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EP0008470A1 - Procédé pour l'électrolyse de solutions aqueuses d'halogénure alcalin - Google Patents

Procédé pour l'électrolyse de solutions aqueuses d'halogénure alcalin Download PDF

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Publication number
EP0008470A1
EP0008470A1 EP79200382A EP79200382A EP0008470A1 EP 0008470 A1 EP0008470 A1 EP 0008470A1 EP 79200382 A EP79200382 A EP 79200382A EP 79200382 A EP79200382 A EP 79200382A EP 0008470 A1 EP0008470 A1 EP 0008470A1
Authority
EP
European Patent Office
Prior art keywords
adjusted
alkali halide
electrolysis
membrane
anode compartment
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
EP79200382A
Other languages
German (de)
English (en)
Other versions
EP0008470B1 (fr
Inventor
Karl Dipl.-Ing. Lohrberg
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6047970&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0008470(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Priority to AT79200382T priority Critical patent/ATE978T1/de
Publication of EP0008470A1 publication Critical patent/EP0008470A1/fr
Application granted granted Critical
Publication of EP0008470B1 publication Critical patent/EP0008470B1/fr
Expired legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells

Definitions

  • the invention relates to a process for the electrolysis of aqueous alkali halide solutions in membrane cells at pH values above 1.0 in the anode compartment, the alkali halide solution being passed through the anode compartment and zones for concentration with alkali halide and for adjusting the pH.
  • the anode and cathode spaces of the electrolysis cell are separated by an ion exchange membrane, through which essentially only the alkali ions can pass. These are electrically neutralized at the cathode and form alkali water and hydrogen in the anode compartment with water. Halogen ions cannot pass through the membrane and are therefore only released in the anode compartment in the form of halogen gas.
  • the object of the invention is to provide a process which is simple to carry out, avoids the disadvantages of the known processes and leads to advantageous results with regard to both halogen yield and alkali yield.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that at least a partial stream of the concentrated solution is brought to a pH at an elevated temperature 1-, 0 and then increases to a pH in the range of 1.0 to 6.0.
  • a partial flow of 15% should only be set to a pH of 0.67.
  • a partial flow of 10% should be brought to a pH of 0.6 if a final pH of 1.7 is desired after the combination with the main flow.
  • the pH is preferably set below 1 at a temperature above 70 ° C., in particular in the range from 80 to 90 ° C., since this promotes decomposition.
  • the method according to the invention does two things:
  • the acidification in particular of a partial stream, below a pH of 1, preferably 0.8, practically quantitatively destroys the halogen oxygen acids or their salts.
  • the pH of the electrolyte to be fed to the anode chamber is set to a value in the range from 1 to 2.5.
  • a partial stream is branched off from this stream for the purpose of virtually complete destruction of the halogen oxygen acids or their salts, so that ultimately a steady state is established in which as much halogen oxygen acids are destroyed by the partial stream treatment as are formed in the anode compartment.
  • the pH is adjusted to 0.6 and the pH of the anolyte after reunification is 1.7, a content of chlorine-oxygen acid or its salts of 20 g / 1 (calculated as sodium chlorate) maintain.
  • a further advantageous embodiment of the invention consists in not degassing the electrolyte emerging from the anode space of the membrane cell prior to strengthening with alkali halide, but rather to adjust it to a pH of about 7 to 10 by adding alkali metal hydroxide solution.
  • the dissolved halogen gas which is present in small amounts, is converted into halogen oxygen acids or their salts, which are largely eliminated anyway by the acidification that occurs after the saturation and removal of the impurities.
  • the membrane cell itself has the known construct tive elements.
  • Polyfluorocarbons are the membrane material. with cation-exchanging groups such as sulfonic acid (SO 3 H), carboxylic acid (COOH) and phosphonic acid (PO 3 H 2 ) groups. Individual fluorine atoms can also be replaced by other halogen atoms, in particular chlorine atoms.
  • suitable membrane materials cf. also D. Bergner lc, page 441, right column ff.
  • the anodes to be used in carrying out the method according to the invention can consist of graphite.
  • the method according to the invention in its preferred embodiment with partial flow separation gives the possibility of changing the pH value of the anolyte during operation of the membrane cell by appropriately dimensioning its quantity and its pH value.
  • signs of aging in the membrane can be compensated for by lowering the pH of the anolyte.
  • Different membrane cells can also be supplied with anolyte of different pH values by differently dimensioning the partial and main streams.
  • Chlorine gas is discharged via line 20.
  • the electrolyte depleted in sodium chloride reaches the treatment room 4 via lines 2 and 3, is mixed there with sodium hydroxide solution supplied via line 5 and adjusted to a pH of 7 to 10.
  • sodium hydroxide solution supplied via line 5 and adjusted to a pH of 7 to 10.
  • dissolved chlorine gas is converted into hypochlorite, from which, depending on pH, temperature and time, some or all of the sodium chlorate is formed.
  • the solution then reaches the saturator 6 and is brought to a concentration of approx. 310 g / l with sodium chloride introduced via 7.
  • the impurities in particular the calcium and magnesium ions, are precipitated by adding sodium hydroxide solution above 9 to a pH of approximately 11.
  • the solution reaches line 12 and is divided into a partial flow 13 and a main flow 14. While the main stream 14 flows in the direction of the anode compartments 1, the partial stream 13 in the device 15 is brought to a pH below 1.0, preferably below 0.8, by adding concentrated hydrochloric acid via line 16. Chlorine oxygen acids or their salts are largely destroyed with the formation of chlorine.
  • the chlorine gas is combined with the chlorine gas originating from the anode spaces 1 of the membrane cells using a line 21.
  • the solution then flows off via line 17 and - mixed with the solution of the main stream 14 - is fed via line 18 or 19 to the anode compartments 1.
  • variable mixing ratios and thus different pH values can be set in the solutions flowing through lines 18 and 19, respectively.
  • the membranes were used for the electrolysis.
  • the membranes consisted of ethylenediamine-modified Nafion R (a product from DuPont).
  • the applied cell voltage was 3.8 volts.
  • the anode compartments 1 of the membrane cells were charged with a brine which contained 310 g / 1 NaCl and had a pH of 1.7 and a temperature of 85 ° C.
  • the residence time of the anelyt in the anode compartments 1 was measured in such a way that the decrease in NaCl was 25 g / l. During this time, approx. 2 g / 1 chlorine oxygen acids (calculated as NaClO 3 ) were formed.
  • the electrolyte solution emerging from the anode compartments 1 was adjusted to pH 8 in the treatment compartment 4 with sodium hydroxide solution, then strengthened again in the saturator 6 to a NaCl concentration of 310 g / 1 and brought to pH 11 in the device 8 with further sodium hydroxide solution, the Contamination was precipitated.
  • the electrolyte was adjusted to pH 1.7 in the initial phase of the process and returned to the anode compartments.
  • the concentration of chlorine-oxygen acid had increased to 22 g / l (calculated as NaClO 3 )
  • a 10% partial stream of the pure sols emerging from the filter device 10 was passed into the device 15 via line 13 and there to pH 0 by adding hydrochloric acid , 6 set.
  • the chlorine oxygen acid content in the partial stream was reduced to 2 g / l.
  • the chlorine gas formed was passed via line 21 to line 20.
  • the concentration of chlorine-oxygen acid would reach 140 g / l after a comparatively short operating time. This would reduce the NaCl solubility to 270 g / 1, which would result in an increase in the separation potential by 50 m / V. The resulting occurrence of side reactions would result in a considerable deterioration in the current yield.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP79200382A 1978-08-26 1979-08-20 Procédé pour l'électrolyse de solutions aqueuses d'halogénure alcalin Expired EP0008470B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79200382T ATE978T1 (de) 1978-08-26 1979-08-20 Verfahren zur elektrolyse waessriger alkalihalogenid-loesungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2837313 1978-08-26
DE19782837313 DE2837313A1 (de) 1978-08-26 1978-08-26 Verfahren zur elektrolyse waessriger alkalihalogenid-loesungen

Publications (2)

Publication Number Publication Date
EP0008470A1 true EP0008470A1 (fr) 1980-03-05
EP0008470B1 EP0008470B1 (fr) 1982-05-05

Family

ID=6047970

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79200382A Expired EP0008470B1 (fr) 1978-08-26 1979-08-20 Procédé pour l'électrolyse de solutions aqueuses d'halogénure alcalin

Country Status (12)

Country Link
US (1) US4247375A (fr)
EP (1) EP0008470B1 (fr)
JP (1) JPS5531199A (fr)
AT (1) ATE978T1 (fr)
BR (1) BR7905453A (fr)
CA (1) CA1158196A (fr)
DE (2) DE2837313A1 (fr)
ES (1) ES483640A1 (fr)
FI (1) FI63260C (fr)
MX (1) MX152740A (fr)
NO (1) NO151973C (fr)
ZA (1) ZA793571B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0081092A1 (fr) * 1981-12-03 1983-06-15 Allied Corporation Préparation d'hydroxides de métaux alcalins par dissociation de l'eau et par hydrolyse
EP0098500A1 (fr) * 1982-07-06 1984-01-18 Olin Corporation Elimination de chlorate d'une saumure de cellule d'électrolyse
EP0093319A3 (en) * 1982-05-03 1984-02-08 Bayer Ag Process for the electrolytic production of chlorine and caustic soda from salt containing sulphate
EP0601604A1 (fr) * 1992-12-10 1994-06-15 Permelec Electrode Ltd Procédé d'électrolyse de solution aqueuse de chlorures alcalins

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4381230A (en) * 1981-06-22 1983-04-26 The Dow Chemical Company Operation and regeneration of permselective ion-exchange membranes in brine electrolysis cells
JPS6068997A (ja) * 1983-09-27 1985-04-19 Fuji Photo Film Co Ltd 平版印刷版用アルミニウム支持体の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1174264A (en) * 1965-11-29 1969-12-17 Hooker Chemical Corp Operation of chlor-alkali cells and anolyte liquid level control.
DE1803638A1 (de) * 1968-10-17 1970-05-27 Bayer Ag Verfahren zur Herstellung von Chlor und Natronlauge
FR2018673A1 (fr) * 1968-09-23 1970-06-26 Hooker Chemical Corp
US4040919A (en) * 1974-10-29 1977-08-09 Hooker Chemicals & Plastics Corporation Voltage reduction of membrane cell for the electrolysis of brine

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3438879A (en) * 1967-07-31 1969-04-15 Hooker Chemical Corp Protection of permselective diaphragm during electrolysis
BE795460A (fr) * 1972-02-16 1973-08-16 Diamond Shamrock Corp Perfectionnements relatifs a des cuves electrolytiques
JPS5318498A (en) * 1976-08-03 1978-02-20 Nippon Soda Co Ltd Preventing method for accumulation of alkali chlorates in salt water in ion exchange membrane method electrolysis of alkali chlorides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1174264A (en) * 1965-11-29 1969-12-17 Hooker Chemical Corp Operation of chlor-alkali cells and anolyte liquid level control.
FR2018673A1 (fr) * 1968-09-23 1970-06-26 Hooker Chemical Corp
DE1803638A1 (de) * 1968-10-17 1970-05-27 Bayer Ag Verfahren zur Herstellung von Chlor und Natronlauge
US4040919A (en) * 1974-10-29 1977-08-09 Hooker Chemicals & Plastics Corporation Voltage reduction of membrane cell for the electrolysis of brine

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0081092A1 (fr) * 1981-12-03 1983-06-15 Allied Corporation Préparation d'hydroxides de métaux alcalins par dissociation de l'eau et par hydrolyse
EP0093319A3 (en) * 1982-05-03 1984-02-08 Bayer Ag Process for the electrolytic production of chlorine and caustic soda from salt containing sulphate
EP0098500A1 (fr) * 1982-07-06 1984-01-18 Olin Corporation Elimination de chlorate d'une saumure de cellule d'électrolyse
EP0601604A1 (fr) * 1992-12-10 1994-06-15 Permelec Electrode Ltd Procédé d'électrolyse de solution aqueuse de chlorures alcalins
US5466347A (en) * 1992-12-10 1995-11-14 Permelec Electrode, Ltd. Method for electrolyzing aqueous solution of alkali chloride

Also Published As

Publication number Publication date
JPS5531199A (en) 1980-03-05
NO151973C (no) 1985-07-31
MX152740A (es) 1985-11-01
JPS636635B2 (fr) 1988-02-10
BR7905453A (pt) 1980-05-20
NO151973B (no) 1985-04-01
US4247375A (en) 1981-01-27
ATE978T1 (de) 1982-05-15
ZA793571B (en) 1980-07-30
EP0008470B1 (fr) 1982-05-05
FI63260B (fi) 1983-01-31
CA1158196A (fr) 1983-12-06
FI63260C (fi) 1983-05-10
DE2837313A1 (de) 1980-03-13
ES483640A1 (es) 1980-04-16
DE2962706D1 (en) 1982-06-24
NO792723L (no) 1980-02-27
FI792470A7 (fi) 1980-02-27

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