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WO2004050550A1 - Procede de production de dioxyde de chlore - Google Patents

Procede de production de dioxyde de chlore Download PDF

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Publication number
WO2004050550A1
WO2004050550A1 PCT/FI2003/000928 FI0300928W WO2004050550A1 WO 2004050550 A1 WO2004050550 A1 WO 2004050550A1 FI 0300928 W FI0300928 W FI 0300928W WO 2004050550 A1 WO2004050550 A1 WO 2004050550A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
sulfur dioxide
chlorate
alcohol
methanol
Prior art date
Application number
PCT/FI2003/000928
Other languages
English (en)
Inventor
Ilkka Renvall
Original Assignee
Kemira Oyj
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kemira Oyj filed Critical Kemira Oyj
Priority to AU2003283468A priority Critical patent/AU2003283468A1/en
Publication of WO2004050550A1 publication Critical patent/WO2004050550A1/fr

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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)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/025—Preparation from chlorites or chlorates from chlorates without any other reaction reducing agent than chloride ions
    • 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

Definitions

  • the present invention relates to a process for the production of chlorine dioxide by reducing chlorate ions under acidic conditions with sulfur dioxide and another compound as reducing agents.
  • Chlorine dioxide is used in considerable amounts for the bleaching of pulp. It is the main delignifying and bleaching chemical when treating chemical pulp in the environmently friendly ECF (Elemental Chlorine Free) bleaching process. Chlorine dioxide also has other important application areas, e.g. the treatment of waste waters.
  • the HCIO 3 is fed to generator as sodium chlorate and the acid that is required to provide hydrogen ions is sulphuric acid.
  • chloride ions are also lost in the process, e.g. as escaped hydrogen chloride and chlorine, it is generated by an overreduction of chlorate:
  • FI 20000867 has reduced sodium chlorate uncompletely by sulfur dioxide in a first reactor, after which the reduction was completed with hydrogen peroxide in a second reactor.
  • FI 20021413 has reduced the chlorate by means of sulfur dioxide in the presence small amounts of formic acid or a salt thereof.
  • the sulfur dioxide and the -C 3 alcohol are used simultaneously or after one another to reduce the chlorate ions, it brings synergy to the process.
  • the -C 3 alcohol itself acts as a reducing agent in the chlorine dioxide process. This is illustrated by the commercial Solvay process, in which the reduction takes place with methanol according to the following formula (5):
  • Reactions (2), (3) and (4) are also valid for a Solvay process, but sulphuric acid is not generated in the reaction (4) when sulphur dioxide is substituted by methanol. The total reaction is very slow, which results in a low yield of chlorine dioxide calculated on the feed of sodium chlorate.
  • the generated formaldehyde could also be reduced further to formic acid and ultimately to carbon dioxide. According to Owen (ibid. p. 173) the methanol is used as an excess of 8%. This contradicts that formaldehyde could further act as reducing agent.
  • the C1-C 3 alcohol acts as an effective solvent for the sulfur dioxide.
  • the content of sulfur dioxide in methanol is 31.3% by weight at 26°C and as much as 71.1% by weight at 0°C.
  • the saturation point of ethanol is 25% by weight.
  • the C 1 -C 3 alcohol absorbs the gas.
  • the inconveniences of gas handling can be avoided altogether.
  • a solution of sulfur dioxide and C1-C 3 alcohol does not have the dangerous properties of pure sulfur dioxide, which is normally transported as liquefied gas.
  • the claimed invention has been described as an improvement of the Mathieson process.
  • the reason is, that it mainly solves the problem caused by using sulfur dioxide.
  • methanol is preferably used as the C 1 -C 3 alcohol
  • the invention can also be seen as an improvement of the Solvay process.
  • sulfur dioxide with methanol in the Solvay process, the yield can be improved considerably.
  • the total amount of reductants can be reduced compared with the Mathieson and Solvay processes.
  • the C 1 -C 3 alcohol used as the second reducing agent is preferably methanol or ethanol, most preferably methanol.
  • the sulfur dioxide and the C1-C 3 alcohol can be used in the form of a mixture in one step or several subsequent steps, separately in several subsequent steps, or parallel as a mixture in some steps and separately in other steps.
  • a process involving only one step can be used, in which sulfur dioxide and C1-C 3 alcohol are present as a mixture.
  • the mixing can also be carried out before or immediately before contacting the reducing agents with the chlorate ions.
  • the sulfur dioxide and the C 1 -C 3 alcohol are used in the form of a solution.
  • the C1-C 3 alcohol not only absorbs gaseous sulfur dioxide, but also keps it in solution, thus facilitating the process radically. It is especially advantageous if the C1-C 3 alcohol solution is saturated with the sulfur dioxide at the ambient temperature. Thus, the concentration of sulfur dioxide in the solution is limited by its solubility in the - C 3 alcohol.
  • a solution of methanol is from 5 to 70% by weight. More preferably the S0 2 concentration is from 20 to 70% by weight, most preferably from 25 to 40% by weight.
  • the chlorate ion may originate from any source producing such ions under the reduction conditions of the claimed process.
  • the source may be chloric acid HC10 3 generated e.g. electrochemically.
  • it is an alkali metal chlorate or an alkaline earth metal chlorate and, most preferably, it is sodium chlorate, NaC10 3 , or a mixture thereof with chloric acid.
  • Sodium chlorate is typically obtained by electrolysis of an aqueous sodium chloride solution.
  • the total amount of reduction agents can be lower than in the Mathieson and Solvay processes.
  • Their stoichiometric exess in the invention is typically at most 10 mol-%, preferably at most 5 mol-%, most preferably at most 0 mol-%, and their stoichiometric deficit is typically at most 20 mol-%), based on the molar amount at chlorate (NaC10 3 ). Still, the unreacted chlorate is kept in the first vessel at an acceptable level.
  • the reduction is typically carried out in an aqueous medium containing the chlorate ions.
  • concentration of the chlorate ion source in the aqueous medium is typically between 10 and 80%o by weight, preferably between 20 and 70% by weight, calculated as sodium chlorate. With other chlorate sources, equimolar amounts are used.
  • the acid conditions may be brought about via acidic chloric acid, but they are preferably accomplished with a mineral acid, most preferably sulphuric and/or hydrochloric acid.
  • the acidity of the mineral acid is typically between 100 and 650 g/1, preferably between 400 and 500 g/1.
  • the other reaction parameters can be optimized normally.
  • the temperature is from about 30°C to about 100°C.
  • the pressure is usually atmospheric or nearly atmospheric.
  • the process according to the invention may be a batch process, but is typically a continuous process. It may be carried out in one or several, preferably in one or two reactors, whereby the sulfur dioxide and the methanol may be distributed between the reactors in any of the above-disclosed ways.
  • the first reactor contains sulfur dioxide and methanol and the second reactor contains a third reducing agent, preferably hydrogen peroxide.
  • Example 1 (a reference example 1)
  • the acidity was about 470 g/1.
  • the chlorate content after the first reaction vessel was 20.5 resp. 20.4 g/1.
  • the yields obtained were 75.0 and 77.4% calculated from the sodium chlorate feed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de dioxyde de chlore, par réduction d'ions chlorate, dans des conditions acides, au moyen de dioxyde de soufre et d'un agent de coréduction. Cet agent de coréduction se présente sous la forme de méthanol.
PCT/FI2003/000928 2002-12-05 2003-12-04 Procede de production de dioxyde de chlore WO2004050550A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003283468A AU2003283468A1 (en) 2002-12-05 2003-12-04 Process for the production of chlorine dioxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20022156A FI115903B (fi) 2002-12-05 2002-12-05 Menetelmä klooridioksidin valmistamiseksi
FI20022156 2002-12-05

Publications (1)

Publication Number Publication Date
WO2004050550A1 true WO2004050550A1 (fr) 2004-06-17

Family

ID=8565045

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2003/000928 WO2004050550A1 (fr) 2002-12-05 2003-12-04 Procede de production de dioxyde de chlore

Country Status (3)

Country Link
AU (1) AU2003283468A1 (fr)
FI (1) FI115903B (fr)
WO (1) WO2004050550A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010096300A3 (fr) * 2009-02-19 2010-12-02 Basf Catalysts Llc Compositions non aqueuses pour production de dioxyde de chlore, et procédés s'y rapportant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933988A (en) * 1966-10-24 1976-01-20 Hooker Chemicals & Plastics Corporation Method of simultaneously producing chlorine dioxide and a sulfate salt
US4929434A (en) * 1989-03-09 1990-05-29 Lobley Derek G Catalytic generation of chlorine dioxide
WO1998013295A1 (fr) * 1996-09-27 1998-04-02 International Paper Company Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs
WO1998013296A1 (fr) * 1996-09-27 1998-04-02 International Paper Company Procede de production de dioxyde de chlore au moyen de methanol, chlorure et peroxyde d'hydrogene comme agents reducteurs
WO2001077012A1 (fr) * 2000-04-12 2001-10-18 Kemira Chemicals Oy Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933988A (en) * 1966-10-24 1976-01-20 Hooker Chemicals & Plastics Corporation Method of simultaneously producing chlorine dioxide and a sulfate salt
US4929434A (en) * 1989-03-09 1990-05-29 Lobley Derek G Catalytic generation of chlorine dioxide
WO1998013295A1 (fr) * 1996-09-27 1998-04-02 International Paper Company Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs
WO1998013296A1 (fr) * 1996-09-27 1998-04-02 International Paper Company Procede de production de dioxyde de chlore au moyen de methanol, chlorure et peroxyde d'hydrogene comme agents reducteurs
WO2001077012A1 (fr) * 2000-04-12 2001-10-18 Kemira Chemicals Oy Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010096300A3 (fr) * 2009-02-19 2010-12-02 Basf Catalysts Llc Compositions non aqueuses pour production de dioxyde de chlore, et procédés s'y rapportant

Also Published As

Publication number Publication date
FI20022156A0 (fi) 2002-12-05
FI115903B (fi) 2005-08-15
FI20022156A7 (fi) 2004-06-06
AU2003283468A1 (en) 2004-06-23

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