WO2020130748A1 - Catalyseur pour la décomposition de composés perfluorés, et procédé de préparation correspondant - Google Patents

Catalyseur pour la décomposition de composés perfluorés, et procédé de préparation correspondant Download PDF

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WO2020130748A1
WO2020130748A1 PCT/KR2019/018312 KR2019018312W WO2020130748A1 WO 2020130748 A1 WO2020130748 A1 WO 2020130748A1 KR 2019018312 W KR2019018312 W KR 2019018312W WO 2020130748 A1 WO2020130748 A1 WO 2020130748A1
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catalyst
decomposing
perfluorinated compound
phosphorus
oxide precursor
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Korean (ko)
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유지선
김민지
김동우
김정배
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주식회사 에코프로
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation

Definitions

  • the present invention relates to a catalyst for decomposing a perfluorinated compound and a method for producing the same, and more particularly, to a catalyst for decomposing a perfluorinated compound containing an active metal and a method for producing the same.
  • PFCs perfluorocompounds
  • CO 2 carbon dioxide
  • PFCs gas contains a large number of fluorine, and currently used in industry is classified into organic gas such as CF 4 , C 3 F 8 and C 2 F 6 and inorganic gas such as NF 3 and SF 6. Can. Compared to carbon dioxide, these PFCs gas have an emission of about one-thousandth, and most of the places generated are limited to the semiconductor industry, especially in the country where the semiconductor display industry is the most developed in the world. Therefore, there is an urgent need for research and development on the development of recovery and replacement materials, as well as decomposition technologies for emissions.
  • the direct combustion method is a method of directly burning waste gas containing PFCs at a high temperature of 1,400°C or higher using combustible gas, and is one of the most convenient PFCs treatment methods.
  • a number of additional problems occur due to the high reaction temperature. That is, nitrogen and oxygen contained in the waste gas together with the PFCs react to generate a large amount of harmful nitrogen oxides (thermal NOx), and the device corrosion is severely caused by HF generated when PFCs are decomposed to treat and treat nitrogen oxides.
  • thermal NOx harmful nitrogen oxides
  • Plasma decomposition method is a technique that decomposes and removes waste gas containing PFCs through a plasma region. It is effective in decomposing PFCs, but uses high energy plasma, so secondary radicals generated by indiscriminate decomposition of PFCs Due to the reaction, there is a problem that various kinds of by-products are generated. In addition, there is also a problem in durability and economical efficiency of the plasma generator for generating plasma stably for a long time.
  • the recovery method is a method of separating and recovering PFCs contained in the waste gas using pressure swing adsorption (PSA) or membrane, etc. It is preferable in terms of recyclability of PFCs, but it is as in the semiconductor process. In the case of treating PFCs that are irregularly discharged in a small amount, it is a low economic method.
  • PSA pressure swing adsorption
  • Catalytic cracking is widely used as an alternative to direct cracking and plasma cracking because it can significantly reduce the generation of nitrogen oxides and device corrosion by inducing PFCs cracking to occur at low temperatures of 500 to 800°C using catalysts and water vapor. It has been studied. However, the operating condition of 500 to 800°C is still a high temperature condition for the catalyst to maintain its activity for a long time without physical or chemical change, and thus the biggest obstacle to securing the durability of the catalyst is the obstacle.
  • One object of the present invention is to provide a catalyst for decomposing a perfluorinated compound having excellent durability.
  • One object of the present invention is to provide a method for preparing a catalyst for decomposing a perfluorinated compound having excellent durability.
  • Catalyst for decomposing perfluorinated compounds including aluminum oxide, zirconium oxide, phosphorus oxide and zinc oxide.
  • the aluminum oxide comprises at least one selected from the group consisting of ⁇ -alumina, ⁇ -alumina and ⁇ -alumina, catalyst for decomposing perfluorinated compounds.
  • the zirconium oxide is a catalyst for decomposing a perfluorinated compound containing zirconia (ZrO 2 ).
  • the phosphorus oxide comprises phosphorus pentoxide (P 2 O 5 ), a catalyst for decomposing perfluorinated compounds.
  • the zinc oxide is zinc oxide (ZnO), a catalyst for decomposing a perfluorinated compound.
  • the phosphorus oxide is included in 0.1 to 10% by weight of the total weight of the catalyst, the catalyst for decomposing a perfluorinated compound.
  • the zirconium oxide is contained in 0.1 to 50% by weight based on the total weight of the catalyst, the catalyst for decomposing the perfluorinated compound.
  • the zinc oxide is included in 0.1 to 50% by weight based on the total weight of the catalyst, the catalyst for decomposing a perfluorinated compound.
  • the perfluorinated compound is CF 4 , CHF 3 , CH 2 F 2 , C 2 F 4 , C 2 F 6 , C 3 F 6 , C 3 F 8 , C 4 F 8 , C 4 A catalyst for decomposing a perfluorinated compound, at least one selected from the group consisting of F 10 , NF 3 and SF 6 .
  • the catalyst for decomposing a perfluorinated compound.
  • zirconium oxide precursor comprises at least one of zirconium acetate hydroxide ((CH 3 CO 2 ) x Zr(OH) y ) and zirconium oxide (ZrO 2 ).
  • the phosphorus oxide precursor is a group consisting of diammonium hydrophosphate ((NH 3 ) 2 HPO 4 ), ammonium dihydrophosphate (NH 3 H 2 PO 4 ) and phosphoric acid (H 3 PO 4 )
  • the zinc oxide precursor is composed of zinc acetate (Zn(CH 3 CO 2 ) 2 ), zinc nitrate hexahydrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) and zinc oxide (ZnO).
  • the aluminum oxide precursor is made of gamma alumina ( ⁇ -Al 2 O 3 ), aluminum trihydroxide (aluminum trihydroxide), boehmite (boehmite) and pseudobomite (pseudo-boehmite) Method for producing a catalyst for decomposing a perfluorinated compound, comprising at least one selected from the group.
  • the catalyst for decomposing a perfluorinated compound not only has a high decomposition efficiency for a perfluorinated compound, but also has a low degree of reduction in the decomposition efficiency of the catalyst due to use and high temperature exposure.
  • FIG. 1 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • FIGS. 2 to 5 are schematic flowcharts showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • FIG. 6 is a graph showing the decomposition ability of a catalyst for decomposing a perfluorinated compound according to Examples and Comparative Examples of the present invention.
  • FIG. 7 is a graph showing the removal efficiency of a perfluorinated compound according to an aging temperature of a catalyst for decomposing a perfluorinated compound according to Examples and Comparative Examples of the present invention.
  • FIG. 8 is a graph showing removal efficiency of a perfluorinated compound according to an aging temperature of a catalyst for decomposing a perfluorinated compound according to Examples and Comparative Examples of the present invention.
  • first, second, A, B, etc. can be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.
  • first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.
  • the term and/or includes a combination of a plurality of related described items or any one of a plurality of related described items.
  • a catalyst for decomposing a perfluorinated compound As a catalyst for decomposing a perfluorinated compound, a catalyst for decomposing a perfluorinated compound having a high decomposition efficiency and a low degree of reduction in the decomposition efficiency of the catalyst over time is proposed.
  • the catalyst for decomposing perfluorinated compounds is characterized by including aluminum oxide, zirconium oxide, phosphorus oxide and zinc oxide.
  • any one or more selected from the group consisting of ⁇ -alumina, ⁇ -alumina and ⁇ -alumina can be used.
  • ⁇ -alumina is preferred in terms of catalytic activity.
  • the zirconium oxide may be zirconia (ZrO 2 ).
  • the zirconium oxide may be included in an amount of 0.1 to 50% by weight based on the total weight of the catalyst. When the content of the zirconium oxide is less than 0.1% by weight, the decomposition efficiency can be easily deteriorated at a high temperature. When the content of the zirconium oxide is more than 50% by weight, the initial decomposition efficiency may decrease.
  • the zirconium oxide may be included in 5 to 30% by weight, 7 to 20% by weight or 12 to 16% by weight of the total weight of the catalyst.
  • the phosphorus oxide may be phosphorus pentoxide (P 2 O 5 ).
  • the phosphorus oxide may be included in an amount of 0.1 to 10% by weight based on the total weight of the catalyst. When the content of the phosphorus oxide is less than 0.1% by weight, the degree of deterioration due to high temperature aging of the catalyst may increase. When the content of the phosphorus oxide is more than 10% by weight, the initial decomposition efficiency may be very reduced.
  • the phosphorus oxide may be included in 1 to 5% by weight, 1 to 4% by weight or 2 to 3% by weight of the total weight of the catalyst.
  • the zinc oxide may be zinc oxide (ZnO).
  • the zinc oxide may be included in 0.1 to 50% by weight of the total weight of the catalyst. When the content of the zinc oxide is less than 0.1% by weight, catalytic activity may be significantly deteriorated at a high temperature. When the content of the zinc oxide is more than 50% by weight, the initial decomposition efficiency may decrease.
  • the zinc oxide may be included in 3 to 20% by weight, 5 to 15% by weight or 7 to 14% by weight of the total weight of the catalyst.
  • the perfluorinated compound to be decomposed is CF 4 , CHF 3 , CH 2 F 2 , C 2 F 4 , C 2 F 6 , C 3 F 6 , C 3 F 8 , C 4 F 8 , C 4 F 10 , It may be any one or more selected from the group consisting of NF 3 and SF 6 .
  • the decomposition efficiency at 600°C is 75% or more
  • the decomposition efficiency at 650°C is 92% or more
  • the decomposition efficiency at 700°C is 99% or more
  • at 750°C The decomposition efficiency is 99% or more, and the decomposition efficiency at 800°C may be 100%.
  • the decomposition efficiency at 600° C. is 50% or more
  • the decomposition efficiency at 650° C. is 81% or more
  • the decomposition efficiency at 700° C. may be 100%.
  • the decomposition efficiency at 500°C may be 54% or higher, the decomposition efficiency at 550°C is 88% or higher, and the decomposition efficiency at 600°C may be 100%.
  • the decomposition efficiency at 350°C is 70% or more
  • the decomposition efficiency at 400°C is 92% or more
  • the decomposition efficiency at 450°C may be 100%.
  • the catalyst for decomposing the perfluorinated compound of the present invention has no difference in the efficiency of decomposing the perfluorinated compound of the catalyst immediately after production and after a certain period of time has passed (that is, aging referred to in the present invention). It is characterized by.
  • the catalyst for decomposing the perfluorinated compound of the present invention has a CF 4 decomposition efficiency at 800°C even immediately after production, and is 100% after aging under conditions of exposing it to air for more than 24 hours at 900°C.
  • the difference in decomposition efficiency may be 1% or less.
  • the difference in decomposition efficiency may be 1% or less at 99% immediately after manufacturing and 99% even after aging.
  • the catalyst can be put into equipment such as a kiln and heated and maintained at a constant temperature.
  • the difference in decomposition efficiency is 1% or less, the durability of the catalyst may be improved.
  • the decomposition efficiency at 700°C is 99% immediately after manufacture, and 89% even after aging, and the difference in decomposition efficiency may be 11% or less.
  • the difference in decomposition efficiency may be 25% or less at 650°C to 92% immediately after manufacturing and 67% after aging.
  • FIG. 1 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • a zirconium oxide precursor, a phosphorus oxide precursor, and a zinc oxide precursor may be dissolved in distilled water to generate a solution (eg, step S10).
  • the phosphorus oxide precursor at least one selected from the group consisting of diammonium hydrophosphate ((NH 3 ) 2 HPO 4 ), ammonium dihydrophosphate (NH 3 H 2 PO 4 ) and phosphoric acid (H 3 PO 4 ) can be used. have.
  • the amount of the phosphorus oxide precursor may be included in an amount of 0.1 to 10% by weight based on the total weight of the catalyst for decomposing the perfluorinated compound, preferably 1 to 5% by weight, 1 to 4% by weight, or 2 to 2% of the total weight of the catalyst 3% by weight.
  • the zinc oxide precursor is at least one selected from the group consisting of zinc acetate (Zn(CH 3 CO 2 ) 2 ), zinc nitrate hexahydrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) and zinc oxide (ZnO). Can be used.
  • the amount of the zinc oxide precursor may be included in an amount of 0.1 to 50% by weight based on the total weight of the catalyst for decomposing the perfluorinated compound, and preferably 3 to 20% by weight, 5 to 15% by weight, or 7 to 7% of the total weight of the catalyst 14% by weight.
  • zirconium oxide precursor at least one of zirconium acetate hydroxide ((CH 3 CO 2 ) x Zr(OH) y ) and zirconium oxide (ZrO 2 ) may be used.
  • the amount of the zirconium oxide precursor may be included in an amount of 0.1 to 50% by weight based on the total weight of the catalyst for decomposing the perfluorinated compound, and preferably 5 to 30% by weight, 7 to 20% by weight, or 12 to 12% of the total weight of the catalyst 16% by weight.
  • An aluminum oxide precursor may be mixed with the solution to produce a catalyst supporting material (eg, step S20).
  • the aluminum oxide precursor at least one selected from the group consisting of gamma alumina ( ⁇ -Al 2 O 3 ), aluminum trihydroxide, boehmite and pseudo-boehmite Can be used.
  • the carrier may be formed through an impregnation method.
  • the carrier can be immersed in an aqueous solution containing the active ingredient to support the active ingredient on the surface of the carrier.
  • the active ingredient can be dispersed in the carrier. Therefore, it is possible to stabilize the catalyst by preventing the sintering of the active catalyst.
  • the aluminum oxide precursor may act as a main catalyst having decomposition activity of a perfluorinated compound, as well as a support for an active metal. It is preferable to use ⁇ -alumina in terms of catalytic activity. In addition, if the transition of ⁇ -alumina to the ⁇ phase can be suppressed, high resolution for PFCs can be maintained for a long time.
  • the carrier may be dried (eg, step S30).
  • the carrier may be dried at a secondary drying temperature higher than the primary drying temperature.
  • secondary drying may be performed at 100°C or higher.
  • Firing for the carrier may be performed (for example, step S40).
  • the firing can be carried out at about 400 to 800 °C.
  • the firing can be carried out under air atmosphere.
  • the phosphorus oxide precursor, the aluminum oxide precursor, the zinc oxide precursor, and the zirconium oxide precursor may be converted to phosphorus oxide, aluminum oxide, zinc oxide, and zirconium oxide, respectively.
  • the carrier may be molded prior to drying.
  • a catalyst having a desired shape and size can be produced.
  • the carrier may be formed into a plate shape, a spherical shape, a square shape, or the like.
  • FIG. 2 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention. Description of the same content as the description with reference to FIG. 1 may be omitted.
  • a phosphorus-containing aqueous solution containing a phosphorus oxide precursor can be prepared (eg, S12).
  • the phosphorus-containing aqueous solution may be prepared by dissolving the phosphorus oxide precursor in water (eg, distilled water).
  • An aluminum oxide precursor may be mixed with the phosphorus-containing aqueous solution to form a phosphorus-aluminum carrier (for example, step S22).
  • the phosphorus-aluminum carrier may be formed by the impregnation method.
  • the phosphorus-aluminum carrier may be formed by supporting and/or adsorbing the phosphorus oxide precursor or the phosphorus oxide on the aluminum oxide precursor or the aluminum oxide particles.
  • the phosphorus-aluminum carrier may be dried and/or fired.
  • a phosphorus-aluminum pre-catalyst comprising phosphorus oxide and aluminum oxide (carrier) can be formed.
  • the phosphorus-aluminum carrier and a zinc oxide precursor may be mixed (eg, step S50).
  • the zinc oxide precursor may be provided as an aqueous solution phase.
  • an aqueous solution of the zinc oxide precursor may be mixed with the phosphorus-aluminum carrier.
  • the phosphorus-aluminum pre-catalyst and the zinc oxide precursor may be mixed.
  • the phosphorus-aluminum carrier mixed with the zinc oxide precursor may be dried and fired.
  • a zinc-phosphorus-aluminum pre-catalyst comprising zinc oxide, phosphorus oxide and aluminum oxide (carrier) can be formed.
  • the zinc oxide can be coated on at least a portion of the surface of the phosphorus-aluminum pre-catalyst particle.
  • the phosphorus-aluminum carrier and a zirconium oxide precursor may be mixed (eg, step S52).
  • the zirconium oxide precursor may be provided as an aqueous solution phase.
  • an aqueous solution of the zirconium oxide precursor may be mixed with the phosphorus-aluminum carrier.
  • the phosphorus-aluminum pre-catalyst, the phosphorus-aluminum carrier (pre-catalyst) mixed with the zinc oxide precursor, or the zinc-phosphorus-aluminum pre-catalyst and the zirconium oxide precursor may be mixed. .
  • the zirconium oxide precursor may be mixed (step S52) after the zinc oxide precursor is mixed (step S50). In some embodiments, the mixing order may be reversed.
  • the zirconium oxide precursor-supported mixture or the pre-catalyst mixture may be dried (eg, step S30).
  • the dried carrier or a mixture of pre-catalysts can be calcined (eg, step S40).
  • a catalyst for decomposing a perfluorinated compound including zirconium oxide, zinc oxide, phosphorus oxide and aluminum oxide (carrier) can be prepared.
  • the zirconium oxide may coat at least a portion of the surface of the phosphorus-aluminum pre-catalyst particles or zinc-phosphorus-aluminum pre-catalyst particles.
  • FIG. 3 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • the phosphorus-aluminum carrier may be mixed with a zinc oxide precursor and a zirconium oxide precursor (eg, step S55).
  • the zinc oxide precursor and the zirconium oxide precursor may be dissolved together in water to form a zinc-zirconium-containing aqueous solution.
  • aqueous solution containing zinc-zirconium is mixed with the phosphorus-aluminum carrier, a solution including zinc, zirconium, phosphorus and aluminum components may be formed.
  • FIG. 4 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • a mixed aqueous solution of a precursor including a zirconium oxide precursor, a phosphorus oxide precursor, a zinc oxide precursor, and an aluminum oxide precursor may be prepared (for example, step S14).
  • step S24 it is possible to form a complex co-precipitate by adjusting the acidity of the precursor mixed aqueous solution (for example, step S24).
  • the precursor mixed aqueous solution may be stirred at an appropriate rate.
  • the concentration in the precursor mixed aqueous solution may be uniform, and the complex co-precipitate having a uniform composition may be formed.
  • the acidity can be adjusted from 8 to 10.
  • the acidity may be adjusted, for example, with sodium hydroxide, potassium hydroxide or ammonium hydroxide.
  • the phosphorus oxide precursor, the aluminum oxide precursor, the zinc oxide precursor, and the zirconium oxide precursor may be converted into hydroxides containing phosphorus, aluminum, zinc, and zirconium, respectively.
  • a catalyst for decomposing a perfluorinated compound may be prepared by drying (eg, step S32) and firing (eg, step S42) of the composite coprecipitate.
  • the complex co-precipitate may be filtered before drying and firing. Through the filtering, it is possible to obtain a complex co-precipitate having an appropriate size to control the size (particle size) of the catalyst for decomposing the perfluorinated compound.
  • FIG. 5 is a schematic flow chart showing a method for preparing a catalyst for decomposing a perfluorinated compound according to exemplary embodiments of the present invention.
  • a mixed aqueous solution of phosphorus-aluminum may be prepared (for example, step S16).
  • the phosphorus-aluminum mixed aqueous solution may be prepared by dissolving a phosphorus oxide precursor and an aluminum oxide precursor in water.
  • a phosphorus-aluminum coprecipitate may be formed (for example, step S26).
  • the phosphorus-aluminum co-precipitate may include aluminum oxide precursor particles and phosphorus oxide precursor particles.
  • the phosphorus-aluminum co-precipitate is an aggregate of aluminum oxide precursor particles and phosphorus oxide precursor particles, or phosphorus oxide precursor particles are supported in the aluminum oxide precursor particles, or the phosphorus oxide precursor is on the surface of the aluminum oxide precursor particles The particles may be adsorbed.
  • the acidity can be adjusted from 8 to 10.
  • the phosphorus-aluminum coprecipitate may be pre-dried and pre-fired (eg, step S60).
  • the preliminary drying and the preliminary firing may be performed in the same manner as the above-described drying and predetermined, respectively.
  • a phosphorus-aluminum pre-catalyst comprising phosphorus oxide and aluminum oxide may be formed from the phosphorus-aluminum coprecipitation by the preliminary firing.
  • the pre-fired phosphorus-aluminum coprecipitate or phosphorus-aluminum catalyst can be mixed with a zirconium oxide precursor and a zinc oxide precursor to form a mixed coprecipitate (eg, step S70).
  • the zirconium oxide precursor and the zinc oxide precursor may be provided as an aqueous solution.
  • an aqueous solution containing the zirconium oxide precursor and the zinc oxide precursor together may be mixed with the phosphorus-aluminum coprecipitate or the phosphorus-aluminum catalyst.
  • the mixed coprecipitate may be formed through a conventional coprecipitation method.
  • the mixed co-precipitate formed may be a mixture of the zirconium oxide precursor particles and the zinc oxide precursor particles with the phosphorus-aluminum coprecipitate or the phosphorus-aluminum pre-catalyst.
  • the zirconium oxide precursor particles and the zinc oxide precursor particles may be at least partially coated on the surface of the phosphorus-aluminum coprecipitate or the phosphorus-aluminum pre-catalyst.
  • the mixed coprecipitate may be dried (eg, step S34) and calcined (eg, step S44) to prepare a catalyst for decomposing a perfluorinated compound.
  • the phosphorus oxide precursor, the aluminum oxide precursor, the zinc oxide precursor, and the zirconium oxide precursor may be converted to phosphorus oxide, aluminum oxide, zinc oxide, and zirconium oxide, respectively.
  • Example 2 After dissolving 15 g of zinc nitrate, 20 g of HPO 4 and 30 g of zirconia in distilled water, the solution was overpaid in the same manner as in Example 1, except that the solution was mixed with 75 g of gamma alumina ( ⁇ -Al 2 O 3 ). A catalyst for decomposing chemical compounds was prepared.
  • Example 2 After dissolving 4 g of zinc nitrate and 8 g of HPO 4 and 8 g of zirconia in distilled water, the solution was overpaid in the same manner as in Example 1, except that the solution was mixed with 75 g of gamma alumina ( ⁇ -Al 2 O 3 ). A catalyst for decomposing chemical compounds was prepared.
  • Example 1 without using HPO 4 , a catalyst for decomposing a perfluorinated compound was prepared according to the composition of Table 1 below.
  • Example 1 a catalyst for decomposing a perfluorinated compound was prepared according to the composition of Table 1, without using zirconia.
  • Example 1 without using zinc nitrate, a catalyst for decomposing a perfluorinated compound was prepared according to the composition of Table 1 below.
  • compositions obtained by analyzing the catalysts of Examples and Comparative Examples by XRF are shown in Table 1 below.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ingredient Content (wt%) Al 2 O 3 75.0 71.5 88.2 95.0 77.2 77.1 76.9 P 2 O 5 2.2 5.2 2.3 4.6 0 2.2 2.2 ZnO 8.0 8.1 6.9 0.1 8.0 20.0 0 ZrO 2 14.0 14.5 4.0 0.2 14.0 0 20.0 Etc 0.8 0.7 0.9 0.1 0.8 0.7 0.9 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Perfluoride removal efficiency (%) (1-(Concentration of perfluoride at reactor outlet / Concentration of perfluoride at reactor inlet)) X 100
  • Table 2 below is a table showing the conversion rate according to the temperature of each perfluorinated compound when using the catalyst of Example 1 Comparative Example 1. Table 2 is shown in the graph of FIG. 6.
  • Example 1 Comparative Example 1 Perfluorinated compounds Reaction temperature (°C) Decomposition rate (%) NF 3 250 25 17 300 45 17 350 70 40 400 92 62 450 100 95 500 100 100 SF 6 400 19 - 450 30 19 500 54 29 550 88 62 600 100 91 650 100 100 C 2 F 6 500 21 - 550 34 8 600 50 20 650 81 51 700 100 100 CF 4 550 50 33 600 75 40 650 92 69 700 99 91 750 99 99 800 100 100 100
  • CF 4 is a temperature of 700° C. Decomposition rate above 99%, C 2 F 6 decomposition rate above 81% at a temperature of 650°C, SF 6 decomposition rate above 88% at a temperature of 550°C, NF 3 decomposition rate above 92% at a temperature of 400°C It was confirmed that it appeared.
  • CF 4 has a decomposition rate of about 91% at a temperature of 700° C.
  • C 2 F 6 has a decomposition rate of about 51% at a temperature of 650° C.
  • SF 6 is 550. It was confirmed that the decomposition rate of about 62% at the temperature of °C, and NF 3 showed the decomposition rate of about 62% at the temperature of 400°C.
  • Example 1 The catalysts prepared in Example 1 and Comparative Example 1 were taken at 7.6 g each, filled into a 3/4 inch Inconel reaction tube, and the reaction temperature was adjusted from 650°C to 800°C at 50°C intervals using an external heater. Tetrafluoromethane was decomposed (Fresh catalytic decomposition) while supplying 3000 ppm of tetrafluoromethane (CF 4 ), H 2 O: 8 vol%, air balance under conditions of a space velocity of 2000/h.
  • CF 4 tetrafluoromethane
  • Example 1 the catalyst prepared in Example 1 and Comparative Example 1 at a temperature of 900 °C at a space velocity of 2000 / h, tetrafluoromethane (CF4) 15000ppm, H 2 O: 16vol%, Temp.: 900 °C, Air balance After aging, tetrafluoromethane was decomposed (aged catalytic decomposition) in the same manner as the fresh catalytic decomposition.
  • CF4 tetrafluoromethane
  • the catalysts of Examples and Comparative Examples were aged in the same manner as in Experimental Example 2, except that the aging temperatures were changed to 900°C and 1,000°C, respectively. Subsequently, tetrafluoromethane was decomposed in the same manner as in Experimental Example 2, using an unaged catalyst (fresh catalyst) and a catalyst aged at 900°C and 1,000°C, respectively.
  • the calculated decomposition rate is shown in Table 4 below, and it is illustrated in the graph of FIG. 8.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Catalyst type Reaction temperature (°C) Decomposition rate (%) Fresh catalyst 650 93 80 87 72 93 79 89 700 99 92 96 90 99 94 98 750 100 99 100 98 100 99 100 800 100 100 100 99 100 100 100 900°C-aged catalyst 650 84 99 69 55 71 31 72 700 96 98 93 88 90 53 92 750 100 90 99 98 99 75 98 800 100 72 100 100 100 100 100 89 100 1,000°C-aged catalyst 650 50 36 33 12 30 11 21 700 64 55 50 24 42 21 38 750 83 77 700 45 71 40 59 800 92 85 78 68 86 61 67
  • Example 1 showed the highest decomposition efficiency immediately after preparation or even after aging at a high temperature.
  • Example 2 which has a higher content of phosphorus oxide than Example 1, a certain durability was secured, but it was confirmed that the initial efficiency was lowered.
  • Example 3 the content of zirconium oxide and zinc oxide was lower than that of Example 1, it was confirmed that the initial performance was excellent, but the durability was deteriorated according to high temperature aging.

Abstract

Selon des modes de réalisation donnés à titre d'exemple, la présente invention concerne un catalyseur destiné à la décomposition de composés perfluorés qui comprend de l'oxyde d'aluminium, de l'oxyde de zirconium, de l'oxyde de phosphore et de l'oxyde de zinc. Selon des modes de réalisation donnés à titre d'exemple, la présente invention concerne un procédé de préparation du catalyseur de décomposition de composés perfluorés consistant à générer une solution par dissolution d'un précurseur d'oxyde de zirconium, d'un précurseur d'oxyde de phosphore et d'un précurseur d'oxyde de zinc dans de l'eau distillée. Mélanger un précurseur d'oxyde d'aluminium dans la solution afin de générer un matériau de support de catalyseur. Faire sécher le matériau de support de catalyseur. Faire cuire le matériau de support de catalyseur.
PCT/KR2019/018312 2018-12-21 2019-12-23 Catalyseur pour la décomposition de composés perfluorés, et procédé de préparation correspondant WO2020130748A1 (fr)

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KR20060086896A (ko) * 1997-06-20 2006-08-01 가부시끼가이샤 히다치 세이사꾸쇼 불소 함유 화합물의 분해 처리 방법, 촉매 및 분해 처리장치
KR20130051191A (ko) * 2011-11-09 2013-05-20 한국화학연구원 할로겐족 산성가스가 함유된 과불화 화합물 분해용 촉매 및 이의 제조방법
KR20170101160A (ko) * 2016-02-25 2017-09-05 주식회사 에코프로 과불화 화합물 분해용 내산성 촉매 및 이의 용도
KR20180073859A (ko) * 2016-12-23 2018-07-03 주식회사 에코프로 과불화화합물 분해 장치 및 분해 방법
KR101869375B1 (ko) * 2017-08-25 2018-07-19 주식회사 에코프로 과불화 화합물을 분해하기 위한 알루미늄 산화물 촉매 및 이를 제조하는 방법

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Publication number Priority date Publication date Assignee Title
KR20060086896A (ko) * 1997-06-20 2006-08-01 가부시끼가이샤 히다치 세이사꾸쇼 불소 함유 화합물의 분해 처리 방법, 촉매 및 분해 처리장치
KR20130051191A (ko) * 2011-11-09 2013-05-20 한국화학연구원 할로겐족 산성가스가 함유된 과불화 화합물 분해용 촉매 및 이의 제조방법
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