EP0293151B1 - Electrolytic production of chlorine dioxide - Google Patents
Electrolytic production of chlorine dioxide Download PDFInfo
- Publication number
- EP0293151B1 EP0293151B1 EP88304644A EP88304644A EP0293151B1 EP 0293151 B1 EP0293151 B1 EP 0293151B1 EP 88304644 A EP88304644 A EP 88304644A EP 88304644 A EP88304644 A EP 88304644A EP 0293151 B1 EP0293151 B1 EP 0293151B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chlorine dioxide
- concentration
- chlorate
- acid solution
- aqueous acid
- 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
Links
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims description 155
- 235000019398 chlorine dioxide Nutrition 0.000 title claims description 81
- 239000004155 Chlorine dioxide Substances 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 38
- -1 chlorate ions Chemical class 0.000 claims description 29
- 239000011260 aqueous acid Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000011262 electrochemically active material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 229910001919 chlorite Inorganic materials 0.000 description 8
- 229910052619 chlorite group Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 235000019647 acidic taste Nutrition 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- 229940005989 chlorate ion Drugs 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VTNHQTZHOLOTIS-UHFFFAOYSA-L [Ra+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O Chemical compound [Ra+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O VTNHQTZHOLOTIS-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- VSQHTVCBHFZBOT-UHFFFAOYSA-M cesium;chlorate Chemical compound [Cs+].[O-]Cl(=O)=O VSQHTVCBHFZBOT-UHFFFAOYSA-M 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 1
- 229940005993 chlorite ion Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000001832 dioxo-lambda(5)-chloranyloxy group Chemical group *OCl(=O)=O 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000621 oxo-lambda(3)-chloranyloxy group Chemical group *OCl=O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- GZXRGRLACABJNC-UHFFFAOYSA-M rubidium(1+);chlorate Chemical compound [Rb+].[O-]Cl(=O)=O GZXRGRLACABJNC-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FRTABACCYANHFP-UHFFFAOYSA-L strontium chlorate Chemical compound [Sr+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O FRTABACCYANHFP-UHFFFAOYSA-L 0.000 description 1
- 230000002277 temperature effect Effects 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Definitions
- the present invention relates to the production of chlorine dioxide by the electrolysis of highly acidic sodium chlorate solutions.
- Chlorine dioxide is used as a bleach in a variety of environments, notably in the bleaching of wood pulp.
- Various chemical processes for the generation of chlorine dioxide by reduction of sodium chlorate in aqueous acid media have been described in the past and are in commercial operation.
- the chemical process may be depicted by the equation (I): 2ClO3 ⁇ + 2Cl ⁇ + 4H+ ⁇ 2ClO2 + Cl2 + 2H2O
- platinum metal oxide catalyst appears to enhance the rate of chemical conversion of chlorate ion to chlorine dioxide, its electrocatalytic properties have a detrimental effect on the electrochemical stability of the desired product, namely chlorine dioxide, when practical current densities are applied to electrodes having a surface of such platinum metal oxides.
- the Hardee article also states that the platinum group metal oxides are the only materials which show activity for the reduction of chlorate and data is presented showing the alleged ineffectiveness of platinum.
- an electrochemical process for the production of chlorine dioxide which is based on an autocatalytic cycle utilizing part of the product, namely chlorine dioxide, for generation of the next portion of the same product.
- this result is achieved by (a) using a cathode constructed of an electrochemically-active material which is also chemically inert and does not catalyse the chemical formation of chlorine dioxide from the aqueous chlorate solution, in the absence of any electric current therethrough, and (b) maintaining a dissolved concentration in the range of about 0.01 to about 15 grams per litre, of chlorine dioxide in the aqueous acid solution throughout the process.
- the mechanism of generation of chlorine dioxide by the electrochemical process of the invention is believed to involve chemical reaction between chlorate ions and electrolytically-produced short-lived chlorite ions to form chlorine dioxide. Part of the chemically-produced chlorine dioxide is electrochemically reduced to form the chlorite ions, while the remainder is removed from the solution as product.
- the electrochemical process of the invention produces the same amount of chlorine dioxide while half the amount of water is produced and half the amount of acid is consumed, as compared to the chemical process.
- the chlorine dioxide which is produced in the process of the invention generally is substantially pure since the reactions involved do not produce chlorine.
- the cathode which is used in the process of the invention may be constructed of any convenient electro-conductive material which is chemically inert (i.e. has no catalytic properties) to the chemical production of chlorine dioxide by reduction of chlorate ions in the acid aqueous reaction medium, in contrast to the materials described in U.S. Patent Nos. 4,426,263 and 4,362,707 referred to above.
- Suitable cathode materials include the platinum group metals and, preferably in view of its cheapness and ease of use, carbon in any form, for example, graphite and vitreous carbon.
- the use of a carbon cathode also is advantageous, since it stabilizes the intermediate state, that is, the chlorite ions, against further electroreduction to a lower valency state, such as ClO ⁇ or Cl ⁇ .
- the chlorine dioxide which is produced electrochemically in this invention generally is obtained free from chlorine, since chlorine is not produced by the reactions depicted by the equations given above. Chlorine generation is possible only if chloride ions are present in the reaction medium.
- the electrochemical process of the invention may be carried out under a wide range of process conditions.
- Essential to the present invention is the provision of an aqueous acid electrolyte solution containing dissolved chlorate ions and having a total acidity greater than that of about 7 normal sulphuric acid. At acidities corresponding to below about 7 normal sulphuric acid, the production of pure chlorine dioxide is not possible.
- the acidity may be provided most conveniently by sulphuric acid although any other strong mineral acid, other than hydrochloric acid, or a mixture of acids, may be employed, such as perchloric acid (HClO4), or nitric acid (HNO3).
- sulphuric acid any other strong mineral acid, other than hydrochloric acid, or a mixture of acids, may be employed, such as perchloric acid (HClO4), or nitric acid (HNO3).
- Hydrochloric acid is avoided, since the introduction of chloride ions would produce the undesired side chemical reaction with chlorate ions to produce chlorine dioxide and chlorine.
- An acid aqueous chlorate solution having a total acidity corresponding to that of about 9 to about 11 normal sulphuric acid is preferred.
- the chlorate ions in the electrolyte are provided preferably by sodium chlorate, since this chemical is the most readily-available form of chlorate.
- alkali metal chlorates such as potassium chlorate, lithium chlorate, rubidium chlorate and cesium chlorate may be used, as well as alkaline earth metal chlorates, such as beryllium chlorate, magnesium chlorate, calcium chlorate, strontium chlorate, barium chlorate and radium chlorate, and mixtures of two or more of such chlorates.
- concentration of chlorate ions in the electrolyte may vary widely from about 0.001 to about 7 molar, preferably about 0.1 to about 2 molar.
- Chlorine dioxide generation ceases if all the produced chlorine dioxide is removed.
- some dissolved chlorine dioxide is necessary at start up.
- a concentration of dissolved chlorine dioxide in the range of about 0.01 to about 15 grams per litre (gpl) may be employed, preferably about 0.1 to about 8 gpl, at the initial startup and during the reaction.
- the concentration of chlorate ion in the electrolyte should be in substantial excess to the concentration of dissolved chlorine dioxide, generally a molar excess of at least about 2:1, preferably at least about 10:1, usually up to about 1000:1.
- the concentration of dissolved chlorine dioxide is maintained at a substantially uniform level during the process by removing chlorine dioxide at the rate of its formation.
- Chlorine dioxide spontaneously decomposes at high partial pressures thereof and it is necessary to dilute the chlorine dioxide well below the decomposition partial pressure, usually below about 100 mmHg (about 1.3 x 104 Nm ⁇ 2).
- Any convenient diluent gas usually air, may be used to trip the generated chlorine dioxide from the electrolytic cell and to provide the required dilution.
- Chlorine dioxide may be recovered from the off-gas stream by dissolution in water.
- the electrical potential applied to the cathode during the electrochemical reaction depends on the material of construction of the electrode and usually varies from about +1.0 to about -0.5 Volts as compared with a saturated calomel electrode (SCE).
- SCE saturated calomel electrode
- the preferred potential is approximately +0.4 Volts while for a platinum electrode, the preferred potential is approximately +0.7 Volts.
- the process usually is operated under constant voltage conditions while the current also preferably is constant.
- the temperature of operation of the cell affects the purity of the chlorine dioxide gas which is obtained. Higher temperatures favour the formation of chloride ions by decomposition of chlorite ions, as described above, in accordance with the equation: 5ClO2 ⁇ + 4H+ ⁇ 4ClO2 + Cl ⁇ + 2H2O As discussed above, formation of chloride ions in this way results in the formation of chlorine, with the consequent loss of efficiency and chlorine dioxide purity. Accordingly, it is preferred to operate at temperatures below about 40°C, more preferably at ambient temperatures of about 20° to about 25°C.
- the process of the present invention may be carried out in any convenient cell arrangement in which anode and cathode electrodes are located and between which current may be passed.
- the cell may be divided physically into anolyte and catholyte chambers by any convenient cation-exchange membrane. With a divided cell arrangement, the aqueous acid chlorate solution is fed to the cathode compartment while water is fed to the anode compartment, the latter containing an electrolyte, such as an acid solution.
- the generation of chlorine dioxide by the process of the invention is accompanied by the formation of by-products.
- the anodic reaction in the cell produces gaseous oxygen, which may be vented in any convenient manner.
- the other by-products are water produced by the electrochemical reaction and a salt of the cation of the chlorate and the anion of the acid consumed in the process. These may be removed respectively by any convenient procedure, such as by evaporation and crystallization outside the cell.
- Chlorine dioxide is produced in pure form from an aqueous acid chlorate solution by passing a cathodic current through the solution from a cathode constructed of material chemically inert with respect to the formation of chlorine dioxide from the solution. Such a result is achieved by maintaining a dissolved concentration of chlorine dioxide in the solution.
- Electrolytic studies were carried out in a divided H-cell using reticulated vitreous carbon foam as the cathode material and platinum foil as the anode material.
- a potentiostatic mode of operation was adopted at a cathodic potential of +0.2 volt vs. Hg/Hg2SO4 as the reference electrode.
- the catholyte of volume approximately 100 ml contained about 10N H2SO4, about 1M NaClO3 and a variable initial dissolved ClO2 concentration.
- gaseous products, ClO2 and Cl2 were stripped to a potassium iodide (KI) trap by bubbling nitrogen and by applying a low level of vacuum. Both the nitrogen flow and the vacuum were adjusted to maintain a substantially constant level of electrolyte in the compartments and, at the same time, to maintain a substantially constant concentration of dissolved chlorine dioxide in the catholyte, so that the stripping rate of chlorine dioxide was approximately equal to the production rate of chlorine dioxide.
- KI potassium iodide
- the electrolyte was analyzed for ClO2, Cl2, ClO3 ⁇ , Cl ⁇ , ClO2 ⁇ and acidity both before and after electrolysis while the KI trap was analyzed and changed every 30 to 60 minutes.
- Chlorite ions postulated as short-lived intermediates in the autocatalytic process were not detected either in the catholyte and anolyte, before and after electrolysis.
- the present invention provides a novel method of producing chlorine dioxide by an autocatalytic cathodic electrochemical reduction of chlorate ions.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88304644T ATE74626T1 (de) | 1987-05-29 | 1988-05-23 | Elektrolytische herstellung von chlordioxid. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000538404A CA1287815C (en) | 1987-05-29 | 1987-05-29 | Electrolytic production of chlorine dioxide |
| CA538404 | 1987-05-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0293151A1 EP0293151A1 (en) | 1988-11-30 |
| EP0293151B1 true EP0293151B1 (en) | 1992-04-08 |
Family
ID=4135775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88304644A Expired - Lifetime EP0293151B1 (en) | 1987-05-29 | 1988-05-23 | Electrolytic production of chlorine dioxide |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0293151B1 (pt) |
| JP (1) | JPS6483680A (pt) |
| AR (1) | AR240068A1 (pt) |
| AT (1) | ATE74626T1 (pt) |
| AU (1) | AU593441B2 (pt) |
| BR (1) | BR8802568A (pt) |
| CA (1) | CA1287815C (pt) |
| DE (1) | DE3869831D1 (pt) |
| ES (1) | ES2032556T3 (pt) |
| FI (1) | FI87935C (pt) |
| NZ (1) | NZ224500A (pt) |
| PT (1) | PT87608B (pt) |
| RU (1) | RU1836492C (pt) |
| ZA (1) | ZA883187B (pt) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7048842B2 (en) | 2001-06-22 | 2006-05-23 | The Procter & Gamble Company | Electrolysis cell for generating chlorine dioxide |
| US8333873B2 (en) | 2001-06-22 | 2012-12-18 | Pur Water Purification Products, Inc. | Apparatus for electrolyzing an electrolytic solution |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1330964C (en) * | 1988-02-16 | 1994-07-26 | Marek Lipsztajn | Production of chlorine dioxide in an electrolytic cell |
| CA2023733C (en) * | 1990-08-21 | 1998-04-14 | Marek Lipsztajn | Chlorine dioxide generation from chloric acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904496A (en) * | 1974-01-02 | 1975-09-09 | Hooker Chemicals Plastics Corp | Electrolytic production of chlorine dioxide, chlorine, alkali metal hydroxide and hydrogen |
| US3884777A (en) * | 1974-01-02 | 1975-05-20 | Hooker Chemicals Plastics Corp | Electrolytic process for manufacturing chlorine dioxide, hydrogen peroxide, chlorine, alkali metal hydroxide and hydrogen |
| US4426263A (en) * | 1981-04-23 | 1984-01-17 | Diamond Shamrock Corporation | Method and electrocatalyst for making chlorine dioxide |
-
1987
- 1987-05-29 CA CA000538404A patent/CA1287815C/en not_active Expired - Lifetime
-
1988
- 1988-02-20 AR AR310909A patent/AR240068A1/es active
- 1988-05-04 ZA ZA883187A patent/ZA883187B/xx unknown
- 1988-05-05 NZ NZ224500A patent/NZ224500A/xx unknown
- 1988-05-09 AU AU15824/88A patent/AU593441B2/en not_active Expired
- 1988-05-23 EP EP88304644A patent/EP0293151B1/en not_active Expired - Lifetime
- 1988-05-23 ES ES198888304644T patent/ES2032556T3/es not_active Expired - Lifetime
- 1988-05-23 DE DE8888304644T patent/DE3869831D1/de not_active Expired - Lifetime
- 1988-05-23 AT AT88304644T patent/ATE74626T1/de not_active IP Right Cessation
- 1988-05-25 JP JP63126046A patent/JPS6483680A/ja active Granted
- 1988-05-26 FI FI882493A patent/FI87935C/fi not_active IP Right Cessation
- 1988-05-26 BR BR8802568A patent/BR8802568A/pt not_active IP Right Cessation
- 1988-05-27 RU SU884355812A patent/RU1836492C/ru active
- 1988-05-27 PT PT87608A patent/PT87608B/pt not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| z. Electroch. 13 (1907) 437 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7048842B2 (en) | 2001-06-22 | 2006-05-23 | The Procter & Gamble Company | Electrolysis cell for generating chlorine dioxide |
| US8333873B2 (en) | 2001-06-22 | 2012-12-18 | Pur Water Purification Products, Inc. | Apparatus for electrolyzing an electrolytic solution |
Also Published As
| Publication number | Publication date |
|---|---|
| FI87935C (fi) | 1993-03-10 |
| JPH0251993B2 (pt) | 1990-11-09 |
| PT87608A (pt) | 1988-06-01 |
| DE3869831D1 (de) | 1992-05-14 |
| NZ224500A (en) | 1989-10-27 |
| ES2032556T3 (es) | 1993-02-16 |
| JPS6483680A (en) | 1989-03-29 |
| AR240068A1 (es) | 1990-01-31 |
| BR8802568A (pt) | 1988-12-20 |
| FI87935B (fi) | 1992-11-30 |
| ATE74626T1 (de) | 1992-04-15 |
| RU1836492C (ru) | 1993-08-23 |
| EP0293151A1 (en) | 1988-11-30 |
| PT87608B (pt) | 1992-09-30 |
| FI882493A (fi) | 1988-11-30 |
| AU593441B2 (en) | 1990-02-08 |
| FI882493A0 (fi) | 1988-05-26 |
| ZA883187B (en) | 1989-03-29 |
| CA1287815C (en) | 1991-08-20 |
| AU1582488A (en) | 1988-12-01 |
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