EP0241633A1 - Procédé pour l'électrolyse de solutions de chlorure alcalin - Google Patents
Procédé pour l'électrolyse de solutions de chlorure alcalin Download PDFInfo
- Publication number
- EP0241633A1 EP0241633A1 EP87100085A EP87100085A EP0241633A1 EP 0241633 A1 EP0241633 A1 EP 0241633A1 EP 87100085 A EP87100085 A EP 87100085A EP 87100085 A EP87100085 A EP 87100085A EP 0241633 A1 EP0241633 A1 EP 0241633A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- space
- anode
- gas
- cell
- 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 23
- 238000005868 electrolysis reaction Methods 0.000 title claims description 22
- 239000003513 alkali Substances 0.000 title claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 12
- 239000007789 gas Substances 0.000 claims abstract description 51
- 210000004027 cell Anatomy 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 210000002421 cell wall Anatomy 0.000 claims abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 239000007868 Raney catalyst Substances 0.000 claims description 16
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 16
- 238000005341 cation exchange Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 26
- 239000000243 solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
Definitions
- the invention relates to a method for the electrolysis of aqueous alkali metal chloride solutions by the membrane method in an electrolysis cell which is equipped with a porous cathode and in which the cell wall together with that side of the cathode which faces away from the cathode space form a closed space ("gas space"). forms.
- the membrane cell for the alkali chloride electrolysis usually consists of two electrolysis chambers, each with a gas-generating electrode, which are separated from one another by a cation exchange membrane.
- perforated materials such as perforated sheets, expanded metal, nets etc. are used as the electrode substrates.
- the perforated electrode structure is necessary so that the resulting gas can be removed to the back of the electrode as quickly as possible, and thus the electrolyte resistance is not unnecessarily increased by the formation of a gas cushion between the anode and the cathode.
- the object was therefore to develop a process for the electrolysis of alkali chloride solutions in which the formation of the gas cushion between the cathode and membrane is eliminated as far as possible.
- this method should be suitable when using porous, foil-like Raney nickel cathodes.
- the method is characterized in that a higher pressure is set in the cathode compartment than in the gas compartment
- the gas space has a device (in practice mostly a pipe connection) for removing hydrogen and possibly condensed water.
- Current densities of at least 500 A / m 2 are preferred, in particular at least 1000 A / m 2 .
- a reasonable upper limit for the current density used is a maximum of 8000 A / m 2 , better a maximum of 6000 A / m 2, in particular a maximum of 4000 A / m 2.
- No gas or gas containing oxygen should be introduced into the gas space of the cell according to the method of the invention.
- Raney nickel electrodes behave particularly favorably, in particular those which consist of a nickel mesh which is covered on at least one side by a compressed mixture of Raney nickel and polytetrafluoroethylene. On the gas side, this Raney nickel electrode can also be covered with a film made of polytetrafluoroethylene. Such electrodes are described in DE-OS 33 42 969, to which express reference is made here.
- the figure shows schematically a cross section through an electrochemical cell for the electrolysis of aqueous alkali chloride solutions, which is equipped with a porous, film-like cathode.
- the cell is divided into an anode compartment (1), a cathode compartment (2) and a gas compartment (3).
- saturated sodium chloride brine is pumped into the anode compartment (1) via a feed line (4).
- Chloride ions are discharged to elemental chlorine at the anode (5).
- Dimensionally stable anodes made of expanded titanium mesh or perforated sheets are preferably used, which are equipped with an activation in order to keep the chlorine overvoltage low.
- the chlorine formed and the depleted brine leave the anode compartment (1) via line (6).
- the cation exchange membrane (7) Between the anode compartment (1) and the cathode compartment (2) is the cation exchange membrane (7) through which sodium ions migrate into the cathode compartment (2).
- Water is fed to the cell in the form of deionized water or dilute sodium hydroxide solution via the feed line (9).
- Alkaline lye is formed in the cathode compartment (2) and leaves the cell via the opening (10).
- Cathode compartment (2) and gas compartment (3) are separated from each other by the porous, foil-like Raney nickel cathode (8).
- the gas compartment (3) is provided with an opening (11) through which the hydrogen generated is removed.
- the porous, foil-like cathode (8) consists of a carrier mesh (13) which is made of nickel, for example, and at the same time serves for power supply and current distribution in the Raney nickel (14) catalyst.
- the cathode can be provided with a thin, porous polytetrafluoroethylene layer (15) on the side facing the gas space.
- This PTFE film is gas-permeable, but liquid-impermeable and is therefore used for gas-liquid separation in the cell. she is not absolutely necessary. If the electrolysis is operated without said film, however, an increased amount of condensate in the gas space (3) is to be expected.
- the pressure is set in a simple manner by providing the line (10) with a throttle valve (12) or extending the line (10) upwards to an overflow in such a way that a defined lye column is formed.
- the gas space is usually at atmospheric pressure, i.e. operated without pressure.
- a 40 cm 2 membrane electrolysis cell equipped with an activated titanium anode and a cation exchange membrane from the company DU PONT of the type Nafion (R) NX 90209, was equipped with a Raney nickel electrode without PTFE foil on the gas space side in accordance with DE-OS 3 342 969 (area 40 cm 2 ) operated so that the cathode separated a 3 mm deep cathode space from a 10 mm deep gas space.
- the operating conditions for the electrolysis were 80 ° C., 3 kA / m 2 , input molecule concentration of 300 g / l, anolyte concentration of 200 g / l and alkali concentration of 33% by weight.
- the cell voltage was 3.12 V under the specified conditions.
- the electrolysis was carried out under the same conditions, with the same electrodes and the same cation exchange membrane as in Example 1, but the gas space was flooded with sodium hydroxide solution. Only the pressure difference between the cathode compartment and the gas compartment was left at 25-30 cm WS (overpressure in the cathode compartment). 98% of the gas came from the gas space and 2% from the cathode space. At a current density of 3 kA / m 2 , the cell voltage was 3.15 V.
- a 450 cm 2 membrane electrolysis cell with an activated titanium anode and a cation exchange membrane of the type Nafion ( R ) NX 90209 was equipped with a Raney nickel cathode with PTFE film on the gas space side in accordance with DE-OS 3 342 696.
- the cathode was 9 cm wide and 50 cm long.
- the electrolysis cell was operated horizontally, so that the anode came to lie above and the cathode below the cation exchange membrane.
- the distance between the cathode and the membrane was about 4 mm.
- the sodium hydroxide solution flowed longitudinally through the cathode compartment.
- the brine in the cell was depleted from 300 g / l to about 220 g / l and 33% by weight sodium hydroxide solution was produced.
- an overpressure in the cathode compartment of 150 cm WS 92% of the hydrogen formed left the cell via the gas compartment; an attack of sodium hydroxide solution in the gas space was not observed.
- the cell voltage was 3.20 V.
- the electrolysis was carried out in a 40 cm 2 cell under the same conditions as in Example 1, but there was pressure equalization between the cathode space and gas space. More than 90% of the hydrogen was generated in the cathode compartment and the cell voltage rose rapidly to values above 3.40 V.
Landscapes
- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87100085T ATE54343T1 (de) | 1986-01-14 | 1987-01-07 | Verfahren zur elektrolyse von alkalichloridl¯sungen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3600759 | 1986-01-14 | ||
| DE19863600759 DE3600759A1 (de) | 1986-01-14 | 1986-01-14 | Verfahren zur elektrolyse von alkalichlorid-loesungen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0241633A1 true EP0241633A1 (fr) | 1987-10-21 |
| EP0241633B1 EP0241633B1 (fr) | 1990-07-04 |
Family
ID=6291756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87100085A Expired - Lifetime EP0241633B1 (fr) | 1986-01-14 | 1987-01-07 | Procédé pour l'électrolyse de solutions de chlorure alcalin |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4790915A (fr) |
| EP (1) | EP0241633B1 (fr) |
| AT (1) | ATE54343T1 (fr) |
| CA (1) | CA1314836C (fr) |
| DE (2) | DE3600759A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9871424B2 (en) | 2013-02-06 | 2018-01-16 | Hitachi Koki Co., Ltd. | Electric tool |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2316091B (en) * | 1996-10-23 | 1999-06-16 | Julian Bryson | Electrolytic treatment of aqueous salt solutions |
| RU2603772C2 (ru) | 2012-06-12 | 2016-11-27 | Монаш Юниверсити | Воздухопроницаемый электрод и способ применения в расщеплении воды |
| JP2016531201A (ja) | 2013-07-31 | 2016-10-06 | アクアハイドレックス プロプライエタリー リミテッドＡｑｕａｈｙｄｒｅｘ Ｐｔｙ Ｌｔｄ | 電気化学的反応を管理するための方法及び電気化学セル |
| DE102016204718A1 (de) | 2016-03-22 | 2017-09-28 | Siemens Aktiengesellschaft | Reaktor |
| DE102016204717A1 (de) * | 2016-03-22 | 2017-09-28 | Siemens Aktiengesellschaft | Reaktor zur Durchführung von gleichgewichtslimitierten Reaktionen |
| AU2020216203A1 (en) | 2019-02-01 | 2021-08-05 | Aquahydrex, Inc. | Electrochemical system with confined electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4488947A (en) * | 1983-06-08 | 1984-12-18 | Olin Corporation | Process of operation of catholyteless membrane electrolytic cell |
| DE3332566A1 (de) * | 1983-09-09 | 1985-03-28 | Hoechst Ag, 6230 Frankfurt | Gasdiffusionselektrode mit hydrophiler deckschicht und verfahren zu ihrer herstellung |
| DE3342969A1 (de) * | 1983-11-28 | 1985-06-05 | Varta Batterie Ag, 3000 Hannover | Poroese gaselektrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5376997A (en) * | 1976-12-20 | 1978-07-07 | Kanegafuchi Chem Ind Co Ltd | Sodium chlorde electrolyzing method using three chamber type ion exhange membrane cell |
| JPS6059304B2 (ja) * | 1977-08-05 | 1985-12-24 | 旭硝子株式会社 | 水平型塩化アルカリ隔膜電解槽 |
-
1986
- 1986-01-14 DE DE19863600759 patent/DE3600759A1/de not_active Withdrawn
-
1987
- 1987-01-07 EP EP87100085A patent/EP0241633B1/fr not_active Expired - Lifetime
- 1987-01-07 DE DE8787100085T patent/DE3763506D1/de not_active Expired - Fee Related
- 1987-01-07 AT AT87100085T patent/ATE54343T1/de not_active IP Right Cessation
- 1987-01-12 US US07/002,142 patent/US4790915A/en not_active Expired - Fee Related
- 1987-01-13 CA CA000527176A patent/CA1314836C/fr not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4488947A (en) * | 1983-06-08 | 1984-12-18 | Olin Corporation | Process of operation of catholyteless membrane electrolytic cell |
| DE3332566A1 (de) * | 1983-09-09 | 1985-03-28 | Hoechst Ag, 6230 Frankfurt | Gasdiffusionselektrode mit hydrophiler deckschicht und verfahren zu ihrer herstellung |
| DE3342969A1 (de) * | 1983-11-28 | 1985-06-05 | Varta Batterie Ag, 3000 Hannover | Poroese gaselektrode |
Non-Patent Citations (1)
| Title |
|---|
| G. MILAZZO "Elektrochemie", 1952 SPRINGER-VERLAG, Wien Seiten 284, 285 abb. 71, insbesondere teile 1, 13; seite 284, zeile 24 seite 285, zeile 32 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9871424B2 (en) | 2013-02-06 | 2018-01-16 | Hitachi Koki Co., Ltd. | Electric tool |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3763506D1 (de) | 1990-08-09 |
| ATE54343T1 (de) | 1990-07-15 |
| US4790915A (en) | 1988-12-13 |
| DE3600759A1 (de) | 1987-07-16 |
| EP0241633B1 (fr) | 1990-07-04 |
| CA1314836C (fr) | 1993-03-23 |
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