CN113877603B - Monolithic catalyst, method for producing the same, and method for purifying exhaust gas containing bromine-containing organic matter - Google Patents
Monolithic catalyst, method for producing the same, and method for purifying exhaust gas containing bromine-containing organic matter Download PDFInfo
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- CN113877603B CN113877603B CN202010627365.2A CN202010627365A CN113877603B CN 113877603 B CN113877603 B CN 113877603B CN 202010627365 A CN202010627365 A CN 202010627365A CN 113877603 B CN113877603 B CN 113877603B
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- Prior art keywords
- alumina
- precursor
- catalyst
- noble metal
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 107
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 55
- 239000005416 organic matter Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 24
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 65
- 239000007789 gas Substances 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 43
- 239000002002 slurry Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 37
- 239000001301 oxygen Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- 229910017052 cobalt Inorganic materials 0.000 claims description 27
- 239000010941 cobalt Substances 0.000 claims description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 238000011068 loading method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 239000012695 Ce precursor Substances 0.000 claims description 14
- 239000012691 Cu precursor Substances 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006255 coating slurry Substances 0.000 claims description 5
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 229910052736 halogen Inorganic materials 0.000 abstract description 13
- 150000002367 halogens Chemical class 0.000 abstract description 13
- 239000002912 waste gas Substances 0.000 abstract description 13
- 230000001988 toxicity Effects 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 74
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 39
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 39
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 18
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 17
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 17
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 238000010926 purge Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- -1 and more preferably Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000012696 Pd precursors Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- UWTUEMKLYAGTNQ-UHFFFAOYSA-N 1,2-dibromoethene Chemical group BrC=CBr UWTUEMKLYAGTNQ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical group BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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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Abstract
The invention relates to the technical field of catalytic combustion and environmental protection, and discloses an integral catalyst, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters, wherein the catalyst comprises an integral carrier containing an alumina coating, and a noble metal active component and a non-noble metal active component which are loaded on the integral carrier; wherein the non-noble metal active component is a composite oxide containing cobalt oxide, cerium oxide and/or copper oxide; the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1. the monolithic catalyst has higher halogen toxicity resistance and stability, and can be used for purifying waste gas containing bromine-containing organic matters, and still has higher catalytic activity and selectivity at lower reaction temperature.
Description
Technical Field
The invention relates to the technical field of catalytic combustion and environmental protection, in particular to an integral catalyst, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters.
Background
Waste gases containing volatile organic compounds are often generated in petrochemical production processes, and if the waste gases are directly discharged into the atmosphere, the waste gases can cause great harm to the atmospheric environment. Most volatile organic compounds have peculiar smell, and generate lesions and even cancerogenesis to human bodies; in particular, the volatile organic waste gas containing halogen has high toxicity, and can generate photochemical reaction with ozone to generate photochemical smog, thereby greatly damaging the global environment.
The treatment method of volatile organic compounds at home and abroad is mainly divided into a physical method and a chemical method. The physical method comprises an adsorption method, a condensation method, a membrane separation method and the like, is a non-destructive method, and has the advantages that volatile organic compounds can be recycled, but the treatment is not thorough, and secondary pollution is easy to cause; the chemical method mainly comprises a direct thermal combustion method, a catalytic combustion method and the like. The chemical method is characterized by thorough treatment. The thermal combustion method is to crack harmful matters in the tail gas at high temperature up to 800-900 deg.c, and this method needs great amount of fuel oil, has high operation cost, high power consumption and low halogen-containing organic matter eliminating rate and produces nitrogen oxide. While catalytic combustion processes reduce the operating temperature by the action of a catalyst, at lower temperatures the activity of the catalyst is not high.
The catalyst for catalytic combustion mainly comprises: noble metal catalysts, such as Pt, pd, rh and the like, are generally high in activity, but poor in halogen resistance, easy to poison, poor in stability, rare in resources and high in price; single metal oxide catalysts, such as copper, manganese, cobalt, etc., which are relatively low cost but generally active; the catalytic activity and the toxicity resistance of the composite oxide catalyst are higher than those of the corresponding single oxide, and as disclosed in CN103252242B, a catalytic combustion catalyst of composite oxides of copper, manganese and cerium is disclosed, but the catalytic activity of the catalyst is still lower, and the reaction temperature is higher.
Disclosure of Invention
The invention aims to solve the problems of high catalytic reaction temperature, low catalyst activity, poor toxicity resistance and poor stability in the prior art, and provides an integral catalyst, a preparation method thereof and a method for purifying waste gas containing bromine-containing organic matters.
In order to achieve the above object, the present invention provides in one aspect a monolith catalyst comprising a monolith support comprising an alumina coating layer and a noble metal active component and a non-noble metal active component supported on the monolith support;
wherein the non-noble metal active component is a composite oxide containing cobalt oxide, cerium oxide and/or copper oxide;
the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
in a second aspect, the present invention provides a process for the preparation of a monolithic catalyst, the process comprising:
(1) Coating slurry containing alumina and/or alumina precursor on a monolithic carrier, and then drying and/or roasting to obtain the monolithic carrier containing alumina coating;
(2) Loading a composite oxide containing cobalt oxide and cerium oxide and/or copper oxide and a noble metal active component on a monolithic carrier containing an alumina coating;
the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
in a third aspect, the present invention provides a monolithic catalyst prepared by the method of preparation of the second aspect.
In a fourth aspect, the present invention provides a method for purifying an exhaust gas containing a bromine-containing organic substance, comprising reacting the exhaust gas containing the bromine-containing organic substance in contact with the monolithic catalyst according to the first or third aspect in an oxygen-containing atmosphere.
Through the technical scheme, the prepared monolithic catalyst has higher halogen toxicity resistance and stability, has higher catalytic activity and selectivity when being used for catalytic combustion of waste gas containing bromine-containing organic matters at lower reaction temperature, and is subjected to catalytic combustion reaction to the first step at lower reaction temperatureThe conversion rate of methyl acetate, paraxylene and dibromomethane can reach more than 99 percent and CO even at 1000 hours 2 The selectivity of the catalyst can reach 99 percent, which shows that the catalyst has higher stability and halogen toxicity resistance.
Drawings
FIG. 1 is an XPS spectrum of cobalt in the monolith catalyst prepared in example 7;
FIG. 2 is an XPS spectrum of cobalt in the monolith catalyst prepared in example 19;
FIG. 3 is an XPS spectrum of cobalt in the monolith catalyst prepared in comparative example 5;
FIG. 4 is an XPS spectrum of cobalt in the monolith catalyst prepared in comparative example 6.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventors of the present invention found through studies that Co in cobalt oxide in a monolithic catalyst 3+ And Co 2+ Under the condition of existence of a specific proportion, the composite oxide containing cobalt oxide, cerium oxide and/or copper oxide and the noble metal active component can generate synergistic action, can obviously improve the halogen toxicity resistance and stability of the catalyst, and has excellent catalytic activity and selectivity at lower reaction temperature in the treatment of waste gas containing bromine-containing organic matters.
In a first aspect, the present invention provides a monolith catalyst comprising a monolith support comprising an alumina coating and a noble metal active component and a non-noble metal active component supported on the monolith support;
wherein the non-noble metal active component is a composite oxide containing cobalt oxide, cerium oxide and/or copper oxide;
the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
according to the invention, preferably, the Co 3+ And Co 2+ The molar ratio of (2) is 0.85-1.5:1. in this preferred case, the halogen poisoning resistance, catalytic activity, selectivity and stability of the monolithic catalyst are further improved.
According to the present invention, it is preferable that the loading amount of the non-noble metal active component is 12 to 110g (for example, may be 12g, 20g, 30g, 40g, 50g, 60g, 70g, 80g, 90g, 100g, 110g, or any value between any two values) in terms of oxide with respect to 1L of the monolith support, more preferably 50 to 100g.
According to the present invention, preferably, the molar ratio of Co and Ce in the non-noble metal active component is 2 to 18 in terms of metal element: 1 (e.g., may be 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, or any value therebetween), more preferably 6-14:1, further preferably 8-12:1.
according to the present invention, preferably, the molar ratio of Co and Cu in the non-noble metal active component is 2 to 12 in terms of metal element: 1 (e.g., may be 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, or any value therebetween), more preferably 5-11.5:1, further preferably from 6 to 10:1.
according to the present invention, the halogen poisoning resistance, catalytic activity, selectivity and stability of the monolithic catalyst are further improved, and preferably, the non-noble metal active component is a composite oxide containing cobalt oxide, cerium oxide and copper oxide.
According to the present invention, the loading amount of the noble metal active ingredient may be selected in a wide range, preferably, the loading amount of the noble metal active ingredient is 200 to 2000mg (for example, may be 200mg, 400mg, 600mg, 800mg, 1000mg, 1200mg, 1400mg, 1600mg, 1800mg, 2000mg, or any value between any two values) in terms of metal element, more preferably 400 to 1500mg, with respect to 1L of the monolith type carrier.
According to the present invention, preferably, the noble metal is selected from at least one of Au, ag, pt, pd, ru, rh, os and Ir.
More preferably, the noble metal is Pt and/or Pd.
Further preferably, the noble metals are Pt and Pd.
Further preferably, the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.01 to 10:1, more preferably 0.5 to 5:1. the use of Pt and Pd in the preferred ratio is more advantageous for improving the catalytic performance of the catalyst.
According to the invention, the alumina coating is preferably present in the monolithic support in an amount of 5 to 20% by weight, preferably 6 to 19% by weight, more preferably 7 to 15% by weight. The alumina coating with the preferable content can further improve the pore channel number and specific surface area of the monolithic carrier, thereby further improving the catalytic activity and selectivity of the catalyst.
According to the present invention, the monolith support has a conventional schematic in the art, and preferably, the monolith support is selected from monolith supports having a parallel cell structure with two open ends.
According to the invention, the porosity of the cross section of the monolithic support can be chosen within a wide range, preferably the porosity of the cross section of the monolithic support is between 30 and 90%, preferably between 45 and 75%. The porosity of the cross section of the monolithic support refers to the ratio of the pore area of the cross section of the monolithic support to the total cross-sectional area.
The cross-sectional area of the channels of the monolithic support according to the invention can be selected within a wide range, preferably the cross-sectional area of each channel is 0.5-1.5 μm 2 More preferably 0.7-1.3 μm 2 。
According to the present invention, the kind of monolithic support may be selected in a wide range, and preferably, the monolithic support is a ceramic monolithic support.
More preferably, the ceramic monolith support is at least one selected from the group consisting of a cordierite monolith support, a mullite monolith support, a zirconia monolith support and an alumina monolith support, and further preferably a cordierite monolith support and/or a mullite monolith support.
In a second aspect, the present invention provides a process for the preparation of a monolithic catalyst, the process comprising:
(1) Coating slurry containing alumina and/or alumina precursor on a monolithic carrier, and then drying and/or roasting to obtain the monolithic carrier containing alumina coating;
(2) Loading a composite oxide containing cobalt oxide and cerium oxide and/or copper oxide and a noble metal active component on a monolithic carrier containing an alumina coating;
the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
according to the present invention, preferably, the method further comprises: in the step (1), the slurry containing the alumina and/or the alumina precursor is stirred and colloid-milled before being coated on the monolithic carrier. Preferably, the stirring conditions include: the stirring time is 0.1-5h, and the rotating speed is 200-1500rpm. Preferably, the conditions of the colloid mill include: the colloid milling time is 0.1-5h, and the size of colloid mill tooth gap is 0.01-1mm.
According to the present invention, the slurry containing alumina and/or alumina precursor and the monolith support are preferably used in such an amount that the content of the alumina coating layer in the monolith support containing the alumina coating layer obtained in step (1) is 5 to 20% by weight, preferably 6 to 19% by weight, more preferably 7 to 15% by weight.
According to the present invention, preferably the slurry containing alumina and/or alumina precursor contains alumina and/or alumina precursor, water and optionally a pore-forming agent, optionally an acid.
According to the invention, preferably the weight ratio of alumina and/or alumina precursor to water, calculated as alumina, is between 0.05 and 0.8:1, more preferably 0.3 to 0.7:1.
the slurry may or may not contain a pore-forming agent, and more preferably contains a pore-forming agent. The existence of the pore-forming agent is more beneficial to improving the specific surface area of the alumina coating and improving the catalytic reaction efficiency of the catalyst.
According to the present invention, preferably, the weight ratio of alumina and/or alumina precursor to pore-forming agent, calculated as alumina, is 1:0.3 to 2.5, more preferably 1:0.35-1.5.
The slurry may or may not contain an acid, and more preferably contains an acid. The presence of the acid is more advantageous for optimizing the coating effect of the alumina-containing slurry.
According to the present invention, the number of coating steps (1) is not particularly limited, and may be one-time or multiple-time, as long as a desired amount of load is obtained, and the number of coating steps may be specifically selected according to the actual situation by those skilled in the art.
According to the invention, preferably the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.01 to 0.2, more preferably 1:0.05-0.15. With this preferred embodiment, it is possible to make the alumina-containing slurry have a proper viscosity, further improving the coating effect of the alumina-containing slurry.
According to the present invention, the coating method in the step (1) is not particularly limited as long as the alumina-containing slurry can be uniformly adhered to the monolith support, and is preferably a positive pressure coating method or a negative pressure coating method, and more preferably a negative pressure coating method. The negative pressure coating is carried out in a coating machine and specifically comprises the following steps: the alumina-containing slurry at one end of the monolith support is coated onto the monolith support by forming a low pressure environment in a coater. Preferably, the pressure in the coater is 0-5kPa. The negative pressure coating employed in the examples of the present invention.
The pressure in the invention is absolute pressure.
According to the present invention, the number of coating steps (1) is not particularly limited, and may be one-time or multiple-time, as long as a desired amount of load is obtained, and the number of coating steps may be specifically selected according to the actual situation by those skilled in the art.
According to the present invention, the kind of the alumina precursor is not particularly limited, and preferably the alumina precursor is pseudo-boehmite and/or alumina sol, more preferably pseudo-boehmite.
According to the present invention, the kind of the pore-forming agent is not particularly limited as long as it can cause pores to be formed in the alumina coating layer without damaging the overall structure of the alumina coating layer, and preferably, the pore-forming agent is at least one selected from urea, carboxymethyl cellulose, cetyl trimethyl ammonium bromide and polyvinyl alcohol, and more preferably, urea.
According to the present invention, the kind of the acid is not particularly limited as long as the viscosity of the alumina-containing slurry can be increased, and preferably the acid is selected from HNO 3 、H 2 SO 4 、HCl、CH 3 COOH (acetic acid) and H 2 C 2 O 4 At least one of (oxalic acid), more preferably nitric acid.
According to the present invention, there is no particular limitation on the conditions of the drying in the step (1), and preferably, the conditions of the drying in the step (1) include: the drying temperature is 80-130 ℃, preferably 100-125 ℃; the drying time is 1-25h, preferably 2-10h.
More preferably, the drying conditions of step (1) include: heating from room temperature to drying temperature at a rate of 0.3-0.8deg.C/min.
According to the invention, the method further comprises: before the drying in the step (1), the monolithic carrier coated with the slurry containing alumina and/or alumina precursor is purged to remove residual liquid, and then is left at room temperature for 0.5-15h. The type of gas used for the purge is selected from a wide range of gases, such as air, nitrogen, helium, and other inert gases. The purging is usually performed by high-pressure purging, and the pressure is not particularly limited as long as the residual liquid can be purged.
According to the present invention, the conditions of the firing in step (1) are not particularly limited, and preferably, the conditions of the firing in step (1) include: roasting in an oxygen-containing atmosphere at a roasting temperature of 300-600 ℃, preferably 450-550 ℃; the calcination time is 3 to 10 hours, preferably 5 to 8 hours.
More preferably, the roasting conditions of step (1) include: and after the drying is finished, heating to a roasting temperature at a speed of 0.3-0.8 ℃/min for roasting.
According to the present invention, the oxygen content in the oxygen-containing atmosphere may be selected in a wide range, and preferably the oxygen content in the oxygen-containing atmosphere is 5 to 25% by volume.
According to the invention, preferably, the oxygen-containing atmosphere contains oxygen and optionally an inert gas.
According to the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas that does not participate in the reaction under the firing conditions in the present invention. From an economic point of view, the oxygen-containing atmosphere may be air.
In the step (2) of the present invention, the composite oxide may be first supported on the monolithic support containing the alumina coating, and then the noble metal active component may be supported, or the noble metal active component may be first supported on the monolithic support containing the alumina coating, and then the composite oxide may be supported, or the composite oxide and the noble metal active component may be jointly supported on the noble metal active component. In order to further improve the catalytic performance of the catalyst prepared, it is preferred that step (2) comprises the steps of:
(2-1) supporting a composite oxide containing cobalt oxide and cerium oxide and/or copper oxide on a monolithic support containing an alumina coating to obtain a semi-finished catalyst;
(2-2) supporting the noble metal active component on the semi-finished catalyst. The preferred embodiment can further improve the halogen poisoning resistance, catalytic activity, selectivity and stability of the monolithic catalyst.
More preferably, the composite oxide contains cobalt oxide, cerium oxide, and copper oxide.
According to the present invention, preferably, the step (2-1) includes: coating slurry containing the composite oxide on a monolithic carrier containing an alumina coating, and then drying and/or roasting to obtain a semi-finished catalyst; and/or the number of the groups of groups,
step (2-2) comprises: a slurry containing a noble metal source is coated on the semi-finished catalyst and then calcined.
According to the present invention, the coating in step (2-1) is performed in the manner described above, and will not be described here.
According to the present invention, the number of coating steps (2-1) is not particularly limited, and may be one-time or multiple-time, as long as the required load is obtained, and the number of coating steps may be specifically selected according to the actual situation by those skilled in the art.
According to the present invention, the solid content of the composite oxide-containing slurry may be selected in a wide range so as to be able to satisfy the coating, and preferably the solid content of the composite oxide-containing slurry is 10 to 35% by weight, preferably 20 to 30% by weight.
According to the present invention, it is preferable that the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the loading of the composite oxide is 12 to 110g, more preferably 50 to 100g, on an oxide basis, relative to 1L of the monolithic support containing the alumina coating in the resulting semi-finished catalyst. The loading of the preferred composite oxide can further improve the halogen toxicity resistance and stability of the monolithic catalyst.
According to the present invention, the conditions for the drying in the step (2-1) may be selected in a wide range, and preferably, the conditions for the drying in the step (2-1) include: the drying temperature is 80-130 ℃, more preferably 100-125 ℃; the drying time is 1 to 25 hours, more preferably 2 to 10 hours.
According to the invention, the method further comprises: before the drying in the step (2-1), the monolith support coated with the slurry containing the composite oxide is purged to remove the residual liquid. The type of gas used for the purge is selected from a wide range of gases, such as air, nitrogen, helium, and other inert gases. The purging is usually performed by high-pressure purging, and the pressure is not particularly limited as long as the residual liquid can be purged.
According to the present invention, the conditions for the firing in step (2-1) may be selected in a wide range, and preferably, the conditions for the firing in step (2-1) include: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 10 hours, more preferably 3.5 to 8 hours.
According to the invention, in the cobalt oxide, the Co 3+ And Co 2+ The molar ratio selection ranges of (a) are as described above and are not described in detail herein.
According to the present invention, the method for producing the composite oxide of step (2) is not particularly limited, and preferably, the composite oxide of step (2) is produced by a coprecipitation method.
According to the present invention, preferably, the preparation method of the composite oxide of step (2) includes: mixing a precursor solution containing cobalt precursor, cerium precursor and/or copper precursor with a precipitant for precipitation reaction to obtain a precipitate, and drying and roasting the precipitate.
According to the present invention, preferably, the preparation method of the composite oxide of step (2) further includes: before mixing the precursor solution containing cobalt precursor and cerium precursor and/or copper precursor with the precipitant, colloid milling is carried out on the precursor solution containing cobalt precursor and cerium precursor and/or copper precursor. Preferably, the conditions of the colloid mill include: the colloid milling time is 0.1-5h, and the size of colloid mill tooth gap is 0.01-1mm.
According to the present invention, preferably, the cobalt precursor and the cerium precursor and/or the copper precursor are used in amounts such that a molar ratio of cobalt to cerium of 2 to 18 in the monolithic catalyst is obtained, calculated as metal element: 1, more preferably from 6 to 14:1, further preferably 8-12:1.
According to the present invention, preferably, the cobalt precursor and the cerium precursor and/or the copper precursor are used in amounts such that a molar ratio of cobalt to copper in the resulting monolithic catalyst is from 2 to 12, calculated as metal element: 1, more preferably 5-11.5:1, further preferably from 6 to 10:1.
more preferably, the precursor solution contains a cobalt precursor, a cerium precursor, and a copper precursor. The catalytic performance of the catalyst can be further improved by adopting the preferred embodiment.
According to the present invention, the kind of the cobalt precursor, the cerium precursor, and the copper precursor is not particularly limited as long as free cobalt ions, cerium ions, and copper ions can be provided, and preferably, the cobalt precursor, the cerium precursor, and the copper precursor are each independently selected from at least one of nitrate, acetate, sulfate, oxalate, and halide of a metal, more preferably nitrate.
According to the present invention, the kind of the precipitant is not particularly limited as long as it can react with cobalt ions, cerium ions and copper ions to produce precipitation, and preferably the precipitant is selected from at least one of carbonates, bicarbonates and hydroxides of alkali metals, more preferably from at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and lithium hydroxide, and more preferably sodium carbonate and/or sodium hydroxide.
According to a preferred embodiment of the present invention, the conditions of the precipitation reaction include: the reaction temperature is 50-85deg.C (e.g., may be 50deg.C, 55deg.C, 60deg.C, 65deg.C, 70deg.C, 75deg.C, 80deg.C, 85deg.C, or any value between any two values), more preferably 55-80deg.C; the pH is 8.5 to 11 (e.g., may be 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or any value therebetween), more preferably 9 to 10.
According to the present invention, preferably, stirring may be further performed during the precipitation reaction. The stirring is beneficial to improving the effect of the precipitation reaction. The rate of agitation may be selected in a wide range, preferably the agitation rate is 200-1500rpm.
According to the present invention, conditions under which the precipitated product is dried are not particularly limited, and preferably, the conditions for drying include: the drying temperature is 100-120 ℃, and the drying time is 2-8h.
According to the present invention, conditions under which the precipitated product is calcined are not particularly limited, and preferably, the conditions for calcination include: in an oxygen-containing atmosphere, the roasting temperature is 400-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 8 hours, more preferably 3.5 to 7 hours.
According to the present invention, there is no particular limitation on the method of coating in step (2-2), and preferably, the method of coating is selected from a water coating method, a dipping method, or a spraying method, and more preferably, a dipping method.
According to the present invention, preferably, the method of coating the slurry containing the noble metal source on the semi-finished catalyst in step (2-2) employs an equivalent impregnation method. The adoption of the optimized equivalent impregnation method is more beneficial to improving the coating effect and reducing the loss of noble metals.
According to the present invention, the content of the noble metal in the noble metal-containing slurry is not particularly limited, and preferably the noble metal content of the noble metal-containing slurry is 0.05 to 0.5% by weight, preferably 0.1 to 0.35% by weight, in terms of metal element.
According to the present invention, the amounts of the slurry containing the noble metal source and the semi-finished catalyst may be selected in a wide range, and preferably, the amounts of the slurry containing the noble metal source and the semi-finished catalyst are such that the loading of the noble metal in terms of metal element is 200 to 2000mg, more preferably 400 to 1500mg, relative to 1L of the monolithic support containing the alumina coating layer in the monolithic catalyst.
According to the present invention, preferably, the noble metal source is selected from a precursor of at least one of Au, ag, pt, pd, ru, rh, os and Ir, more preferably a precursor of Pt and/or a precursor of Pd, and still more preferably a precursor of Pt and a precursor of Pd.
According to the present invention, the amounts of the Pt precursor and the Pd precursor may be selected in a wide range, and preferably, the amounts of the Pt precursor and the Pd precursor are such that the molar ratio of Pt and Pd supported on the surface of the monolithic support containing the alumina coating layer is 0.01 to 10 in terms of metal element: 1, more preferably 0.05 to 5:1.
according to the present invention, the kinds of the Pt precursor and the Pd precursor are not particularly limited, and preferably, the Pt precursor and the Pd precursor are each independently a soluble acid and/or a soluble salt of a metal.
More preferably, the Pt precursor is at least one selected from chloroplatinic acid, platinum nitrate and platinum chloride, and further preferably chloroplatinic acid.
More preferably, the precursor of Pd is at least one selected from palladium nitrate, tetraaminopalladium nitrate and palladium chloride, and further preferably palladium chloride.
According to the present invention, the conditions for the firing in step (2-2) may be selected in a wide range, and preferably, the conditions for the firing in step (2-2) include: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃, more preferably 450-550 ℃; the calcination time is 3 to 10 hours, more preferably 4 to 8 hours.
According to the present invention, preferably, the method further comprises: in step (2-2), a slurry containing a noble metal source is coated on the semi-finished catalyst before calcination, and then dried. The drying conditions may be selected in a wide range, and preferably include: the drying temperature is 80-130 ℃, more preferably 100-125 ℃; the drying time is 1 to 25 hours, more preferably 3.5 to 7 hours.
According to the present invention, the oxygen content in the oxygen-containing atmosphere may be selected in a wide range, and preferably the oxygen content in the oxygen-containing atmosphere is 5 to 20% by volume.
According to the invention, preferably, the oxygen-containing atmosphere contains oxygen and optionally an inert gas.
According to the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas that does not participate in the reaction under the firing conditions in the present invention.
In a third aspect, the present invention provides a monolithic catalyst prepared by the preparation method of the second aspect. The monolithic catalyst has higher halogen toxicity resistance and still has higher catalytic activity and selectivity at lower reaction temperature. The structural composition and component content of the monolithic catalyst are as described in the first aspect, and are not described herein.
In a fourth aspect, the present invention provides a method for purifying exhaust gas containing bromine-containing organic matter, wherein the exhaust gas containing bromine-containing organic matter is contacted with the monolithic catalyst according to the first aspect or the third aspect in an oxygen-containing atmosphere to perform catalytic combustion.
Specifically, in the presence of oxygen-containing atmosphere, the waste gas containing bromine-containing organic matters contacts with a catalyst to perform catalytic combustion to generate carbon dioxide and water, and if the waste gas also contains the bromine-containing organic matters, hydrogen bromide and/or bromine simple substance are also generated.
According to the present invention, in order to further enhance the effect of purifying the exhaust gas containing the bromine-containing organic matter, it is preferable that the conditions of the catalytic combustion include: the temperature is 200-450 ℃, preferably 250-400 ℃; volume space velocity of 3000-30000h -1 Preferably 5000-25000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 0-3MPa, preferably 0-2MPa.
In the present invention, the exhaust gas containing the bromine-containing organic matter may be any exhaust gas which can be treated by a catalytic combustion method in industry. The composition of the waste gas containing the bromine-containing organic matters and the content selection range of the bromine-containing organic matters are wider. The inventor of the present invention found during the research that the catalyst provided by the present invention is particularly suitable for the treatment of exhaust gas containing bromine-containing organic matters.
According to a preferred embodiment of the present invention, the bromine-containing organic matter is contained in the exhaust gas in an amount of 0.1 to 150ppm, more preferably 0.1 to 100ppm, in terms of Br element.
According to a preferred embodiment of the present invention, the bromine-containing organic includes, but is not limited to, at least one of monobromomethane, dibromomethane, monobromoethane, dibromoethane, monobromoethylene, and dibromoethylene.
According to the present invention, preferably, the offgas containing the bromine-containing organic matter further includes an ester compound and/or an aromatic hydrocarbon. The ester compounds include, but are not limited to, methyl acetate, ethyl acetate, preferably methyl acetate; the aromatic hydrocarbon includes, but is not limited to, at least one of benzene, toluene, xylene, ethylbenzene, diethylbenzene, n-propylbenzene, and isopropylbenzene.
In the embodiments of the present invention, methyl acetate, paraxylene and dibromomethane are exemplified as the exhaust gas containing the bromine-containing organic matter, and the present invention is not limited thereto.
According to the present invention, the oxygen content in the oxygen-containing atmosphere may be selected in a wide range as long as the exhaust gas containing the bromine-containing organic matter can be allowed to react, and in order to further enhance the purification effect, it is preferable that the oxygen content in the oxygen-containing atmosphere is 3 to 100% by volume.
According to the invention, preferably, the oxygen-containing atmosphere contains oxygen and optionally an inert gas.
According to the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas which does not participate in the reaction under the reaction conditions in the present invention.
It will be appreciated by those skilled in the art that the monolith catalyst may also be reduced prior to the catalytic reaction, and the method of reduction is not particularly limited and may be a reduction method conventionally used in the art, for example, the method of reduction includes: and (3) in a mixed atmosphere of hydrogen and inert gas, carrying out reduction treatment on the catalyst for 3-10h at the temperature of 250-350 ℃. Preferably, the hydrogen content in the mixture of hydrogen and inert gas is 1-10% by volume. Preferably, the inert gas is selected from at least one of nitrogen, helium, neon and argon. It is understood that the inert gas according to the present invention refers to a gas that does not participate in the reaction under the reducing conditions in the present invention.
The present invention will be described in detail by examples. In the following examples of the present invention,
Co 3+ And Co 2 The molar ratio of + is determined by XPS analysis;
methyl acetate conversion = amount of reacted methyl acetate species/(amount of unreacted methyl acetate species + amount of reacted methyl acetate species);
para-xylene conversion = amount of para-xylene reacted/(amount of para-xylene unreacted + amount of para-xylene reacted);
dibromomethane conversion = amount of reacted dibromomethane material +.f (amount of unreacted dibromomethane material + amount of reacted dibromomethane material);
CO 2 the selectivity of (1) = the amount of material of the reactant converted to carbon dioxide +.a-);
pseudo-boehmite is a commercial product of Jiangsu three-agent practical Co., ltd, and the content of alumina is 72% by weight;
the firing in the following examples and comparative examples was carried out under an air atmosphere without particular limitation.
Example 1
(1) Mixing 150g of pseudo-boehmite calculated as aluminum oxide, 75g of urea and 15g of concentrated nitric acid (68% by mass) with 300g of water, stirring for 30 minutes at a rotation speed of 500rpm, and then colloid milling for 30 minutes by using a colloid mill (the width of tooth gaps of the colloid mill is 0.05 mm) to obtain slurry containing aluminum oxide;
The slurry containing alumina was applied to a cordierite monolith type support (having a parallel cell structure with both ends open, a porosity of 60%, and a cross-sectional area of each cell of 1 mm) in a coater under a condition of 3kPa 2 ) After the coating is finished, blowing residual liquid in the integral carrier by adopting high-pressure nitrogen, standing for 10 hours at room temperature, then drying by heating from 20 ℃ to 110 ℃ at a heating rate of 0.5 ℃/min, then roasting by heating from 110 ℃ to 550 ℃ at 0.5 ℃/min for 6 hours, and obtaining the integral carrier containing the alumina coating, wherein the alumina coating accounts for 10% of the total mass of the alumina coating and the integral carrier through multiple dipping, drying and roasting.
(2) Preparing cobalt nitrate hexahydrate and cerium nitrate hexahydrate into aqueous solution according to the mol ratio shown in table 1, adding sodium carbonate solution into the aqueous solution under the condition of stirring at 60 ℃ until the pH value is 9.5, filtering, drying the obtained precipitate at 110 ℃ for 5 hours, and roasting at 500 ℃ for 6 hours to obtain composite oxide particles containing cobalt oxide and cerium oxide;
dispersing the obtained composite oxide particles into water, then carrying out colloid milling for 30min by using a colloid mill (the size of colloid mill teeth is 0.05 mm), preparing slurry containing the composite oxide, coating the slurry containing the composite oxide on an integral carrier containing an alumina coating in a coating machine under the condition of 3kPa, drying the slurry remained in a pore channel by adopting high-pressure nitrogen after the coating is finished, drying at 110 ℃ for 5h and roasting at 550 ℃ for 6h, and carrying out multiple impregnation, drying and roasting to obtain a semi-finished catalyst, wherein the loading amount of the composite oxide is 80g/L in terms of oxide relative to 1L of the integral carrier containing the alumina coating.
Preparing chloroplatinic acid and palladium chloride into an aqueous solution containing platinum element and palladium element (the mass fraction of noble metal platinum and palladium is 0.1 percent by weight), impregnating a semi-finished catalyst with the aqueous solution containing platinum element and palladium element, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 6 hours to prepare a monolithic catalyst, wherein the loading of platinum and palladium is 400mg/L relative to 1L monolithic carrier containing alumina coating, and the mole ratio of platinum element and palladium element in the monolithic carrier is 0.25:1. co in the obtained monolithic support 3+ And Co 2+ The molar ratio of (2) is shown in Table 1.
(3) The monolithic catalyst obtained in the step (2) is subjected to reduction treatment, specifically: the catalyst was subjected to reduction treatment at 300℃for 6 hours in a mixed atmosphere of hydrogen and nitrogen (containing 5% by volume of hydrogen). In a mixed atmosphere of oxygen and nitrogen (oxygen content: 10 vol%), at a pressure of 0.1MPa and a volume space velocity of 20000h -1 Under the conditions of that waste gas containing bromine-containing organic matters and containing 1000ppm of methyl acetate, 500ppm of paraxylene and 100ppm of dibromomethane are contacted with the integral catalyst after reduction treatment to carry out catalytic combustion, the reaction temperature is gradually increased from 200 ℃ at the speed of 0.1 ℃/min, and the methyl acetate is recorded respectively Minimum reaction temperature T1 at 99% ester conversion, minimum reaction temperature T2 at 99% para-xylene conversion and minimum reaction temperature T3 at 99% dibromomethane conversion, and CO at 20h of reaction progress was calculated 2 Is selected from the group consisting of (1).
(4) Under the condition that the temperature T3 and other catalytic combustion conditions are unchanged, the catalytic combustion reaction is carried out, and the conversion rate of methyl acetate, paraxylene and dibromomethane and the CO are carried out until 1000h 2 The selectivities of (2) are shown in Table 2.
Examples 2 to 3
A monolithic catalyst was prepared and a reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 1, except that cobalt nitrate hexahydrate and cerium nitrate hexahydrate were formulated into an aqueous solution in accordance with the molar ratios shown in Table 1.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Examples 4 to 6
A monolithic catalyst was prepared and a reaction was catalyzed by the method of example 1, except that cerium nitrate hexahydrate was replaced with copper nitrate hexahydrate, and cobalt nitrate hexahydrate and copper nitrate hexahydrate were formulated into aqueous solutions according to the molar ratios shown in Table 1.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 7
A monolithic catalyst was prepared and a reaction was catalyzed by the method of example 1, except that cobalt nitrate hexahydrate and cerium nitrate hexahydrate were replaced with cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate, and cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were formulated into aqueous solutions according to the molar ratios shown in table 1. The XPS spectrum of Co in the obtained monolithic catalyst is shown in figure 1.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 8
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios of Table 1, and a sodium carbonate solution was added thereto to a pH of 8.5 with stirring at 60 ℃.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 9
A monolithic catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios of Table 1, and a sodium carbonate solution was added thereto to a pH of 9 with stirring at 60 ℃.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 10
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios shown in Table 1, and a sodium carbonate solution was added thereto to a pH of 10 with stirring at 60 ℃.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 11
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing bromine-containing organics as in example 7, except that the alumina coating was 19% of the total mass of the alumina coating and monolith support.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 12
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7 except that the composite oxide was supported at 105g/L in terms of oxide relative to 1L of the monolith support having an alumina coating.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 13
A monolithic catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that the molar ratio of the platinum element to the palladium element in the monolithic catalyst was 0.1:1.
the content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 14
A monolithic catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that the molar ratio of the platinum element to the palladium element in the monolithic catalyst was 0.5:1.
the content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 15
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7 except that the loading of platinum and palladium in terms of metal element was 800mg/L with respect to 1L of the monolith support having an alumina coating.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 16
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7 except that the loading of platinum and palladium in terms of metal element was 1500mg/L with respect to 1L of the monolith support having an alumina coating.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 17
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter according to the method of example 7, except that in step (3), an exhaust gas containing a bromine-containing organic matter containing 2000ppm of methyl acetate, 700ppm of paraxylene and 200ppm of dibromomethane was contacted with the monolith catalyst obtained in step (2) to react.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 18
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter according to the method of example 7, except that in step (3), an exhaust gas containing a bromine-containing organic matter containing 3000ppm of methyl acetate, 1000ppm of paraxylene and 300ppm of dibromomethane was contacted with the monolith catalyst obtained in step (2) to react.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 19
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios shown in Table 1, and a sodium carbonate solution was added thereto to a pH of 9.5 with stirring at 70 ℃. The XPS spectrum of Co in the obtained monolithic catalyst is shown in figure 2.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 20
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios shown in Table 1, and a sodium carbonate solution was added thereto to a pH of 8 with stirring at 60 ℃.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 21
A monolithic catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that the molar ratio of the platinum element to the palladium element in the obtained monolithic carrier was 10:1.
the content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Example 22
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7 except that the loading of the non-noble metal active component was 50g in terms of oxide relative to 1L of the monolith support.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 1
A monolithic catalyst was prepared and a reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in the same manner as in example 7, except that in step (2), the monolithic support containing an alumina coating was impregnated with an aqueous solution containing a platinum element and a palladium element directly without carrying out the loading of the composite oxide.
The content of each component of the obtained monolithic catalyst is shown in table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 2
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter according to the method of example 7, except that cerium nitrate hexahydrate and copper nitrate hexahydrate were replaced with cobalt nitrate hexahydrate, and cobalt nitrate hexahydrate was formulated into an aqueous solution in terms of metal elements.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 3
A monolithic catalyst was prepared and a reaction was carried out by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate and copper nitrate hexahydrate were replaced with cerium nitrate hexahydrate, and cerium nitrate hexahydrate was formulated into an aqueous solution in terms of metal elements.
The content of each component of the obtained monolithic catalyst is shown in table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 4
A monolithic catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic matter in accordance with the method of example 7, except that cobalt nitrate hexahydrate and cerium nitrate hexahydrate were replaced with copper nitrate hexahydrate, and copper nitrate hexahydrate was formulated into an aqueous solution in terms of metal elements.
The content of each component of the obtained monolithic catalyst is shown in table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 5
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios shown in Table 1, and a sodium carbonate solution was added thereto to a pH of 9.5 with stirring at 20 ℃. The XPS spectrum of Co in the obtained monolithic catalyst is shown in figure 3.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
Comparative example 6
A monolith catalyst was prepared and reacted by catalyzing an exhaust gas containing a bromine-containing organic compound according to the method of example 7, except that cobalt nitrate hexahydrate, cerium nitrate hexahydrate and copper nitrate hexahydrate were prepared as aqueous solutions according to the molar ratios shown in Table 1, and a sodium carbonate solution was added thereto to a pH of 9.5 with stirring at 40 ℃. The XPS spectrum of Co in the obtained monolithic catalyst is shown in FIG. 4.
The content of each component and Co of the obtained monolithic catalyst 3+ And Co 2+ The molar ratio of (2) is shown in Table 1; t1, T2 and T3 and CO 2 The selectivities of (2) are shown in Table 2.
When running to 1000h, the conversion rate of methyl acetate, paraxylene and dibromomethane and CO 2 The selectivities of (2) are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the monolithic catalyst prepared by the embodiment of the technical scheme of the invention can still obtain the effect that the conversion rate of methyl acetate, paraxylene and dibromomethane reaches more than 99% at a lower reaction temperature, and the CO is generated when the reaction is carried out for 20h 2 The selectivity of the catalyst can reach 99 percent, which proves that the monolithic catalyst has higher catalytic activity and selectivity, and can still ensure the conversion rate of methyl acetate, paraxylene and dibromomethane when the catalytic combustion reaction is carried out for 1000h at the temperature of T3 Up to 99% or more and CO 2 The selectivity of the catalyst can reach 99 percent, which shows that the catalyst has higher stability and halogen toxicity resistance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (72)
1. A monolith catalyst for treating exhaust gas containing a bromine-containing organic matter, characterized in that the catalyst comprises a monolith support comprising an alumina coating and a noble metal active component and a non-noble metal active component supported on the monolith support; the loading of the non-noble metal active component is 12-110g calculated by oxide relative to 1L of integral carrier; the loading amount of the noble metal active component is 200-2000mg calculated by metal element relative to 1L of integral carrier;
wherein the non-noble metal active component is a composite oxide containing cobalt oxide, cerium oxide and/or copper oxide; the molar ratio of Co to Ce in the non-noble metal active ingredient is 2-18:1, a step of; the molar ratio of Co to Cu in the non-noble metal active component is 2-12:1, a step of;
The cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
2. the catalyst of claim 1, wherein the Co 3+ And Co 2+ The molar ratio of (2) is 0.85-1.5:1.
3. the catalyst according to claim 1, wherein the loading amount of the non-noble metal active component is 50 to 100g in terms of oxide with respect to 1L of the monolith support.
4. The catalyst according to claim 1, wherein the molar ratio of Co and Ce in the non-noble metal active component is 6 to 14 in terms of metal element: 1, a step of;
the molar ratio of Co to Cu in the non-noble metal active component is 5-11.5 in terms of metal element: 1.
5. the catalyst according to claim 4, wherein the molar ratio of Co and Ce in the non-noble metal active component is 8 to 12 in terms of metal element: 1, a step of;
the molar ratio of Co to Cu in the non-noble metal active component is 6-10 based on metal element: 1.
6. the catalyst of claim 1, wherein the non-noble metal active component is a composite oxide comprising cobalt oxide, cerium oxide, and copper oxide.
7. The catalyst according to claim 1, wherein the loading amount of the noble metal active component is 400 to 1500mg in terms of metal element with respect to 1L of the monolith support.
8. The catalyst of claim 1, wherein the noble metal is selected from at least one of Au, ag, pt, pd, ru, rh, os and Ir.
9. The catalyst of claim 8, wherein the noble metal is Pt and/or Pd.
10. The catalyst of claim 9, wherein the noble metals are Pt and Pd.
11. The catalyst according to claim 10, wherein the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.01 to 10:1.
12. the catalyst according to claim 11, wherein the noble metal active component has a molar ratio of Pt to Pd, calculated as metal element, of 0.05 to 5:1.
13. the catalyst of claim 1, wherein the alumina coating is present in the monolith support in an amount of from 5 to 20 wt.%.
14. The catalyst of claim 13, wherein the alumina coating is present in the monolith support in an amount of from 6 to 19 wt%.
15. The catalyst of claim 14, wherein the alumina coating is present in the monolith support in an amount of from 7 to 15 wt%.
16. The catalyst of any one of claims 1-15, wherein the monolithic support has a porosity of 30-90% in cross section.
17. The catalyst of claim 16, wherein the monolith support is a ceramic monolith support.
18. The catalyst according to claim 17, wherein the ceramic monolith support is selected from at least one of a cordierite monolith support, a mullite monolith support, a zirconia monolith support and an alumina monolith support.
19. A method for preparing a monolithic catalyst for treating exhaust gas containing bromine-containing organic matter, the method comprising:
(1) Coating slurry containing alumina and/or alumina precursor on a monolithic carrier, and then drying and/or roasting to obtain the monolithic carrier containing alumina coating;
(2) Loading a non-noble metal active component and a noble metal active component on a monolithic carrier containing an alumina coating, wherein the non-noble metal active component is a composite oxide containing cobalt oxide and cerium oxide and/or copper oxide;
the loading of the non-noble metal active component is 12-110g calculated by oxide relative to 1L of integral carrier; the loading amount of the noble metal active component is 200-2000mg calculated by metal element relative to 1L of integral carrier;
The molar ratio of Co to Ce in the non-noble metal active ingredient is 2-18:1, a step of; the molar ratio of Co to Cu in the non-noble metal active component is 2-12:1, a step of;
the cobalt oxide contains Co 3+ And Co 2+ The Co is 3+ And Co 2+ The molar ratio of (2) is 0.85-2.2:1.
20. the production method according to claim 19, wherein the slurry containing alumina and/or an alumina precursor and the monolith support are used in such an amount that the alumina coating layer is contained in an amount of 5 to 20% by weight in the monolith support containing the alumina coating layer obtained in step (1).
21. The production method according to claim 20, wherein the slurry containing alumina and/or an alumina precursor and the monolith support are used in such an amount that the alumina coating layer is contained in an amount of 6 to 19% by weight in the monolith support containing the alumina coating layer obtained in step (1).
22. The production method according to claim 21, wherein the slurry containing alumina and/or an alumina precursor and the monolith support are used in such an amount that the alumina coating layer is contained in an amount of 7 to 15% by weight in the monolith support containing the alumina coating layer obtained in step (1).
23. The method according to claim 19, wherein the slurry containing alumina and/or alumina precursor contains alumina and/or alumina precursor, water, and optionally a pore-forming agent, and optionally an acid.
24. The preparation method according to claim 23, wherein the weight ratio of alumina and/or alumina precursor to water is 0.05-0.8 in terms of alumina: 1.
25. the method of claim 24, wherein the weight ratio of alumina and/or alumina precursor to water calculated as alumina is 0.3-0.7:1.
26. the method of claim 23, wherein the weight ratio of alumina and/or alumina precursor to pore former is 1:0.3-2.5.
27. The method of claim 26, wherein the weight ratio of alumina and/or alumina precursor to pore former is 1:0.35-1.5.
28. The method of claim 23, wherein the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.01-0.2.
29. The method of claim 28, wherein the weight ratio of alumina and/or alumina precursor to acid, calculated as alumina, is 1:0.05-0.15.
30. The method of claim 19, wherein the alumina precursor is pseudo-boehmite and/or an alumina sol.
31. The method of claim 23, wherein the pore-forming agent is selected from at least one of urea, carboxymethyl cellulose, cetyltrimethylammonium bromide, and polyvinyl alcohol.
32. The process according to claim 23, wherein the acid is selected from HNO 3 、H 2 SO 4 、HCl、CH 3 COOH and H 2 C 2 O 4 At least one of them.
33. The method of claim 19, wherein the drying conditions of step (1) comprise: the drying temperature is 80-130 ℃; the drying time is 1-25h.
34. The method of claim 33, wherein the drying conditions of step (1) comprise: the drying temperature is 100-125 ℃; the drying time is 2-10h.
35. The method of claim 19, wherein the firing conditions of step (1) comprise: roasting in an oxygen-containing atmosphere at a roasting temperature of 300-600 ℃; the roasting time is 3-10h.
36. The method of claim 35, wherein the firing temperature is 450-550 ℃; the roasting time is 5-8h.
37. The preparation method according to any one of claims 19 to 36, wherein step (2) comprises the steps of:
(2-1) supporting a composite oxide containing cobalt oxide and cerium oxide and/or copper oxide on a monolithic support containing an alumina coating to obtain a semi-finished catalyst;
(2-2) supporting the noble metal active component on the semi-finished catalyst.
38. The production method according to claim 37, wherein the composite oxide in step (2) contains cobalt oxide, cerium oxide, and copper oxide.
39. The production method according to claim 37, wherein step (2-1) comprises: coating slurry containing the composite oxide on a monolithic carrier containing an alumina coating, and then drying and/or roasting to obtain a semi-finished catalyst;
and/or, the step (2-2) comprises: a slurry containing a noble metal source is coated on the semi-finished catalyst and then calcined.
40. The process according to claim 39, wherein the slurry containing the composite oxide has a solid content of 10 to 35% by weight.
41. The process according to claim 40, wherein the slurry containing the composite oxide has a solid content of 20 to 30% by weight.
42. The process according to claim 39, wherein the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the amount of the composite oxide is 12 to 110g in terms of oxide relative to 1L of the monolithic support containing the alumina coating in the semi-finished catalyst.
43. The process according to claim 42, wherein the slurry containing the composite oxide and the monolithic support containing the alumina coating are used in amounts such that the amount of the composite oxide supported on the oxide is 50 to 100g relative to 1L of the monolithic support containing the alumina coating in the semi-finished catalyst.
44. The method according to claim 39, wherein the drying conditions of step (2-1) include: the drying temperature is 80-130 ℃; the drying time is 1-25h.
45. The process of claim 44, wherein the drying conditions of step (2-1) comprise: the drying temperature is 100-125 ℃; the drying time is 2-10h.
46. The process of claim 39, wherein the conditions of the firing of step (2-1) comprise: in an oxygen-containing atmosphere, the roasting temperature is 300-600 ℃; the roasting time is 3-10h.
47. The method of claim 46, wherein the firing temperature is 450-550 ℃; the roasting time is 3.5-8h.
48. The preparation method according to any one of claims 19 to 36, wherein the composite oxide of step (2) is prepared by a coprecipitation method, specifically comprising:
Mixing a precursor solution containing cobalt precursor, cerium precursor and/or copper precursor with a precipitant for precipitation reaction to obtain a precipitate, and drying and roasting the precipitate.
49. The process of claim 48, wherein the cobalt precursor and the cerium precursor and/or the copper precursor are used in amounts such that the molar ratio of cobalt to cerium in the resulting monolithic catalyst is from 2 to 18, calculated as the metal element: 1, a step of; the mole ratio of cobalt to copper is 2-12:1.
50. the process according to claim 49, wherein the cobalt precursor and the cerium precursor and/or the copper precursor are used in such amounts, in terms of metal elements, that the molar ratio of cobalt to cerium in the monolithic catalyst obtained is from 6 to 14:1, a step of; the mole ratio of cobalt to copper is 5-11.5:1.
51. the process according to claim 50, wherein the cobalt precursor and the cerium precursor and/or the copper precursor are used in such amounts, in terms of metal elements, that the molar ratio of cobalt to cerium in the monolithic catalyst obtained is from 8 to 12:1, a step of; the mole ratio of cobalt to copper is 6-10:1.
52. the method of claim 48, wherein the precursor solution comprises a cobalt precursor, a cerium precursor, and a copper precursor.
53. The method of preparing as claimed in claim 52, wherein the cobalt precursor, cerium precursor, and copper precursor are each independently selected from at least one of nitrate, acetate, sulfate, oxalate, and halide of a metal.
54. The process of claim 48, wherein the precipitating agent is at least one of an alkali metal carbonate, bicarbonate, and hydroxide.
55. The process of claim 54 wherein said precipitating agent is selected from at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and lithium hydroxide.
56. The process of claim 48, wherein the precipitation reaction conditions comprise: the reaction temperature is 50-85 ℃; the pH value is 8.5-11.
57. The process of claim 56, wherein the reaction temperature is 55-80 ℃; the pH value is 9-10.
58. The process of claim 48, wherein the conditions for drying the precipitated product comprise: the drying temperature is 100-120 ℃, and the drying time is 2-8h.
59. The process of claim 48, wherein the conditions for calcining the precipitated product comprise: in an oxygen-containing atmosphere, the roasting temperature is 400-600 ℃; the roasting time is 3-8h.
60. The process of claim 59, wherein the conditions for calcining the precipitated product comprise: in an oxygen-containing atmosphere, the roasting temperature is 450-550 ℃; the roasting time is 3.5-7h.
61. The process according to claim 39, wherein the slurry containing the noble metal source and the semi-finished catalyst are used in such an amount that the loading of the noble metal in terms of metal element is 200 to 2000mg relative to 1L of the alumina-coated monolith support in the resulting monolith catalyst.
62. The process of claim 61 wherein the slurry containing the noble metal source and the semi-finished catalyst are used in amounts such that the loading of the noble metal, calculated as metal element, in the resulting monolithic catalyst is 400 to 1500mg relative to 1L of the alumina-coated monolithic support.
63. The process according to claim 39, wherein the noble metal source is selected from precursors of at least one of Au, ag, pt, pd, ru, rh, os and Ir.
64. The method of claim 63, wherein the noble metal source is a precursor of Pt and/or a precursor of Pd.
65. The method of claim 64, wherein the noble metal source is a precursor of Pt and a precursor of Pd.
66. The method of claim 65, wherein the precursor of Pt and the precursor of Pd are each independently an acid and/or a salt of a metal.
67. The method of preparing as claimed in claim 66, wherein the precursor of Pt is selected from at least one of chloroplatinic acid, platinum nitrate, and platinum chloride;
the precursor of Pd is selected from at least one of palladium nitrate, tetraaminopalladium nitrate and palladium chloride.
68. A method for purifying exhaust gas containing bromine-containing organic matter, characterized in that the exhaust gas containing bromine-containing organic matter is contacted with the monolithic catalyst according to any one of claims 1 to 18 in an oxygen-containing atmosphere to perform catalytic combustion.
69. The method according to claim 68A method, wherein the conditions of catalytic combustion comprise: the temperature is 200-450 ℃; volume space velocity of 3000-30000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 0-3MPa.
70. The method of claim 68 or 69, wherein the conditions of catalytic combustion comprise: the temperature is 250-400 ℃; volume space velocity of 5000-25000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 0-2MPa.
71. The process as set forth in claim 68 wherein the bromine-containing organic matter is contained in the offgas in an amount of 0.1 to 100ppm based on the element Br.
72. The method of claim 68, wherein the oxygen-containing atmosphere comprises oxygen and optionally an inert gas;
the oxygen content in the oxygen-containing atmosphere is 3-100% by volume;
the inert gas is selected from at least one of nitrogen, helium, neon and argon.
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