EP0903425A1 - Vefahren zur Elektrolyse einer Salzlösung - Google Patents

Vefahren zur Elektrolyse einer Salzlösung Download PDF

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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
Application number
EP98402268A
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English (en)
French (fr)
Other versions
EP0903425B1 (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
Original Assignee
Arkema France SA
Elf Atochem SA
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Application filed by Arkema France SA, Elf Atochem SA filed Critical Arkema France SA
Publication of EP0903425A1 publication Critical patent/EP0903425A1/de
Application granted granted Critical
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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)
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 true EP0903425A1 (de) 1999-03-24
EP0903425B1 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

Citations (4)

* 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
DE4438275A1 (de) * 1993-10-27 1995-05-11 Permelec Electrode Ltd Elektrolyse einer Salzlösung und dafür geeignete Elektrolysezelle
EP0686709A2 (de) * 1994-06-06 1995-12-13 Permelec Electrode Ltd. Verfahren zur Elektrolyse von Salzlösungen
DE19622427A1 (de) * 1995-06-05 1996-12-12 Permelec Electrode Ltd Elektrolysezelle

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* 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
DE4438275A1 (de) * 1993-10-27 1995-05-11 Permelec Electrode Ltd Elektrolyse einer Salzlösung und dafür geeignete Elektrolysezelle
EP0686709A2 (de) * 1994-06-06 1995-12-13 Permelec Electrode Ltd. Verfahren zur Elektrolyse von Salzlösungen
DE19622427A1 (de) * 1995-06-05 1996-12-12 Permelec Electrode Ltd Elektrolysezelle

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
EP0903425B1 (de) 2007-10-31
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

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