US2717237A - Production of chlorine dioxide - Google Patents

Production of chlorine dioxide Download PDF

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Publication number
US2717237A
US2717237A US295551A US29555152A US2717237A US 2717237 A US2717237 A US 2717237A US 295551 A US295551 A US 295551A US 29555152 A US29555152 A US 29555152A US 2717237 A US2717237 A US 2717237A
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chlorite
chlorine dioxide
chlorine
production
electrolysis
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US295551A
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Erika G Rempel
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Bayer AG
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Bayer AG
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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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof

Definitions

  • This invention relates to an electrolytic process for the production of chlorine dioxide substantially free from chlorine.
  • Chlorine dioxide is produced by a number of different processes, one of which is the electrolysis of an aqueous solution of a chlorite in the presence of a chloride.
  • This process is subject to certain disadvantages when used for large scale production since, if the chlorite is fed to the electrolytic process in insufiicient quantities, or if the feed of chlorite is unexpectedly interrupted, there is a danger of the chlorite present in the electrolytic cell being exhausted so that chlorine is developed instead of chlorine dioxide. If the electrolysis takes this course, it may be disadvantageous or even hurtful for certain fields of applications, since chlorine dioxide is very often used to treat substances which are not stable. to chlorine.
  • the present invention provides a process for the production of substantially chlorine-free chlorine dioxide by electrolysis of an aqueous solution of a chlorite, such as sodium chlorite, wherein the electrolysis is carried out in the presence of a water-soluble sulfate.
  • a chlorite such as sodium chlorite
  • the process of the invention has the advantage that substantially chlorine-free chlorine dioxide is produced while the electrolysis proceeds normally, and that if the feed of chlorite solution decreases or even stops, the evolution of chlorine dioxide simultaneously also de creases or stops, without any quantity of chlorine being evolved as the electrolysis proceeds.
  • the process of the invention may be carried out in an electrolytic cell consisting substantially of a platinum 2,717,237 Patented Sept. 6, 1955 anode, a diaphragm and a lead cathode.
  • the heat evolved in the anode compartment is preferably dissipated by a cooling device.
  • the chlorine dioxide, developed in the anode compartment during electrolysis, is expelled and diluted by a controlled quantity of an inert gas, for instance air, which is introduced at the bottom of the anode by means of a distributor device.
  • a feed solution containing controlled amounts of a chlorite and a sulfate is continuously introduced into the anode compartment by means of an automatic contrivance, while an appropriate quantity of caustic soda solution is discharged from the cathode compartment through an overflow.
  • the desired concentration of chlorine dioxide is varied and adjusted by regulating the air supply within a predetermined range.
  • Example 1 The anode compartment of an electrolytic cell is charged and subsequently fed at a rate of 25 ccs. per hour, with a solution containing per litre 200 grams of NaClOz and grams of NazSO4. A current of 1.251.4 amperes at a voltage of 6.15-6.25 volts is passed through the cell, and the air flow is 25 litres per hour. In this way a gas with a chlorine dioxide content of between 3.2 and 4.1 per cent by volume is obtained. The amount of chlorine dioxide thus formed is about 2.3-3 grams per hour. The content of C12, is between 0.04 and 0.09 per cent by volume.
  • said chlorite is an alkali metal chlorite and said sulfate is an alkali metal sulfate.

Description

United States Patent PRODUCTION OF CHLORINE DIGXIDE Nikolaus Rempel, deceased, late of Leve'rkusen-Bayerwerk, Germany, by Erika G. Rempel, administratrix, Leverkusen-Bayerwerk, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Application June 25, 1952, Serial No. 295,551
4 Claims. (Cl. 204--101) This invention relates to an electrolytic process for the production of chlorine dioxide substantially free from chlorine.
Chlorine dioxide is produced by a number of different processes, one of which is the electrolysis of an aqueous solution of a chlorite in the presence of a chloride. This process is subject to certain disadvantages when used for large scale production since, if the chlorite is fed to the electrolytic process in insufiicient quantities, or if the feed of chlorite is unexpectedly interrupted, there is a danger of the chlorite present in the electrolytic cell being exhausted so that chlorine is developed instead of chlorine dioxide. If the electrolysis takes this course, it may be disadvantageous or even hurtful for certain fields of applications, since chlorine dioxide is very often used to treat substances which are not stable. to chlorine.
It has now been found that practically chlorine-free chlorine-dioxide is obtained by electrolysis of an aqueous solution of a chlorite, such as an alkali metal chlorite, for instance, sodium chlorite, by carrying out the electrolysis in the presence of a water-soluble sulfate, such as an alkali metal sulfate.
Accordingly, the present invention provides a process for the production of substantially chlorine-free chlorine dioxide by electrolysis of an aqueous solution of a chlorite, such as sodium chlorite, wherein the electrolysis is carried out in the presence of a water-soluble sulfate.
The process of the invention has the advantage that substantially chlorine-free chlorine dioxide is produced while the electrolysis proceeds normally, and that if the feed of chlorite solution decreases or even stops, the evolution of chlorine dioxide simultaneously also de creases or stops, without any quantity of chlorine being evolved as the electrolysis proceeds.
The process of the invention may be carried out in an electrolytic cell consisting substantially of a platinum 2,717,237 Patented Sept. 6, 1955 anode, a diaphragm and a lead cathode. The heat evolved in the anode compartment is preferably dissipated by a cooling device. The chlorine dioxide, developed in the anode compartment during electrolysis, is expelled and diluted by a controlled quantity of an inert gas, for instance air, which is introduced at the bottom of the anode by means of a distributor device. A feed solution containing controlled amounts of a chlorite and a sulfate is continuously introduced into the anode compartment by means of an automatic contrivance, while an appropriate quantity of caustic soda solution is discharged from the cathode compartment through an overflow. The desired concentration of chlorine dioxide is varied and adjusted by regulating the air supply within a predetermined range.
The invention is further illustrated by the following example:
Example The anode compartment of an electrolytic cell is charged and subsequently fed at a rate of 25 ccs. per hour, with a solution containing per litre 200 grams of NaClOz and grams of NazSO4. A current of 1.251.4 amperes at a voltage of 6.15-6.25 volts is passed through the cell, and the air flow is 25 litres per hour. In this way a gas with a chlorine dioxide content of between 3.2 and 4.1 per cent by volume is obtained. The amount of chlorine dioxide thus formed is about 2.3-3 grams per hour. The content of C12, is between 0.04 and 0.09 per cent by volume.
What is claimed is:
1. In the process for the production of substantially chlorine-free chlorine dioxide by electrolysis of a chlorite, the improvement which comprises electrolyzing an aqueous solution of a chlorite in the presence of a water-soluble metal sulfate.
2. Improvement according to claim 1, in which said chlorite is an alkali metal chlorite and said sulfate is an alkali metal sulfate.
3. Improvement according to claim 2, in which said alkali metal chlorite is sodium chlorite and in which said alkali metal sulfate is sodium sulfate.
4. In the process for the production of substantially chlorine-free chlorine dioxide by electrolysis of a chlorite, the improvement which comprises electrolyzing an aqueous solution consisting essentially of 200 grams of sodium chlorite per liter in the presence of 80 grams of sodium sulfate per liter.
References Cited in the file of this patent UNITED STATES PATENTS 2,163,793 Logan June 27, 1939

Claims (1)

1. IN THE PROCESS FOR THE PRODUCTION OF SUBSTANTIALLY CHLORINE-FREE CHLORINE DIOXIDE BY ELECTROLYSIS OF A CHLORITE, THE IMPROVEMENT WHICH COMPRISES ELECTROLYZING AN QUEOUS SOLUTION OF A CHLORITE IN THE PRESENCE OF A WATER-SOLUBLE METAL SULFATE.
US295551A 1952-06-25 1952-06-25 Production of chlorine dioxide Expired - Lifetime US2717237A (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3109789A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Preparation of phosphine
DE3118795A1 (en) * 1980-05-13 1982-03-11 The Japan Carlit Co., Ltd., Tokyo "METHOD AND DEVICE FOR PRODUCING CHLORDIOXIDE"
US4426263A (en) 1981-04-23 1984-01-17 Diamond Shamrock Corporation Method and electrocatalyst for making chlorine dioxide
US4731169A (en) * 1986-10-29 1988-03-15 Tenneco Canada Inc. Selective removal of chlorine from solutions of chlorine dioxide and chlorine
US5041196A (en) * 1989-12-26 1991-08-20 Olin Corporation Electrochemical method for producing chlorine dioxide solutions
US5084149A (en) * 1989-12-26 1992-01-28 Olin Corporation Electrolytic process for producing chlorine dioxide
US5089095A (en) * 1990-03-30 1992-02-18 Olin Corporation Electrochemical process for producing chlorine dioxide from chloric acid
US5092970A (en) * 1989-12-20 1992-03-03 Olin Corporation Electrochemical process for producing chlorine dioxide solutions from chlorites
US5106465A (en) * 1989-12-20 1992-04-21 Olin Corporation Electrochemical process for producing chlorine dioxide solutions from chlorites
US5108560A (en) * 1990-03-30 1992-04-28 Olin Corporation Electrochemical process for production of chloric acid from hypochlorous acid
US5158658A (en) * 1990-10-31 1992-10-27 Olin Corporation Electrochemical chlorine dioxide generator
US5167777A (en) * 1990-10-30 1992-12-01 Olin Corporation Process and apparatus for the removal of oxyhalide species from aqueous solutions
US5294319A (en) * 1989-12-26 1994-03-15 Olin Corporation High surface area electrode structures for electrochemical processes
US5965004A (en) * 1996-03-13 1999-10-12 Sterling Pulp Chemicals, Ltd. Chlorine dioxide generation for water treatment
US6203688B1 (en) 1997-10-17 2001-03-20 Sterling Pulp Chemicals, Ltd. Electrolytic process for producing chlorine dioxide
US6274009B1 (en) 1999-09-03 2001-08-14 International Dioxide Inc. Generator for generating chlorine dioxide under vacuum eduction in a single pass
US6306281B1 (en) 1999-11-30 2001-10-23 Joseph Matthew Kelley Electrolytic process for the generation of stable solutions of chlorine dioxide
US20030082095A1 (en) * 2001-10-22 2003-05-01 Halox Technologies, Inc. Electrolytic process and apparatus
US20040071627A1 (en) * 2002-09-30 2004-04-15 Halox Technologies, Inc. System and process for producing halogen oxides
US6740223B2 (en) 2001-06-22 2004-05-25 Superior Plus Inc. Electrolytic process for the production of chlorine dioxide
US20050034997A1 (en) * 2003-08-12 2005-02-17 Halox Technologies, Inc. Electrolytic process for generating chlorine dioxide
US20050163700A1 (en) * 2002-09-30 2005-07-28 Dimascio Felice System and process for producing halogen oxides
WO2011086579A1 (en) 2010-01-18 2011-07-21 Prophylaxis Process for producing stable and pure liquid form of chlorine dioxide
US10046990B2 (en) 2011-06-06 2018-08-14 Ecolab Usa Inc. Electrolytic method of generating chloride dioxide with improved theoretical yield
US10814358B2 (en) 2017-02-09 2020-10-27 Karcher North America, Inc. Floor cleaning device with disinfection capabilities
ES2887610A1 (en) * 2020-06-22 2021-12-23 Cecotec Res And Development SELF-MOVING CLEANING APPARATUS WITH SURFACE DISINFECTION MEANS (Machine-translation by Google Translate, not legally binding)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2163793A (en) * 1937-06-08 1939-06-27 Mathieson Alkall Works Inc Production of chlorine dioxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2163793A (en) * 1937-06-08 1939-06-27 Mathieson Alkall Works Inc Production of chlorine dioxide

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3109789A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Preparation of phosphine
DE3118795A1 (en) * 1980-05-13 1982-03-11 The Japan Carlit Co., Ltd., Tokyo "METHOD AND DEVICE FOR PRODUCING CHLORDIOXIDE"
US4426263A (en) 1981-04-23 1984-01-17 Diamond Shamrock Corporation Method and electrocatalyst for making chlorine dioxide
US4731169A (en) * 1986-10-29 1988-03-15 Tenneco Canada Inc. Selective removal of chlorine from solutions of chlorine dioxide and chlorine
US5092970A (en) * 1989-12-20 1992-03-03 Olin Corporation Electrochemical process for producing chlorine dioxide solutions from chlorites
US5106465A (en) * 1989-12-20 1992-04-21 Olin Corporation Electrochemical process for producing chlorine dioxide solutions from chlorites
US5041196A (en) * 1989-12-26 1991-08-20 Olin Corporation Electrochemical method for producing chlorine dioxide solutions
US5084149A (en) * 1989-12-26 1992-01-28 Olin Corporation Electrolytic process for producing chlorine dioxide
US5294319A (en) * 1989-12-26 1994-03-15 Olin Corporation High surface area electrode structures for electrochemical processes
US5298280A (en) * 1989-12-26 1994-03-29 Olin Corporation Process for producing an electrode by electroless deposition
US5089095A (en) * 1990-03-30 1992-02-18 Olin Corporation Electrochemical process for producing chlorine dioxide from chloric acid
US5108560A (en) * 1990-03-30 1992-04-28 Olin Corporation Electrochemical process for production of chloric acid from hypochlorous acid
US5167777A (en) * 1990-10-30 1992-12-01 Olin Corporation Process and apparatus for the removal of oxyhalide species from aqueous solutions
US5158658A (en) * 1990-10-31 1992-10-27 Olin Corporation Electrochemical chlorine dioxide generator
US5965004A (en) * 1996-03-13 1999-10-12 Sterling Pulp Chemicals, Ltd. Chlorine dioxide generation for water treatment
US6203688B1 (en) 1997-10-17 2001-03-20 Sterling Pulp Chemicals, Ltd. Electrolytic process for producing chlorine dioxide
US6274009B1 (en) 1999-09-03 2001-08-14 International Dioxide Inc. Generator for generating chlorine dioxide under vacuum eduction in a single pass
US6881320B1 (en) 1999-09-03 2005-04-19 International Dioxide, Inc. Generator for generating chlorine dioxide under vacuum eduction in a single pass
US6306281B1 (en) 1999-11-30 2001-10-23 Joseph Matthew Kelley Electrolytic process for the generation of stable solutions of chlorine dioxide
US6740223B2 (en) 2001-06-22 2004-05-25 Superior Plus Inc. Electrolytic process for the production of chlorine dioxide
US6869517B2 (en) 2001-10-22 2005-03-22 Halox Technologies, Inc. Electrolytic process and apparatus
US20030082095A1 (en) * 2001-10-22 2003-05-01 Halox Technologies, Inc. Electrolytic process and apparatus
US20040071627A1 (en) * 2002-09-30 2004-04-15 Halox Technologies, Inc. System and process for producing halogen oxides
US6913741B2 (en) 2002-09-30 2005-07-05 Halox Technologies, Inc. System and process for producing halogen oxides
US20050163700A1 (en) * 2002-09-30 2005-07-28 Dimascio Felice System and process for producing halogen oxides
US7241435B2 (en) 2002-09-30 2007-07-10 Halox Technologies, Inc. System and process for producing halogen oxides
US20050034997A1 (en) * 2003-08-12 2005-02-17 Halox Technologies, Inc. Electrolytic process for generating chlorine dioxide
US7179363B2 (en) 2003-08-12 2007-02-20 Halox Technologies, Inc. Electrolytic process for generating chlorine dioxide
WO2011086579A1 (en) 2010-01-18 2011-07-21 Prophylaxis Process for producing stable and pure liquid form of chlorine dioxide
US10046990B2 (en) 2011-06-06 2018-08-14 Ecolab Usa Inc. Electrolytic method of generating chloride dioxide with improved theoretical yield
US10814358B2 (en) 2017-02-09 2020-10-27 Karcher North America, Inc. Floor cleaning device with disinfection capabilities
ES2887610A1 (en) * 2020-06-22 2021-12-23 Cecotec Res And Development SELF-MOVING CLEANING APPARATUS WITH SURFACE DISINFECTION MEANS (Machine-translation by Google Translate, not legally binding)

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