EP0008470B1 - Verfahren zur Elektrolyse wässriger Alkalihalogenid-Lösungen - Google Patents
Verfahren zur Elektrolyse wässriger Alkalihalogenid-Lösungen Download PDFInfo
- Publication number
- EP0008470B1 EP0008470B1 EP79200382A EP79200382A EP0008470B1 EP 0008470 B1 EP0008470 B1 EP 0008470B1 EP 79200382 A EP79200382 A EP 79200382A EP 79200382 A EP79200382 A EP 79200382A EP 0008470 B1 EP0008470 B1 EP 0008470B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adjusted
- solution
- value
- alkali metal
- membrane
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910001508 alkali metal halide Inorganic materials 0.000 title abstract description 7
- 150000008045 alkali metal halides Chemical class 0.000 title abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 title description 9
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- 239000003513 alkali Substances 0.000 claims description 17
- 150000004820 halides Chemical class 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical class [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- -1 Halogen ions Chemical class 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- 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
- 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
Definitions
- the invention relates to a method for the electrical analysis 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 pH adjustment.
- amalgam has the advantage of permitting the production of highly concentrated alkali lye of high purity, but due to the use of mercury requires high costs for environmental protection.
- diaphragm process does not require such expenditure, but only enables the production of alkali lye of considerably lower concentration, which also has considerable alkali halide contents.
- 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 cathode 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 OH ions formed in the cathode space migrate through the membrane into the anode space.
- the OH ions form with halogen gas - depending on the pH of the anolyte chlorine-oxygen acids or their salts, especially hypochlorite and chlorate, which can only be destroyed by adding acid.
- the pH of the anolyte is in the range from about 1 to 5, preferably 3.0 to 4.0 (DE-A-2 409 193) or at about 2 ( DE-A-2 631 523).
- the anolyte is adjusted to a pH in the range from 0 to 3 and preferably from 1 to 2.5 by means of hydrochloric acid.
- the alkali metal halide solution enriched with alkali metal halide is adjusted to a pH of 0.2 to 4.5 and preferably 1.5 to 4.
- the temperature of the anolyte is kept in the range of 85 to 100 ° C.
- 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 only a partial stream of the enriched alkali metal halide solution is adjusted to a pH below 1.0.
- a partial flow of 15% should only be set to a pH of 0.67.
- a part Stream of 10% should be brought to a pH of 0.6 if, after combining with the main stream, a final pH of 1.7 is desired.
- 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 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 in turn 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 recombining is 1.1, a content of chlorine-oxygen acid or its salts of 20 g / l (calculated as sodium chlorate ) maintained.
- a further advantageous embodiment of the invention consists in not degassing the electrolyte emerging from the anode space of the membrane cell before strengthening with alkali metal halide, but instead 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 constructive elements.
- Polyfluorohydrocarbons with cation-exchanging groups such as, for example, sulfonic acid (SO, H), carboxylic acid (COOH) and phosphonic acid (PO 3 H 2 ) groups, are suitable as membrane material.
- Individual fluorine atoms can also be replaced by other halogen atoms, in particular chlorine atoms.
- suitable membrane materials cf. also D. Bergner 1. c., page 441, right column ff.
- the anodes to be used in carrying out the method according to the invention can consist of graphite.
- titanium, niobium or tantalum electrodes coated with noble metal or noble metal oxide or so-called dimensionally stable anodes, in which the electrocatalytic effect of mixed oxides of noble metals and film-forming metals, in particular titanium, originate, are particularly advantageous.
- the method according to the invention in its preferred embodiment with partial flow separation gives the possibility of changing the pH of the anolyte during operation of the membrane cell by appropriately dimensioning its quantity and its pH.
- 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 passes into the saturator 6 and is brought to a concentration of about 310 g / l with sodium chloride introduced over 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 treatment in the filter device 10 and discharge of the precipitated impurities via line 11 reaches the Lö - solution in line 12 and is introduced into a partial stream 13 and a principal stream 14 split.
- 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® (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 / l NaCl and had a pH of 1.7 and a temperature of 85 ° C.
- the residence time of the anolyte 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 / l 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 / l and brought to pH 11 in the device 8 with additional sodium hydroxide solution, the contamination was felled.
- 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 via line 13 into the device 15 and there to pH 0 by adding hydrochloric acid , 6 set. As a result of this measure, the content of chlorine-oxygen acid in the partial stream was reduced to 2 g / l.
- the chlorine gas formed was passed via line 21 to line 20.
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)
- Electroluminescent Light Sources (AREA)
- Developing Agents For Electrophotography (AREA)
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 |
---|---|---|---|
DE19782837313 DE2837313A1 (de) | 1978-08-26 | 1978-08-26 | Verfahren zur elektrolyse waessriger alkalihalogenid-loesungen |
DE2837313 | 1978-08-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0008470A1 EP0008470A1 (de) | 1980-03-05 |
EP0008470B1 true EP0008470B1 (de) | 1982-05-05 |
Family
ID=6047970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79200382A Expired EP0008470B1 (de) | 1978-08-26 | 1979-08-20 | Verfahren zur Elektrolyse wässriger Alkalihalogenid-Lösungen |
Country Status (12)
Country | Link |
---|---|
US (1) | US4247375A (es) |
EP (1) | EP0008470B1 (es) |
JP (1) | JPS5531199A (es) |
AT (1) | ATE978T1 (es) |
BR (1) | BR7905453A (es) |
CA (1) | CA1158196A (es) |
DE (2) | DE2837313A1 (es) |
ES (1) | ES483640A1 (es) |
FI (1) | FI63260C (es) |
MX (1) | MX152740A (es) |
NO (1) | NO151973C (es) |
ZA (1) | ZA793571B (es) |
Families Citing this family (6)
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 |
US4391680A (en) * | 1981-12-03 | 1983-07-05 | Allied Corporation | Preparing alkali metal hydroxide by water splitting and hydrolysis |
DE3216418A1 (de) * | 1982-05-03 | 1983-11-03 | Bayer Ag, 5090 Leverkusen | Verfahren zur elektrolytischen herstellung von chlor und natronlauge aus sulfathaltigem salz |
US4481088A (en) * | 1982-07-06 | 1984-11-06 | Olin Corporation | Removal of chlorate from electrolyte cell brine |
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 |
JP3115440B2 (ja) * | 1992-12-10 | 2000-12-04 | ペルメレック電極株式会社 | 塩化アルカリ水溶液の電解方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL136394C (es) * | 1965-11-29 | 1900-01-01 | ||
US3438879A (en) * | 1967-07-31 | 1969-04-15 | Hooker Chemical Corp | Protection of permselective diaphragm during electrolysis |
US3616328A (en) * | 1968-09-23 | 1971-10-26 | Hooker Chemical Corp | Catholyte recirculation in diaphragm chlor-alkali cells |
DE1803638A1 (de) * | 1968-10-17 | 1970-05-27 | Bayer Ag | Verfahren zur Herstellung von Chlor und Natronlauge |
BE795460A (fr) * | 1972-02-16 | 1973-08-16 | Diamond Shamrock Corp | Perfectionnements relatifs a des cuves electrolytiques |
US4040919A (en) * | 1974-10-29 | 1977-08-09 | Hooker Chemicals & Plastics Corporation | Voltage reduction of membrane cell for the electrolysis of brine |
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 |
-
1978
- 1978-08-26 DE DE19782837313 patent/DE2837313A1/de not_active Withdrawn
-
1979
- 1979-07-16 ZA ZA00793571A patent/ZA793571B/xx unknown
- 1979-07-30 US US06/062,270 patent/US4247375A/en not_active Expired - Lifetime
- 1979-08-02 MX MX178756A patent/MX152740A/es unknown
- 1979-08-08 FI FI792470A patent/FI63260C/fi not_active IP Right Cessation
- 1979-08-20 DE DE7979200382T patent/DE2962706D1/de not_active Expired
- 1979-08-20 EP EP79200382A patent/EP0008470B1/de not_active Expired
- 1979-08-20 AT AT79200382T patent/ATE978T1/de active
- 1979-08-22 CA CA000334282A patent/CA1158196A/en not_active Expired
- 1979-08-22 NO NO792723A patent/NO151973C/no unknown
- 1979-08-24 BR BR7905453A patent/BR7905453A/pt unknown
- 1979-08-25 ES ES483640A patent/ES483640A1/es not_active Expired
- 1979-08-27 JP JP10899579A patent/JPS5531199A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
ATE978T1 (de) | 1982-05-15 |
ES483640A1 (es) | 1980-04-16 |
FI792470A (fi) | 1980-02-27 |
NO792723L (no) | 1980-02-27 |
JPS5531199A (en) | 1980-03-05 |
CA1158196A (en) | 1983-12-06 |
US4247375A (en) | 1981-01-27 |
JPS636635B2 (es) | 1988-02-10 |
NO151973B (no) | 1985-04-01 |
DE2962706D1 (en) | 1982-06-24 |
FI63260B (fi) | 1983-01-31 |
NO151973C (no) | 1985-07-31 |
MX152740A (es) | 1985-11-01 |
EP0008470A1 (de) | 1980-03-05 |
FI63260C (fi) | 1983-05-10 |
DE2837313A1 (de) | 1980-03-13 |
ZA793571B (en) | 1980-07-30 |
BR7905453A (pt) | 1980-05-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3118795C2 (de) | Verfahren und Vorrichtung zur kontinuierlichen Herstellung von Chlordioxid durch Elektrolyse | |
DE2419690C3 (de) | Verfahren zur Entfernung von Dichromaten aus bei der Elektrolyse anfallenden, mit Chloraten angereicherten Alkalimetallchlorat-Alkalimetallchloridlösungen | |
DE2547101A1 (de) | Verfahren zur gewinnung der saeure aus ihrer metallsalzloesung und hierfuer geeignete elektrolysezelle | |
DE3013538A1 (de) | Chloralkali-elektrolysezelle | |
DE1140907B (de) | Verfahren zur Gewinnung von Chlor aus Soleloesungen | |
DE3001614A1 (de) | Verfahren zum elektrolytischen zersetzen von chlorwasserstoffsaeure in einer elektrolysiervorrichtung | |
EP0008470B1 (de) | Verfahren zur Elektrolyse wässriger Alkalihalogenid-Lösungen | |
DE69312655T2 (de) | Verfahren zur Elektrolyse einer wässrigen Lösung von Alkalichlorid | |
DE10138215A1 (de) | Verfahren zur elektrochemischen Herstellung von Chlor aus wässrigen Lösungen von Chlorwasserstoff | |
DE10106932A1 (de) | Verfahren zur Herstellung von Natriumpersulfat | |
DD298004A5 (de) | Verfahren zur herstellung von alkalidichromaten und chromsaeuren durch elektrolyse | |
DE2843479B2 (de) | Verfahren zur Elektrolyse von Natriumchlorid in einer eine Ionenaustauschermembran enthaltenden Zelle | |
DE2432416A1 (de) | Verfahren zur gewinnung von elektrolytisch hergestellten alkalichloraten | |
EP0011326A1 (de) | Verfahren zur Herstellung von Chlordioxid und gegebenenfalls Chlor aus Chlorwasserstoff und elektrolytisch gewonnenem Alkalichlorat | |
DE2948343C2 (es) | ||
DE2124045C3 (de) | Verfahren zur elektrolytischen Her stellung von reinem Chlor, Wasserstoff und reinen konzentrierten Alkaliphosphat lösungen und Elektrolyslerzelle zur Durch führung des Verfahrens | |
DE69410142T2 (de) | Verfahren zur Chlor-Alkali Elektrolyse mit Diaphragma und Zelle dazu | |
EP1167579B1 (de) | Chloralkalielektrolyse-Verfahren in Membranzellen unter Elektrolyse von ungereinigtem Siedesalz | |
DD262679A5 (de) | Verfahren zur entfernung von chrom-vi-ionen aus waessrigen loesungen | |
DE3875382T2 (de) | Elektrochemisches verfahren. | |
WO2009144019A1 (de) | Verfahren zur herstellung eines hypohalogenithaltigen biozids | |
DE2419857A1 (de) | Verfahren zur elektrolyse von alkalimetallchloriden | |
DE3729669A1 (de) | Verfahren zur herstellung von alkalimetallnitraten | |
EP3114087B1 (de) | Verfahren und vorrichtung zur herstellung wässriger chlordioxidlösungen | |
DE2434921B2 (de) | Elektrolysezelle und Verfahren zur Elektrolyse ionisierbarer chemischer Verbindungen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
17P | Request for examination filed | ||
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
REF | Corresponds to: |
Ref document number: 978 Country of ref document: AT Date of ref document: 19820515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 2962706 Country of ref document: DE Date of ref document: 19820624 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19820820 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19820831 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: UHDE GMBH Effective date: 19830204 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19830505 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19830531 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19830613 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19830630 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19830831 Year of fee payment: 5 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 19831103 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19840914 Year of fee payment: 6 |
|
BERE | Be: lapsed |
Owner name: METALL-G. A.G. Effective date: 19840820 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state | ||
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 79200382.4 Effective date: 19850612 |