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WO2001077012A1 - Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs - Google Patents

Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs Download PDF

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Publication number
WO2001077012A1
WO2001077012A1 PCT/FI2001/000368 FI0100368W WO0177012A1 WO 2001077012 A1 WO2001077012 A1 WO 2001077012A1 FI 0100368 W FI0100368 W FI 0100368W WO 0177012 A1 WO0177012 A1 WO 0177012A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
chlorine dioxide
reducing agent
chlorate
fed
Prior art date
Application number
PCT/FI2001/000368
Other languages
English (en)
Inventor
Ilkka Renvall
Anna Sundquist
Seppo Pohjanvesi
Jarmo Reunanen
Pentti ELLILÄ
Original Assignee
Kemira Chemicals Oy
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 Chemicals Oy filed Critical Kemira Chemicals Oy
Priority to AU2001256376A priority Critical patent/AU2001256376A1/en
Publication of WO2001077012A1 publication Critical patent/WO2001077012A1/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
    • 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
    • C01B11/026—Preparation from chlorites or chlorates from chlorate ions in the presence of a peroxidic compound, e.g. hydrogen peroxide, ozone, peroxysulfates

Definitions

  • the invention relates to a process for continuously producing chlorine dioxide from an alkali metal chlorate and sulfuric acid by using reducing agents at atmospheric or nearly atmospheric pressure.
  • the invention specifically makes existing chloride dioxide processes more efficient without significant investment.
  • the amount of waste acid may, however, in certain cases be so high that all of the waste acid cannot be exploited without disturbing the sulfur-sodium balance of the mill. In such a case the waste acid has to be directed, for example, to effluent and through this into watercourses.
  • the waste acid When methanol is used as the reducing agent, the waste acid also contains organic matter formed in the reaction, which in the said case increases the biologic (BOC) and chemical oxygen consumption (COC) of the mill effluents.
  • One known process for producing chlorine dioxide is the Mathieson process, wherein sulfur dioxide is used as the reducing agent in at least two reactors in series, operating at atmospheric or nearly atmospheric pressure.
  • reaction mediator is the chloride ion even if no chloride ions were added to the reaction system.
  • the stoichiometry of the process is described in a publication (Dennis Owen, Operation and Maintenance of Chlorine Dioxide Generators, TAPPI 1989 Bleach Plant Operations, p. 157) with the following reaction equation:
  • Chloric acid HC10 3 forms from sodium chlorate in acid conditions. The chlorine generated further reacts with the sulfur dioxide reducing agent to hydrochloric acid.
  • reaction medium does not have a sufficient quantity of chloride ions to maintain the reaction, and chloride ions must be formed from chlorate via so-called overreduction, whereby the efficiency of chlorine dioxide formation is lowered.
  • the reaction can be described as follows when sulfur dioxide is used:
  • sodium chloride is added in several chlorine dioxide processes at the time the reactor is being started.
  • the efficiency of the process can also be raised by using in the feed solution a few per cent of sodium chloride, calculated from the weight of the sodium chlorate fed in. If the amount of the chloride fed in exceeds by approximately 6 % by weight the amount of chlorate fed in, there is the risk that the final chlorine dioxide solution will also contain chlorine, which in present-day bleaching processes is no longer desirable.
  • the problem with a secondary reactor is that the primary reactor does not contain a sufficient quantity of chloride ions for performing the reaction. For this reason a portion of the chlorate has to be left unreacted or, if the reaction is carried out too far, chloride ions are formed by overreduction, which causes a drop in the efficiency. Overreduction is observable as an increase in the sulfuric acid concentration even if sulfuric acid is not separately added into the secondary reactor. Both cases lead to the situation that the efficiency ratio of chlorine dioxide production decreases and causes a difficult optimization and operating problem in the process, i.e. how much chlorate is it profitable to leave unreacted.
  • the process makes it possible to decrease the production in the first reactor by rendering the conditions milder, and to compensate for this decrease by more efficient production in the secondary reactor.
  • the production of chlorine dioxide can be increased and varied within a wide range while achieving a high, higher than previously, overall efficiency. Production can thus be increased by maintaining the production capacity of the first reactor unchanged and by gaining additional production through more efficient production in the second reactor.
  • the reaction can be carried out in favorable conditions in the first reactor, and the reaction of chlorate can be carried out efficiently to completion in the second reactor.
  • a process for continuous production of chlorine dioxide by feeding an alkali metal chlorate, sulfuric acid, and sulfur dioxide or methanol as the reducing agent into the first reactor and by allowing them to react therein at atmospheric or nearly atmospheric pressure, the temperature being 30 - 100 °C, from which reactor the gas mixture containing chlorine dioxide is directed via a scrubber to an absorption tower, where the chlorine dioxide is absorbed, and by directing the reaction solution containing unreacted alkali metal chlorate from the first reactor to the second reactor, into which hydrogen peroxide is fed as a reducing agent, from which second reactor the gas mixture containing chlorine dioxide is directed via the scrubber to the absorption tower.
  • a process for increasing the production capacity of an existing or known apparatus for continuous production of chlorine dioxide which apparatus has a first reactor into which an alkali metal chlorate, sulfuric acid, and sulfur dioxide or methanol as the reducing agent are fed at atmospheric or nearly atmospheric pressure, the temperature being 30-100 °C, and from which reactor the gas mixture containing chlorine dioxide is directed via a scrubber to an absorption tower, where the chlorine dioxide is absorbed, and a second reactor into which the unreacted reaction solution containing alkali metal chlorate from the first reactor and additionally hydrogen peroxide as a reducing agent are fed, and from which second reactor the gas mixture containing chlorine dioxide is directed via the scrubber to the absorption tower.
  • an inert gas such as air or nitrogen or a mixture of these, is fed into the first reactor and the second reactor, whereupon a gas mixture containing mainly chlorine dioxide and the inert gas leaves the first reactor, and a gas mixture likewise containing mainly chlorine dioxide and the inert gas leaves the second reactor.
  • the alkali metal chlorate fed into the first reactor is preferably sodium chlorate.
  • the only byproduct is oxygen, whereby the overall amount of detrimental byproducts is further decreased.
  • the process according to the invention can be carried out in all types of known continuous-working reaction apparatuses wherein atmospheric or nearly atmospheric pressure is used.
  • the reactors used in the Mathieson and Solvay processes are especially suitable.
  • the process is carried out in two reactor steps by using two reactors.
  • the process can also be implemented by using three reactors if there is a need for further increase of the capacity.
  • the third reactor it is preferable to use hydrogen peroxide as the reducing agent.
  • the second reactor is as large as or smaller than the first reactor.
  • air is used as the inert gas in the process according to the invention.
  • nitrogen or a mixture of nitrogen and air. It is especially safe to use nitrogen when the process is being started.
  • Carbon dioxide and process exit gases are also possible.
  • reactor 1 It is preferable to maintain in reactor 1 a chlorate concentration higher than 15 g/1.
  • concentration of sulfuric acid is preferably within a range of 100 -
  • the sulfur dioxide used for reduction is preferably added in an amount of
  • Example 1 The apparatus of Example 1 was altered so that the liquid level in the 1 st reactor was 3750 mm and in the 2 nd reactor 1500 mm.
  • 500 1/h (NTP) of nitrogen was fed into reactor 1 and 300 1/h (NTP) into reactor 2.
  • Sulfur dioxide in total 4.46 mol/h was fed as a reducing agent into both reactors so that 85 % was fed into reactor 1 and 15 % into reactor 2.

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)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé de production continue de dioxyde de chlore qui consiste à laisser réagir du chlorate de sodium, de l'acide sulfurique et un agent réducteur dans un réacteur (1) à une pression égale ou voisine de la pression atmosphérique, avec une alimentation continue dans le réacteur d'un gaz inerte et à une température comprise entre 30 et 100 °C. Le mélange gazeux sortant du réacteur (1), constitué principalement de dioxyde de chlore et de gaz inerte, est dirigé, via un laveur (3), vers une tour d'absorption (4) dans laquelle le dioxyde de chlore est absorbé. On alimente un réacteur (2) avec la solution de réaction contenant le chlorate de sodium qui n'a pas réagi, avec un agent réducteur et un gaz inerte. Le mélange gazeux sortant du réacteur (2), contenant principalement du dioxyde de chlore et du gaz inerte, est dirigé, via le laveur (3), vers la tour d'absorption (4). L'agent réducteur utilisé dans le réacteur (1) est constitué de dioxyde de soufre et de méthanol, et l'agent réducteur utilisé dans le réacteur (2) est du peroxyde d'hydrogène.
PCT/FI2001/000368 2000-04-12 2001-04-12 Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs WO2001077012A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001256376A AU2001256376A1 (en) 2000-04-12 2001-04-12 Process for producing chlorine dioxide by the combined use of different reducingagents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20000867A FI108536B (fi) 2000-04-12 2000-04-12 Menetelmä klooridioksidin valmistamiseksi eri pelkistimien yhteiskäytöllä
FI20000867 2000-04-12

Publications (1)

Publication Number Publication Date
WO2001077012A1 true WO2001077012A1 (fr) 2001-10-18

Family

ID=8558184

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2001/000368 WO2001077012A1 (fr) 2000-04-12 2001-04-12 Procede de production de dioxyde de chlore par l'utilisation combinee de differents agents reducteurs

Country Status (3)

Country Link
AU (1) AU2001256376A1 (fr)
FI (1) FI108536B (fr)
WO (1) WO2001077012A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004011369A1 (fr) * 2002-07-26 2004-02-05 Kemira Oyj Procede de preparation d'oxyde de chlore
WO2004050550A1 (fr) * 2002-12-05 2004-06-17 Kemira Oyj Procede de production de dioxyde de chlore
WO2006033609A1 (fr) * 2004-09-24 2006-03-30 Akzo Nobel N.V. Procede de production de dioxyde de chlore
RU2304558C2 (ru) * 2003-03-03 2007-08-20 Акцо Нобель Н.В. Способ получения диоксида хлора
WO2009010456A1 (fr) * 2007-07-13 2009-01-22 Akzo Nobel N.V. Procédé de fabrication de dioxyde de chlore
US10501345B2 (en) 2017-08-17 2019-12-10 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US11130677B2 (en) 2017-03-24 2021-09-28 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US11535541B2 (en) 2017-02-27 2022-12-27 Ecolab Usa Inc. Method for onsite production of chlorine dioxide
US11970393B2 (en) 2018-07-05 2024-04-30 Ecolab Usa Inc. Decomposition mediation in chlorine dioxide generation systems through sound detection and control

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005698A1 (fr) * 1988-11-24 1990-05-31 Eka Nobel Ab Procede pour la production de dioxyde de chlore
US5380517A (en) * 1993-02-26 1995-01-10 Eka Nobel Inc. Process for continuously producing chlorine dioxide
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005698A1 (fr) * 1988-11-24 1990-05-31 Eka Nobel Ab Procede pour la production de dioxyde de chlore
US5380517A (en) * 1993-02-26 1995-01-10 Eka Nobel Inc. Process for continuously producing chlorine dioxide
US5380517B1 (en) * 1993-02-26 1999-01-19 Eka Nobel Inc Process for continuously producing chlorine dioxide
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004011369A1 (fr) * 2002-07-26 2004-02-05 Kemira Oyj Procede de preparation d'oxyde de chlore
WO2004050550A1 (fr) * 2002-12-05 2004-06-17 Kemira Oyj Procede de production de dioxyde de chlore
RU2304558C2 (ru) * 2003-03-03 2007-08-20 Акцо Нобель Н.В. Способ получения диоксида хлора
KR100916974B1 (ko) * 2004-09-24 2009-09-14 악조 노벨 엔.브이. 이산화염소의 제조 방법
RU2355626C2 (ru) * 2004-09-24 2009-05-20 Акцо Нобель Н.В. Способ производства двуокиси хлора
WO2006033609A1 (fr) * 2004-09-24 2006-03-30 Akzo Nobel N.V. Procede de production de dioxyde de chlore
AU2005285645B2 (en) * 2004-09-24 2010-12-16 Akzo Nobel Chemicals International B.V. A process for the production of chlorine dioxide
WO2009010456A1 (fr) * 2007-07-13 2009-01-22 Akzo Nobel N.V. Procédé de fabrication de dioxyde de chlore
US8168153B2 (en) 2007-07-13 2012-05-01 Akzo Nobel N.V. Process for the production of chlorine dioxide
RU2477255C2 (ru) * 2007-07-13 2013-03-10 Акцо Нобель Н.В. Способ производства диоксида хлора
US11535541B2 (en) 2017-02-27 2022-12-27 Ecolab Usa Inc. Method for onsite production of chlorine dioxide
US11130677B2 (en) 2017-03-24 2021-09-28 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US10501345B2 (en) 2017-08-17 2019-12-10 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US11225421B2 (en) 2017-08-17 2022-01-18 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US11970393B2 (en) 2018-07-05 2024-04-30 Ecolab Usa Inc. Decomposition mediation in chlorine dioxide generation systems through sound detection and control

Also Published As

Publication number Publication date
AU2001256376A1 (en) 2001-10-23
FI108536B (fi) 2002-02-15
FI20000867A0 (fi) 2000-04-12
FI20000867L (fi) 2001-10-13

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