CN107398295A - A kind of catalyst and preparation method for catalytic purification VOC - Google Patents
A kind of catalyst and preparation method for catalytic purification VOC Download PDFInfo
- Publication number
- CN107398295A CN107398295A CN201710657365.5A CN201710657365A CN107398295A CN 107398295 A CN107398295 A CN 107398295A CN 201710657365 A CN201710657365 A CN 201710657365A CN 107398295 A CN107398295 A CN 107398295A
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- Prior art keywords
- catalyst
- noble metal
- carrier
- base metal
- type base
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 41
- 239000010953 base metal Substances 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims description 32
- 239000002808 molecular sieve Substances 0.000 claims description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000005416 organic matter Substances 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- 230000035939 shock Effects 0.000 abstract description 2
- 239000000567 combustion gas Substances 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- 230000003068 static effect Effects 0.000 description 38
- 238000003756 stirring Methods 0.000 description 37
- 239000003643 water by type Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 18
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 17
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 16
- 230000008859 change Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 235000011837 pasties Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000520 microinjection Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 pharmacy Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical class [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- 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
- 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
- B01J29/44—Noble metals
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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
- 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
- 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
- B01J29/48—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst and preparation method for catalytic purification VOC, the catalyst, it is calcined and is made at 350 1000 DEG C after being mixed by support type base metal catalysts with loaded noble metal catalyst, wherein support type base metal catalysts are made up of carrier and the base metal being carried on carrier, and loaded noble metal catalyst is made up of carrier and the noble metal being carried on carrier and auxiliary agent.The mass ratio of support type base metal catalysts and loaded noble metal catalyst is 1:99~99:1.Catalyst prepared by the present invention has high activity, especially shows high activity, high thermal stability, high hydrothermal stability, high thermal shock performance, long-life to conventional VOCs such as aromatic hydrocarbons, oxygen-bearing organic matter, alkene, alkane；Preparing raw material is easy to get, and preparation technology is easy, and bullion content low cost is low.The catalyst applies also for the catalytic combustion elimination of volatile organic matter, and the industry such as the production of zero level air, combustion gas/fuel handling, gas deoxidation purifying.
Description
Technical field
The present invention relates to catalyst technical field, specifically a kind of catalysis for catalytic purification VOC
Agent and preparation method.
Background technology
VOC (Volatile Organic Compounds, VOCs) is saturated vapor under a kind of normal temperature
Pressure is more than organic compound of the boiling point below 260 DEG C under 70Pa, normal pressure, or vapour pressure is more than or equal under the conditions of 20 DEG C
10Pa has corresponding volatile organic compound, its mainly include alkanes, aromatic hydrocarbons, esters, aldehydes, halogenated hydrocarbons and other
Deng most common to have benzene,toluene,xylene, styrene, trichloro ethylene, ethyl acetate, formaldehyde etc..Most of such material is originally
Body has toxicity (such as benzene homologues are defined as strong carcinogen by the World Health Organization) or is easy to participate in atmospheric photochemical reaction
Cause the production process of the industry such as photochemical pollution, petrochemical industry, fine chemistry industry, paint, pharmacy, leather, textile printing and dyeing
In largely discharge such material, the living environment of serious threat to the mankind.Therefore, it is particularly necessary to VOCs purified treatment.
Catalysis oxidation (burning) method is proved to be one of most effectual way of purifying VOCs waste gas extensively, and it refers in catalyst
In the presence of VOCs can at a lower temperature (reaction temperature is generally below 500 DEG C) occur oxidation reaction, generate nontoxic CO2 and
H2O.The core technology of this method is the research and development of effective catalyst.
Applied to VOCs be catalyzed burning purification catalyst it is common be divided into simple metal oxide, composite oxides
(such as perovskite, spinelle, hexa-aluminate) and loaded noble metal catalyst etc., wherein loaded noble metal catalyst show
Go out high activity, high stability and by it is widely studied and application.But the disadvantage of such catalyst is that cost is higher, therefore
By reducing bullion content or by optimizing catalytic component/preparation technology so that it shows high work to broad spectrum activity VOCs
Property etc. approach so as to reducing the Main way that cost is such catalyst research and development at present.In addition, existing VOCs catalysis combustion
Burn cleaning catalyst also generally existing catalytic activity and stability be not high, hydrothermal stability is bad, high temperature heat-resistant impact property compared with
Difference, the life-span is shorter and generates the defects of complex process cost is high.
The content of the invention
It is an object of the invention to provide a kind of catalyst for catalytic purification VOC and preparation side
Method, to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of catalyst for catalytic purification VOC, by support type base metal catalysts and support type
It is calcined and is made at 350-1000 DEG C after noble metal catalyst mixing, wherein support type base metal catalysts by carrier and is carried on
Base metal composition on carrier, loaded noble metal catalyst are made up of carrier and the noble metal being carried on carrier and auxiliary agent.
As the further scheme of the present invention：Base metal includes the one or more in transition metal and rare earth metal, mistake
Crossing metal includes：Cr, Mn, Fe, Co, Ni, Zn, Cu, rare earth metal include：Y、La、Ce、Pr、Nd、Sm.
As the further scheme of the present invention：Noble metal includes the one or more in Pt, Pd, Ru, Ag, Au, Rh and Ir.
As the further scheme of the present invention：Carrier includes oxide-based carrier and one kind or more in molecular sieve carrier
Kind, oxide-based carrier includes Al2O3、SiO2、TiO2、ZrO2And its their composite oxides, molecular sieve carrier include X,
Y, M, A, CHA, MFI, Beta, phosphate aluminium molecular sieve.
As the further scheme of the present invention：Auxiliary agent includes alkali metal, alkaline-earth metal, one kind in rare earth metal or more
Kind.
As the further scheme of the present invention：Noble metal includes two kinds or two kinds in Pt, Pd, Ru, Ag, Au, Rh and Ir
More than, more preferably Pt and Pd；Auxiliary agent is combined by alkaline-earth metal or alkali metal with rare earth metal.
As the further scheme of the present invention：Auxiliary agent is made up of K and La.
As the further scheme of the present invention：The carrier of support type base metal catalysts uses oxide-based carrier；Load
The carrier of type noble metal catalyst uses molecular sieve carrier.
As the further scheme of the present invention：In support type base metal catalysts, base metal mass content is 0.1wt%-
50wt% (in terms of support type base metal catalysts), noble metal mass content is 0.01wt%- in loaded noble metal catalyst
50wt%, auxiliary agent mass content are 0.01wt%-20wt% (in terms of loaded noble metal catalyst).
As the further scheme of the present invention：In support type base metal catalysts, base metal mass content is 5wt%-
15wt% (in terms of support type base metal catalysts), noble metal mass content is 0.1wt%, helped in loaded noble metal catalyst
Agent mass content is 0.1wt%-5wt% (in terms of loaded noble metal catalyst).
As the further scheme of the present invention：The mass ratio of support type base metal catalysts and loaded noble metal catalyst
For 1:99~99:1.
As the further scheme of the present invention：The mass ratio of support type base metal catalysts and loaded noble metal catalyst
For 1:5~5:1.
A kind of preparation method of catalyst for catalytic purification VOC, comprises the following steps：
(1) support type base metal catalysts and loaded noble metal catalyst are made respectively, by the low-priced gold of obtained support type
Metal catalyst is directly carried out in next step with loaded noble metal catalyst, or is handled and entered again by dry and baking modes
Row is in next step；
(2) support type base metal catalysts and loaded noble metal catalyst are sufficiently mixed uniformly, then in 350-1000
It is calcined and is made at DEG C.
As the further scheme of the present invention：The preparation side of support type base metal catalysts and loaded noble metal catalyst
Method is using equi-volume impregnating, coprecipitation or directly synthesizes.
As the further scheme of the present invention：The preparation side of support type base metal catalysts and loaded noble metal catalyst
Method uses equi-volume impregnating.
As the further scheme of the present invention：The dry temperature of support type base metal catalysts and loaded noble metal catalyst
Spend for 100-200 DEG C, sintering temperature is 450-850 DEG C.
As the further scheme of the present invention：In step (2), mixed method includes that mechanical lapping is dry-mixed, mechanical lapping is wet
Mixed, solution medium mixing, ultrasonic wave mixing.
As the further scheme of the present invention：In step (2), mixed method uses mechanical lapping wet mixing.
As the further scheme of the present invention：In step (2), sintering temperature is 450-850 DEG C.
VOCs method for preparing catalyst involved in the present invention can be used known to all those skilled in the art of the present invention
Method prepares two components of support type base metal catalysts and loaded noble metal catalyst respectively, particularly preferably, according to
" equi-volume impregnating " well known by persons skilled in the art carries out the load of metal component, and its specific steps includes：
(1) preparation of support type base metal catalysts：Base metal soluble-salt is dissolved in deionized water, then will oxidation
Species carrier or molecular sieve support dispersion are uniform in above-mentioned solution ＆ stir, then static placement 0.5-48 hours at room temperature,
4-48 hours are dried at 50-150 DEG C again, 2-24 hours are calcined at 350-1000 DEG C, produce support type base metal catalysts；
(2) preparation of loaded noble metal catalyst：Precious metal soluble salt and promoter soluble salt are dissolved in necessarily
Then that support dispersion is uniform in above-mentioned solution ＆ stir in the deionized water of amount, then static placement 0.5-48 is small at room temperature
When, then dry 4-48 hours at 50-150 DEG C, 2-24 hours are calcined at 350-1000 DEG C, produce carried noble metal catalysis
Agent；
(3) the support type base metal catalysts and loaded noble metal catalyst and then by (1) and (2) step obtained pass through
Mechanical lapping is well mixed, then mixed uniformly powder is calcined into 2-48 hours at 350-1000 DEG C, produces catalyst.
As the further scheme of the present invention：In step (1), support type base metal catalysts：Static placement 12- at room temperature
24 hours, then dry 4-48 hours at 50-150 DEG C, 4-8 hours are calcined at 400-550 DEG C.
As the further scheme of the present invention：In step (2), loaded noble metal catalyst：Static placement 12- at room temperature
24 hours, then dry 4-48 hours at 50-150 DEG C, 4-8 hours are calcined at 400-550 DEG C.
As the further scheme of the present invention：In step (3), 8-12 hours are calcined at 550-750 DEG C.
As the further scheme of the present invention：Base metal soluble-salt, precious metal soluble salt, promoter soluble salt include
Nitrate, carbonate, oxalates, formates, sulfate, chloride.
As the further scheme of the present invention：Base metal soluble-salt uses nitrate, and precious metal soluble salt uses nitre
Hydrochlorate or chloride, promoter soluble salt use nitrite or chloride.
Compared with prior art, the beneficial effects of the invention are as follows：
Catalyst prepared by the present invention has high activity, especially to conventional VOCs for example aromatic hydrocarbons, oxygen-bearing organic matter, alkene,
Alkane shows high activity, high thermal stability, high hydrothermal stability, high thermal shock performance, long-life；Preparing raw material is easy
, preparation technology is easy, and bullion content low cost is low.It is organic that the catalyst applies also for other volatility in industrial waste gas
The catalytic combustion elimination of thing such as halogenated hydrocarbons, sulfur-bearing VOCs etc..
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/ZSM-5 components；
(3) it is 1 by mass ratio：1 10%Ce/Al obtained above2O3Component and 0.75%Pt0.25%Pd1%K1%
La/ZSM-5 components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 2
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then that 4g is sharp
The titanium oxide of titanium ore type adds in above-mentioned solution and stirs to obtain sticky solid, at room temperature static placement 24h, is finally done at 80 DEG C
Dry 24h, 4h is calcined at 450 DEG C, 10%Ce/TiO is made2Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/ZSM-5 components；
(3) by obtained 10%Ce/TiO2Component and 0.75%Pt0.25%Pd1%K1%La/ZSM-5 components press quality
Than 1：1 ratio, which adds, obtains pasty solid, then by being sufficiently mixed after mechanical lapping 30min, 110 DEG C in 3ml deionized waters
Lower drying is simultaneously calcined 12h at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 3
(1) 0.5g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g
Aluminum oxide adds in above-mentioned solution and stirs to obtain sticky solid, at room temperature static placement 24h, finally dried at 80 DEG C 24h,
4h is calcined at 450 DEG C, 5%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd0.5% is made
K1%La/ZSM-5 components；
(3) it is 1 by mass ratio：1 5%Ce/Al obtained above2O3Component and 0.75%Pt0.25%Pd1%K1%
La/ZSM-5 components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 4
(1) 1.28g Mn (NO are weighed3)2(50%) it is dissolved in 9ml deionized waters and is configured to clear solution, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 5%Mn/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/ZSM-5 components；
(3) it is 1 by mass ratio：1 5%Mn/Al obtained above2O3Component and 0.75%Pt0.25%Pd1%K1%
La/ZSM-5 components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 5
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g Beta molecular sieve powders are then scattered in above-mentioned solution ＆ stir, in room temperature
Under static placement 24h, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1%K1% is made
La/Beta components；
(3) it is 1 by mass ratio obtained above：1 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%
La/Beta components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 6
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g Y molecular sieve powder is then scattered in above-mentioned solution ＆ stir, at room temperature
Static placement 24h, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1%K1% is made
La/Y components；
(3) it is 1 by mass ratio obtained above：1 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%
La/Y components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 7
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g SSZ-13 molecular sieve powders are then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/SSZ-13 components；
(3) it is 1 by mass ratio obtained above：1 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%
La/SSZ-13 components are mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 8
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl, 0.12g La (NO are weighed3)3、3ml H2PtCl6(10mg/ml) and 1ml Na2PdCl4
(10mg/ml) is dissolved in 5ml deionized waters, then by 4g Al2O3It is uniform that powder is scattered in above-mentioned solution ＆ stir, in room temperature
Under static placement 24h, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1%K1% is made
La/Al2O3Component；
(3) by 10%Ce/Al obtained above2O3Component and 0.75%Pt0.25%Pd1%K1%La/Al2O3Component is pressed
Mass ratio 1：1 ratio, which adds, obtains pasty solid in 3ml deionized waters, then by being sufficiently mixed after mechanical lapping 30min,
Dried at 110 DEG C and and be calcined 12h at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 9
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.068g NaNO are weighed2With 0.12g La (NO3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
Na1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%Na1%La/ZSM-5 components press matter
Measure ratio 1：1 ratio is mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 10
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.061g BaCl are weighed2With 0.12g La (NO3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
Ba1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%Ba1%La/ZSM-5 components press matter
Measure ratio 1：1 ratio is mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 11
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.09g Pr (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%Pr/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%Pr/ZSM-5 components press quality
Than 1：1 ratio, which adds, obtains pasty solid, then by being sufficiently mixed after mechanical lapping 30min, 110 DEG C in 3ml deionized waters
Lower drying is simultaneously calcined 12h at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 12
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%La/ZSM-5 components press quality
Than 1：1 ratio is mixed by mechanical lapping, and 12h is calcined at 750 DEG C, that is, VOCs catalyst is made.
Embodiment 13
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.04g KCl and 0.12g La (NO are weighed3)3It is dissolved in 1.5ml H2PtCl6(10mg/ml) and 0.5ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.375%Pt0.125% is made
Pd0.5%K1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.375%Pt0.125%Pd0.5%K1%La/ZSM-5 components are pressed
Mass ratio 1：1 ratio, which adds, obtains pasty solid in 3ml deionized waters, then by being sufficiently mixed after mechanical lapping 30min, and
12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 14
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.08g KCl and 0.12g La (NO are weighed3)3It is dissolved in 3ml H2PtCl6(10mg/ml) and 1ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.75%Pt0.25%Pd1% is made
K1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.75%Pt0.25%Pd1%K1%La/ZSM-5 components press quality
Than 2：1 ratio is mixed by mechanical lapping, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Embodiment 15
(1) 4.76 grams of zirconium carbonates, 2.44 grams of cerous carbonates, 0.245 gram of praseodymium oxide and 0.245 gram of rubidium oxide is weighed to add
In 150ml deionized waters, 5ml nitric acid and 3ml hydrogen peroxide are added into above-mentioned suspension, the stirring and dissolving under 40 degree；Then by 4g
Aluminum oxide adds in above-mentioned 8.7ml solution and stirs to obtain sticky solid, at room temperature static placement 24h, is finally dried at 80 DEG C
24h, 4h is calcined at 450 DEG C, 50%CeZrPrNd/Al is made2O3Component；
(2) 0.04g KCl and 0.12g La (NO are weighed3)3It is dissolved in 1.5ml H2PtCl6(10mg/ml) and 0.5ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.375%Pt0.125% is made
Pd0.5%K1%La/ZSM-5 components；
(3) by obtained 50%CeZrPrNd/Al2O3Component and 0.375%Pt0.125%Pd0.5%K1%La/ZSM-5
Component in mass ratio 1：1 ratio, which adds, obtains pasty solid in 3ml deionized waters, then by abundant after mechanical lapping 30min
Mixing, and 12h is calcined at 650 DEG C, that is, VOCs catalyst is made.
Catalyst activity evaluation is carried out in normal pressure microreactor, by micro-injection pump by benzene,toluene,xylene
(three's volume ratio is 1 to mixture：1：1) vaporizer vaporization is injected, total concentration control is 1000ppm, and reaction gas is air, flow velocity
For 100ml/min, catalyst amount 100mg.VOCs concentration uses gas-chromatography (FID) on-line analysis before and after reaction, urges
Activity (the T of agent50, corresponding reaction temperature when conversion ratio is 50%；T99, corresponding reaction temperature when conversion ratio is 99%)
It is shown in Table 1.
The reactivity worth of the catalyst of table 1
Embodiment 16
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.04g KCl and 0.12g La (NO are weighed3)3It is dissolved in 0.5ml H2PtCl6(10mg/ml) and 1.5ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.125%Pt0.375% is made
Pd0.5%K1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.125%Pt0.375%Pd0.5%K1%La/ZSM-5 components are pressed
Mass ratio 1：1 ratio, which adds, obtains pasty solid in 3ml deionized waters, then by being sufficiently mixed after mechanical lapping 30min, and
4h is calcined at 450 DEG C, that is, VOCs catalyst is made.
The catalysis that the catalyst that embodiment 13 and 16 is obtained is used for acetic acid, acrylic acid, phthalic anhydride, cis-butenedioic anhydride is burnt.Its activity
Evaluation is carried out in normal pressure microreactor, by micro-injection pump by the mixed solution of acetic acid and acrylic acid (acetic acid and propylene
The mass ratio of acid is 2：3) to inject vaporizer vaporization or phthalic anhydride, cis-butenedioic anhydride are directly heated into vaporization, total concentration control is 2000ppm,
Reaction gas is air, flow velocity 100ml/min, catalyst amount 100mg.VOCs concentration uses gas-chromatography before and after reaction
(FID) on-line analysis, the activity (T of catalyst50, corresponding reaction temperature when conversion ratio is 50%；T99, when conversion ratio is 99%
Corresponding reaction temperature) it is shown in Table 2.
The embodiment 13 of table 2, the reactivity worth of 16 catalyst
Embodiment 17
(1) 1g Ce (NO are weighed3)3·6H2O is dissolved in the clear solution that Ce is configured in 9ml deionized waters, then by 4g oxygen
Change in the above-mentioned solution of aluminium addition and stir to obtain sticky solid, static placement 24h, finally dries 24h, 450 at 80 DEG C at room temperature
4h is calcined at DEG C, 10%Ce/Al is made2O3Component；
(2) 0.04g KCl and 0.12g La (NO are weighed3)3It is dissolved in 1.5ml RuCl3(10mg/ml) and 0.5ml
Na2PdCl4In (10mg/ml) solution, it is uniform that 4g ZSM-5 molecular sieve powder is then scattered in above-mentioned solution ＆ stir, in room
Static placement 24h under temperature, finally dry 24h at 80 DEG C again, be calcined 4h at 450 DEG C, 0.375%Ru0.125% is made
Pd0.5%K1%La/ZSM-5 components；
(3) by obtained 10%Ce/Al2O3Component and 0.375%Ru0.125%Pd0.5%K1%La/ZSM-5 components are pressed
Mass ratio 1：1 ratio, which adds, obtains pasty solid in 3ml deionized waters, then by being sufficiently mixed after mechanical lapping 30min, and
12h is calcined at 550 DEG C, that is, VOCs catalyst is made.
Catalyst is used for the activity rating of chloride volatile organic matter (CVOCs) catalysis burning in normal pressure microreactor
Carry out, dichloroethanes or chlorobenzene are injected into vaporizer by micro-injection pump vaporizes, and total concentration control is 1000ppm, reaction gas
For air, flow velocity 100ml/min, catalyst amount 100mg.CVOCs concentration uses gas-chromatography (FID) before and after reaction
On-line analysis, the T of catalyst99(corresponding reaction temperature when conversion ratio is 99%) is 300 DEG C (dichloroethanes) and 275 DEG C of (chlorine
Benzene).
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (10)
1. a kind of catalyst for catalytic purification VOC, it is characterised in that be catalyzed by support type base metal
Agent is calcined at 350-1000 DEG C after being mixed with loaded noble metal catalyst and is made, and wherein support type base metal catalysts are by carrying
Body and the base metal composition being carried on carrier, loaded noble metal catalyst by carrier and the noble metal being carried on carrier and
Auxiliary agent forms.
2. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that low-priced gold
Category includes the one or more in transition metal and rare earth metal, and transition metal includes：Cr, Mn, Fe, Co, Ni, Zn, Cu, rare earth
Metal includes：Y、La、Ce、Pr、Nd、Sm.
3. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that your gold
Category includes the one or more in Pt, Pd, Ru, Ag, Au, Rh and Ir.
4. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that carrier
Including the one or more in oxide-based carrier and molecular sieve carrier, oxide-based carrier includes Al2O3、SiO2、TiO2、
ZrO2And its their composite oxides, molecular sieve carrier include X, Y, M, A, CHA, MFI, Beta, phosphate aluminium molecular sieve.
5. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that auxiliary agent
Including the one or more in alkali metal, alkaline-earth metal, rare earth metal.
6. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that load
In type base metal catalysts, base metal mass content is 0.1wt%-50wt%.
7. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that load
In type noble metal catalyst, noble metal mass content is 0.01wt%-50wt%.
8. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that load
In type noble metal catalyst, auxiliary agent mass content is 0.01wt%-20wt%.
9. the catalyst according to claim 1 for catalytic purification VOC, it is characterised in that load
The mass ratio of type base metal catalysts and loaded noble metal catalyst is 1:99~99:1.
A kind of 10. preparation of catalyst for catalytic purification VOC as described in claim 1-9 is any
Method, it is characterised in that comprise the following steps：
(1) support type base metal catalysts and loaded noble metal catalyst are made respectively, obtained support type base metal is urged
Agent is directly carried out in next step with loaded noble metal catalyst, or is handled and carried out down again by dry and baking modes
One step；
(2) support type base metal catalysts and loaded noble metal catalyst are sufficiently mixed uniformly, then at 350-1000 DEG C
Roasting is made.
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