EP0903425B1 - Vefahren zur Elektrolyse einer Salzlösung - Google Patents

Vefahren zur Elektrolyse einer Salzlösung Download PDF

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Publication number
EP0903425B1
EP0903425B1 EP98402268A EP98402268A EP0903425B1 EP 0903425 B1 EP0903425 B1 EP 0903425B1 EP 98402268 A EP98402268 A EP 98402268A EP 98402268 A EP98402268 A EP 98402268A EP 0903425 B1 EP0903425 B1 EP 0903425B1
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EP
European Patent Office
Prior art keywords
cathode
membrane
oxygen
compartment
temperature
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.)
Expired - Lifetime
Application number
EP98402268A
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English (en)
French (fr)
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EP0903425A1 (de
Inventor
Françoise Andolfatto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema France SA
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    • 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 method for electrolysis of a brine, and more specifically to an aqueous solution of sodium chloride by means of a membrane electrolysis cell and a gas electrode, said electrode being placed directly against the membrane and in a cathode compartment powered solely by gas.
  • the present invention relates to a process for producing an aqueous solution of sodium hydroxide by electrolysis of an aqueous solution of sodium chloride using an "oxygen reduction cathode" having a yield of sodium hydroxide (current efficiency) and improved membrane life.
  • a conventional membrane electrolysis cell comprises a placed gas electrode in the cathode compartment of the electrolysis cell to divide this compartment into a solution compartment on the ion exchange membrane side and a gas compartment on the opposite side.
  • the gas electrode is usually obtained by molding a mixture of a hydrophobic substance such as a polytetrafluoroethylene resin (hereinafter referred to as PTFE) and a supported catalyst or catalyst so that it presents hydrophobic properties preventing the passage of liquids.
  • PTFE polytetrafluoroethylene resin
  • a supported catalyst or catalyst so that it presents hydrophobic properties preventing the passage of liquids.
  • PTFE polytetrafluoroethylene resin
  • a supported catalyst or catalyst so that it presents hydrophobic properties preventing the passage of liquids.
  • such a gas electrode progressively loses its hydrophobic properties when it is exposed to a high temperature of the order of 90 ° C and to an aqueous solution of sodium hydroxide of high concentration of about 32% or more.
  • the gas electrode consists of a mixture comprising mainly a carbonaceous material and a resin, it has a mechanical fragility and tends to crack.
  • the soda produced must have a titer of between 30 and 35%, otherwise the current efficiency will be reduced by increasing the back migration. hydroxyl ions in the membrane, and physically degrade the membrane. These specifications are given by chlor-alkali membrane manufacturers, and are valid for all types of membranes. This involves adding water to dilute the soda produced, 4.5 moles of water per mole of soda (to have a 33% soda).
  • the electroosmotic flow through the membrane brings into the cathode compartment 3.5 moles of water per mole of Na + , when the concentration of NaCl in the anode compartment is 220 g / l.
  • the amount of water available in contact with the membrane will be at most 3.5 moles of water per mole of sodium hydroxide, assuming that the water required for the electrochemical reaction is provided by the gas.
  • a method of electrolysis of an aqueous solution of sodium chloride has now been found by means of an oxygen reduction membrane and cathode electrolysis cell comprising a cation exchange membrane which divides the cell into a compartment. anode and a cathode compartment in which said cathode is placed directly against the cation exchange membrane, said cathode compartment being fed with a humidified gas containing oxygen, characterized in that, to obtain a weight concentration of sodium hydroxide between the exchange membrane cation and the cathode less than 38.8%, an aqueous chloride solution is used.
  • sodium (anolyte) having a sodium chloride concentration of less than 200 g / l and preferably of between 160 g / l and 190 g / l and that the water moistening the oxygen-containing gas is under form of water vapor.
  • the temperature of the cathode compartment may be greater than the temperature of the anode compartment.
  • the temperature of the cathode compartment may be greater than 5 ° C. to 20 ° C. at the temperature of the anode compartment and, preferably, greater than 10 ° C. to 15 ° C.
  • the cathode compartment is fed with an oxygen-containing gas, previously wetted by bubbling in water heated to a temperature ranging from 50 ° C. to 100 ° C. and preferably at a temperature of between 80 ° C. and 100 ° C.
  • the humidified oxygen will be introduced into the cathode compartment so that the water humidifying the oxygen is in the form of water vapor. This can be achieved by keeping the temperature of the bubbler lower than or equal to that of the cathode compartment.
  • the volume content of water vapor of the humidified gas containing oxygen is between 10% and 80% and preferably between 20% and 60%.
  • the oxygen-containing gas may be air, oxygen-enriched air or even oxygen. Preferably, oxygen will be used.
  • the volume concentration of oxygen in the gas is less than 20%, and preferably at least 50%.
  • the gases enriched with oxygen are preferably decarbonated beforehand.
  • the weight concentration of sodium hydroxide between the cation exchange membrane and the cathode is less than 38.8%, preferably less than 37%.
  • the method of the invention has the advantage of leading to a high yield of sodium hydroxide (current yield), to improve the lifetime of the cation exchange membranes and not to significantly disturb the voltage of the cell.
  • the sodium hydroxide obtained by the process according to the present invention has a purity equivalent to the sodium hydroxide obtained by conventional methods of hydrogen evolution cathodes.
  • the invention may be implemented with a device as described below.
  • a capillary placed between the cathodic seal and the membrane (not shown in FIG. 1) makes it possible to take sodium hydroxide between the membrane and the cathode in order to measure its concentration. The chlorine comes out at (15).
  • An aqueous solution of NaCl is introduced into the anode compartment (1) by (3) at a weight concentration of NaCl as defined above and humidified gas containing oxygen in the cathode compartment (11) by (12); the water moistening the gas containing oxygen being in the form of water vapor.
  • the temperature of the electrolysis is set to 80-90 ° C
  • the temperature of the cathode compartment may be greater than the temperature of the anode compartment.
  • the present invention it is advantageous to operate with a flow rate of oxygen 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 electrolytic cell of aqueous sodium chloride solution as shown in FIG. 1 is used.
  • the electrolysis is carried out with a source of energy 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 platinum carbon shaped with PTFE on a nickel silver grid. (10% platinum on carbon, 0.56 mg Pt per cm 2 ).
  • This cathode is marketed by E-TEK, Inc.
  • the cation exchange membrane (9) is a Nafion N966 membrane, produced by the departments du Pont de Nemours.
  • the gas used is pure oxygen.
  • the operating conditions are identical to those of Example 3, except that the weight concentration 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)

Claims (8)

  1. Verfahren zur Elektrolyse einer wässrigen Natriumchloridlösung mittels einer Elektrolysezelle mit Membran und mit einer Sauerstoffreduktionskathode, die eine Kationenaustauschmembran umfasst, die die Zelle in ein Anodenkompartiment und ein Kathodenkompartiment, in dem die Kathode direkt gegen die Kationenaustauschmembran angeordnet ist, teilt, wobei das Kathodenkompartiment mit einem befeuchteten, Sauerstoff enthaltenden Gas versorgt wird, dadurch gekennzeichnet, dass, um eine Gewichtskonzentration der Sole zwischen der Kationenaustauschmembran und der Kathode unterhalb von 38,8 % zu erhalten, eine wässrige Natriumchloridlösung (Anolyt) verwendet wird, die eine Gewichtskonzentration an Natriumchlorid von weniger als 200 g/l aufweist und dadurch, dass das Wasser, das das Sauerstoff enthaltende Gas befeuchtet, in Form von Wasserdampf vorliegt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Gewichtskonzentration an Natriumchlorid der wässrigen Natriumchloridlösung zwischen 160 g/l und 190 g/l liegt.
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das Gas Sauerstoff ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Volumengehalt an Wasserdampf des befeuchteten, Sauerstoff enthaltenden Gases zwischen 10 % und 80 % liegt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Volumengehalt an Wasserdampf des befeuchteten, Sauerstoff enthaltenden Gases zwischen 20 % und 60 % liegt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, ferner dadurch gekennzeichnet, dass die Temperatur des Kathodenkompartiments über der Temperatur des Anodenkompartiments liegt.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die Temperatur des Kathodenkompartiments um 5 °C bis 20 °C über der Temperatur des Anodenkompartiments liegt.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Temperatur des Kathodenkompartiments um 10 °C bis 15 °C über der Temperatur des Anodenkompartiments liegt.
EP98402268A 1997-09-23 1998-09-15 Vefahren zur Elektrolyse einer Salzlösung Expired - Lifetime EP0903425B1 (de)

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 EP0903425A1 (de) 1999-03-24
EP0903425B1 true EP0903425B1 (de) 2007-10-31

Family

ID=9511354

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98402268A Expired - Lifetime EP0903425B1 (de) 1997-09-23 1998-09-15 Vefahren zur Elektrolyse einer Salzlösung

Country Status (12)

Country Link
US (1) US6080298A (de)
EP (1) EP0903425B1 (de)
JP (1) JP3073968B2 (de)
KR (1) KR100313259B1 (de)
CN (1) CN1107744C (de)
AT (1) ATE377100T1 (de)
BR (1) BR9803590A (de)
CA (1) CA2245144C (de)
DE (1) DE69838632T2 (de)
ES (1) ES2296325T3 (de)
FR (1) FR2768751B1 (de)
NO (1) NO322395B1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
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
WO2018180726A1 (ja) 2017-03-30 2018-10-04 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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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
JPS5641392A (en) * 1979-09-11 1981-04-18 Toyo Soda Mfg Co Ltd Electrolytic method of alkali chloride aqueous solution
JP3400508B2 (ja) * 1993-10-27 2003-04-28 ペルメレック電極株式会社 塩水電解方法及び電解槽
JP3344828B2 (ja) * 1994-06-06 2002-11-18 ペルメレック電極株式会社 塩水の電解方法
JPH08333693A (ja) * 1995-06-05 1996-12-17 Permelec Electrode Ltd 電解槽

Also Published As

Publication number Publication date
FR2768751B1 (fr) 1999-10-29
CN1107744C (zh) 2003-05-07
CA2245144C (fr) 2002-08-13
JP3073968B2 (ja) 2000-08-07
ES2296325T3 (es) 2008-04-16
FR2768751A1 (fr) 1999-03-26
DE69838632T2 (de) 2008-08-28
CN1219610A (zh) 1999-06-16
NO984306D0 (no) 1998-09-17
US6080298A (en) 2000-06-27
JPH11152591A (ja) 1999-06-08
KR100313259B1 (ko) 2002-02-19
NO984306L (no) 1999-03-24
NO322395B1 (no) 2006-10-02
KR19990029993A (ko) 1999-04-26
DE69838632D1 (de) 2007-12-13
ATE377100T1 (de) 2007-11-15
CA2245144A1 (fr) 1999-03-23
BR9803590A (pt) 1999-12-14
EP0903425A1 (de) 1999-03-24

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