartiment anodique et un compartiment cathodique dans lequel ladite cathode est placée directement contre la membrane échangeuse de cations, ledit compartiment cathodique étant alimenté par un gaz humidifié contenant de l'oxygène, caractérisé en ce que, pour obtenir une concentration pondérale en soude entre la membrane échangeuse de cations et la cathode inférieure à 38,8 %, on utilise une solutions aqueuse de chlorure de sodium (anolyte) ayant une concentration pondérale en chlorure de sodium inférieure à 200 g/l et en ce que l'eau humidifiant le gaz contenant de l'oxygène est sous forme de vapeur d'eau.
- Procédé selon la revendication 1, caractérisé en ce que la concentration pondérale en chlorure de sodium de la solution aqueuse de chlorure de sodium est comprise entre 160 g/l et 190 g/l.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le gaz est de l'oxygène.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la teneur volumique en vapeur d'eau du gaz humidifié contenant de l'oxygène est comprise entre 10 % et 80 %.
- Procédé selon la revendication 4, caractérisé en ce que la teneur volumique en vapeur d'eau du gaz humidifié contenant de l'oxygène est comprise entre 20 % et 60 %.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce que, en outre, la température du compartiment cathodique est supérieure à la température du compartiment anodique.
- Procédé selon la revendication 6 caractérisé en ce que la température du compartiment cathodique est supérieure de 5°C à 20°C à la température du compartiment anodique.
- Procédé selon la revendication 7, caractérisé en ce que la température du compartiment cathodique est supérieur de 10°C à 15°C à la température du compartiment anodique.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9711795 | 1997-09-23 | ||
FR9711795A FR2768751B1 (fr) | 1997-09-23 | 1997-09-23 | Procede d'electrolyse d'une saumure |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0903425A1 true EP0903425A1 (fr) | 1999-03-24 |
EP0903425B1 EP0903425B1 (fr) | 2007-10-31 |
Family
ID=9511354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98402268A Expired - Lifetime EP0903425B1 (fr) | 1997-09-23 | 1998-09-15 | Procédé d'éléctrolyse d'une saumure |
Country Status (12)
Country | Link |
---|---|
US (1) | US6080298A (fr) |
EP (1) | EP0903425B1 (fr) |
JP (1) | JP3073968B2 (fr) |
KR (1) | KR100313259B1 (fr) |
CN (1) | CN1107744C (fr) |
AT (1) | ATE377100T1 (fr) |
BR (1) | BR9803590A (fr) |
CA (1) | CA2245144C (fr) |
DE (1) | DE69838632T2 (fr) |
ES (1) | ES2296325T3 (fr) |
FR (1) | FR2768751B1 (fr) |
NO (1) | NO322395B1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050011753A1 (en) * | 2003-06-23 | 2005-01-20 | Jackson John R. | Low energy chlorate electrolytic cell and process |
FR2930541B1 (fr) * | 2008-04-29 | 2010-05-21 | Solvay | Procede d'epuration de solutions aqueuses |
KR101239145B1 (ko) | 2009-03-17 | 2013-03-06 | 김영준 | 음식물 쓰레기에 포함된 염화나트륨 수용액을 전기 분해하는 장치 |
CN102134724B (zh) * | 2010-12-31 | 2012-06-20 | 北京化工大学 | 阴离子膜电解槽装置用于纯碱生产中废液脱盐的方法 |
CN106148992A (zh) * | 2015-04-20 | 2016-11-23 | 李坚 | 离子膜催化法或电渗析催化法水制氢及其应用 |
JP7061997B2 (ja) | 2017-03-30 | 2022-05-02 | 株式会社カネカ | 水酸化ナトリウム及び/又は塩素の製造方法、並びに2室法型食塩水電解槽 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4221644A (en) * | 1979-08-14 | 1980-09-09 | Diamond Shamrock Corporation | Air-depolarized chlor-alkali cell operation methods |
DE4438275A1 (de) * | 1993-10-27 | 1995-05-11 | Permelec Electrode Ltd | Elektrolyse einer Salzlösung und dafür geeignete Elektrolysezelle |
EP0686709A2 (fr) * | 1994-06-06 | 1995-12-13 | Permelec Electrode Ltd. | Procédé d'électrolyse de saumures |
DE19622427A1 (de) * | 1995-06-05 | 1996-12-12 | Permelec Electrode Ltd | Elektrolysezelle |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5641392A (en) * | 1979-09-11 | 1981-04-18 | Toyo Soda Mfg Co Ltd | Electrolytic method of alkali chloride aqueous solution |
-
1997
- 1997-09-23 FR FR9711795A patent/FR2768751B1/fr not_active Expired - Fee Related
-
1998
- 1998-09-15 AT AT98402268T patent/ATE377100T1/de not_active IP Right Cessation
- 1998-09-15 ES ES98402268T patent/ES2296325T3/es not_active Expired - Lifetime
- 1998-09-15 DE DE69838632T patent/DE69838632T2/de not_active Expired - Lifetime
- 1998-09-15 EP EP98402268A patent/EP0903425B1/fr not_active Expired - Lifetime
- 1998-09-17 NO NO19984306A patent/NO322395B1/no not_active IP Right Cessation
- 1998-09-21 JP JP10266805A patent/JP3073968B2/ja not_active Expired - Fee Related
- 1998-09-21 KR KR1019980038977A patent/KR100313259B1/ko not_active IP Right Cessation
- 1998-09-22 BR BR9803590-8A patent/BR9803590A/pt not_active IP Right Cessation
- 1998-09-22 CA CA002245144A patent/CA2245144C/fr not_active Expired - Fee Related
- 1998-09-23 CN CN98120557A patent/CN1107744C/zh not_active Expired - Fee Related
- 1998-09-23 US US09/158,889 patent/US6080298A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4221644A (en) * | 1979-08-14 | 1980-09-09 | Diamond Shamrock Corporation | Air-depolarized chlor-alkali cell operation methods |
DE4438275A1 (de) * | 1993-10-27 | 1995-05-11 | Permelec Electrode Ltd | Elektrolyse einer Salzlösung und dafür geeignete Elektrolysezelle |
EP0686709A2 (fr) * | 1994-06-06 | 1995-12-13 | Permelec Electrode Ltd. | Procédé d'électrolyse de saumures |
DE19622427A1 (de) * | 1995-06-05 | 1996-12-12 | Permelec Electrode Ltd | Elektrolysezelle |
Also Published As
Publication number | Publication date |
---|---|
FR2768751A1 (fr) | 1999-03-26 |
ATE377100T1 (de) | 2007-11-15 |
DE69838632D1 (de) | 2007-12-13 |
JPH11152591A (ja) | 1999-06-08 |
NO322395B1 (no) | 2006-10-02 |
CA2245144A1 (fr) | 1999-03-23 |
NO984306D0 (no) | 1998-09-17 |
JP3073968B2 (ja) | 2000-08-07 |
CN1219610A (zh) | 1999-06-16 |
KR19990029993A (ko) | 1999-04-26 |
ES2296325T3 (es) | 2008-04-16 |
BR9803590A (pt) | 1999-12-14 |
NO984306L (no) | 1999-03-24 |
CN1107744C (zh) | 2003-05-07 |
CA2245144C (fr) | 2002-08-13 |
KR100313259B1 (ko) | 2002-02-19 |
US6080298A (en) | 2000-06-27 |
EP0903425B1 (fr) | 2007-10-31 |
DE69838632T2 (de) | 2008-08-28 |
FR2768751B1 (fr) | 1999-10-29 |
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