EP1339636A1 - Method for generating chlorine dioxide - Google Patents
Method for generating chlorine dioxideInfo
- Publication number
- EP1339636A1 EP1339636A1 EP01980620A EP01980620A EP1339636A1 EP 1339636 A1 EP1339636 A1 EP 1339636A1 EP 01980620 A EP01980620 A EP 01980620A EP 01980620 A EP01980620 A EP 01980620A EP 1339636 A1 EP1339636 A1 EP 1339636A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- chlorine dioxide
- ams
- chlorite
- solution
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
Definitions
- the invention relates to chlorine dioxide and more particularly relates to its preparation from chlorites with a view to its use in all applications of disinfection, cleaning and oxidation of pollutants.
- chlorine dioxide Due to its oxidizing and biocidal properties, chlorine dioxide is widely used for the treatment of drinking water, water from cooling circuits and water from equipment in contact with foodstuffs. It is also used for the washing treatment of gaseous effluents (elimination of odors and VOCs), for the disinfection of storage and transport facilities for drinking water, as well as for the elimination of pollutants (dyes , sulfides, mercaptans, etc.) in industrial waters or, in the petroleum sector, for desulfurization.
- chlorine dioxide is a toxic gas, difficult to handle, non-storable at high concentration and explosive in mixture with air, it is generally prepared at the time of its use in dilute solution.
- the most used consists of reacting an acid with a chlorite, in particular sodium chlorite.
- the most commonly used acid is hydrochloric acid because it leads to a very high chlorine dioxide yield. Indeed, for an HCl / NaCIO 2 molar ratio of 2.2, the yield of chlorine dioxide following the reaction:
- hydrochloric acid provides a considerable amount of chlorides which cause corrosion of the installations (cooling circuits, pipes, exchangers, etc.).
- AMS considerably reduces the amount of chlorides present in the chlorine dioxide solution compared to hydrochloric acid.
- AMS has other advantages, including the following:
- AMS can be directly substituted for hydrochloric acid without changing the generator. Indeed, AMS is available in a 70% aqueous solution and is easier to handle (non-volatile, odorless, stable).
- AMS is easily biodegradable (100% in 28 days), non-viscous and does not evaporate.
- AMS is approved for cleaning equipment in contact with foodstuffs. 4. Unlike chlorite and hydrochloric acid, there is no possible confusion between AMS and sodium chlorite because the names of the products are very different. This is important from a security point of view.
- the subject of the invention is therefore a process for generating chlorine dioxide by reaction of a chlorite with an acid, characterized in that the acid used is an alkanesulfonic acid, linear or branched, containing from 1 to 12 carbon atoms , or a mixture of such acids.
- alkanesulfonic acids can be mentioned, ethanesulfonic, propanesulfonic, butanesulfonic and octranesulfonic acids.
- the chlorite used to generate the chlorine dioxide is preferably sodium chlorite, but it would not be departing from the scope of the present invention to use any chlorite provided that the counterion of the chlorite is not an activator decomposition of chlorine dioxide.
- such chlorites include ammonium chlorite, potassium chlorite and calcium chlorite.
- the reaction for generating chlorine dioxide is generally carried out in an aqueous medium at chlorine dioxide concentrations of 0.001 to 10%, preferably between 0.1 and 3%.
- the acid / chlorite molar ratio can range from 0.1 to 50, but is preferably between 1 and 10.
- the temperature and the reaction pressure are not critical parameters and can vary within wide limits.
- the temperature is generally between 3 and 120 ° C, preferably between 15 and 40 ° C.
- the pressure can range from 1 to 20 bars, but it is preferable to work at atmospheric pressure or at a pressure of up to 7 bars.
- reaction time can range from 1 minute to 8 hours. It is preferably between 10 and 50 minutes.
- the invention aims to completely replace hydrochloric acid, it would not be departing from the scope of the present invention to use a mixture of alkanesulfonic acid with up to 10% hydrochloric acid or another acid.
- the mixture was diluted with moderately mineralized city water (pH 7.7) at a flow rate of 10 l / h.
- the amount of NaCIO 2 used was 962 mg / l and, based on equation (2), should lead to a theoretical production of CIO 2 equal to 573 mg / l.
- the concentration of CIO 2 in the solution obtained after dilution with tap water being 495 mg / l, the generator yield was 86%.
- Example 1 was repeated, but replacing the aqueous AMS solution at 264 g / l with an aqueous HCl solution at 102 g / l or by an aqueous AMS solution at 537 g / l.
- the contact time in the reactor being 15 minutes and the flow rate of each reagent being 174 ml / h, a total flow rate of 19.46 l / h was obtained after dilution with city water.
- the CIO 2 solutions generated in this example were stored in transparent glass vials, placed in daylight. The concentration of CIO 2 was monitored over 15 days in order to evaluate the decomposition of the solution.
- the acid concentration of the other solutions was chosen so as to have an acid / NaClO 2 molar ratio equal to 2.2.
- Example 1 was reproduced, but by varying the flow rate of the reactants and therefore the residence time in the reactor.
- Bacti-Count T samplers which are representative of total germs and allow a count between 10 3 and 10 7 bacteria per milliliter. A blank was previously made to know the concentration of bacteria in the water leaving the treatment plant.
- Chlorine dioxide solutions were prepared in situ by directly mixing aqueous solutions of AMS and sodium chlorite.
- the plates were then immersed for 24 hours, at 60 ° C. and with stirring by magnetic bar, in one liter of a solution of 0.103 mol / 1 of acid in demineralized water, this solution being placed in a reactor topped a refrigerant.
- the aluminum wafers were treated as described in 8.1.
- the XC18 steel plates were treated as follows: degreasing with trichlorethylene, polishing with 400 and 600 paper, rinsing and drying with compressed air. After testing, the XC18 steel plates were immersed in a 10% HCl solution with a few drops of corrosion inhibitor (Norust CM 150 from CECA), then rubbed with a rubberized tip to remove rust, rinsed with water and dried with compressed air.
- corrosion inhibitor Norust CM 150 from CECA
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0015678 | 2000-12-04 | ||
FR0015678A FR2817545B1 (en) | 2000-12-04 | 2000-12-04 | PROCESS FOR GENERATING CHLORINE DIOXIDE |
PCT/FR2001/003271 WO2002046095A1 (en) | 2000-12-04 | 2001-10-22 | Method for generating chlorine dioxide |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1339636A1 true EP1339636A1 (en) | 2003-09-03 |
Family
ID=8857199
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01980620A Withdrawn EP1339636A1 (en) | 2000-12-04 | 2001-10-22 | Method for generating chlorine dioxide |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040033190A1 (en) |
EP (1) | EP1339636A1 (en) |
JP (1) | JP2004515435A (en) |
CA (1) | CA2430633A1 (en) |
FR (1) | FR2817545B1 (en) |
WO (1) | WO2002046095A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8668779B2 (en) * | 2002-04-30 | 2014-03-11 | Nalco Company | Method of simultaneously cleaning and disinfecting industrial water systems |
US7252096B2 (en) * | 2003-04-08 | 2007-08-07 | Nalco Company | Methods of simultaneously cleaning and disinfecting industrial water systems |
JP2017530936A (en) * | 2014-07-01 | 2017-10-19 | アドヴァ・バー−オンAdva BAR−ON | System and method for releasing chlorine dioxide |
CA2995761C (en) * | 2015-08-17 | 2020-06-16 | Baker Hughes, A Ge Company, Llc | In-situ generation of chlorine dioxide using methanesulfonic acid for remediation of scale and sulfide |
FR3070694B1 (en) | 2017-09-01 | 2020-07-03 | Arkema France | METAL CORROSION INHIBITORS |
WO2020090539A1 (en) * | 2018-10-29 | 2020-05-07 | 大幸薬品株式会社 | Chlorine dioxide generator |
DE102019117728B4 (en) | 2019-07-01 | 2021-11-25 | Prominent Gmbh | Method and device for generating chlorine dioxide |
WO2021002262A1 (en) * | 2019-07-02 | 2021-01-07 | 大幸薬品株式会社 | Chlorine dioxide generation device and chlorine dioxide generation method |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US651996A (en) * | 1899-09-20 | 1900-06-19 | Sarah Octavia Hubbard | Iron-rest. |
IT1036712B (en) * | 1975-07-16 | 1979-10-30 | Conforto Gaetano | PROCEDURE AND EQUIPMENT FOR THE PRODUCTION OF CHLORINE DIOXIDE BY MEANS OF A SOLUTION OF SODIUM CHLORITE AND ACID CYCLE RESIN |
US4084747A (en) * | 1976-03-26 | 1978-04-18 | Howard Alliger | Germ killing composition and method |
US4891216A (en) * | 1987-04-14 | 1990-01-02 | Alcide Corporation | Disinfecting compositions and methods therefor |
JPH02104509A (en) * | 1988-10-12 | 1990-04-17 | Daicel Chem Ind Ltd | Aqueous bactericidal composition |
CN1023205C (en) * | 1989-06-23 | 1993-12-22 | 栾和林 | Prepartion method of chlorine dioxide and controlling box |
US4981216A (en) * | 1990-01-31 | 1991-01-01 | Sonoco Products Co. | Easy opening bag pack and supporting rack system and fabricating method |
US5407656A (en) * | 1992-03-04 | 1995-04-18 | Arco Research Co., Inc. | Method and compositions for the production of chlorine dioxide |
US5380518A (en) * | 1992-03-04 | 1995-01-10 | Arco Research Co., Inc. | Method for the production of chlorine dioxide |
US6046243A (en) * | 1993-02-12 | 2000-04-04 | Bernard Technologies, Inc. | Compositions for sustained release of a gas |
US6749869B1 (en) * | 1997-09-26 | 2004-06-15 | Ecolab | Acidic aqueous chlorite teat dip providing shelf life, sanitizing capacity and tissue protection |
-
2000
- 2000-12-04 FR FR0015678A patent/FR2817545B1/en not_active Expired - Fee Related
-
2001
- 2001-10-22 CA CA002430633A patent/CA2430633A1/en not_active Abandoned
- 2001-10-22 WO PCT/FR2001/003271 patent/WO2002046095A1/en not_active Application Discontinuation
- 2001-10-22 JP JP2002547839A patent/JP2004515435A/en not_active Withdrawn
- 2001-10-22 EP EP01980620A patent/EP1339636A1/en not_active Withdrawn
- 2001-10-22 US US10/432,993 patent/US20040033190A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO0246095A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20040033190A1 (en) | 2004-02-19 |
JP2004515435A (en) | 2004-05-27 |
FR2817545B1 (en) | 2003-01-03 |
FR2817545A1 (en) | 2002-06-07 |
CA2430633A1 (en) | 2002-06-13 |
WO2002046095A1 (en) | 2002-06-13 |
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Legal Events
Date | Code | Title | Description |
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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 |
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17P | Request for examination filed |
Effective date: 20030519 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: SUTY, HERVE Inventor name: MEKARBANE, PIERRE |
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GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
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RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ARKEMA |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20040811 |