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WO1998013295A1 - Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs - Google Patents

Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs Download PDF

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Publication number
WO1998013295A1
WO1998013295A1 PCT/US1997/017758 US9717758W WO9813295A1 WO 1998013295 A1 WO1998013295 A1 WO 1998013295A1 US 9717758 W US9717758 W US 9717758W WO 9813295 A1 WO9813295 A1 WO 9813295A1
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WO
WIPO (PCT)
Prior art keywords
acid
reaction
hydrogen peroxide
reducing agents
chlorine dioxide
Prior art date
Application number
PCT/US1997/017758
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English (en)
Other versions
WO1998013295A9 (fr
Inventor
Arthur J. Nonni
Robert J. Graff
Raymond Liu
Jerry N. Voss
Timothy R. Hammond
George Y. Pan
Jean J. Renard
Original Assignee
International Paper Company
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 International Paper Company filed Critical International Paper Company
Priority to CA002267295A priority Critical patent/CA2267295A1/fr
Priority to AU47424/97A priority patent/AU4742497A/en
Publication of WO1998013295A1 publication Critical patent/WO1998013295A1/fr
Publication of WO1998013295A9 publication Critical patent/WO1998013295A9/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
    • C01B11/026—Preparation from chlorites or chlorates from chlorate ions in the presence of a peroxidic compound, e.g. hydrogen peroxide, ozone, peroxysulfates

Definitions

  • the present invention relates to a method for producing chlorine dioxide.
  • Chlorine dioxide is employed in a wide variety of industrial applications, including bleaching wood pulp for paper making, bleaching textiles, treating water, and abating odors.
  • the use of chlorine dioxide for bleaching wood pulp has increased because chlorine dioxide is more environmentally friendly than chlorine or hypochlorite, which can leave larger quantities of chlorinated organic compounds in bleaching effluent.
  • sodium chlorate is reacted with a reducing agent in a strongly acidic aqueous medium.
  • a metal chloride salt, sulfur dioxide, methanol, or hydrogen peroxide is commonly used as the reducing agent.
  • the typical acid used is sulfuric acid or hydrochloric acid, generally to obtain an acidity of between about 3 to 10 N for the reaction mixture.
  • the reduction of sodium chlorate with sodium chloride can be represented by the following formula:
  • a principle disadvantage of this process is the formation of half a mole of chlorine gas for each mole of chlorine dioxide produced. At one time this chlorine gas was used for bleaching pulp. This use, however, is now disfavored because of environmental concerns. Less chlorine gas is generated if sodium chloride is replaced by sulfur dioxide or methanol in this process.
  • the methanol based process is termed the Solvay process, while the sulfur dioxide process is termed the Mathieson process.
  • the reaction between chlorate and either sulfur dioxide or methanol is very slow, resulting in a low rate of chlorine dioxide generation. The following reactions occur initially, resulting in generation of chloride ion, which acts as a reducing agent:
  • the chloride ions reduce chlorates present in the reaction mixture according to formula (1) shown above, resulting in the production of chlorine gas.
  • the chlorine gas reacts with the sulfur dioxide or methanol to regenerate chloride ions according to the following formula:
  • Hydrogen peroxide has been used as a reducing agent in chlorine dioxide generation to eliminate production of chlorine. Using hydrogen peroxide also results in a significantly faster chlorine dioxide generation rate than other processes.
  • the reaction using hydrogen peroxide is represented by the following formula:
  • the present invention relates to a method for producing chlorine dioxide by reacting alkali metal chlorate with reducing agents in an aqueous acidic medium, wherein the reducing agents are methanol and hydrogen peroxide. It has been determined that combining hydrogen peroxide and methanol causes an unexpectedly strong enhancement in the rate of chlorine dioxide generation. BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 is a schematic representation of a continuous process embodiment of the invention.
  • Figure 2 is a graph showing chlorine dioxide generation using the process of the invention at atmospheric pressure, 60' C, and 12N H 2 SO 4 .
  • the points on the graph shown with a " D " indicate chlorine dioxide generation rates for combinations of methanol and hydrogen peroxide reducing agent in the equivalent strength ratios indicated.
  • the dotted line connecting the points for 100 mole% CH 3 OH and 100 mole% H 2 O 2 shows the expected chlorine dioxide generation rate for a combination of hydrogen peroxide and methanol reducing agents.
  • Figure 3 is a graph showing chlorine dioxide generation using the process of the invention at a sub-atmospheric pressure of 300 mm Hg, 60' C, and 10 N H 2 SO 4 .
  • the points on the graph shown with a " D " indicate the amount of chlorine dioxide generated for 100% methanol, combinations of methanol and hydrogen peroxide, and 100% hydrogen peroxide.
  • the dotted line shows the expected amount of chlorine dioxide generation for a combination of methanol and hydrogen peroxide reducing agents.
  • the point on the graph shown with a " + " indicates the amount of chlorine dioxide generated for a combination of sodium chloride, methanol, and hydrogen peroxide in a 10:80:10 equivalent strength molar ratio.
  • the invention results in surprising benefits at atmospheric pressure.
  • Preferred pressures are between about 400 and 900 mm Hg. It has been determined, however, that the benefits of the invention can also be enjoyed when the process is carried out at sub-atmospheric pressure, a preferred sub-atmospheric pressure being from about 100 mm Hg to 400 mm Hg.
  • a preferred sub-atmospheric pressure being from about 100 mm Hg to 400 mm Hg.
  • the method of the invention is preferably carried out as a continuous process.
  • sodium chlorate is reacted with hydrogen peroxide and methanol reducing agents in the presence of concentrated sulfuric acid.
  • the reactants can be introduced together, but preferably are introduced separately into a conventional reaction vessel.
  • the reaction can be carried out at atmospheric pressure, with air, or other inert gas such as nitrogen, circulating through the reaction vessel.
  • the reaction should be maintained substantially in a steady state by continuously feeding the reactants, and by ensuring that they are evenly distributed in the reaction medium.
  • the chlorine dioxide gas that is generated can be collected and absorbed outside of the reaction vessel. Water vapor and other gaseous byproducts should also be continuously removed from the reaction vessel, and vented to a chlorine dioxide absorber.
  • Reaction medium containing alkali metal salt Na 2 SO 4 in Figure 1
  • unreacted chlorate acid and reducing agents should also be continuously removed (e.g. , "H 2 SO 4 Effluent" in Figure 1).
  • Sodium acid sulfate deposited in the reaction at sub- atmospheric conditions can be removed and subjected to a metathesis reaction to form neutral sodium sulfate and acidic aqueous solution.
  • the reaction medium that is withdrawn from a reaction vessel running at atmospheric pressure is cascaded into a second reaction vessel operating at sub-atmospheric pressure, such as a "single vessel process" (SVPTM) reactor.
  • the withdrawn medium from a reaction vessel at atmospheric pressure contains largely sulfuric acid, with lesser amounts of chlorine dioxide, sodium chlorate, sodium sulfate, and hydrogen peroxide.
  • the withdrawn medium, new reducing agents, sodium chlorate, and sulfuric acid are preferably added separately to the second vessel, and the second vessel kept at a sub-atmospheric pressure of between 100 and 400 mm Hg, preferably between 100 and 300 mm Hg.
  • Chlorine dioxide gas is recovered outside of the first and second reaction vessels.
  • the only by-product generated in the second reactor can be a neutral metal salt, or acidic salt cake, depending on the acidity of the reaction medium.
  • catalysts that enhance the generation of chlorine dioxide are added to the reaction as well.
  • Such catalysts include, e.g., silver nitrate, manganese sulfate, vanadium pentoxide, ruthenium oxide, rhodium oxide, and palladium oxide.
  • the process is conducted in a temperature range of between about 20° C and about 140° C, preferably between about 35° C and 80° C, and most preferably between about 50° C and 75° C.
  • Suitable acids for use in the reaction include, e.g. , sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and chloric acid. Sulfuric acid is preferred.
  • the acid normality is maintained in the aqueous reaction medium between about 1 N to 15 N, preferably between about 4 N and 12 N. Most preferably, the normality is maintained at between about 7 N and 10 N for atmospheric conditions, and between about 4 N and 5 N or 7 N to 10 N for subatmospheric conditions. Performance of the process at 7 N to IO N generates acid salt cake while performance at 4 N to 5 N generates neutral saltcake.
  • Alkali metal chlorates that can be used in this process include, e.g., sodium chlorate and potassium chlorate. Sodium chlorate is preferred.
  • the alkali metal chlorate concentration employed in the reaction is between about 0.01 M and saturation concentration, preferably between about 0.01 M and 4 M. It is most preferably between about 0.05 M and 0.3 M at a pressure between about 400 and 900 mm Hg, and between about 0.3 M and 1.5 M at a pressure between about 100 and 400 mm Hg.
  • the optimum percentage of hydrogen peroxide with respect to the total amount of reducing agent used in the process, on an equivalent strength basis, depends on the chemical costs, chlorine dioxide demand, and byproduct demands.
  • the amount of total reducing agent consumed in the reaction is preferably from about 100% to 120% of the stoichiometrically calculated amount.
  • the method of the invention can be practiced by adding hydrogen peroxide to an existing chlorine dioxide generator that uses a methanol reducing agent.
  • the method can also be practiced by adding methanol to an existing generator that uses a hydrogen peroxide reducing agent.
  • hydrogen peroxide can be added to an existing generator that uses methanol reducing agent, or a combination of hydrogen peroxide and methanol can be added to an existing generator that uses sulfur dioxide reducing agent.
  • EXAMPLE 1 PARTIAL SUBSTITUTION OF METHANOL REDUCING AGENT WITH HYDROGEN PEROXIDE AT ATMOSPHERIC PRESSURE
  • Figure 2 shows the amount of chlorine dioxide (in grams) generated over 1.5 minutes when methanol was used alone, methanol was mixed with hydrogen peroxide in a 9: 1 equivalent strength ratio, methanol was mixed with hydrogen peroxide in a 7:3 equivalent strength ratio, and hydrogen peroxide was used alone.
  • the amount of chorine expected to have been generated is shown by the dotted line.
  • EXAMPLE 2 PARTIAL SUBSTITUTION OF METHANOL WITH HYDROGEN PEROXIDE AT SUB-ATMOSPHERIC PRESSURE
  • Example 3 The experiment described in Example 1 was carried out as described therein, except that the process was carried out at a sub-atmospheric pressure of 300 mm Hg and 490 grams/liter of sulfuric acid was used to obtain a reaction mixture having an acid normality of 10 N. The results of this experiment are shown in Figure 3. At a 9: 1 equivalent strength ratio of methanol: hydrogen peroxide, (i.e., a 10% equivalent strength of hydrogen peroxide) a chlorine dioxide rate of 7.6 x 10 '2 moles/(liter-minute) was obtained.
  • hydrogen peroxide i.e., a 10% equivalent strength of hydrogen peroxide

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  • 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

La présente invention concerne un procédé de production de dioxyde de chlore obtenu par réaction d'un chlorate de métal alcalin avec du méthanol et du peroxyde d'hydrogène en milieu aqueux acide. La combinaison de ces agents favorise de manière inattendue la génération de dioxyde de chlore.
PCT/US1997/017758 1996-09-27 1997-09-29 Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs WO1998013295A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002267295A CA2267295A1 (fr) 1996-09-27 1997-09-29 Procede de production de dioxyde de chlore au moyen de methanol et de peroxyde d'hydrogene comme agents reducteurs
AU47424/97A AU4742497A (en) 1996-09-27 1997-09-29 Method for producing chlorine dioxide using methanol and hydrogen peroxide as reducing agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US720,088 1985-04-05
US72008896A 1996-09-27 1996-09-27

Publications (2)

Publication Number Publication Date
WO1998013295A1 true WO1998013295A1 (fr) 1998-04-02
WO1998013295A9 WO1998013295A9 (fr) 1998-07-02

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AU (1) AU4742497A (fr)
CA (1) CA2267295A1 (fr)
WO (1) WO1998013295A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050550A1 (fr) * 2002-12-05 2004-06-17 Kemira Oyj Procede de production de dioxyde de chlore
WO2005080262A1 (fr) * 2004-02-23 2005-09-01 Akzo Nobel N.V. Procede de production de dioxyde de chlore
CN110382409A (zh) * 2018-08-30 2019-10-25 广西博世科环保科技股份有限公司 一种甲醇与双氧水组合还原制备高纯度二氧化氯的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091167A (en) * 1990-08-31 1992-02-25 Eka Nobel Ab Process for the production of chlorine dioxide
US5091166A (en) * 1990-08-31 1992-02-25 Eka Nobel Ab Process for the production of chlorine dioxide
US5273733A (en) * 1992-04-14 1993-12-28 Eka Nobel Inc. Process for the production of chlorine dioxide
US5380517A (en) * 1993-02-26 1995-01-10 Eka Nobel Inc. Process for continuously producing chlorine dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5091167A (en) * 1990-08-31 1992-02-25 Eka Nobel Ab Process for the production of chlorine dioxide
US5091166A (en) * 1990-08-31 1992-02-25 Eka Nobel Ab Process for the production of chlorine dioxide
US5273733A (en) * 1992-04-14 1993-12-28 Eka Nobel Inc. Process for the production of chlorine dioxide
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050550A1 (fr) * 2002-12-05 2004-06-17 Kemira Oyj Procede de production de dioxyde de chlore
WO2005080262A1 (fr) * 2004-02-23 2005-09-01 Akzo Nobel N.V. Procede de production de dioxyde de chlore
AU2005214291B2 (en) * 2004-02-23 2008-07-03 Akzo Nobel N.V. Process for production of Chlorine Dioxide
EA010599B1 (ru) * 2004-02-23 2008-10-30 Акцо Нобель Н.В. Способ получения диоксида хлора
CN110382409A (zh) * 2018-08-30 2019-10-25 广西博世科环保科技股份有限公司 一种甲醇与双氧水组合还原制备高纯度二氧化氯的方法

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Publication number Publication date
AU4742497A (en) 1998-04-17
CA2267295A1 (fr) 1998-04-02

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