WO2010098586A2 - 촉매체 및 상기를 사용한 포름알데히드의 제거 방법 - Google Patents
촉매체 및 상기를 사용한 포름알데히드의 제거 방법 Download PDFInfo
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- WO2010098586A2 WO2010098586A2 PCT/KR2010/001159 KR2010001159W WO2010098586A2 WO 2010098586 A2 WO2010098586 A2 WO 2010098586A2 KR 2010001159 W KR2010001159 W KR 2010001159W WO 2010098586 A2 WO2010098586 A2 WO 2010098586A2
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- WIPO (PCT)
- Prior art keywords
- ceramic
- catalyst
- paper
- zeolite
- catalyst body
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 109
- 239000010457 zeolite Substances 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000010970 precious metal Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 230000003197 catalytic effect Effects 0.000 description 10
- -1 aldehyde compounds Chemical class 0.000 description 8
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- 238000010304 firing Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
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- 238000000354 decomposition reaction Methods 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
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- 241000218631 Coniferophyta Species 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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- B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
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- B01J29/88—Ferrosilicates; Ferroaluminosilicates
Definitions
- the present invention relates to a catalyst body capable of efficiently removing harmful gases such as formaldehyde and a method for removing formaldehyde using the same.
- harmful chemicals include aldehyde compounds such as formaldehyde, and such compounds are mainly contained in interior materials such as paints, wallpaper, plastic or synthetic floorings, carpets, windows or doors.
- Representative examples of the method of removing the above-mentioned harmful chemicals include a catalytic material in which a precious metal such as palladium, gold or silver is supported on a metal oxide carrier such as titanium dioxide, and a residential environment such as an apartment, building, house, school, hospital or office. Chemicals emitted from walls or floors laid in the interior can have a very bad effect on the human body. Accordingly, researches on techniques for efficiently removing such chemicals are being conducted.
- harmful chemicals include aldehyde compounds such as formaldehyde, and such compounds are mainly contained in interior materials such as paints, wallpaper, plastic or synthetic floorings, carpets, windows or doors.
- a catalyst material in which a noble metal such as palladium, gold or silver is supported on a metal oxide carrier such as titanium dioxide is used. It is used on a ceramic structure.
- Japanese Patent Laid-Open No. 1997-94436 discloses a catalyst for oxidizing formaldehyde gas, in which a metal oxide carrier carrying a noble metal is supported on a cordierite-based ceramic structure.
- the present invention has been made in view of the above-described problems of the prior art, and provides a porous ceramic structure capable of maximizing the resolution of the supported catalyst component, and a catalyst body including the catalyst component supported in the structure and a method of using the same. The purpose.
- the present invention as a means for solving the above problems, a ceramic structure containing a porous ceramic paper; And it provides a catalyst body comprising a catalyst component supported on the ceramic structure.
- the present invention provides a method for removing formaldehyde comprising the step of contacting the catalyst body of the present invention with formaldehyde as another means for solving the above problems.
- the catalyst component is supported on a structure made of ceramic paper having excellent properties such as porosity and specific surface area, thereby maximizing the effective area to which the supported catalyst component and the material to be treated can react, thereby exhibiting more excellent performance.
- Sieve can be provided.
- FIG. 1 is a view showing a porous ceramic structure according to an aspect of the present invention.
- FIG. 2 is a graph showing the conversion rate of formaldehyde according to the change in space velocity and contact temperature of the reactor in the method of removing formaldehyde according to an aspect of the present invention.
- the present invention is a ceramic structure containing a porous ceramic paper; And it relates to a catalyst body comprising a catalyst component supported on the ceramic structure.
- a ceramic structure prepared using porous ceramic paper is used as a support for supporting the catalyst component.
- the porous ceramic paper may be produced by, for example, a general papermaking method using various ceramic fibers as a raw material.
- the ceramic structure manufactured through the porous ceramic paper has higher productivity than the existing cordierite-based structure manufactured by the extrusion method, and the pore characteristics (eg, pore size and porosity) can be easily controlled. There is an advantage to this.
- the catalytic reaction occurs only in a portion where the catalyst component exists on the surface of the structure, but in the case of porous ceramic paper, Since the pore property of the catalyst can be controlled well, the supported catalyst remains fixed inside the paper, and the gas to be treated is diffused into the paper, thereby maximizing the effective contact area between the catalyst component and the reactant material. Can be.
- the ceramic structure of the present invention may have a structure including a ceramic corrugated paper 112 and a ceramic plate paper 111 attached to the corrugated paper, as shown in FIG. 1. Since the ceramic structure has a three-dimensional network structure as described above, it is possible to further maximize the reaction region of the catalyst component included. Ceramic plate-like and corrugated papers (hereinafter sometimes referred to as "ceramic papers”) may be produced using ceramic fibers.
- the ceramic fibers used for producing the ceramic paper may generally have a diameter of 1 ⁇ m to 6 ⁇ m, and the average length thereof is preferably 0.6 mm to 10 mm. If the length is less than 0.6 mm, the strength of the ceramic paper may be lowered, or the desired pore characteristics may not be obtained. If the length is more than 10 mm, it may be difficult to uniformly disperse the fibers in the slurry as a raw material. There is a fear that non-uniformity is caused or desired pore characteristics are not obtained.
- the ceramic fiber used by this invention is a material excellent in heat resistance.
- a material excellent in heat resistance examples include aluminum and / or silicon, and specifically, one or more selected from the group consisting of silica, alumina, silica-alumina, aluminosilicate, alumino borosilicate and mullite, It is not limited to this.
- the ceramic paper of the present invention may further include 5 parts by weight to 30 parts by weight of organic fibers, based on 100 parts by weight of the ceramic fiber.
- organic fibers examples include natural fibers such as conifer pulp, wood fibers or hemps; And synthetic fibers such as nylon, rayon, polyester, polypropylene, polyethylene, aramid or acrylic, and one or more of the above may be used.
- Such organic fibers are preferably contained in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the ceramic fiber in the ceramic paper. If the content is less than 5 parts by weight, it is difficult to maintain the tensile strength of the ceramic green paper, making it difficult to corrugate during the manufacturing process. If the content exceeds 30 parts by weight, the porosity of the ceramic structure is excessively increased or the strength of the structure is increased. There is a risk of deterioration.
- the ceramic paper of the present invention may also further comprise 5 parts by weight to 20 parts by weight of the binder together with the aforementioned ceramic fibers and organic fibers.
- the kind of binder which can be used by this invention is not specifically limited, It is preferable to use an organic binder.
- binders examples include epoxy based binders, sodium carboxymethyl cellulose (CMC), polyacrylamide (PAM), polyethylene oxide (PEO), methyl cellulose, hydroxyethyl cellulose, purified starch, dextrin, polyvinyl alcohol, Polyvinyl butyral, polymethyl (meth) acrylate, polyethylene glycol, paraffin, wax emulsion, and microcrystalline wax.
- Such a binder is preferably included in the ceramic paper in an amount of 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the ceramic fiber. If the content is less than 5 parts by weight, there is a fear that the bonding force between the fibers is lowered, if it exceeds 20 parts by weight, the flowability and adhesion of the ceramic green paper is increased, there is a fear that the workability is lowered.
- the thickness of the ceramic paper of this invention containing the above components exists in the range of 200 micrometers-500 micrometers. If the thickness of the ceramic paper is less than 200 ⁇ m, there is a risk that the catalytic activity is reduced by reducing the space for supporting the catalyst component and the area where the reaction material is diffused when using the structure, if the thickness exceeds 500 ⁇ m, the reaction material should be diffused There is a fear that the amount of the catalyst component that cannot be participating in the catalytic reaction increases because the region to be excessively large.
- the ceramic paper also preferably has a porosity of 60 to 90%.
- porosity used in the present invention means the volume of pores relative to the total volume of the ceramic structure. If the porosity of the ceramic paper is less than 60%, there may be a decrease in the amount of catalyst components that can be supported, and the diffusion efficiency of the reaction material may be lowered. If it exceeds 90%, the pore present becomes too large and the diffusion efficiency is rather high. However, there is a fear that the effective reaction area is reduced.
- the method for producing the porous ceramic structure of the present invention as described above is not particularly limited.
- the porous ceramic structure may include a first step of forming a ceramic corrugated paper by corrugating ceramic green paper;
- It can be produced by a method comprising a fourth step of firing the ceramic paper subjected to the third step.
- the ceramic green paper used in the first step may be prepared using a slurry including ceramic fibers, organic fibers and a binder.
- the method for producing the ceramic green paper is not particularly limited, and for example, a general papermaking method may be used.
- the specific type and content of each component constituting the slurry in the above is as described above.
- the slurry may be prepared by dissolving the aforementioned components in a general solvent such as water, wherein the content of ceramic fibers in the slurry may be 50% by weight to 80% by weight based on solids, and 70% by weight to 80% by weight. It is more preferable that is.
- the content of the ceramic fiber is not particularly limited as long as the concentration of the slurry is maintained to such an extent that the entire process can be smoothly maintained.
- a vacuum pump is connected to a paper making device to smoothly remove water during the process, to remove excess water through the pump, and to remove excess water through an additional means such as a press. You can also remove it.
- the slurry used for the ceramic green paper may also further comprise a pH adjuster, in view of further improvement of the adhesion of the binder component and the fiber component.
- the specific kind of the pH adjuster is not particularly limited, and a general means such as ammonium aluminum sulfate (alum) can be used.
- the content of the pH adjuster is not particularly limited and may be added, for example, in an amount capable of maintaining the pH of the slurry in the range of 5.5 to 6.5.
- the waveform shaping method for producing the ceramic corrugated paper in the first step using the ceramic green paper is not particularly limited, and can be performed using, for example, a generalized corrugating apparatus.
- the corrugating apparatus used in the present invention is configured such that the depth of the valley of the drum is about 1 to 5 mm, the pitch is about 1 to 5 mm, respectively, and the surface temperature and the feeding speed of the paper are adjustable. Preferred, but not limited to.
- the second step is the step of attaching the ceramic corrugated paper prepared in the manner as described above to the ceramic plate-shaped paper.
- Attachment of the plate-shaped and corrugated paper in this step may be prepared by placing the ceramic plate-shaped paper on the lower portion of the ceramic corrugated paper, applying an adhesive to the contact surface, and then bonding.
- the adhesive may use an adhesive generally used in the art, which is not particularly limited.
- the present invention it is possible to enter the third step through a process such as winding the ceramic green paper manufactured by attaching the plate-like and corrugated paper in the form of cochlear or cylindrical shape.
- the third step of the present invention is a step of coating the ceramic molded body prepared as above with a binder material. After passing through the binder coating process and undergoing a sintering process to be described later, ceramic paper or the like may be strongly aggregated by the coated binder to prepare a final structure.
- the kind of the binder that can be used in the above is not particularly limited, and a general binder component known in the art may be used. In this invention, it is especially preferable to use an inorganic binder precursor solution as said binder.
- the binder can be uniformly applied to the surface of the paper through the capillary effect of the ceramic green paper having a porosity, and improves the bonding force between the ceramic fibers in the firing process described later Therefore, the mechanical strength of the whole structure can be remarkably improved.
- Examples of the inorganic binder precursor solution that can be used at this time include, but are not limited to, a kind of silica sol, silane solution, siloxane solution, alumina sol, zirconia sol, aluminum silicate solution or aluminum phosphate solution.
- the method of coating the binder on the ceramic paper in the third step is not particularly limited.
- the binder may be performed by a conventional method such as impregnation, coating or spraying.
- the ceramic green paper is dried after the coating step with the primary coating solution as described above, and can be applied to the subsequent firing step.
- the drying process may be carried out at a temperature of room temperature to 200 °C, but the drying temperature and time is not particularly limited as long as it is controlled to allow sufficient drying.
- the above-described coating and drying process of the binder may be repeated several times.
- the fourth step of the present invention is a step of firing the ceramic green paper subjected to the coating treatment as described above, and when the inorganic binder precursor solution is used as the binder component, the inorganic binder precursor solution uniformly coated on the paper during the process By forming strong bonds, the mechanical strength of the structure can be improved.
- the conditions of the firing process are not particularly limited, and for example, it may be carried out at a temperature of 400 °C to 1,200 °C in a vacuum, inert gas or air. If the said temperature is less than 400 degreeC, there exists a possibility that removal of an organic component may be inadequate, and when it exceeds 1,200 degreeC, there exists a possibility that intensity
- the above-described coating and / or firing step may be performed only once, in order to further improve the mechanical strength of the structure, the above-described coating, drying and firing processes may be repeatedly performed several times in sequence.
- the catalyst body of the present invention is characterized in that it comprises a catalyst component supported on the structure together with the porous ceramic structure that can be produced through the above process.
- the type of catalyst component that can be used at this time is not particularly limited, and any conventional catalyst component used for removing harmful substances such as formaldehyde can be used without limitation.
- zeolite particularly as the catalyst component, zeolite; Precious metal materials supported on the zeolite; And catalyst compositions comprising an active metal.
- zeolite is used as a carrier for supporting a noble metal material exhibiting catalytic activity.
- zeolite used in the present invention is a generic term for crystalline aluminosilicate, and is used as a concept including a naturally produced zeolite and an artificially synthesized zeolite.
- the zeolite as a carrier of the catalytically active material as described above, it is possible to provide a catalyst composition exhibiting excellent catalytic activity while using a small amount of the catalytically active material.
- the zeolite used in the present invention preferably has a specific surface area of 400 m 2 / g or more, and more preferably 600 m 2 / g or more.
- specific surface area used in the present invention means a surface area per unit mass of a zeolite as a carrier, and when the specific surface area of the zeolite is less than 400 m 2 / g, the amount of catalytically active material that can be adsorbed is reduced, so that the catalyst There exists a possibility that activity may fall.
- the kind of zeolite which can be used in the above is not particularly limited, and various zeolites known in the art may be used.
- zeolites examples include one or more types of mordenite, ferrierite, ZSM-5, ⁇ -zeolite, Ga-silicate, Ti-silicate, Fe-silicate or Mn-silicate. Can be mentioned. In this invention, it is especially preferable to use the said (beta) -zeolite among these.
- ⁇ -zeolite has superior properties such as porosity and specific surface area as compared with other types of zeolites, and can further improve the effects of the present invention.
- the precious metal material supported on the zeolite in the catalyst component of the present invention exhibits catalytic activity for decomposing and removing harmful gases such as formaldehyde, and the specific kind thereof is not particularly limited.
- the precious metal material ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt) or gold (Au) Or the like, or a combination of two or more, but is not limited thereto.
- palladium may be used, in particular, in terms of excellent catalytic activity compared to price.
- the noble metal material may be included in an amount of 0.25 to 1 parts by weight based on 100 parts by weight of zeolite used as a carrier. If the content is less than 0.25 parts by weight, there is a fear that the catalytic activity is lowered, if it exceeds 1 parts by weight, the relative effective area of the zeolite carrier is reduced, and also the catalyst activity is lowered, or the price of the final composition may be too expensive have.
- the catalyst component of the present invention may also comprise an active metal in addition to each component described above. As such, since the active metal is included, even when a small amount of precious metal is included in the catalyst composition, excellent catalytic activity can be exhibited.
- the type of active metal that can be used in the present invention is not particularly limited as long as it can exhibit the above-described characteristics, and for example, one or more kinds of manganese (Mn), cerium (Ce), and cobalt (Co) may be used. have.
- the active metal as described above may be included in the catalyst composition supported on the zeolite, which is a carrier together with the precious metal material, and the content thereof may be 5 to 20 parts by weight based on 100 parts by weight of the zeolite. If the content is less than 5 parts by weight, the degree of contribution of the active metal to the catalytic activity may be reduced. If the content is more than 20 parts by weight, the relative content of the catalytically active component such as a noble metal material is reduced, resulting in a decrease in the performance of the catalyst composition. There is a concern.
- the method for preparing the catalyst composition including the respective components is not particularly limited.
- the catalyst composition may be prepared by a process such as a general impregnation method, precipitation method or sol-gel method using each of the above-described components or precursors thereof.
- the method for supporting the catalyst component prepared in the above manner in the above-described porous ceramic structure is not particularly limited.
- the ceramic structure may be immersed in a slurry or suspension containing the catalyst component, or the catalyst component may be supported by a method of applying or coating the surface of the structure.
- the material may be used to support the catalyst component in the porous ceramic structure.
- the invention also relates to a method for removing formaldehyde comprising the step of contacting the catalyst body according to the invention described above with formaldehyde.
- formaldehyde in the method for removing formaldehyde according to the present invention, can be converted into carbon dioxide by contacting a gas containing an aldehyde compound to be removed with the catalyst body of the present invention.
- the reactor space velocity may be 1000 to 5000 h ⁇ 1 , preferably 1000 to 3500 h ⁇ 1 , more preferably 1000 to 2000 h ⁇ 1 days Can be.
- reactor space velocity means a value calculated when dividing the amount (m 3 / h) of feed gas flowing into the reactor by the volume (m 3 ) occupied by the reactor.
- amount of formaldehyde-containing gas injected into the catalyst reactor equipped with the catalyst body according to the present invention is measured by the volume of gas per hour, and the amount is divided by the volume of the catalyst reactor to form the reactor. The rate at which the aldehyde containing gas is injected can be calculated.
- the reactor space velocity is less than 1000 h -1, there is a fear that the efficiency decreases because the reaction process time is too long compared to the conversion efficiency of formaldehyde exceeding 5000 h -1, in order to remove the formaldehyde Since high temperature energy is required, energy efficiency may be lowered.
- the reactor may include all known catalytic reactors commonly used in decomposition catalytic reactions, and the reaction process using the reactor may also be carried out through decomposition catalyst systems known in the art.
- the contact temperature of the gas containing the aldehyde compound and the catalyst body is not particularly limited, but may be 40 to 300 °C, preferably 40 to 200 °C or more, more preferably 150 to 200 °C Can be.
- the reactor space velocity should be lower accordingly, so there is a fear that the efficiency according to the reaction time is lowered, if it exceeds 300 °C, the efficiency is high in that the energy consumption due to the temperature rise is large There is a risk of deterioration.
- the reactor space velocity and the contact temperature of the formaldehyde and the catalyst body may be appropriately selected and adjusted within the range according to the reaction time, energy consumption according to heating, and the required conversion rate.
- the space velocity and contact temperature of the reactor are not limited to the ranges exemplified above.
- a slurry solution was prepared by mixing a catalyst component including 0.25 parts by weight of palladium (Pd) and 20 parts by weight of manganese (Mn) with distilled water at a weight ratio of 3: 7, based on 100 parts by weight of ⁇ -zeolite.
- a final slurry solution was prepared by mixing a solution containing alumina sol binder by weight in a weight ratio of 1: 4.
- alumina-silica fiber having an average length of 600 to 1000 ⁇ m was added to 2000 ml of water, followed by vigorous stirring to disperse the fibers. Subsequently, coniferous pulp was added as 25 parts by weight based on 100 parts by weight of the ceramic fiber as an organic fiber, and an acrylic binder was added in an amount of 10 parts by weight based on the fiber.
- the prepared green paper was corrugated at a feed rate of 2 to 10 m / min at a surface temperature of 150 ° C. using a wave forming device (model name: KIER, bone: 2 mm, pitch: 3 mm, a chemical device). , Ceramic corrugated paper was prepared.
- a ceramic green paper was prepared in the same manner as in (1) except that the corrugation process was not performed, and this was used as the ceramic plate-shaped paper.
- a base paper was prepared by attaching the ceramic plate paper and corrugated paper prepared in (1) and (2), and the base paper was made into a cylinder having a diameter of 3.5 cm and a height of 5 cm. Subsequently, the prepared cylindrical green compact was supported on silica sol (solid content concentration: 20%), and then taken out and dried in an oven at 120 ° C.
- the mixture was naturally dried at room temperature for 1 hour, then calcined at a temperature of 950 ° C. for 60 minutes, and cooled in a furnace to prepare a ceramic structure.
- the final slurry solution of the catalyst component prepared in Preparation Example 1 was coated on the ceramic structure prepared in Preparation Example 2 and then dried at 110 ° C. This process was repeated to adjust the catalyst component to 20 wt% coating on the ceramic structure.
- the catalyst structure coated with the ceramic structure was calcined at 300 ° C. for 5 hours to prepare a catalyst body.
- Example 1 Using the catalyst body of Example 1, the decomposition reaction of formaldehyde (HCHO) according to the space velocity (1,000, 3,500 and 5,000 h - 1) of the reactor was measured.
- the reactor space velocity was calculated by dividing the amount of feed gas flowing into the reactor by the volume occupied by the reactor.
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Abstract
Description
Claims (15)
- 다공성 세라믹 페이퍼를 함유하는 세라믹 구조체; 및상기 세라믹 구조체에 담지된 촉매 성분을 포함하는 촉매체.
- 제 1 항에 있어서, 세라믹 구조체는 세라믹 파형 페이퍼 및 상기 파형 페이퍼에 부착된 세라믹 판형 페이퍼를 포함하는 것을 특징으로 하는 촉매체.
- 제 1 항에 있어서, 세라믹 페이퍼는 평균 길이는 0.6 mm 내지 10 mm인 세라믹 섬유를 포함하는 것을 특징으로 하는 촉매체.
- 제 1 항에 있어서, 세라믹 페이퍼는 두께가 200 내지 500 ㎛인 것을 특징으로 하는 촉매체.
- 제 1 항에 있어서, 세라믹 페이퍼는 기공률이 60 내지 90%인 것을 특징으로 하는 촉매체.
- 제 1 항에 있어서, 촉매 성분은 제올라이트; 상기 제올라이트에 담지된 귀금속 물질; 및 활성 금속을 포함하는 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 제올라이트는 비표면적이 400m2/g 이상인 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 제올라이트는 모르데나이트, 페리에라이트, ZSM-5, β-제올라이트, Ga-실리케이트, Ti-실리케이트, Fe-실리케이트 또는 Mn-실리케이트인 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 귀금속 물질이 루테늄, 로듐, 팔라듐, 은, 오스뮴, 이리듐, 백금 및 금으로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 귀금속 물질은 제올라이트 100 중량부에 대하여 0.25 중량부 내지 1 중량부로 포함되는 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 활성 금속이 망간, 세륨 및 코발트로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 촉매체.
- 제 6 항에 있어서, 활성 금속은 제올라이트 100 중량부에 대하여 5 중량부 내지 20 중량부로 포함되는 것을 특징으로 하는 촉매체.
- 제 1 항 내지 제 12 항 중 어느 한 항에 따른 촉매체를 포름알데히드와 접촉시키는 단계를 포함하는 포름알데히드의 제거 방법.
- 제 13 항에 있어서, 반응기 공간속도는 1000 내지 5000 h-1인 것을 특징으로 하는 포름알데히드의 제거 방법.
- 제 14 항에 있어서, 접촉 온도는 40℃ 이상인 것을 특징으로 하는 포름알데히드의 제거 방법.
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EP10746425A EP2402084A4 (en) | 2009-02-25 | 2010-02-24 | CATALYST, AND PROCESS FOR REMOVING FORMALDEHYDES USING THE SAME |
CN201080007630.1A CN102316980B (zh) | 2009-02-25 | 2010-02-24 | 催化剂体和使用所述催化剂体的除去甲醛的方法 |
JP2011550073A JP2012517343A (ja) | 2009-02-25 | 2010-02-24 | 触媒体及びこれを使用したホルムアルデヒドの除去方法 |
US13/202,693 US20110305617A1 (en) | 2009-02-25 | 2010-02-24 | Catalyst and method for removing formaldehyde using the same |
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KR1020090015934A KR101322050B1 (ko) | 2009-02-25 | 2009-02-25 | 촉매체 및 상기를 사용한 포름알데히드의 제거 방법 |
KR10-2009-0015934 | 2009-02-25 |
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CN115870006B (zh) * | 2022-11-29 | 2024-05-31 | 北京工业大学 | 一种用于低浓度甲醛降解的陶瓷基复合材料及其制备方法 |
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- 2010-02-24 JP JP2011550073A patent/JP2012517343A/ja active Pending
- 2010-02-24 WO PCT/KR2010/001159 patent/WO2010098586A2/ko active Application Filing
- 2010-02-24 EP EP10746425A patent/EP2402084A4/en not_active Withdrawn
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CN115870006A (zh) * | 2022-11-29 | 2023-03-31 | 北京工业大学 | 一种用于低浓度甲醛降解的陶瓷基复合材料及其制备方法 |
CN115870006B (zh) * | 2022-11-29 | 2024-05-31 | 北京工业大学 | 一种用于低浓度甲醛降解的陶瓷基复合材料及其制备方法 |
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CN102316980B (zh) | 2015-07-01 |
EP2402084A2 (en) | 2012-01-04 |
US20110305617A1 (en) | 2011-12-15 |
EP2402084A4 (en) | 2012-07-11 |
JP2012517343A (ja) | 2012-08-02 |
KR20100096864A (ko) | 2010-09-02 |
KR101322050B1 (ko) | 2013-10-25 |
WO2010098586A3 (ko) | 2010-12-02 |
CN102316980A (zh) | 2012-01-11 |
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