WO2005037430A1 - Ceramic catalyst having improved absorption and disintegration properties for vapor phase compounds and preparation method thereof - Google Patents
Ceramic catalyst having improved absorption and disintegration properties for vapor phase compounds and preparation method thereof Download PDFInfo
- Publication number
- WO2005037430A1 WO2005037430A1 PCT/KR2004/002671 KR2004002671W WO2005037430A1 WO 2005037430 A1 WO2005037430 A1 WO 2005037430A1 KR 2004002671 W KR2004002671 W KR 2004002671W WO 2005037430 A1 WO2005037430 A1 WO 2005037430A1
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- WIPO (PCT)
- Prior art keywords
- salt
- water
- sduble
- porous ceramic
- daim
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000000919 ceramic Substances 0.000 title claims abstract description 83
- 239000012808 vapor phase Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000001875 compounds Chemical class 0.000 title abstract description 12
- 238000010521 absorption reaction Methods 0.000 title abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000002184 metal Substances 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 69
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 52
- 238000010304 firing Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- -1 aluminum compound Chemical class 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001868 cobalt Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000440 bentonite Substances 0.000 claims description 11
- 229910000278 bentonite Inorganic materials 0.000 claims description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 10
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 10
- 150000001661 cadmium Chemical class 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 10
- 239000010433 feldspar Substances 0.000 claims description 10
- 159000000003 magnesium salts Chemical class 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- 159000000008 strontium salts Chemical class 0.000 claims description 10
- 150000003681 vanadium Chemical class 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- 159000000009 barium salts Chemical class 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 150000001722 carbon compounds Chemical class 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 3
- SGPGESCZOCHFCL-UHFFFAOYSA-N Tilisolol hydrochloride Chemical compound [Cl-].C1=CC=C2C(=O)N(C)C=C(OCC(O)C[NH2+]C(C)(C)C)C2=C1 SGPGESCZOCHFCL-UHFFFAOYSA-N 0.000 claims 26
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 8
- 229910052782 aluminium Inorganic materials 0.000 claims 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 150000002894 organic compounds Chemical class 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/16—Clays or other mineral silicates
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- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
Definitions
- the present invention relates to a ceramic catalyst having absorption and disintegration properties for vapor phase chemicals and a preparation method thereof.
- the present invention relates to a metal oxide contained porous ceramic catalyst capable of absorbing and disintegrating vapor phase chemicals which is obtained by impregnating a water-soluble metal salt into ceramic material and then firing to disperse a metal oxide therein and a preparation method thereof.
- an object of the present invention is to provide a ceramic catalyst having absorption and disintegration properties for vapor phase compounds even at a bw temperature of less than 100 ° C regardless of an assistance of light, and a preparation method thereof.
- a porous ceramic catalyst containing a metal oxide capable of absorbing and disintegrating vapor phase chemicals obtained by immersing water-soluble metal salt in a porous ceramic material, firing, and then uniformly dispersing a metal oxide in the ceramic material, and a preparation method thereof.
- the present invention relates to a ceramic catalyst having absorption and disintegration properties for vapor phase chemicals and a preparation method thereof.
- the present invention relates to a metal oxide contained porous ceramic catalyst capable of absorbing and disintegrating vapor phase chemicals which is obtained by impregnating a water-soluble metal salt into ceramic material and then firing to disperse a metal oxide therein and a preparation method thereof.
- a porous ceramic catalyst containing a metal oxide of the present invention is a non-photoassisted room temperature catalyst capable of disintegrating vapor phase organic compounds at a bw temperature such as an ordinary room temperature regardless of light, and can easily disintegrate organic vapor phase compositions without additionaly irradiating light or without additionaly heating temperature up to a high temperature.
- the present invention provides a porous ceramic catalyst containing a metal oxide capable of absorbing and disintegrating vapor phase compositions at a bw temperature, obtained by mixing a mixture of 70 to 99.5 wt% of a porous ceramic material and 0.5 to 30 wt% of a water-soluble metal salt with water, then shaping, drying and firing, to make a metal oxide derived from the metal salt uniformly dispersed in the ceramic material.
- the porous ceramic catalyst of the present invention may also be obtained by further adding a combustible material to the mixture of the porous ceramic material and the water-soluble metal salt and mixing, wherein the added amount of the combustible material is 70 wt% or less based on the total weight of the mixture of the porous ceramic material and the water-soluble metal salt.
- the porous ceramic catalyst of the present invention may also be additionaly coated with metal salt aqueous solution in which 1 to 20 wt% of a water-soluble metal salt is dissolved.
- the present invention is to provide a preparation method of a porous ceramic catalyst containing a metal oxide comprising the steps of:
- the preparation method of a porous ceramic catalyst may comprise the step of additionaly mixing the mixture of the porous ceramic material and water-soluble metal salt with a combustible material, wherein the amount of the combustible material is 70 wt% or less based on the weight of the mixture of the porous ceramic material and water-soluble metal salt.
- the preparation method of a porous ceramic catalyst may further comprise the step (d) of impregnating the obtained porous ceramic catalyst containing a metal oxide into metal salt aqueous solution containing 1 to 20 wt% of water- solution metal salt for at least five minutes, sufficiently drying, and secondarily firing at a temperature of 40 0 ° C to 1,400 ° C, to coat the porous ceramic catalyst containing a metal oxide with a metal oxide.
- the porous ceramic material used in the present invention is preferably a powder form, and may be one or more materials selected from a group consisting of porous alumina (Al O ), day, kaolin, flint pebble, pottery stone, feldspar, veinstone, zeolite, 2 3 bentonite, aluminum compounds (e.g., aluminum sulfate), a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of porous silica (SiO ). 2
- the water- soluble metal salt used in the present invention may be one or more materials selected from a group consisting of water-soluble cobalt salts [e.g., Co(C H O ) ], magnesium salts [e.g., Mg(C H O ) ], strontium salts [e.g., Sr(C H O ) ], barium 2 2 2 3 2 2 2 3 2 2 salt [e.g., Ba(C H O ) ], vanadium salts [e.g., V (SO ) ], chrome salts [e.g., Cr(NO ) ], 2 3 2 2 2 2 4 3 3 3 manganese salts [e.g., Mn(C H O ) ], ferric salts (e.g., FeCl ), nickel salts (e.g., NiSO 2 3 2 3 4 ), copper salts (e.g., CuCl ), zinc salts (e.g., ZnCl ), cadmium salts [e.g
- the 2 water-s uble metal salt may be a water-soluble cobalt salt [e.g., Co(C H O ) ], or a 2 3 2 2 mixture of the water-soluble cobalt salt with one or more salts selected from the group consisting of magnesium salts [e.g., Mg(C H O ) ], strontium salts [e.g., Sr(C H O ) ], 2 3 2 2 2 3 2 2 2 barium salt [e.g., Ba(C H O ) ], vanadium salts [e.g., V (SO ) ], chrome salts [e.g., 2 3 2 2 2 4 3 Cr(NO ) ], manganese salts [e.g., Mn(C H O ) ], ferric salts (e.g., FeCl ), nickel salts 3 3 2 3 2 2 3 (e.g., NiSO ), copper salts (e.g., CuCl ), zinc salts (e.g., M
- the above water-s uble metal salts have a characteristic to be changed into a corresponding metal oxide, when fired at a temperature of 400 ° C to 1400 ° C. Accordingly, by mixing the water-sduble metal salt and a porous ceramic material with water and then firing the mixture at a temperature of 400 ° C to 1400 ° C, a ceramic catalyst in which a metal oxide is uniformly dispersed in ceramic layers can be obtained.
- a combustible material may be optionaly used.
- the combustible material is preferably a powder form, and can be completely disintegrated into water, carbon dioxide and so forth, by being reacted with oxygen at a high temperature.
- the combustible material may be a powder type hydrocarbon compound consisting of carbon, hydrogen and oxygen, such as adipic acid, melanin, sugar, stearic acid, paraffin, etc.; a powder type carbon compound such as carbon black, fine coal, graphite powder, etc.; or a mixture thereof.
- the combustible material is completely disintegrated into water and carbon dioxide to form a porous ceramic layer having a uniform pore, when mixed with a ceramic material, and fired at a temperature of 40 0 ° C to 1,400 ° C.
- the vapor phase compounds which can be absorbed and/or disintegrated by the ceramic catalyst of the present invention indude al odorous materials, and especialy indude aldehydes, alcohds, amines and benzenes.
- the amount of the water-sduble metal salt is less than 0.5 wt% , the amount of the metal oxide derived therefrom is deficient, whereby the disintegration ablty of a final product is greatly deteriorated.
- the amount of the water-sduble metal salt exceeds 30 wt%, the derived metal oxide is unevenly dispersed in ceramic pores, whereby the disintegration ablty is deteriorated.
- 0.5 to 10 wt% of the water-sduble metal salt may be used.
- a combustible material may be added to and mixed with the mixture of the ceramic material and the water-sduble metal salt, in the amount of 70 wt% or less based on the weight of the mixture.
- the amount of the combustible material exceeds 70 wt% of the weight of the mixture of the ceramic material and the water- sduble metal salt, the formed pores are too large or can be destroyed.
- 25 to 65 wt% of the combustible material is used.
- water is used in the amount of 50 to 250 wt% based on the total weight of the sdid materials.
- the amount of water is less than 50 wt% of the total sdid materials, the kneaded paste is so crumbly that the water-sduble metal salt con not be uniformly dispersed in the ceramic pore.
- the amount of water is more than 250 wt% of the total sdid materials, a problem can be caused in forming pores in the ceramic catalyst during a drying or firing process.
- the firing temperature is bwer than 400 ° C, the water-sduble metal salt is not disintegrated, whereby a metal oxide can not be generated in the ceramic layer.
- the firing temperature is higher than 1400 ° C, the generated metal oxide or metal may be changed into a liquid state to be extricated.
- the firing time is bnger than one hour.
- the porous ceramic catalyst containing a metal oxide may be immersed for at least five minutes into metal salt aqueous sdution in which 1 to 20 wt% of water-sduble metal salt is dissdved, and then sufficiently dried. Then, the porous ceramic catalyst is secondarily fired at the temperature of 40 0 ° C to 1,400 ° C to prepare a ceramic catalyst coated with a metal oxide. By said coating, the ceramic catalyst has various pores and disintegration properties.
- the amount of water-sduble metal salt contained in the metal salt aqueous sdution is less than 1 wt%, the amount of a metal oxide generated from the metal salt to be coated on the ceramic material is very little to deteriorate the coating effect. Also, when the amount of water-sduble metal salt contained in the metal salt aqueous sdution is more than 20 wt%, the amount of the generated metal oxide is excessive to greatly bwer the uniformity of the metal oxide coating. Most preferably, the contend of the metal salt in the metal salt aqueous sdution is approximately 5 to 15 wt%.
- the secondary firing temperature is 40 0 to 1,400 ° C, and the firing time is bnger than 30 minutes.
- the porous ceramic catalyst according to the present invention has excellent absorption and disintegration properties for vapor phase organic compounds even at a bw temperature of bwer than 1 00 ° C, such as an ordinary room temperature (approximately 25 ° C), and has an ability to disintegrate water and carbon dioxide at a high temperature of higher than 1 00 ° C.
- FIG. 1 shows a preparation process of a ceramic catalyst according to one embodiment of the present invention, in which the fd wing processes are carried out subsequently: Mixing Process (1) of mixing water-sduble metal salt A, ceramic material B, and combustible material C to obtain the mixture thereof having a uniform composition ratio; Shaping Process (2) of adding distiled water D to the mixture in an amount enough to completely dissdve the water-sduble metal salt and kneading to shape into the desired form; Drying Process (3) of sufficiently drying the shaped catalyst material at an ordinary room temperature; and Bring Process (4) of firing the shaped catalyst material at a temperature of 40 0 to 1,400 ° C.
- FIG. 2 shows an experimental apparatus for disintegrating vapor phase organic compounds used in the present invention.
- gas or vaporous compound is injected into a hermetic sealed stainless container 1 through a septum 2 until the concentrate thereof reach to the desired level.
- the compounds to be injected are liquid phase, the compounds are injected into an evaporation plate 3 to gradualy vaporize.
- a catalyst for absorbing and disintegrating vapor phase compounds is inputted to a catalyst input (stacked) vessel 4 having a bottom of a 500 mesh stainless wire netting.
- a fan 5 connected to an external power source through an electric wire and a concent 6 hbws fluid inside the stainless container 1 to the bottom of the catalyst stacked vessel to continuously circulate the fluid inside the stainless container.
- the ceramic catalyst of the present invention can absorb and disintegrate vapor phase composition even at a bw temperature of bwer than 100 ° C, especialy, at an ordinary room temperature of approximately 25 °C, without light assistance .
- FIG. 1 shows a preparation process of a ceramic catalyst according to one embodiment of the present invention, in which each reference numeral denotes the fdbws;
- FIG. 2 shows an experimental apparatus for disintegrating vapor phase organic compounds used in the present invention, in which each reference numeral denotes the fdbws;
- Example 1 Disintegration property of ceramic catalyst depending on the ceramic material used
- the obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to an experimental device (Hg. 2) for disintegrating vapor phase organic compounds.
- an experimental device Hg. 2 for disintegrating vapor phase organic compounds.
- 1000 ppm of propionic aldehyde (C H CHO) was 2 3 injected into the experimental device through the septum, and then maintained for 24 hours at an ordinary room temperature (25 °C to 30 °C) and 60 °C, respectively.
- the disintegration ratio for propionic aldehyde inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fdb wing table 1.
- Example 2 Disintegration property 1 of ceramic catalyst depending on metal oxide [75] [76] 97 weight parts of ceramic material in which 20 weight parts of porous alumina, 20 weight parts of kadin, 20 weight parts of zedite, 20 weight parts of veinstone, and 20 weight parts of bentonite were mixed, 2 weight parts of cobalt acetate, and 1 weight parts of water-sduble metal salt as shown in the fd wing table 2 were mixed with one another. Then, 60 weight parts of fine coal powder with an average diameter of 0.2 ⁇ m was added to the mixture to prepare a ceramic catalyst material mixture.
- the mixture was mixed with distiled water in the 1.5-times weight of the mixture, and kneaded. Then, the kneaded mixture was shaped as a cylindrical shape having the diameter of 3 cm and the length of 10 cm, and then dried for 72 hours at an ordinary room temperature. The dried material was fired in an electric furnace for 12 hours at the temperature of 1100 ° C, and then coded at an ordinary room temperature to fabricate a ceramic catalyst.
- the obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to the ex- perimental device (Hg. 2) for disintegrating vapor phase organic compounds.
- Hg. 2 ex- perimental device
- 1000 ppm of butand (C H OH) was injected to the 4 9 experimental device through the septum, and then maintained for 24 hours at an ordinary room temperature (25 °C to 30 °C) and 60 °C, respectively.
- the disintegration ratio for butand inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fd wing table 2.
- a ceramic catalyst of the present invention prepared by mixing a ceramic material with water-sduble metal salt and firing the mixture to disperse a metal oxide generated from the metal salt in the ceramic material has excellent absorbing and disintegrating properties for vapor phase organic compounds at a bw temperature of bwer than 100 °C, especialy, at an ordinary room temperature of approximately 25 °C.
- Example 3 Disintegration property 2 of ceramic catalyst depending on metal oxide
- [85] 97 weight parts of ceramic material, in which 20 weight parts of porous alumina, 20 weight parts of feldspar, 20 weight parts of zedite, 20 weight parts of veinstone, and 20 weight parts of bentonite were mixed, was mixed with 2 weight parts of cobalt acetate and 1 weight parts of water-sduble metal salt shown in the fd wing table 3. Then, 60 weight parts of fine coal powder with the average pup diameter of 0.2 ⁇ m was added to the mixture to prepare a ceramic catalyst material mixture.
- the mixture was mixed with distiled water in the 1.5-times weight of the mixture, and then kneaded. Then, the kneaded mixture was shaped as a cylindrical shape having the diameter of 3 cm and the length of 10 cm, and dried for 72 hours at an ordinary room temperature. The dried material was fired in an electric furnace for 12 hours at the temperature of 900 ° C, and then coded at an ordinary room temperature to prepare a ceramic catalyst.
- the obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to the experimental device (Hg. 2) for disintegrating vapor phase organic compounds. Sufficient amount of water was inputted into the evaporation plate and the experimental device was sealed to make a humidity inside a container saturated. Then, 2000 ppm of carbon dioxide (CO ) was injected to the experimental device through the 2 septum, and maintained for 72 hours with being heated to the temperature of 120 °C. The amounts of carbon dioxide CO and byproducts inside the experimental device 2 were measured by using a gas chromatography (HP-5890). The result was shown in the fd wing table 3.
- CO carbon dioxide
- the porous ceramic catalyst containing a metal oxide of the present invention has a disintegration property for carbon dioxide at a high temperature such as higher than 100 °C.
- Example 4 Disintegration property of ceramic catalyst additionaly coated with a metal oxide
- a ceramic catalyst prepared according to the process in Example 1 using porous alumina as a ceramic material was immersed into 10 wt% metal salt aqueous sdution for 3 hours, and dried for 24 hours at an ordinary room temperature.
- the dried metal salt contained catalyst was fired for 1 hour in an electric oven at a temperature of 1000 °C , and then coded to an ordinary room temperature, to fabricate a ceramic catalyst of the present invention.
- the obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and 5 g of the ceramic catalyst was inputted to the experimental device (Hg. 2) for disintegrating vapor phase organic compounds.
- the experimental device Hg. 2
- 1000 ppm of propionic aldehyde (C H CHO) was 2 3 injected to the experimental device through the septum, and maintained for 24 hours at an ordinary room temperature (25 °C to 30°C) and 60 °C respectively.
- the disintegration ratio for the propionic aldehyde inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fd wing table 4.
- a ceramic catalyst of the present invention which is additionaly coated with a metal salt aqueous sdution, has an excellent disintegration property for vapor phase organic compounds at a bw temperature, such as 60 °C or even at an ordinary room temperature.
- the metal oxide contained porous ceramic catalyst having various pores of the present invention which is obtained by dispersing a water-sduble metal salt into a ceramic material, or optionaly, by additionaly coating the ceramic catalyst with a metal salt aqueous sdution, has an remarkably improved disintegration property for vapor phase organic compounds.
- the porous ceramic catalyst can absorb and disintegrate vapor phase organic compounds even at a bw temperature, such as bwer than 100 °C, or even at an ordinary room temperature. Accordingly, the porous catalyst containing a metal oxide of the present invention has a great industrial applicability to various fields, such as a removal for odorous materials.
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Abstract
Disclosed are a ceramic catalyst containing a metal oxide having absorption and disintegration properties for vapor phase compounds prepared from a porous ceramic material, water-soluble metal salt, and optionally a combustible material, and a preparation method thereof comprising the step of mixing a porous ceramic material with a water-soluble metal salt and firing to a metal oxide generated from the metal salt uniformly dispersed in a ceramic material. The ceramic catalyst can absorb and disintegrate vapor phase composition even at a low temperature of lower than 100 ° C, especially, at an ordinary room temperature of approximately 25 °C, without light assistance .
Description
Description CERAMIC CATALYST HAVING IMPROVED ABSORPTION AND DISINTEGRATION PROPERTIES
FOR VAPOR PHASE COMPOUNDS AND PREPARATION METHOD THEREOF
[i] Technical Field
[2]
[3] The present invention relates to a ceramic catalyst having absorption and disintegration properties for vapor phase chemicals and a preparation method thereof. In particular, the present invention relates to a metal oxide contained porous ceramic catalyst capable of absorbing and disintegrating vapor phase chemicals which is obtained by impregnating a water-soluble metal salt into ceramic material and then firing to disperse a metal oxide therein and a preparation method thereof.
[4] Background Art
[5]
[6] Conventional catalysts for disintegrating vapor phase chemicals including bad- smeϊng materials have been able to perform their functions only at a high temperature of more than 100 ° C, and materials to which the catalysts can show their disintegrating function were limited (JP 2001-38207 and US 6,344,987). Accordingly, it was impossible to utffize the conventional disintegration catalysts for disintegrating bad-smeϊng materials in the actual life or for disintegrating industrial volatile materials at a bw temperature of less than 100 ° C. In order to utilize such catalysts, the temperature of the vapor phase compounds have to be maintained at more than 100 ° C or the vapor phase compounds have to be artificialy heated so as to have a temperature of more than 100 ° C. As the result, many problems have occurred, for example, the applicability of the catalyst was very limited, and that it was very expensive to disintegrate vapor phase chemicals.
[7] Disclosure of Invention Technical Problem
[8]
[9] Therefore, an object of the present invention is to provide a ceramic catalyst having absorption and disintegration properties for vapor phase compounds even at a bw temperature of less than 100 ° C regardless of an assistance of light, and a preparation method thereof.
[10] To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided a porous ceramic catalyst containing a metal oxide capable of absorbing and disintegrating vapor phase chemicals obtained by immersing water-soluble metal salt in a porous ceramic material, firing, and then uniformly dispersing a metal oxide in the ceramic material, and a preparation method thereof.
[11] The foregoing and other objects, features, aspects and advantages of the present invention wfl become more apparent from the folowing detailed description of the present invention when taken in conjunction with the accompanying drawings.
[12] Technical Solution
[13]
[14] Reference wfll now be made in detail to the preferred embodiments of the present invention, examples of which are fllustrated in the accompanying drawings.
[15] The present invention relates to a ceramic catalyst having absorption and disintegration properties for vapor phase chemicals and a preparation method thereof. In particular, the present invention relates to a metal oxide contained porous ceramic catalyst capable of absorbing and disintegrating vapor phase chemicals which is obtained by impregnating a water-soluble metal salt into ceramic material and then firing to disperse a metal oxide therein and a preparation method thereof.
[16] A porous ceramic catalyst containing a metal oxide of the present invention is a non-photoassisted room temperature catalyst capable of disintegrating vapor phase organic compounds at a bw temperature such as an ordinary room temperature regardless of light, and can easily disintegrate organic vapor phase compositions without additionaly irradiating light or without additionaly heating temperature up to a high temperature.
[17] The present invention provides a porous ceramic catalyst containing a metal oxide capable of absorbing and disintegrating vapor phase compositions at a bw temperature, obtained by mixing a mixture of 70 to 99.5 wt% of a porous ceramic material and 0.5 to 30 wt% of a water-soluble metal salt with water, then shaping, drying and firing, to make a metal oxide derived from the metal salt uniformly
dispersed in the ceramic material. The porous ceramic catalyst of the present invention may also be obtained by further adding a combustible material to the mixture of the porous ceramic material and the water-soluble metal salt and mixing, wherein the added amount of the combustible material is 70 wt% or less based on the total weight of the mixture of the porous ceramic material and the water-soluble metal salt. The porous ceramic catalyst of the present invention may also be additionaly coated with metal salt aqueous solution in which 1 to 20 wt% of a water-soluble metal salt is dissolved.
[ 18] Further, the present invention is to provide a preparation method of a porous ceramic catalyst containing a metal oxide comprising the steps of:
[19] (a) mixing 70 to 99.5 wt% of a porous ceramic material with 0.5 to 30 wt% of a water-soluble metal salt
[20] (b) kneading the obtained mixture with water and then shaping as a desired shape; and
[21] (c) sufficiently drying the shaped material at an ordinary room temperature, and firing at a temperature of 40 0 ° C to 1,400 ° C to make a metal oxide derived from the metal salt uniformly dispersed in the shaped material.
[22] Further, the preparation method of a porous ceramic catalyst may comprise the step of additionaly mixing the mixture of the porous ceramic material and water-soluble metal salt with a combustible material, wherein the amount of the combustible material is 70 wt% or less based on the weight of the mixture of the porous ceramic material and water-soluble metal salt.
[23] After the step (c), the preparation method of a porous ceramic catalyst may further comprise the step (d) of impregnating the obtained porous ceramic catalyst containing a metal oxide into metal salt aqueous solution containing 1 to 20 wt% of water- solution metal salt for at least five minutes, sufficiently drying, and secondarily firing at a temperature of 40 0 ° C to 1,400 ° C, to coat the porous ceramic catalyst containing a metal oxide with a metal oxide.
[24] The porous ceramic material used in the present invention is preferably a powder form, and may be one or more materials selected from a group consisting of porous alumina (Al O ), day, kaolin, flint pebble, pottery stone, feldspar, veinstone, zeolite, 2 3 bentonite, aluminum compounds (e.g., aluminum sulfate), a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of porous silica (SiO ). 2
[25] The water- soluble metal salt used in the present invention may be one or more materials selected from a group consisting of water-soluble cobalt salts [e.g., Co(C H
O ) ], magnesium salts [e.g., Mg(C H O ) ], strontium salts [e.g., Sr(C H O ) ], barium 2 2 2 3 2 2 2 3 2 2 salt [e.g., Ba(C H O ) ], vanadium salts [e.g., V (SO ) ], chrome salts [e.g., Cr(NO ) ], 2 3 2 2 2 4 3 3 3 manganese salts [e.g., Mn(C H O ) ], ferric salts (e.g., FeCl ), nickel salts (e.g., NiSO 2 3 2 2 3 4 ), copper salts (e.g., CuCl ), zinc salts (e.g., ZnCl ), cadmium salts [e.g., Cd(C H O ) ], 2 2 2 3 2 2 tin salts (e.g., SnCl ), tithmuth salts (e.g., BiPO ), sodium salt [e.g., sodium 2 4 hydroxide(NaOH), sodium sulfide(NaS), sodium sulfate(Na SO ), sodium sulfite(Na 2 4 2 SO ), sodium iodide(Nal)], calcium hydroxide [Ca(OH) ], lithium hydroxide (LiOH), 3 2 potassium hydroxide (KOH) and barium hydroxide [Ba(OH) ]. More preferably, the 2 water-s uble metal salt may be a water-soluble cobalt salt [e.g., Co(C H O ) ], or a 2 3 2 2 mixture of the water-soluble cobalt salt with one or more salts selected from the group consisting of magnesium salts [e.g., Mg(C H O ) ], strontium salts [e.g., Sr(C H O ) ], 2 3 2 2 2 3 2 2 barium salt [e.g., Ba(C H O ) ], vanadium salts [e.g., V (SO ) ], chrome salts [e.g., 2 3 2 2 2 4 3 Cr(NO ) ], manganese salts [e.g., Mn(C H O ) ], ferric salts (e.g., FeCl ), nickel salts 3 3 2 3 2 2 3 (e.g., NiSO ), copper salts (e.g., CuCl ), zinc salts (e.g., ZnCl ), cadmium salts [e.g., 4 2 2 Cd(C H O ) ], tin salts (e.g., SnCl ), tithmuth salts (e.g., BiPO ), sodium salt [e.g., 2 3 2 2 2 4 sodium hydroxide(NaOH), sodium sulfide(NaS), sodium sulfate(Na SO ), sodium 2 4 sulfite(Na SO ), sodium iodide(Nal)], calcium hydroxide [Ca(OH) ], lithium 2 3 2 hydroxide (LiOH), potassium hydroxide (KOH) and barium hydroxide [Ba(OH) ]. 2
[26] The above water-s uble metal salts have a characteristic to be changed into a corresponding metal oxide, when fired at a temperature of 400 ° C to 1400 ° C. Accordingly, by mixing the water-sduble metal salt and a porous ceramic material with water and then firing the mixture at a temperature of 400 ° C to 1400 ° C, a ceramic catalyst in which a metal oxide is uniformly dispersed in ceramic layers can be obtained.
[27] In the present invention, a combustible material may be optionaly used. The combustible material is preferably a powder form, and can be completely disintegrated into water, carbon dioxide and so forth, by being reacted with oxygen at a high temperature. The combustible material may be a powder type hydrocarbon compound consisting of carbon, hydrogen and oxygen, such as adipic acid, melanin, sugar, stearic acid, paraffin, etc.; a powder type carbon compound such as carbon black, fine coal, graphite powder, etc.; or a mixture thereof. The combustible material is completely disintegrated into water and carbon dioxide to form a porous ceramic layer having a uniform pore, when mixed with a ceramic material, and fired at a temperature of 40 0 ° C to 1,400 ° C.
[28] The vapor phase compounds which can be absorbed and/or disintegrated by the
ceramic catalyst of the present invention indude al odorous materials, and especialy indude aldehydes, alcohds, amines and benzenes.
[29] Hereinafter, a preparation method of the ceramic catalyst having absorption and disintegration properties for vapor phase compounds according to the present invention wΛ be fllustrated in more detail.
[30] Step (a): 70 to 99.5 wt% of the ceramic material in a porous powder form is mixed with 0.5 to 30 wt% of the water-sduble metal salt so that the total weight can be 100%. When the amount of the water-sduble metal salt is less than 0.5 wt% , the amount of the metal oxide derived therefrom is deficient, whereby the disintegration ablty of a final product is greatly deteriorated. When the amount of the water-sduble metal salt exceeds 30 wt%, the derived metal oxide is unevenly dispersed in ceramic pores, whereby the disintegration ablty is deteriorated. Most preferably, 0.5 to 10 wt% of the water-sduble metal salt may be used.
[31] In order to form a porous ceramic layer having more uniform pores in size and distribution, a combustible material may be added to and mixed with the mixture of the ceramic material and the water-sduble metal salt, in the amount of 70 wt% or less based on the weight of the mixture. When the amount of the combustible material exceeds 70 wt% of the weight of the mixture of the ceramic material and the water- sduble metal salt, the formed pores are too large or can be destroyed. Most preferably, 25 to 65 wt% of the combustible material is used.
[32] Step (b): Then, the mixture of the ceramic material, the water-sduble metal salt and the optional combustible material is kneaded with water and shaped into a desired form. Preferably, water is used in the amount of 50 to 250 wt% based on the total weight of the sdid materials. When the amount of water is less than 50 wt% of the total sdid materials, the kneaded paste is so crumbly that the water-sduble metal salt con not be uniformly dispersed in the ceramic pore. Also, when the amount of water is more than 250 wt% of the total sdid materials, a problem can be caused in forming pores in the ceramic catalyst during a drying or firing process.
[33] It is preferable to repeatedly perform the mixing process and the kneading process so that the water-sduble metal salt can be uniformly impregnated into the pores of the porous ceramic material in the condition of being dissdved in water.
[34] Step (c): Subsequently, the shaped material obtained in said process is sufficiently dried at an ordinary room temperature and fired at a temperature of 40 0 ° C to 1,400 ° C, whereby the metal oxide derived from the metal salt can be uniformly dispersed into the pores of the ceramic material, to fabricate the porous ceramic catalyst
containing a metal oxide of the present invention. When the firing temperature is bwer than 400 ° C, the water-sduble metal salt is not disintegrated, whereby a metal oxide can not be generated in the ceramic layer. When the firing temperature is higher than 1400 ° C, the generated metal oxide or metal may be changed into a liquid state to be extricated. Preferably, the firing time is bnger than one hour.
[35] Step (d): Optionaly, further to said processes, the porous ceramic catalyst containing a metal oxide may be immersed for at least five minutes into metal salt aqueous sdution in which 1 to 20 wt% of water-sduble metal salt is dissdved, and then sufficiently dried. Then, the porous ceramic catalyst is secondarily fired at the temperature of 40 0 ° C to 1,400 ° C to prepare a ceramic catalyst coated with a metal oxide. By said coating, the ceramic catalyst has various pores and disintegration properties. When the amount of water-sduble metal salt contained in the metal salt aqueous sdution is less than 1 wt%, the amount of a metal oxide generated from the metal salt to be coated on the ceramic material is very little to deteriorate the coating effect. Also, when the amount of water-sduble metal salt contained in the metal salt aqueous sdution is more than 20 wt%, the amount of the generated metal oxide is excessive to greatly bwer the uniformity of the metal oxide coating. Most preferably, the contend of the metal salt in the metal salt aqueous sdution is approximately 5 to 15 wt%. Preferably, the secondary firing temperature is 40 0 to 1,400 ° C, and the firing time is bnger than 30 minutes.
[36] The porous ceramic catalyst according to the present invention has excelent absorption and disintegration properties for vapor phase organic compounds even at a bw temperature of bwer than 1 00 ° C, such as an ordinary room temperature (approximately 25 ° C), and has an ability to disintegrate water and carbon dioxide at a high temperature of higher than 1 00 ° C.
[37] FIG. 1 shows a preparation process of a ceramic catalyst according to one embodiment of the present invention, in which the fd wing processes are carried out subsequently: Mixing Process (1) of mixing water-sduble metal salt A, ceramic material B, and combustible material C to obtain the mixture thereof having a uniform composition ratio; Shaping Process (2) of adding distiled water D to the mixture in an amount enough to completely dissdve the water-sduble metal salt and kneading to shape into the desired form; Drying Process (3) of sufficiently drying the shaped catalyst material at an ordinary room temperature; and Bring Process (4) of firing the shaped catalyst material at a temperature of 40 0 to 1,400 ° C.
[38] FIG. 2 shows an experimental apparatus for disintegrating vapor phase organic
compounds used in the present invention. For an experiment, gas or vaporous compound is injected into a hermetic sealed stainless container 1 through a septum 2 until the concentrate thereof reach to the desired level. When the compounds to be injected are liquid phase, the compounds are injected into an evaporation plate 3 to gradualy vaporize. A catalyst for absorbing and disintegrating vapor phase compounds is inputted to a catalyst input (stacked) vessel 4 having a bottom of a 500 mesh stainless wire netting. A fan 5 connected to an external power source through an electric wire and a concent 6 hbws fluid inside the stainless container 1 to the bottom of the catalyst stacked vessel to continuously circulate the fluid inside the stainless container.
[39] Advantageous Effects
[40]
[41] The ceramic catalyst of the present invention can absorb and disintegrate vapor phase composition even at a bw temperature of bwer than 100 ° C, especialy, at an ordinary room temperature of approximately 25 °C, without light assistance .
[42] Description of Drawings
[43]
[44] The accompanying drawings, which are induded to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, fllustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
[45]
[46] In the drawings:
[47] FIG. 1 shows a preparation process of a ceramic catalyst according to one embodiment of the present invention, in which each reference numeral denotes the fdbws;
[48] A: water-sduble metal salt,
[49] B: ceramic material,
[50] C combustible material,
[51] D: distiled water,
[52] E: catalyst,
[53] 1: mixing process,
[54] 2: shaping process,
[55] 3: drying process, and
[56] 4: firing process.
[57] FIG. 2 shows an experimental apparatus for disintegrating vapor phase organic compounds used in the present invention, in which each reference numeral denotes the fdbws;
[58] 1 : hermetic sealed reaction container,
[59] 2: septum,
[60] 3: evaporation plate,
[61] 4: catalyst input vessel,
[62] 5: fan, and
[63] 6: electric controler.
[64] Best Mode
[65] Examples
[66] Example 1 : Disintegration property of ceramic catalyst depending on the ceramic material used
[67]
[68] 90 weight parts of ceramic material is mixed with 1 weight part of each of ferric chbride, manganese acetate, vanadium sulfate, magnesium acetate, cobalt acetate, zinc chbride, cadmium acetate, barium nitrate and tin chbride. Then, 50 weight parts of stearic acid powder with an average partide diameter of 20 μm was added to the mixture to prepare a ceramic catalyst material mixture. As the ceramic material, as shown in the fdbwing table 1, porous alumina, kaolin, veinstone, zedite and a fired material containing 50 wt% of porous alumina and 50 wt% of porous silica were in- dividualy used.
[69] To the mixture, distiled water in the same weight as the mixture was added, and kneaded, then, the kneaded mixture was shaped as the cylindrical shape with the diameter of 3 cm and the length of 10 cm, and dried for 72 hours at an ordinary room temperature. The dried material was fired in an electric oven for 10 hours at the temperature of 1000 ° C, and then coded at an ordinary room temperature to fabricate a ceramic catalyst.
[70] The obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to an experimental device (Hg. 2) for disintegrating vapor phase organic compounds. After the experimental device was sealed, 1000 ppm of propionic aldehyde (C H CHO) was 2 3
injected into the experimental device through the septum, and then maintained for 24 hours at an ordinary room temperature (25 °C to 30 °C) and 60 °C, respectively. The disintegration ratio for propionic aldehyde inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fdb wing table 1.
[71] [72] [ Table 1 1
[73] [74] Example 2: Disintegration property 1 of ceramic catalyst depending on metal oxide [75] [76] 97 weight parts of ceramic material in which 20 weight parts of porous alumina, 20 weight parts of kadin, 20 weight parts of zedite, 20 weight parts of veinstone, and 20 weight parts of bentonite were mixed, 2 weight parts of cobalt acetate, and 1 weight parts of water-sduble metal salt as shown in the fd wing table 2 were mixed with one another. Then, 60 weight parts of fine coal powder with an average diameter of 0.2 μm was added to the mixture to prepare a ceramic catalyst material mixture.
[77] The mixture was mixed with distiled water in the 1.5-times weight of the mixture, and kneaded. Then, the kneaded mixture was shaped as a cylindrical shape having the diameter of 3 cm and the length of 10 cm, and then dried for 72 hours at an ordinary room temperature. The dried material was fired in an electric furnace for 12 hours at the temperature of 1100 ° C, and then coded at an ordinary room temperature to fabricate a ceramic catalyst.
[78] The obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to the ex-
perimental device (Hg. 2) for disintegrating vapor phase organic compounds. After the experimental device was sealed, 1000 ppm of butand (C H OH) was injected to the 4 9 experimental device through the septum, and then maintained for 24 hours at an ordinary room temperature (25 °C to 30 °C) and 60 °C, respectively. The disintegration ratio for butand inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fd wing table 2.
[79] [80] [ Table 2 ]
[81] [82] As shown in the above table 2, a ceramic catalyst of the present invention prepared by mixing a ceramic material with water-sduble metal salt and firing the mixture to disperse a metal oxide generated from the metal salt in the ceramic material has excelent absorbing and disintegrating properties for vapor phase organic compounds at a bw temperature of bwer than 100 °C, especialy, at an ordinary room temperature of approximately 25 °C.
[83] [84] Example 3: Disintegration property 2 of ceramic catalyst depending on metal oxide [85] [86] 97 weight parts of ceramic material, in which 20 weight parts of porous alumina, 20 weight parts of feldspar, 20 weight parts of zedite, 20 weight parts of veinstone, and 20 weight parts of bentonite were mixed, was mixed with 2 weight parts of cobalt acetate and 1 weight parts of water-sduble metal salt shown in the fd wing table 3. Then, 60 weight parts of fine coal powder with the average partide diameter of 0.2 μm was added to the mixture to prepare a ceramic catalyst material mixture.
[87] The mixture was mixed with distiled water in the 1.5-times weight of the mixture, and then kneaded. Then, the kneaded mixture was shaped as a cylindrical shape having the diameter of 3 cm and the length of 10 cm, and dried for 72 hours at an ordinary room temperature. The dried material was fired in an electric furnace for 12 hours at the temperature of 900 ° C, and then coded at an ordinary room temperature to prepare a ceramic catalyst.
[88] The obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and then 5 g of the ceramic catalyst was inputted to the experimental device (Hg. 2) for disintegrating vapor phase organic compounds. Sufficient amount of water was inputted into the evaporation plate and the experimental device was sealed to make a humidity inside a container saturated. Then, 2000 ppm of carbon dioxide (CO ) was injected to the experimental device through the 2 septum, and maintained for 72 hours with being heated to the temperature of 120 °C. The amounts of carbon dioxide CO and byproducts inside the experimental device 2 were measured by using a gas chromatography (HP-5890). The result was shown in
the fd wing table 3.
[89]
[90] [ Table 3 1
[91] [92] As shown in the above table 3, the porous ceramic catalyst containing a metal oxide
of the present invention has a disintegration property for carbon dioxide at a high temperature such as higher than 100 °C.
[93]
[94] Example 4: Disintegration property of ceramic catalyst additionaly coated with a metal oxide
[95] [96] A ceramic catalyst prepared according to the process in Example 1 using porous alumina as a ceramic material was immersed into 10 wt% metal salt aqueous sdution for 3 hours, and dried for 24 hours at an ordinary room temperature. The dried metal salt contained catalyst was fired for 1 hour in an electric oven at a temperature of 1000 °C , and then coded to an ordinary room temperature, to fabricate a ceramic catalyst of the present invention.
[97] The obtained cylindrical ceramic catalyst was ground so that an average diameter thereof could be 1 mm, and 5 g of the ceramic catalyst was inputted to the experimental device (Hg. 2) for disintegrating vapor phase organic compounds. After the experimental device was sealed, 1000 ppm of propionic aldehyde (C H CHO) was 2 3 injected to the experimental device through the septum, and maintained for 24 hours at an ordinary room temperature (25 °C to 30°C) and 60 °C respectively. The disintegration ratio for the propionic aldehyde inside the experimental device was measured by using a gas chromatography (HP-5890). The result was shown in the fd wing table 4.
[98] [99] [ Table 4 ]
[100]
[101] As shown in the above table 4, a ceramic catalyst of the present invention, which is additionaly coated with a metal salt aqueous sdution, has an excelent disintegration property for vapor phase organic compounds at a bw temperature, such as 60 °C or even at an ordinary room temperature.
[102] Industrial Applicability
[103]
[104] As aforementioned, the metal oxide contained porous ceramic catalyst having various pores of the present invention, which is obtained by dispersing a water-sduble metal salt into a ceramic material, or optionaly, by additionaly coating the ceramic catalyst with a metal salt aqueous sdution, has an remarkably improved disintegration property for vapor phase organic compounds. Especialy, the porous ceramic catalyst can absorb and disintegrate vapor phase organic compounds even at a bw temperature, such as bwer than 100 °C, or even at an ordinary room temperature. Accordingly, the porous catalyst containing a metal oxide of the present invention has a great industrial applicability to various fields, such as a removal for odorous materials.
[105] As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broady within its spirit and scope as defined in the appended daims, and therefore al changes and modifications that fal within the metes and bounds of the daims, or equivalence of such metes and bounds are therefore intended to be embraced by the appended daims.
[106]
Claims
[1] A porous ceramic catalyst containing a metal oxide having absorbing and disintegrating properties for vapor phase chemicals, obtained by mixing 70 to 99.5 wt% of a porous ceramic material and 0.5 to 30 wt% of water- sduble metal salt with water, shaping, drying and firing, and characterized in containing a metal oxide uniformly dispersed in the ceramic material.
[2] The porous ceramic catalyst containing a metal oxide of daim 1, wherein a combustible material is additionaly mixed with the mixture of the porous ceramic material and the water-sduble metal salt, and in the amount of the combustible material is 70 wt% or less of the weight of the mixture of the porous ceramic material and the water-sduble metal salt.
[3] The porous ceramic catalyst containing a metal oxide of daim 1, additionaly coated with metal salt aqueous sdution containing 1 to 20 wt% of water-sduble metal salt and thereby has a various pore distribution and a various disintegration property.
[4] The porous ceramic catalyst containing a metal oxide of daim 2, additionaly coated with metal salt aqueous sdution containing 1 to 20 wt% of water-sduble metal salt and thereby has a various pore distribution and a various disintegration property.
[5] The porous ceramic catalyst containing a metal oxide of daim 1, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O ), day, kadin, flint pebble, 2 3 pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[6] The porous ceramic catalyst containing a metal oxide of daim 2, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O ), day, kadin, flint pebble, 2 3 pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[7] The porous ceramic catalyst containing a metal oxide of daim 3, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O ), day, kadin, flint pebble, 2 3
pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[8] The porous ceramic catalyst containing a metal oxide of daim 4, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O ), day, kadin, flint pebble, 2 3 pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[9] The porous ceramic catalyst containing a metal oxide of daim 1, wherein the water-sduble metal salt is a water-sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[10] The porous ceramic catalyst containing a metal oxide of daim 2, wherein the water-sduble metal salt is a water-sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[11] The porous ceramic catalyst containing a metal oxide of daim 3, wherein the water-sduble metal salt is a water-sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[12] The porous ceramic catalyst containing a metal oxide of daim 4, wherein the water-sduble metal salt is a water-sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt,
cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[13] The porous ceramic catalyst containing a metal oxide of daim 2, wherein the combustible material is a powder type hydrocarbon compound composed of carbon, hydrogen, and oxygen, induding adipic acid, melanin, sugar, stearic acid, and paraffin; a powder type carbon compound selected from the group consisting of carbon black, fine coal and graphite powder; or a mixture thereof.
[14] The porous ceramic catalyst containing a metal oxide of daim 4, wherein the combustible material is a powder type hydrocarbon compound composed of carbon, hydrogen, and oxygen, induding adipic acid, melanin, sugar, stearic acid, and paraffin; a powder type carbon compound selected from the group consisting of carbon black, fine coal and graphite powder; or a mixture thereof.
[15] A method for preparing a porous ceramic catalyst containing a metal oxide comprising the steps of: (a) mixing 70 to 99.5 wt% of porous ceramic material with 0.5 to 30 wt% of water-sduble metal salt (b) kneading the mixture of the porous ceramic material and the water- sduble metal salt with water and then shaping the kneading material in a desired form; and (c) drying the shaped material at an ordinary room temperature, firing at a temperature of 400 °C to 1,400 °C, to uniformly disperse a metal oxide generated from the metal salt in the ceramic material.
[16] The method of daim 15, wherein a combustible material is added to the mixture of the porous ceramic material and the water-sduble metal salt, in the amount of 70 wt% or less based on the weight of the mixture to the mixture of the porous ceramic material and the water-sduble metal salt.
[17] The method of daim 15, fd wing to steps (a) to (c), further comprising the step (d) of immersing the obtained porous ceramic catalyst containing a metal oxide into metal salt aqueous sdution containing 1 to 20 wt% of water-sduble metal salt for at least five minutes, sufficiently drying and then secondarily firing at a temperature of 400 °C to 1,400 °C, to coat the porous ceramic catalyst containing a metal oxide with a metal oxide.
[18] The method of daim 16, fdbwing to steps (a) to (c), further comprising
the step (d) of immersing the obtained porous ceramic catalyst containing a metal oxide into metal salt aqueous sdution containing 1 to 20 wt% of water-sduble metal salt for at least five minutes, sufficiently drying and then secondarily firing at a temperature of 400 °C to 1,400 °C, to coat the porous ceramic catalyst containing a metal oxide with a metal oxide.
[19] The method of daim 15, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O 2 3 ), day, kadin, flint pebble, pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[20] The method of daim 16, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O 2 3 ), day, kadin, flint pebble, pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[21] The method of daim 17, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O 2 3 ), day, kadin, flint pebble, pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[22] The method of daim 18, wherein the porous ceramic material is at least one materials selected from the group consisting of porous alumina (Al O 2 3 ), day, kadin, flint pebble, pottery stone, feldspar, veinstone, zedite, bentonite, aluminum compound, and a fired material containing at least 10 wt% of porous alumina and at least 50 wt% of silica (SiO ). 2
[23] The method of daim 15, wherein the water-sduble metal salt is a water- sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[24] The method of daim 16, wherein the water-sduble metal salt is a water- sduble cobalt salt, or a mixture of a water-sduble cobalt salt and at least one materials selected from the group consisting of magnesium salt,
strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[25] The method of daim 17, wherein the water-sduHe metal salt is a water- sduHe cobalt salt, or a mixture of a water-sduHe cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, tithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[26] The method of daim 18, wherein the water-sduHe metal salt is a water- sduHe cobalt salt, or a mixture of a water-sduHe cobalt salt and at least one materials selected from the group consisting of magnesium salt, strontium salt, barium salt, vanadium salt, chrome salt, manganese salt, ferric salt, nickel salt, copper salt, zinc salt, cadmium salt, tin salt, bithmuth salt, sodium salt, calcium hydroxide, lithium hydroxide, potassium hydroxide and barium hydroxide.
[27] The method of daim 16, wherein the combustiHe material is a powder type hydrocarbon compound composed of carbon, hydrogen, and oxygen, induding adipic acid, melanin, sugar, stearic acid, and paraffin; a powder type carbon compound selected from the group consisting of carbon Hack, fine coal and graphite powder; or a mixture thereof.
[28] The method of daim 18, wherein the combustiHe material is a powder type hydrocarbon compound composed of carbon, hydrogen, and oxygen, induding adipic acid, melanin, sugar, stearic acid, and paraffin; a powder type carbon compound selected from the group consisting of carbon Hack, fine coal and graphite powder; or a mixture thereof.
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| KR10-2004-0075224 | 2004-09-20 | ||
| KR1020040075224A KR100665235B1 (en) | 2003-10-18 | 2004-09-20 | Ceramic catalyst having absorption and disintegration properties for vapor phase chemicals and preparation method thereof |
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| WO2005037430A1 true WO2005037430A1 (en) | 2005-04-28 |
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