WO2005077496A1 - Procédé et appareil pour traiter un gas contenant des composés contenant du fluor - Google Patents

Procédé et appareil pour traiter un gas contenant des composés contenant du fluor Download PDF

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Publication number
WO2005077496A1
WO2005077496A1 PCT/JP2005/002682 JP2005002682W WO2005077496A1 WO 2005077496 A1 WO2005077496 A1 WO 2005077496A1 JP 2005002682 W JP2005002682 W JP 2005002682W WO 2005077496 A1 WO2005077496 A1 WO 2005077496A1
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gas
treatment column
stage
column
hollow interior
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PCT/JP2005/002682
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English (en)
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WO2005077496A8 (fr
Inventor
Yoichi Mori
Tadakazu Nishikawa
Masaaki Osato
Hiroaki Ogamino
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Ebara Corporation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Definitions

  • the present invention relates to treatment of a gas containing fluorine-containing compounds.
  • the present invention relates to a method and apparatus for treating a waste gas containing fluorine-containing compounds, especially PFCs, discharged from a process of dry cleaning the inner surface of a semiconductor manufacturing apparatus or the like or a process of etchinganyofvarious films suchas anoxide filmin the semiconductor industry.
  • the present invention relates to a method and apparatus for treating a waste gas enabling decontamination treatment to be carried out efficiently on a waste gas containing fluorine-containing compounds and also an oxidizing gas such as F 2 , Cl 2 or Br 2 , an acidic gas such as HF, HC1, HBr, SiF 4 , SiCl 4 , SiBr 4 or COF 2 , or CO.
  • an oxidizing gas such as F 2 , Cl 2 or Br 2
  • an acidic gas such as HF, HC1, HBr, SiF 4 , SiCl 4 , SiBr 4 or COF 2 , or CO.
  • the present invention relates to a method and apparatus for recovering fluorine from a gas containing fluorine-containing compounds .
  • fluorine-containing compounds such as fluorinated hydrocarbons such as CHF 3 and perfluoro compounds (PFCs) such as CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 5 F 8 , SF 6 and NF 3 are used, and it is considered to be an urgent task to establish systems for removing such fluorine-containing compounds contained in waste gases from such processes since these fluorine-containing compounds contribute to global warming.
  • fluorine-containing compounds such as fluorinated hydrocarbons such as CHF 3 and perfluoro compounds (PFCs) such as CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 5 F 8 , SF 6 and NF 3 are used, and it is considered to be an urgent task to establish systems for removing such fluorine-containing compounds contained in waste gases from such processes since these fluorine-containing compounds contribute to global warming.
  • PFCs perfluoro compounds
  • FIG. 1 is a conceptual drawing of a gas treatment apparatus according to an embodiment of the present invention.
  • FIG. 2 is a conceptual drawing of a gas treatment apparatus according to another embodiment of the present invention.
  • the present inventors carriedout assiduous studies to develop a novel waste gas treatment method that resolves the above problems , and as a result discovered that by first adding water to a gas containing PFCs, andmaking the resulting mixture contact a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier to decompose the PFCs into HF as a first step, and then reacting the HF produced with calcium hydroxide to convert the fluorine into calcium fluoride as a second step, it is possible to decompose the PFCs in the gas, and moreover recover the fluorine in a reusable form; the present inventors thus arrived at the present invention.
  • one embodiment of the present invention relates to a method of treating a gas containing a fluorine-containing compound, comprising reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting said gas with calcium hydroxide in a second step.
  • a catalyst comprising tungsten oxide supported on an alumina-zirconiumcomposite oxide carrier has alreadybeen proposed as a catalyst for decomposing a fluorine compound gas (Japanese Patent No. 2569421).
  • Japanese Patent No. 2569421 Japanese Patent No. 2569421
  • the object is to decompose a freon gas only, and there is no consideration whatsoever of applying this catalyst to decomposition of a PFC gas.
  • a method in which a PFC gas is reacted with water in the presence of a catalyst so as to decompose the PFC into HF has also already been proposed (Japanese Patent No. 3217034).
  • the present invention provides a method in which a gas containing fluorine-containing compounds such as PFCs, especially a waste gas from any of various semiconductor manufacturing processes, is treated, whereby the fluorine-containing compounds can be decomposed, and moreover the fluorine can easily be recovered in a reusable form; this technical idea is not taught in the above prior art documents.
  • fluorine-containing compounds that can be treated using the method of the present invention include fluorinated hydrocarbons such as CHF 3 and perfluoro compounds (PFCs) such as CF 4 , C 2 F 6 , C 3 F 8 , SF 6 and NF 3 .
  • gases containing such fluorine-containing compounds include waste gases discharged in processes of dry cleaning the inner surfaces of semiconductor manufacturing apparatuses or the like and processes of etching various films in the semiconductor industry.
  • gases containing such fluorine-containing compounds include waste gases discharged in processes of dry cleaning the inner surfaces of semiconductor manufacturing apparatuses or the like and processes of etching various films in the semiconductor industry.
  • a PFC-decomposing catalyst that can be used in the present Invention, a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, i.e. an A1 2 0 3 -Zr0 2 -W0 3 catalyst , as described in above-mentioned Japanese Patent No. 2569421 can be used.
  • This catalyst can be prepared, for example, by dissolving a zirconium salt and aluminum oxyhydroxide (AIOOH) in deionized water, adding ammonia to precipitate the product, then filtering, cleaning the filter cake in awet state, extrusionmolding, then firing, further impregnating with ammonium tungstate, and then firing again.
  • AIOOH aluminum oxyhydroxide
  • a waste gas containing an oxidizing gas such as fluorine gas in addition to PFCs or the like can also be treatedand thus madeharmless .
  • Another embodiment of the present invention thus relates to a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds and oxidizing gases, characterized by having the steps described above.
  • a waste gas discharged from a semiconductor manufacturing process may contain not only PFCs but also an oxidizing gas such as F 2 , Cl 2 or Br 2 or the like. Oxidizing gases such as F 2 , Cl 2 and Br 2 cannot be completely treated with only water in the case of carryingoutwet treatment , but ratheranalkaline agent orareducing agent must be used, and hence there have been problems such as management or the apparatus becoming complex, and the cost being high.
  • such oxidizing gases can be decomposed together with the fluorine-containing compounds such as PFCs.
  • the fluorine-containing compounds and so on in the gas to be treated are first reacted with water in the presence of the catalyst of the present invention and thus converted into HF in the first step, and then the HF produced is reactedwith calciumhydroxide to produce calcium fluoride in the second step.
  • the reactions in the case that CF as a PFC and F 2 as an oxidizing gas in the waste gas are decomposedusing themethod of the present invention are shown below.
  • the second stage treatment column contains a mixture of calcium hydroxide and calcium fluoride after the treatment of the gas to be treated has been carried out .
  • Fluorine gas can be produced very easily by taking out this mixture and treating it with an inorganic acid such as hydrochloric acid or sulfuric acid.
  • a waste gas containing an acidic gas in addition to PFCs and an oxidizing gas can also be treated and thus made harmless.
  • a waste gas discharged from a semiconductor manufacturing process may contain not only PFCs and oxidizing gases but also an acidic gas such as HF, SiF 4 , COF 2 , HC1, HBr, SiCl 4 or SiBr 4 .
  • a gas containing such an acidic gas in addition to PFCs and oxidizing gases can be treated and thus made harmless.
  • the acidic gas is hydrolyzed upon contact with water, in particular in the case of SiF 4 , Si0 2 is produced.
  • Si0 2 is produced.
  • the gas to be treated when the gas to be treated contains a considerable amount of an acidic gas such as SiF 4 , it is preferred that the gas to be treated is passed through an acidic gas removal column to remove the acidic gas before being subjected to the first step.
  • Another embodiment of the present invention thus relates to a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds, oxidizing gases and acidic gases, comprising carrying out pretreatment of passing the gas through an acidic gas removal column to decompose acidic gases in the gas, and then reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting the gas with calcium hydroxide in a second step.
  • an acidic gas removal column usedwith the above objective
  • one having a well known constitution used for removing an acidic gas such as SiF or HF in the art can be used, for example a column packed with a zeolite can be suitably used.
  • a specific example of an acidic gas removal column that can be used in the method of the present invention is a GTE dry waste gas treatment apparatus manufactured by Ebara Corporation.
  • a waste gas discharged from a semiconductor manufacturing process may contain CO, and moreover CO is produced as a byproduct during the PFC decomposition reaction in the first step of the method of the present invention; it is thus necessary to decompose and remove this CO.
  • a gas containing CO in addition to fluorine-containing compounds , oxidizing gases and acidic gases can be treated and thus made harmless.
  • oxygen is added to the gas to be treated, whereby the CO can be decomposed.
  • the timing of adding the oxygen to the gas to be treated may be before the first step of reacting the gas to be treated with water in the presence of the catalyst, or during the first step.
  • another embodiment of the present invention relates to a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds, oxidizing gases and CO, comprising adding oxygen to the gas, and reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting the gas with calciumhydroxide in a second step.
  • the CO in the gas to be treated is oxidatively decomposed into C0 2 by the oxygen in the first stage treatment column (see the following formula).
  • the PFCs in the gas to be treated are reacted with water in the first stage reaction and thus decomposed into HF, and then this HF is reacted with calcium hydroxide and thus converted into calcium fluoride.
  • Calcium fluoride is the principal constituent of fluorite, which is known as a raw material in fluorine manufacture, and can be treated with an acid to produce fluorine gas .
  • the mixture of calcium hydroxide and calcium fluoride produced in the second stage treatment column can be treated with an inorganic acid such as hydrochloric acid or sulfuric acid, whereby fluorine gas can be produced very easily.
  • the fluorine can thus be recovered in areusable formveryefficiently fromthe gas containing fluorine-containing compounds.
  • the gas to be treated containing fluorine-containing compounds and so on is reacted with water in the presence of a prescribed catalyst in the first stage, and is then reacted with calcium hydroxide in the second stage.
  • the reaction temperature in the first stage reaction is generally 550 to 900°C, preferably 600 to 850°C, more preferably 750 to 800°C.
  • the reaction temperature in the second stage reaction may generally be room temperature.
  • the temperature in this case is preferably 500 to 800°C, more preferably 550 to 750°C, yet more preferably approximately 600°C.
  • FIG. 1 A conceptual drawing of a gas treatment apparatus able to implement the method according to an embodiment of the present invention is shown in FIG. 1.
  • This apparatus comprises a first stage treatment column 2, a second stage treatment column 3, a gas introduction pipe 1 through which the gas to be treated is introduced into the first stage treatment column 2, awater supplypipe 9 through which water is supplied into the gas introduction pipe 1, a column-connecting pipe 4 that connects the first stage treatment column 2 and the second stage treatment column 3 together and is for supplying the gas discharged from the first stage treatment column 2 into the second stage treatment column 3, and an exhaust pipe 5 throughwhich the gas producedafter thereaction is discharged from the second stage treatment column 3.
  • a catalyst 6 comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier is packedinto the first stage treatment column 2.
  • calcium hydroxide 7 is packed into the second stage treatment column 3.
  • Heating apparatuses 8a and 8b are disposed around the periphery of the first stage treatment column 2 and the second stage treatment column 3 respectively, whereby the inside of each treatment column is heated to and kept at a prescribed temperature.
  • the gas to be treated containing fluorine-containing compounds and so on passes through the gas introduction pipe 1 , water is added thereto through the water supply pipe 9 , and then the gas is introduced into the first stage treatment column 2 , and reacted with the water at a prescribed heating temperature under the presence of the catalyst 6 comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier.
  • the fluorine-containing compounds such as PFCs and oxidizing gases in the gas to be treated are decomposed to produce HF. Note that in FIG.
  • the water supply pipe 9 may instead be connected to the inside of the first stage treatment column 2 so that water is supplied directly into the first stage treatment column 2.
  • the gas produced from the first stage treatment column 2 is fed through the column-connecting pipe 4 into the second stage treatment column 3 , and here the HF is reacted with the calcium hydroxide to produce CaF 2 , which is adsorbed by and thus remains in the calcium hydroxide.
  • C0 2 produced in the first stage treatment column 2 and steam produced in the second stage treatment column 3 are discharged through the exhaust pipe 5.
  • the packing material (calcium hydroxide) in the second stage treatment column 3 remains in the column in the form of a mixture with the calcium fluoride produced through the desired reaction adsorbed thereon .
  • the treatment agent i.e. the mixture of calcium fluoride and calcium hydroxide, can be removed, and treatedwith an inorganic acid such as hydrochloric acid or sulfuric acid, thus producing fluorine gas.
  • fluorine can thus be recovered in a reusable formveryeasilyfromagas containingfluorine-containingcompounds .
  • oxygen can be added to the gas to be treated via an oxygen supply pipe 10, whereby oxidation of the CO into C0 2 can be carried out at the same time in the first stage treatment column 2.
  • the oxygen supply pipe 10 may be connected directly to the first stage treatment column 2.
  • FIG. 2 A conceptual drawing of a gas treatment apparatus according to another embodiment of the present invention having this form is shown in FIG. 2.
  • constituent elements the same as ones in FIG. 1 are represented by the same reference numerals as in FIG.1, and description thereof will be omitted here.
  • the gas treatment apparatus shown in FIG. 2 is characterized in that a single column 2 is divided into two sections, and a catalyst 6 comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier is packed into a first stage reaction section on the upstream side, while calciumhydroxide 7 is packed into a second stage reaction section on the downstream side.
  • the gas to be treated is first reacted with water in the presence of the catalyst 6 of the present invention in the first stage reaction section, thus converting the PFCs and so on into HF, and then this HF reacts with the calcium hydroxide 7 in the second stage reaction section and is thus converted into CaF 2 .
  • the inside of the treatment column 2 is heated to a prescribed temperature by a heating apparatus 8a.
  • the calcium hydroxide having the calcium fluoride adsorbed thereon can be removed from the second stage reaction section of the treatment column, and treated with an inorganic acid such as hydrochloric acidor sulfuric acid, whereby fluorine gas can be produced.
  • Thepresent invention alsorelates to apparatuses for treating a gas containing fluorine-containing compounds as described above.
  • a gas containing fluorine-containing compounds and so is treated, whereby fluorine can be recovered in a reusable form.
  • Another embodiment of the present invention thus relates to a method and apparatus for recovering fluorine from a gas containing fluorine-containing compounds, having a constitution as described above.
  • Amethod of treating a gas containing a fluorine-containing compound comprising reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting said gas with calcium hydroxide in a second step.
  • a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds and oxidizing gases comprising reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting the gas with calcium hydroxide in a second step.
  • a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds, oxidizing gases and acidic gases comprising carrying out pretreatment of passing the gas through an acidic gas removal column to decompose acidic gases in the gas , and then reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting the gas with calcium hydroxide in a second step.
  • a method of carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds, oxidizing gases, acidic gases and CO comprising carrying out pretreatment of passing the gas through an acidic gas removal column to decompose acidic gases in the gas , and then adding oxygen to the gas, and reacting the gas with water in the presence of a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier in a first step, and then reacting the gas with calcium hydroxide in a second step. 6.
  • An apparatus for treating a gas containing a fluorine-containing compound comprising: a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which the gas canpass , heatingmeans capable ofheating thehollowinterior to aprescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; and column-connecting piping
  • An apparatus for carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds and oxidizing gases comprising: a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which the gas canpass , heatingmeans capable ofheating thehollowinterior to a prescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; and column-connecting piping for introducing the gas discharged fromthe first stage treatment column into the second stage treatment column.
  • An apparatus for carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases and acidic gases comprising: an acidic gas removal column through which the gas is passed to decompose and thus remove acidic gases in the gas; a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which a gas passed through the acidic gas removal column can pass , heating means capable of heating the hollow interior to a prescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; and column-connect
  • An apparatus for carrying out decontamination treatment on a gas to be treated containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases and CO comprising: a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which the gas canpass , heatingmeans capable ofheating thehollowinterior to a prescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; column-connecting piping for introducing the gas discharged from the first stage treatment column into the second stage treatment column; and means for adding oxygen to the gas before
  • An apparatus for carrying out decontamination treatment on a gas to be treated containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases , acidic gases and CO comprising: an acidic gas removal column through which the gas is passed to decompose and thus remove acidic gases in the gas; a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which the gas from the acidic gas removal column can pass, heating means capable of heating the hollow interior to a prescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; column-
  • the second stage treatment column further has heating means capable of heating the hollow interior to a prescribed temperature.
  • the hollow interior of the first stage treatment column is heated to 550 to 900°C.
  • the hollow interior of the second stage treatment column is heated to 500 to 800°C. 17.
  • An apparatus for treating a gas containing a fluorine-containing compound comprising: a treatment column having a hollow interior through which the gas can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the treatment column; and an exhaust pipe for discharging gas produced from the second stage reaction section of the treatment column.
  • An apparatus for carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds and oxidizing gases comprising: a treatment column having a hollow interior through which the gas can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the treatment column; and an exhaust pipe for discharging gas produced from the second stage reaction section of the treatment column.
  • An apparatus for carrying out decontamination treatment on a gas containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases andacidic gases comprising: an acidic gas removal column through which the gas is passed to decompose and thus remove acidic gases in the gas; a treatment column having a hollow interior through which a gas passed through the acidic gas removal column can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas that has passed through the acidic gas removal column into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the treatment column; and an exhaust
  • An apparatus for carrying out decontamination treatment on a gas to be treated containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases and CO comprising: a treatment column having a hollow interior through which the gas can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the treatment column; an exhaust pipe for discharging gas produced from the second stage reaction section of the treatment column; and means for adding oxygen to the gas before the gas is introduced into the first stage reaction section or an oxygen introduction pipe for introducing oxygen
  • An apparatus for carrying out decontamination treatment on a gas to be treated containing at least one selected from the group consisting of fluorine-containing compounds , oxidizing gases , acidic gases and CO comprising: an acidic gas removal column through which the gas is passed to decompose and thus remove acidic gases in the gas; a treatment column having a hollow interior through which a gas passed through the acidic gas removal column can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas that has passed through the acidic gas removal column into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the
  • An apparatus for treating a gas containing a fluorine-containing compound and recovering fluorine comprising: a first stage treatment column comprising a hollow interior that is packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier and through which the gas canpass, heatingmeans capable ofheating thehollowinterior to aprescribed temperature, a gas introduction port for introducing the gas into the hollow interior, and means for adding water to the gas before the gas is introduced into the first stage treatment column or a water introduction pipe for adding water into the first stage treatment column; a second stage treatment column comprising a hollow interior that is packed with calcium hydroxide and through which gas discharged from the first stage treatment column can pass, and an exhaust pipe for discharging gas produced from the hollow interior of the second stage treatment column; and column-connecting piping for introducing the gas discharged from the first stage treatment column into the second stage treatment column.
  • An apparatus for treating a gas containing a fluorine-containing compound and recovering fluorine comprising: a treatment column having a hollow interior through which the gas can pass, the hollow interior being divided into a first stage reaction section packed with a catalyst comprising tungsten oxide supported on an alumina-zirconium composite oxide carrier, and a second stage reaction section that receives gas discharged from the first stage reaction section and is packed with calcium hydroxide; heating means capable of heating the hollow interior of the treatment column to a prescribed temperature; a gas introduction port for introducing the gas into the first stage reaction section; means for adding water to the gas before the gas is introduced into the first stage reaction section of the treatment column or a water introduction pipe for adding water into the first stage reaction section of the treatment column; and an exhaust pipe for discharging gas produced from the second stage reaction section of the treatment column.
  • Example 1 A test of treating a mixed gas of PFCs (C 4 F 8 , C 2 F 6 , CF 4 ) , SiF 4 as an acidic gas, and CO using the method of the present invention was carriedout .
  • an Al 2 0 3 -Zr ⁇ 2 - ⁇ 3 catalyst of the present invention was packed into the first column, andCa(OH) 2 was packed into the second column, and the two columns were connected together in series.
  • a catalyst made by S ⁇ d-Chemie (ESW-1; granules of diameter 2 mm and length 5 mm) having an A1 2 0 3 : Zr0 2 :W0 3 composition ratio (molar ratio) of 0.75:0.2:0.05 was used, and this was packed to a layer height of 100 mm (amount packed 49 mL) .
  • the Ca(OH) 2 a commercial product (made by Yabashi Kogyo; 0.5 to 1.68 mm granules) was used, and again this was packed to a layer height of 100 mm (amount packed 49 mL).
  • a thermocouple was placed for measuring the temperature inside the catalyst layer of the first column, and the first column was put into a ceramic electric tube furnace. The catalyst layer of the first column was heated to 750°C, and the catalyst layer of the second column was made to be at room temperature.
  • the total gas flow rate was 410 seem, the inflow concentrations of the various gases were 1340 ppm for CF 8 , 390 ppm for C 2 F 6 , 500 ppm for CF 4 , 440 ppm for SiF , 3.0% for CO, and 4.1% for 0 2 , and the amount of H 2 0 introduced was 0.005 mL/min.
  • the outlet gas from each column was sampled, and analysis of the PFCs, CO and C0 2 was carried out using a gas chromatograph mass spectrometer (AGS-7000U manufactured by Anelva) , while analysis of SiF 4 and HF was carried out using an FT-IR analyzer (Infinity 6000 manufactured by Matson) .
  • the removal rate for each PFC was determined from the following equation.
  • PFC removal rate (%) (PFC inflow concentration - PFC outlet concentration) / PFC inflow concentration x 100
  • Example 2 Two columns packed with catalysts were connected together in series as in Example 1, a thermocouple was placed on each column, and the columns were put into ceramic electric tube furnaces .
  • the first column was heated to 750°C as in Example 1, and the second column was heated to 600°C.
  • Gas was passed through under the same conditions as in Example 1, and the outlet gas was analyzed.
  • the outlet gas concentrations and removal rates for each column after passing the gas through for 8 hours are shown in Table 2. Mainly HF leaked out from the outlet of the first column, and at the outlet of the second column the HF had been removed to below the limit of detection.
  • the PFC removal rates were yet better than in Example 1.
  • Example 3 After continuing to pass the gas through for 32 hours, 3 ppm of HF was leaking out from the outlet of the second column, which is at the level of the acceptable concentration. The total amount of F in the PFCs that had passed through up to this point in time was 10.0 g on a weight basis.
  • the Ca(OH) 2 layer of the second column was processed as in Example 1 to determine the amount of F recovered, whereupon this amount was 9.92 g, and hence the F recovery rate was 99.2%.
  • Example 3 The same two catalysts (Al 2 0 3 -Zr0 2 -W0 3 catalyst and Ca(OH) 2 ) as in Example 1 were used.
  • a gas containing fluorine-containing compounds is treated, whereby the fluorine-containing compounds such as PFCs and so on can be decomposed, and moreover the fluorine can be recovered in a reusable form.
  • Agas containingPFCs can thus be subjectedto decontamination treatment, and moreover there is a contribution to fluorine recycling, and hence the industrial value is great.

Abstract

L'objectif de la présente invention consiste à fournir un procédé et un appareil pour traiter un rejet gazeux contenant des composés contenant du fluor, selon lequel les PFC peuvent être décomposés de façon efficace et en plus le fluor provenant du produit de la décomposition peut être récupéré pour être réutilisé de façon efficace. Un mode de réalisation de la présente invention concerne un procédé de traitement d'un gaz contenant un composé contenant du fluor, procédé caractérisé en ce qu'on fait réagir le gaz avec de l'eau en présence d'un catalyseur comprenant de l'oxyde de tungstène supporté sur un support en oxyde composite d'alumine-zirconium dans une première étape et qu'on le fait ensuite réagir avec de l'hydroxyde de calcium dans un
PCT/JP2005/002682 2004-02-17 2005-02-15 Procédé et appareil pour traiter un gas contenant des composés contenant du fluor WO2005077496A1 (fr)

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KR101977928B1 (ko) * 2017-06-09 2019-05-14 한국에너지기술연구원 촉매반응-산성가스제거반응 일체형 다단 pfc 처리용 장치 및 이를 이용한 pfc 처리 공정
KR102466748B1 (ko) * 2020-05-07 2022-11-14 코아텍주식회사 과불화화합물 가스의 촉매 분해 장치
KR20240020224A (ko) * 2022-08-04 2024-02-14 주식회사 에코프로에이치엔 과불화화합물 분해용 촉매

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JPH03229618A (ja) * 1990-02-05 1991-10-11 Ebara Res Co Ltd Ｃ１ｆ▲下３▼を含有する排ガスの処理方法
JPH10128061A (ja) * 1996-11-05 1998-05-19 Central Glass Co Ltd フッ化水素ガスの乾式処理方法
JPH10337439A (ja) * 1997-06-09 1998-12-22 Hitachi Ltd 含フッ素有機ハロゲン化合物の排ガス処理装置およびその処理方法
JPH11179201A (ja) * 1997-12-19 1999-07-06 Ube Ind Ltd 含フッ素化合物分解処理用触媒および含フッ素化合物 分解処理方法
JP2003117350A (ja) * 2001-10-10 2003-04-22 Ebara Corp フッ素含有化合物を含む排ガスの処理方法及び装置
JP2003340239A (ja) * 2002-05-31 2003-12-02 Hitachi Ltd 過弗化物処理装置

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Publication number Priority date Publication date Assignee Title
JPH03229618A (ja) * 1990-02-05 1991-10-11 Ebara Res Co Ltd Ｃ１ｆ▲下３▼を含有する排ガスの処理方法
JPH10128061A (ja) * 1996-11-05 1998-05-19 Central Glass Co Ltd フッ化水素ガスの乾式処理方法
JPH10337439A (ja) * 1997-06-09 1998-12-22 Hitachi Ltd 含フッ素有機ハロゲン化合物の排ガス処理装置およびその処理方法
JPH11179201A (ja) * 1997-12-19 1999-07-06 Ube Ind Ltd 含フッ素化合物分解処理用触媒および含フッ素化合物 分解処理方法
JP2003117350A (ja) * 2001-10-10 2003-04-22 Ebara Corp フッ素含有化合物を含む排ガスの処理方法及び装置
JP2003340239A (ja) * 2002-05-31 2003-12-02 Hitachi Ltd 過弗化物処理装置

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JP2005230609A (ja) 2005-09-02

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