CA2796113A1 - Methods for making chlorous acid and chlorine dioxide - Google Patents

Methods for making chlorous acid and chlorine dioxide Download PDF

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Publication number
CA2796113A1
CA2796113A1 CA2796113A CA2796113A CA2796113A1 CA 2796113 A1 CA2796113 A1 CA 2796113A1 CA 2796113 A CA2796113 A CA 2796113A CA 2796113 A CA2796113 A CA 2796113A CA 2796113 A1 CA2796113 A1 CA 2796113A1
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CA
Canada
Prior art keywords
chlorous acid
acid
chlorine dioxide
exchange material
catalytic material
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CA2796113A
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French (fr)
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CA2796113C (en
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Richard Sampson
Allison Sampson
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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)
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/02—Processes using inorganic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/02—Processes using inorganic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • 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
    • 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
    • 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)
    • C01B11/028—Separation; Purification
    • 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
    • C01B11/08—Chlorous acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins

Abstract

Chlorous acid is generated from a chlorite salt precursor, a chlorate salt precursor, or a combination of both by ion exchange. The ion exchange material facilitates the generation of chlorous acid by simultaneously removing unwanted cations from solution and adding hydrogen ion to solution. Chlorine dioxide is generated in a controlled manner from chlorous acid by catalysis. Chlorine dioxide can be generated either subsequent to the generation of chlorous acid or simultaneously with the generation of chlorous acid. For catalysis of chlorous acid to chlorine dioxide, the chlorous acid may be generated by ion exchange or in a conventional manner. Ion exchange materials are also used to purify the chlorous acid and chlorine dioxide solutions, without causing degradation of said solutions, to exchange undesirable ions in the chlorous acid and chlorine dioxide solutions with desirable ions, such as stabilizing ions, and to adjust the pH of chlorous acid and chlorine dioxide solutions.

Claims (42)

1. A process for generating chlorous acid and chlorine dioxide which comprises contacting a chlorite salt precursor with a cation exchange material in the hydrogen form and a catalytic material in a moist environment for a time sufficient to form chlorous acid and chlorine dioxide together.
2. The process as claimed in claim 1, wherein said catalytic material is on said cation exchange material.
3. The process as claimed in claim 1, wherein said catalytic material is an ion exchange material.
4. A process for generating chlorous acid and chlorine dioxide which comprises contacting a chlorite salt precursor and an acid with a catalytic material in a moist environment for a time sufficient to form chlorous acid and chlorine dioxide together.
5. The process as claimed in claim 4, wherein said catalytic material is on said cation exchange material.
6. The process as claimed in claim 4, wherein said catalytic material is an ion exchange material.
7. A process for generating chlorous acid which comprises contacting an acid with an anion exchange material in the chlorite form in a moist environment for a time sufficient to form chlorous acid.
8. The process as claimed in claim 7, wherein said anion exchange material is mixed with an additive.
9. A process for generating chlorous acid and chlorine dioxide which comprises contacting an acid with an anion exchange material in the chlorite form and a catalytic material in a moist environment for a time sufficient to form chlorous acid and chlorine dioxide together.
10. The process as claimed in claim 9, wherein said catalytic material is on said anion exchange material.
11. A process as claimed in claim 9, wherein said catalytic material is an ion exchange material.
12. A process for generating unstable chlorous acid which comprises: contacting a chlorite salt precursor or chlorate salt precursor with a cation exchange material in the hydrogen form, or contacting a chlorate salt precursor and an acid with an anion exchange material in a reducing ionic form, or contacting an acid with an anion exchange material in a chlorite or chlorate form, in a moist environment for a time sufficient to form unstable chlorous acid.
13. The process as claimed in claim 12, further comprising contacting said unstable chlorous acid with a substantially insoluble catalytic material in a moist environment for a time sufficient to form chlorine dioxide.
14. The process as claimed in claim 12, wherein said cation exchange material is mixed with an additive.
15. The process as claimed in claim 12, wherein either of said anion exchange materials is mixed with an additive.
16. The process as claimed in claim 12, wherein a chlorite ion is first exchanged onto said anion exchange material.
17. The process as claimed in claim 13, wherein said chlorous acid and chlorine dioxide are generated together in a single step.
18. The process as claimed in claim 13 or claim 17, wherein said catalytic material is exchanged onto said cation exchange material.
19. The process as claimed in claim 13 or claim 17, wherein said catalytic material is an ion exchange material.
20. A process for generating chlorous acid and chlorine dioxide which comprises contacting a chlorate salt precursor or a chlorite salt precursor and a cation exchange material in the hydrogen form, or a chlorate salt precursor, an acid and an anion exchange material in a reducing ionic form, or an acid and an anion exchange material in the chlorate form or chlorite form, with a catalytic material in a moist environment for a time sufficient to form chlorous acid and chlorine dioxide together.
21. The process as claimed in claim 20, wherein said catalytic material is on said cation exchange material.
22. The process as claimed in claim 20, wherein said catalytic material is on said anion exchange material.
23. A process as claimed in claim 20, wherein said catalytic material is an ion exchange material.
24. The process as claimed in claim 20, wherein said catalytic material is an ion exchange material in a reducing ionic form.
25. The process as claimed in claim 20, wherein said acid is a reducing agent.
26. The process as claimed in claim 20, wherein said acid is mixed with a reducing agent.
27. The process as claimed in claim 12, wherein said chlorous acid is in a solution having a pH less than 4Ø
28. The process as claimed in claim 12, wherein said chlorous acid is in a solution having a pH less than 2.4.
29. The process as claimed in claim 12, wherein said chlorous acid is present in solution in an amount less than 2,000 mg/liter.
30. The process as claimed in claim 12, wherein said chlorous acid is present in solution in an amount less than 832 mg/liter.
31. A process for generating chlorine dioxide, the process comprising:

feeding a dilute aqueous chlorite salt solution into a cation exchange column, wherein the cation exchange column contains a strong cation exchange material;

contacting the dilute aqueous chlorite salt solution with the strong cation exchange material to produce an effluent containing chlorous acid; and feeding the effluent chlorous acid into contact with a platinum catalyst in a moist environment for a time sufficient to produce chlorine dioxide.
32. A process for generating chlorine dioxide which comprises contacting chlorous acid with a catalytic material in a moist environment for a time sufficient to form chlorine dioxide.
33. The process according to claim 32, wherein the catalytic material is selected from the group consisting of platinum, palladium, manganese dioxide, and carbon.
34. The process according to claim 33, wherein the catalytic material is platinum.
35. The process according to claim 33, wherein the catalytic material is palladium.
36. The process according to claim 33, wherein the catalytic material is manganese dioxide.
37. The process according to claim 33, wherein the catalytic material is carbon.
38. The process according to claim 33, wherein the catalytic material is deposited on a substrate.
39. The process according to claim 38, wherein the substrate is a zeolite.
40. The process according to claim 38, wherein the substrate is an inorganic cation resin.
41. The process according to claim 38, wherein the substrate is acid-washed carbon particles.
42. The process according to claim 38, wherein the substrate is an anion exchange material.
CA2796113A 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide Expired - Lifetime CA2796113C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/919,918 2001-08-02
US09/919,918 US7087208B2 (en) 2001-08-02 2001-08-02 Methods for making chlorous acid and chlorine dioxide
CA2456028A CA2456028C (en) 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA2456028A Division CA2456028C (en) 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide

Publications (2)

Publication Number Publication Date
CA2796113A1 true CA2796113A1 (en) 2003-02-13
CA2796113C CA2796113C (en) 2015-06-16

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CA2796113A Expired - Lifetime CA2796113C (en) 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide
CA2456028A Expired - Lifetime CA2456028C (en) 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide

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CA2456028A Expired - Lifetime CA2456028C (en) 2001-08-02 2002-07-29 Methods for making chlorous acid and chlorine dioxide

Country Status (16)

Country Link
US (5) US7087208B2 (en)
EP (2) EP1414741A2 (en)
JP (1) JP2004536761A (en)
KR (2) KR20040039276A (en)
CN (4) CN101844746A (en)
AU (1) AU2002322737B2 (en)
BR (1) BRPI0211872B8 (en)
CA (2) CA2796113C (en)
ES (1) ES2679768T3 (en)
IL (2) IL160153A0 (en)
IN (1) IN2012DN01085A (en)
MX (1) MXPA04001020A (en)
NO (1) NO20040894L (en)
NZ (1) NZ531419A (en)
WO (1) WO2003011750A2 (en)
ZA (1) ZA200401086B (en)

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KR20040039276A (en) 2004-05-10
US7087208B2 (en) 2006-08-08
CA2456028A1 (en) 2003-02-13
WO2003011750A2 (en) 2003-02-13
IL160153A0 (en) 2004-07-25
ZA200401086B (en) 2005-11-30
CN1549791A (en) 2004-11-24
WO2003011750A3 (en) 2003-10-02
EP2263973B1 (en) 2018-05-30
IL160153A (en) 2007-07-24
ES2679768T3 (en) 2018-08-30
US7824556B2 (en) 2010-11-02
MXPA04001020A (en) 2005-06-06
NO20040894L (en) 2004-03-01
CN101844746A (en) 2010-09-29
US20060034749A1 (en) 2006-02-16
KR20090114484A (en) 2009-11-03
BR0211872A (en) 2004-09-21
US20140234201A1 (en) 2014-08-21
US20060171875A1 (en) 2006-08-03
CN101348238A (en) 2009-01-21
BRPI0211872B8 (en) 2016-05-31
EP1414741A2 (en) 2004-05-06
CA2456028C (en) 2012-11-27
CN101348239B (en) 2011-10-05
AU2002322737B2 (en) 2007-11-01
EP2263973A1 (en) 2010-12-22
US10894715B2 (en) 2021-01-19
CA2796113C (en) 2015-06-16
IN2012DN01085A (en) 2015-04-10
US20030064018A1 (en) 2003-04-03
JP2004536761A (en) 2004-12-09
US20050196337A1 (en) 2005-09-08
BR0211872B1 (en) 2014-01-07
NZ531419A (en) 2005-12-23
CN101348239A (en) 2009-01-21

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