CN111871451B - CHA molecular sieve synthesized by novel structure template agent, SCR catalyst and application thereof - Google Patents
CHA molecular sieve synthesized by novel structure template agent, SCR catalyst and application thereof Download PDFInfo
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- CN111871451B CN111871451B CN202010797167.0A CN202010797167A CN111871451B CN 111871451 B CN111871451 B CN 111871451B CN 202010797167 A CN202010797167 A CN 202010797167A CN 111871451 B CN111871451 B CN 111871451B
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- Prior art keywords
- molecular sieve
- cha
- copper
- aluminum
- acid
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 163
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 118
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 20
- -1 indan-5-yl Chemical group 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004129 indan-1-yl group Chemical group [H]C1=C([H])C([H])=C2C(=C1[H])C([H])([H])C([H])([H])C2([H])* 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 59
- 229910021536 Zeolite Inorganic materials 0.000 claims description 57
- 239000010457 zeolite Substances 0.000 claims description 57
- 239000002002 slurry Substances 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000000741 silica gel Substances 0.000 claims description 22
- 229910002027 silica gel Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052878 cordierite Inorganic materials 0.000 claims description 14
- 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 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011268 mixed slurry Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Chemical class 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Chemical class 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910052642 spodumene Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical class [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Chemical class 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- JRMAQQQTXDJDNC-UHFFFAOYSA-M 2-ethoxy-2-oxoacetate Chemical compound CCOC(=O)C([O-])=O JRMAQQQTXDJDNC-UHFFFAOYSA-M 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 238000012993 chemical processing Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-M ethyl sulfate Chemical compound CCOS([O-])(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-M 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
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- 238000005169 Debye-Scherrer Methods 0.000 description 3
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- SUBDBMMJDZJVOS-UHFFFAOYSA-N 5-methoxy-2-{[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]sulfinyl}-1H-benzimidazole Chemical compound N=1C2=CC(OC)=CC=C2NC=1S(=O)CC1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-UHFFFAOYSA-N 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical class [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- GNUJKXOGRSTACR-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 GNUJKXOGRSTACR-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 208000032005 Spinocerebellar ataxia with axonal neuropathy type 2 Diseases 0.000 description 1
- IOYNQIMAUDJVEI-BMVIKAAMSA-N Tepraloxydim Chemical compound C1C(=O)C(C(=N/OC\C=C\Cl)/CC)=C(O)CC1C1CCOCC1 IOYNQIMAUDJVEI-BMVIKAAMSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical class NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000010335 hydrothermal treatment Methods 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8625—Nitrogen oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B01D2251/2062—Ammonia
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Abstract
The invention discloses a CHA molecular sieve synthesized by a novel structure template agent, an SCR catalyst and application thereof, belonging to the field of chemical synthesis technology and application thereof. One or more of N, N, N-trialkyl- (indan-5-yl) quaternary ammonium, N, N, N-trialkyl- (indan-1-yl) quaternary ammonium or N, N, N-trialkyl- (indan-4-yl) quaternary ammonium compounds are used as an organic template to synthesize the CHA molecular sieve, the mole ratio of the silicon dioxide to the aluminum oxide of the product is 6-80, the average grain diameter is less than or equal to 500nm, the total specific surface area is more than or equal to 400m < 2 >/g, the total pore volume is more than or equal to 0.20ml/g, and the micropore volume is more than or equal to 0.10ml/g; the crystal grain size in the (-210) crystal plane direction is 50-160 nm. The molecular sieve of the invention has high hydrothermal stability under the condition of not having large crystal grains, and shows high nitrogen oxide reduction characteristics after high-temperature high-humidity exposure, particularly shows high nitrogen oxide reduction characteristics in a temperature range of 200-550 ℃.
Description
Technical Field
The invention relates to a CHA molecular sieve synthesized by a novel structural template agent, an SCR catalyst and application thereof, belonging to the field of chemical synthesis technology and application thereof.
Background
The silicon-aluminum zeolite molecular sieve is a CHA type topological structure, has a three-dimensional pore structure and orthogonal symmetry, a one-dimensional main channel is formed by double eight-membered rings, the pore size is 0.38nm multiplied by 0.38nm, and the framework density is 14.5. The CHA molecular sieve topology is formed by double 6 rings (d 6 r) connected through 4-membered ringsThe crystal face of the d6r faces to the cha big cage, cu ions can be stabilized in the d6r at high temperature, and the Cu ions are allowed to migrate, so that the molecular sieve is the unique physicochemical characteristic of the small-pore molecular sieve with the potential of SCR reaction. Analysis of dehydrated Cu-SSZ-13 molecular sieves by Rietveld Structure refinement in the literature (J.Phys.chem.C 2010,114, 1633-1640) first revealed Cu 2+ Unique on the face of d6 r. In subsequent studies dehydrated Cu ions ([ CuOH ] located near the 8-membered ring were also confirmed]Presence of a + active site. The SSZ-13 and SSZ-62 molecular sieves are typical CHA-structure silicoaluminophosphate molecular sieves, and are widely used as cracking catalysts, MTO reaction catalysts, nitrogen oxide reduction catalysts, and as nitrogen oxide reduction catalysts using Selective Catalytic Reduction (SCR). The characteristics of the active sites of the Cu-SSZ-13 molecular sieve catalyst in the NH3-SCR reaction have been widely researched, and the active sites of the framework of the SSZ-13 molecular sieve are all equivalent, so that the catalyst is easier to characterize.
Patent CN201611070989 discloses a molecular sieve material with CHA topology formed by self-assembly of silica tetrahedron and alumina tetrahedron, si/Al molar ratio between 4 and 8, BET specific surface area between 400 and 800m2/g, and crystal grain between 0.8 and 20 μm. Alkyl ammonium hydroxide and adamantyl ammonium hydroxide are used as double templates in the preparation of the molecular sieve, and the molecular sieve can be applied to the technical field of separation of CO2/N2 and N2/O2 mixed gas. Patent CN201780032379 discloses synthesis of CHA-type zeolite with a silica/alumina molar ratio of 10.0 to 55.0 using N, N-trialkyl adamantyl ammonium salt and N, N-trialkyl cyclohexyl ammonium salt as composite templating agents. In the literature (Microporous and Mesoporous Materials 255 (2018) 192-199), an SSZ-13 molecular sieve with the particle size of 50-300 nm is synthesized by crystallization at low (95 ℃) and high (210 ℃) temperature sections, has obvious hydrothermal stability and has equivalent catalytic performance in the aspect of ammonia selective catalytic reduction (NH 3-SCR) nitrogen oxide (NOx).
The synthesis method of SSZ-13 molecular sieve with CHA structure and the catalytic performance of the SSZ-13 molecular sieve as SCR catalyst are disclosed in many documents above, which shows that the catalyst with good thermal stability and good dispersion of supported metal is preferable, and the conventional method adopts N, N, N-trialkyl-1-adamantyl ammonium salt and alkaline combination thereof as template agent, which is expensive, low in utilization rate and difficult to recycle, and needs template agent with low cost and easy post-treatment to synthesize the silicon-aluminum zeolite molecular sieve with small crystal grain, large specific surface area, large pore volume and good thermal stability.
Disclosure of Invention
The invention aims to provide a novel structure template agent synthesized CHA molecular sieve used for removing NO by selective reduction x The molecular sieve has high Al content, small grain size, large specific surface area and pore volume, can provide more ion exchange sites and solid acid amount, forms the SCR catalyst after exchanging with transition metal ions such as copper ions, iron ions and the like, has high reduction rate of nitrogen oxides in a low-temperature area compared with the prior SCR catalyst, and has high hydrothermal stability at high temperature. The present invention relates to removal of nitrogen oxides emitted from internal combustion engines, and provides a nitrogen oxide removal catalyst composed of a silicoaluminophosphate zeolite molecular sieve having a CHA structure, a production method of the catalyst, and a nitrogen oxide removal method in which nitrogen oxides are reacted with at least one of ammonia water, urea, and an organic amine using the catalyst.
The invention aims to solve the technical problem of overcoming the defect that the activity of an SCR catalyst for synthesizing a molecular sieve by using supported iron and copper is lower at low temperature through a hydrothermal durability test in the prior art, and provides a copper-based SCR catalyst which still has higher activity at low temperature after the hydrothermal durability test and a preparation method thereof.
The invention provides a novel structural template for synthesizing a CHA molecular sieve, which is synthesized by adopting an organic template, wherein the organic template is one or more of N, N, N-trialkyl- (indan-5-yl) quaternary ammonium onium, N, N, N-trialkyl- (indan-1-yl) quaternary ammonium onium or N, N, N-trialkyl- (indan-4-yl) quaternary ammonium onium compounds which are mixed in any proportion, the mole ratio of silicon dioxide to aluminum oxide of the CHA molecular sieve is 6-80, the average grain diameter is less than or equal to 500nm, and the total specific surface area (S) is measured by a BET method (specific surface area analysis method) BET )≥400m 2 G, total pore volume (V) total ) Not less than 0.20ml/g, micropore volume (V) micro ) Not less than 0.10ml/g; the molecular sieve is 4-40 degree at 2 theta(iii) at least one XRD diffraction peak within each of the following tables, and having the characteristics set forth in the following table:
* The relative intensity is an intensity relative to a peak intensity of 2 θ =20.40 to 20.90
The molecular sieve has a CHA topological structure, the range of the half-value width (FWHM) of a crystal plane of X-ray crystal diffraction (-210) is 0.1-0.2 degrees, and the grain diameter size in the crystal plane (-210) direction is 50-160 nm calculated by a Debye-Scherrer formula. After the molecular sieve is treated by saturated steam at 600-850 ℃, the four-coordination aluminum accounts for more than or equal to 90 percent of the total aluminum content, and the six-coordination aluminum accounts for less than or equal to 10 percent of the total aluminum content.
The organic template agent is N, N, N-trialkyl- (indan-5-yl) quaternary ammonium shown as a formula I, N, N, N-trialkyl- (indan-1-yl) quaternary ammonium shown as a formula II, and N, N, N-trialkyl- (indan-4-yl) quaternary ammonium shown as a formula III:
wherein R1 and R2 are independently selected from methyl or deuterated methyl, C2-C4 straight-chain or branched-chain alkyl, and R3 is selected from C1-C5 straight-chain or branched-chain alkyl; x - The counter anion which is a quaternary ammonium onium ion includes any of hydroxide, halide, sulfate, bisulfate, carbonate, bicarbonate, oxalate, phosphate, carboxylate, alkyl-substituted sulfate, carbonate or oxalate.
Further, in the above technical solution, the halide includes chloride ion, bromide ion, or iodide ion; carboxylates include formate, acetate, propionate; alkyl substituted sulphate, carbonate or oxalate includes methyl sulphate, ethyl sulphate, methyl carbonate, ethyl carbonate, methyl oxalate or ethyl oxalate.
The pore structure data of the molecular sieve was determined using a Micromeritics ASAP 2460 model static nitrogen adsorption apparatus. And (3) testing conditions are as follows:the sample was placed in a sample handling system and evacuated to 1.33X 10 at 350 deg.C -2 Pa, keeping the temperature and the pressure for 15h, and purifying the sample. Measuring the specific pressure p/p of the purified sample at-196 deg.C under liquid nitrogen 0 And (3) obtaining a nitrogen adsorption-desorption isothermal curve according to the adsorption quantity and the desorption quantity of the nitrogen under the condition. Then, the BET total specific surface area (S) is calculated using the BET formula BET ) Calculating the specific surface area (S) of the sample micropore by adopting a t-plot method micro ) And micropore volume (V) micro ) Total pore volume in P/P 0 Adsorption amount calculation at 0.98: specific surface area of outer pores (S) exter )=S BET –S micro (ii) a External pore volume (V) exter )=V total -V micro )。
The invention also provides a synthesis method of the CHA molecular sieve, which comprises the following steps:
1) Fully dissolving and dispersing zeolite molecular sieve, naOH and deionized water with the molar ratio of silicon dioxide to aluminum oxide of 2-30 to obtain slurry with the molar ratio of nNa 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O = (0.5-2.5): 1, (0.0333-0.5): 5-20), and aging is carried out in a crystallization kettle at 60-120 ℃ for 6-48 hours to obtain silicon-aluminum gel;
2) Adding a silicon source, an organic template agent OSDA, a metal salt M and deionized water into the silicon-aluminum gel obtained in the step 1), fully and uniformly mixing, supplementing NaOH according to the system alkalinity requirement, and mixing the components of the slurry according to the molar ratio nNa 2 O:nSiO 2 :nA1 2 O 3 :nOSDA:nM:nH 2 O = (0.05-0.5) 1, (0.0125-0.20), (0.01-0.5), (0.05-0.5) and (10-100); adding acid solution to control alkali hydroxyl OH in mixed slurry - With SiO 2 In a molar ratio of nOH-/nSiO 2 =0.1 to 1.0; adding CHA molecular sieve seed crystal with SiO in the slurry 2 And A1 2 O 3 0.5-15% of the total mass; the metal salt M is NaCl or NaNO 3 、Na 2 SO 4 、Na 3 PO 4 、NaBr、NaF、KCl、KNO 3 、K 2 SO 4 、KBr、KF、K 3 PO 4 Any of them, preferably NaCl,NaNO 3 、Na 2 SO 4 、Na 3 PO 4 Any one of the above; wherein the CHA molecular sieve seed crystal is a CHA molecular sieve synthesized by adopting N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template according to the method of an example of a patent US 6709644.
3) Stirring the mixture obtained in the step 2), transferring the mixture into a hydrothermal crystallization reaction kettle, crystallizing for 8-120 hours at the autogenous pressure and the temperature of 125-200 ℃, and filtering, washing, drying and roasting the obtained crystallized product to obtain molecular sieve raw powder;
4) Mixing the molecular sieve raw powder obtained in the step 3) with an ammonium salt solution with the concentration of 0.1-5.0 mol/L according to the solid-liquid mass ratio of 1: (5-50) carrying out ion exchange at 60-100 ℃, wherein each time of exchange is 0.5-6 hours, and repeatedly exchanging the obtained filter cake with an ammonium ion solution for 1-3 times until the Na ion content in the molecular sieve sample is lower than 500ppm; then filtering and separating out a solid product, repeatedly washing the solid product by using deionized water until the solid product is neutral, drying a filter cake at the temperature of between 100 and 130 ℃ for 12 to 48 hours, and roasting the filter cake at the temperature of between 400 and 600 ℃ for 2 to 16 hours to obtain the CHA molecular sieve. After the molecular sieve raw powder prepared in the step 3) and the CHA molecular sieve are treated by saturated steam at 600-850 ℃, the four-coordination aluminum accounts for more than or equal to 90 percent of the total aluminum content, and the six-coordination aluminum accounts for less than or equal to 10 percent of the total aluminum content.
The invention adopts 27 The Al MAS NMR characterization method observed the formation of non-framework aluminum and the reduction of framework aluminum, as well as the discrimination of the coordination state of aluminum. In the zeolite molecular sieve aluminum spectrum, signals between delta 55 ppm and 65ppm come from framework four-coordinate aluminum, signals at delta 0ppm come from non-framework six-coordinate aluminum, and resonance peaks of the non-framework four-coordinate aluminum and the non-framework five-coordinate aluminum which belong to signals about delta 30 ppm to 45ppm are superposed. For characterizing molecular sieves in the invention 27 Fitting the peak of the Al MAS NMR spectrogram into a Gaussian curve by using a generally adopted Gaussian fitting mode, wherein the abscissa position represents the chemical shift of the four-coordinate aluminum, namely the four-coordinate aluminum in different chemical environments; and the corresponding peak areas represent the amount of the corresponding tetracoordinated aluminum. It is provided with 27 In the Al MAS NMR spectrum, characteristic peaks are all at 55-65ppm, and no hexacoordinate aluminum characteristic peak is at 0ppm, which indicates that the coordination of Al exists in a four-coordination form, and Al is connected with four surrounding Si through OThen, no Al bonding to Al via O (hexacoordinated aluminum) and no Al bonding to the terminal hydroxyl group (defect) occurred.
Further, in the above-described embodiment, the zeolite molecular sieve in the molar ratio range of silica to alumina in step 1) is any one of FAU type zeolite, MFI type zeolite, BEA type zeolite, MOR type zeolite, LTA type zeolite, and EMT type zeolite, preferably any one of FAU type zeolite, MFI type zeolite, BEA type zeolite, and MOR type zeolite, and more preferably any one of X molecular sieve, Y molecular sieve, and USY molecular sieve having FAU type structure; in the step 2) of the synthesis method, the silicon source is selected from one or more of silica sol, water glass, white carbon black, sodium metasilicate, column chromatography silica gel, macroporous silica gel, fine pore silica gel, amorphous silica gel, B-type silica gel, methyl silicate, ethyl silicate, propyl silicate, butyl silicate, ultrafine silica powder, activated clay, organosilicon, diatomite and gas phase method silica gel, and preferably any one or more of silica sol, water glass, column chromatography silica gel, white carbon black, macroporous silica gel, coarse pore silica gel, microporous silica gel, amorphous silica gel, B-type silica gel, methyl silicate and ethyl silicate.
Further, in the above technical solution, the acid solution in step 2) is selected from any one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, citric acid, carbolic acid, oxalic acid, and benzoic acid.
Further, in the above technical solution, the kind of the ammonium salt in step 4) is any one of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium acetate, or a mixture of two or more of them mixed at any ratio.
The invention also provides an SCR catalyst for denitration, wherein the CHA molecular sieve is subjected to ion exchange with a soluble metal salt solution, then forms slurry with the solid content of 25.0-48.0 wt% with a binder and deionized water, and is coated on a carrier of a porous regular material or an integral filter substrate to form a proper coating layer, so that the SCR catalyst of the metal-promoted CHA molecular sieve is obtained.
Further, in the above technical solution, the soluble metal salt is selected from one or a combination of several of soluble salts of copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver, preferably any one or two of copper salt and iron salt, and further preferably copper salt; the copper salt is one or more of copper nitrate, copper chloride, copper acetate or copper sulfate; the concentration of copper ions in the water solution of the soluble salt of copper is 0.1-0.5 mol/L.
Further, in the above technical solution, the binder is selected from any one or a mixture of several of silica sol, aluminum sol or pseudo-boehmite; the porous regular material or the monolithic filter base material is prepared from any one of cordierite, alpha-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate.
The invention also provides the application of the SCR catalyst, which is applied to the selective catalyst reduction process of nitrogen oxides in the tail gas of the internal combustion engine, the purification of the gas containing nitrogen oxides generated in the refining industrial process, and the purification treatment of the gas containing nitrogen oxides from a refining heater and a boiler, a furnace, the chemical processing industry, a coke oven, a municipal waste treatment device and an incinerator.
Nitrogen Oxides (NO) according to the invention x ) Including a variety of compounds, such as nitrous oxide (N) 2 O), nitric Oxide (NO), nitrogen dioxide (NO) 2 ) Dinitrogen trioxide (N) 2 O 3 ) Dinitrogen tetroxide (N) 2 O 4 ) And dinitrogen pentoxide (N) 2 O 5 ) And the like.
The treatment comprises NO x Wherein prior to contacting said catalyst with said gas stream, is contacted with NO x Measured as 100% by weight of NO 2 The content is 80% by weight or less, wherein preferably 5 to 70% by weight, more preferably 10to 60% by weight, more preferably 15 to 55% by weight, even more preferably 20 to 50% by weight of NO is contained 2 And (4) content. An oxidation catalyst located upstream of the catalyst oxidizes nitrogen monoxide in the gas to nitrogen dioxide and the resulting gas is then contacted with a catalyst containing nitrogen prior to the mixture being introduced into the zeolite catalystA nitrogen reductant mixture, wherein the oxidation catalyst is adapted to produce a gas stream into the zeolite catalyst, the gas stream having a ratio of 4:1 to 1:3 NO: NO2 volume ratio.
Reducing agents (urea, NH) are generally used 3 Etc.), several chemical reactions occur, all of which represent reactions that reduce NOx to elemental nitrogen. In particular, the dominant reaction mechanism at low temperature is represented by formula (1).
4NO+4NH 3 +O 2 →4N2+6H 2 O (1)
Non-selective reaction with competing oxygen, or formation of 2-fold products, or non-productive consumption of NH 3 . As such a non-selective reaction, for example, NH represented by the formula (2) 3 Is completely oxidized.
4NH 3 +5NO 2 →4NO+6H 2 O (2)
Furthermore, NO present in NOx 2 And NH 3 The reaction of (3) is considered to proceed by means of the reaction formula.
3NO 2 +4NH 3 →(7/2)N 2 +6H 2 O (3)
And NH 3 With NO and NO 2 The reaction between (a) and (b) is represented by the reaction formula (4).
NO+NO 2 +2NH 3 →2N 2 +3H 2 O (4)
The reaction rates of the reactions (1), (3) and (4) greatly differ depending on the reaction temperature and the kind of the catalyst used, and the rate of the reaction (4) is usually 2 to 10 times the rate of the reactions (1) and (3).
In the SCR catalyst, in order to improve NOx purification ability at low temperature, it is necessary to make the reaction of formula (4) dominant, not the reaction of formula (1). The reaction of formula (4) is dominant at low temperatures, preferably increasing NO 2 This is obvious.
Therefore, copper has an excellent ability to adsorb NO at a low temperature of 150 to 300 ℃, and has a stronger ability to oxidize NO. The oxidation reaction of NO is represented by formula (5).
NO+1/2O 2 →NO 2 (5)
The invention relates to an SCR catalyst for denitration, which is an SCR catalyst for obtaining a metal-promoted SSZ-13 eutectic molecular sieve by carrying out ion exchange on synthesized silicon-aluminum zeolite molecular sieve raw powder and a soluble metal salt solution.
The soluble metal salt used in the preparation process of the catalyst is selected from one or a combination of more of soluble salts of copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver, preferably any one or two of copper salt and iron salt, and further preferably copper salt. The copper salt is one or more of copper nitrate, copper chloride, copper acetate or copper sulfate; the concentration of copper ions in the copper salt aqueous solution is 0.1-1.5 mol/L.
The amount of Cu in the copper-based SCR molecular sieve catalyst is 0.03 to 20wt%, based on the weight of the copper-based SCR catalyst, wherein the amount of Cu is preferably 0.2 to 15 wt%, more preferably 0.5 to 10 wt%, more preferably 1.0 to 8.0wt%, more preferably 1.5 to 5.0 wt%, more preferably 2.0 to 4.0 wt%, more preferably 2.5 to 3.5 wt%, more preferably 2.7 to 3.3 wt%, more preferably 2.9 to 3.1 wt%.
In certain embodiments of the invention, the washcoat of the eutectic molecular sieve SCR catalyst is preferably a solution, suspension or slurry that is applied to a porous structured material (i.e., a honeycomb monolithic catalyst support structure having a plurality of parallel channels running axially through the entire assembly) or a monolithic filter substrate, such as a wall-flow filter, etc., with suitable coatings including a surface coating, a coating that penetrates a portion of the substrate, a coating that penetrates the substrate, or some combination thereof.
The porous regular material comprises a honeycomb flow-through regular carrier which is prepared from cordierite, alpha-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate materials; the carrier is preferably a cordierite porous honeycomb flow-through monolith carrier having a loading capacity of 170 to 270g/L.
The two most common substrate designs to which the SCR catalyst of the invention can be applied are plate and honeycomb. Preferred substrates, particularly for mobile applications, include flow-through monoliths having a so-called honeycomb geometry, which comprise a plurality of adjacent, parallel channels that are open at both ends and generally extend from an inlet face to an outlet face of the substrate, and which result in a high surface area to volume ratio. For certain applications, it is preferred that the honeycomb flow-through monolith have a high cell density, for example, about 600 to 800 cells per square inch, and/or an average internal wall thickness of about 0.18 to 0.35mm, preferably about 0.20 to 0.25mm. For certain other applications, the honeycomb flow-through monolith preferably has a low pore density of about 150 to 600 pores per square inch, more preferably about 200 to 400 pores per square inch.
The catalyst in the embodiments of the invention shows that high NOx conversion is obtained in a much wider temperature window. The temperature range for increasing the conversion efficiency may be from about 150 to 650 c, preferably from 200 to 500 c, more preferably from 200 to 450 c, or most significantly preferably from 200 to 400 c. Within these temperature ranges, the conversion efficiency after exposure to a reducing atmosphere, even after exposure to a reducing atmosphere and high temperatures (e.g., up to 850 ℃) can be greater than 55% to 100%, more preferably greater than 90% efficiency, and even more preferably greater than 95% efficiency.
The SCR catalyst prepared by the CHA structure molecular sieve has better hydrothermal stability and wider ignition activity window temperature (200-500 ℃), has good low-temperature and high-temperature ignition activity, has a more proper pore structure and grain size distribution, is beneficial to the diffusion of NOx molecules, enhances the adhesion of metal copper ions, and reduces the possibility of aggregation caused by the hydrothermal action.
The molecular sieve has more reasonably distributed acidity and good hydrothermal stability, overcomes the limitations of the components, and has excellent NOx reducibility particularly at low temperature after the provided SCR catalyst is subjected to durable treatment at high temperature in the atmosphere containing hydrothermal steam. Better meets the requirements of industrial application and has wide application prospect.
The silicoaluminophosphate zeolite molecular sieve of the present invention is more suitable for a high-crystallinity CHA-type zeolite as a catalyst or a catalyst carrier than a conventional CHA-type zeolite, and particularly suitable for a nitrogen oxide reduction catalyst or a carrier thereof, and further a nitrogen oxide reduction catalyst or a carrier thereof in the presence of ammonia or urea.
The molecular sieve of the present invention is a silicoaluminophosphate zeolite molecular sieve having high heat resistance without having a large crystal grain size, and is a catalyst which exhibits high nitrogen oxide reduction characteristics even after exposure to high temperature and high humidity, particularly high nitrogen oxide reduction characteristics at a temperature range of 200 to 550 ℃.
Drawings
FIG. 1 is an XRD diffractogram of the SSZ-13 molecular sieve synthesized in example 1.
FIG. 2 is an XRD diffractogram of the SSZ-13 molecular sieve synthesized in example 2.
FIG. 3 is an XRD diffractogram of the SSZ-13 molecular sieve synthesized in example 3.
FIG. 4 is an SEM topography of the SSZ-13 molecular sieve synthesized in example 1.
FIG. 5 is an SEM topography of the SSZ-13 molecular sieve synthesized in example 2.
FIG. 6 is an SEM topography of the SSZ-13 molecular sieve synthesized in example 3.
Detailed Description
The embodiments and the effects of the present invention are further illustrated by examples and comparative examples, but the scope of the present invention is not limited to the contents listed in the examples.
The eutectic molecular sieve of the present invention is identified by finding the lattice plane spacing (d) from the XRD pattern by the Powder method of X-ray Diffraction (X-ray Diffraction) analysis, and comparing the obtained Data with Data collected from the XRD database of the International society for synthetic zeolites or the PDF (Powder Diffraction File) of ICDD (International Centre for Diffraction Data). As XRD measurement conditions in the embodiment of the present invention, the following conditions may be mentioned:
ray source: cuK α -ray λ =1.540598, assay mode: step-scan 2 θ step-scan scale: 0.02626 °, measurement range: 2 θ =5 ° to 60 °.
And substituting X-ray diffraction data into a Debye-Scherrer formula to calculate the grain size Dhkl, wherein the Debye-Scherrer formula is as follows: d (hkl) = k λ/β cos θ; wherein D (hkl) is the grain diameter along the direction vertical to the crystal face hkl and has unit nm; k is the Scherrer constant; λ is the incident X-ray wavelength in nm; theta is the Bragg diffraction angle in degrees; beta is the half-peak broadening of the diffraction peak. The wavelength λ is 0.15406nm when Cuka is used as the X-ray source, and 0.15418nm when Cuka1 is used as the X-ray source. Measured by a PANALYTICAL X-ray diffractometer by using CuK alpha monochromatic light radiation, the tube voltage is 45kV, the current is 40mA, and the 2 theta is in a range of 15-35 degrees.
Example 1
A CHA type SSZ-13 molecular sieve and an SCR catalyst preparation method are disclosed:
1) Mixing 45.59g HY molecular sieve (Si/Al to nSiO) 2 /nAl 2 O 3 =5.20, dry basis 78.1%), 26.68g NaOH flake caustic soda and 69.98g deionized water, and the molar ratio of the components of the slurry is nNa 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O =0.75, 10, aging in a crystallization kettle at 85 ℃ for 36 hours to obtain a silica-alumina gel;
2) 507.51g of silica gel solution (Na) was added to the mixed silica-alumina gel mixture obtained in step 1) 2 O:0.24wt%,SiO 2 :30.36 wt%), 265.61g of N, N-diethyl-N' -methyl- (indan-4-yl) ammonium hydroxide (concentration 20wt%, expressed as OSDA), 56.31g of NaOH flake caustic, 21.25g of NaCl and 163.85g of deionized water were thoroughly and ultrasonically mixed well so that the components of the mixed slurry were in molar ratio nNa 2 O:nSiO 2 :nA1 2 O 3 :nOSDA:nNaCl:nH 2 O = 0.35; addition of 5% of nOH in the HCl solution conditioning system - /nSiO 2 The ratio =0.78, and SiO is added into the mixed slurry 2 And A1 2 O 3 Taking 9.45g of CHA molecular sieve accounting for 5.0 percent of the total mass as seed crystal; stirring the above mixture, transferring into hydrothermal crystallization reaction kettle, crystallizing at 140 deg.C under autogenous pressure for 36 hr, quenching to stop crystallization, filtering, and collecting the filtrateWashing to be nearly neutral in pH value, drying at 120 ℃ for 12 hours, and roasting at 540 ℃ for 4 hours to obtain SSZ-13 molecular sieve raw powder;
3) Performing ion exchange on the SSZ-13 molecular sieve raw powder in the step 2) and an ammonium nitrate solution with the concentration of 1.0mol/L for 2 hours at 80 ℃ according to the solid-liquid mass ratio of 1, and then repeatedly exchanging the filter cake obtained by filtering with a fresh ammonium nitrate solution twice under the same conditions, so that the Na ion content in the sample is lower than 500ppm. Then filtering and separating the solid product, repeatedly washing the solid product to be neutral by using deionized water, and drying the obtained filter cake at 110 ℃ for 12h to obtain the ammonium type molecular sieve NH 4 SSZ-13, then heating to 450 ℃ and roasting for 12 hours to obtain the H-type SSZ-13 molecular sieve (namely the CHA-type molecular sieve).
4) Adding 50.0g of the H-type SSZ-13 molecular sieve obtained in the step 3) into a copper nitrate aqueous solution with the concentration of 0.15mol/L, dropwise adding dilute nitric acid into the solution to adjust the pH value to 6.5, uniformly stirring, then placing into a heat-resistant container, and placing into a dryer with a pressure reducing valve; vacuumizing the pressure in the dryer to be below 10Torr by using a vacuum pump, degassing at room temperature for 1 hour, heating to 90 ℃, drying for 12 hours, and roasting the dried sample at the temperature of 500 ℃ for 4 hours under normal atmospheric pressure; the copper modified SSZ-13 molecular sieve was obtained and the catalyst prepared according to XRF analysis results had 3.2% copper (II) ions based on the total weight of the molecular sieve catalyst, i.e. a copper loading of 3.2wt%.
5) Taking 40.0g of the copper-modified molecular sieve obtained in the above 4), and 20.0g of silica Sol (SiO) 2 The content is as follows: 30.0 wt%) and 81.54g of deionized water are uniformly mixed to prepare catalyst slurry with the solid content of 32.5wt%, the catalyst slurry is coated on a honeycomb-shaped porous regular material (400 cpsi, the diameter of 20mm and the length of 40 mm) made of cordierite by an immersion method, redundant slurry drops are blown off by compressed air, the catalyst slurry is dried for 24 hours at 105 ℃, the catalyst slurry is coated for 2 times under the same condition and is calcined for 2 hours at 500 ℃ to prepare the SCR catalyst, the loading on the regular material is 232.7g/L (the weight of the weight increased by the regular material after calcination is divided by the space volume occupied by the regular material, the definitions of the subsequent examples and comparative examples are the same), and the obtained SCR catalyst is marked as A,the relevant preparation parameters and species are shown in tables 1, 2, 3 and 4.
Example 2
The process for synthesizing the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that the slurry components in step 1) are present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), the type of the zeolite molecular sieve, the silicon-aluminum ratio of the zeolite molecular sieve, the aging temperature and the aging time, the molar ratio of the components of the mixed slurry, the type of the organic template agent, the type of the silicon source, the adding amount of seed crystal, the type of the added acid, the type of the metal salt M, the crystallization temperature and the crystallization time in the step 2), 50.0g of the H-type SSZ-13 molecular sieve is taken in the step 4), different types, concentrations, solution volumes and metal load amounts of soluble metal salts are adopted, 40.0g of the copper modified CHA-type SSZ-13 molecular sieve is taken in the step 5), and 20.0g of silica sol (SiO 2) 2 The contents are as follows: 30.0 wt%) and 76.50g of deionized water were mixed uniformly to prepare a catalyst slurry having a solid content of 33.7wt%, which was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 3
The process for synthesizing the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that the slurry components in step 1) are present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), the type of the zeolite molecular sieve, the silicon-aluminum ratio of the zeolite molecular sieve, the aging temperature and the aging time, the molar ratio of the components of the mixed slurry, the type of the organic template agent, the type of the silicon source, the adding amount of seed crystal, the type of the added acid, the type of the metal salt M, the crystallization temperature and the crystallization time in the step 2), 50.0g of the H-type SSZ-13 molecular sieve is taken in the step 4), different types, concentrations, solution volumes and metal load amounts of soluble metal salts are adopted, 40g of the copper modified CHA-type SSZ-13 molecular sieve is taken in the step 5), and 20.0g of silica Sol (SiO) 2 The content is as follows: 30.0 wt%) and 104.87g of deionized water were uniformly mixed to prepare a catalyst slurry having a solid content of 27.9wt%, and the catalyst slurry was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 4
The process for synthesizing the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that the slurry components in step 1) are present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), the type of the zeolite molecular sieve, the silicon-aluminum ratio of the zeolite molecular sieve, the aging temperature and the aging time, the molar ratio of the components of the mixed slurry, the type of the organic template agent, the type of the silicon source, the adding amount of seed crystal, the type of the added acid, the type of the metal salt M, the crystallization temperature and the crystallization time in the step 2), 50.0g of the H-type SSZ-13 molecular sieve is taken in the step 4), different types, concentrations, solution volumes and metal load amounts of soluble metal salts are adopted, 40g of the copper modified CHA-type SSZ-13 molecular sieve is taken in the step 5), and 20.0g of silica Sol (SiO) 2 The contents are as follows: 30.0 wt%) and 59.17g of deionized water were uniformly mixed to prepare a catalyst slurry having a solid content of 38.6wt%, and the catalyst slurry was coated on a cordierite structured material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 5
The process for the synthesis of the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that in step 1) the slurry composition is present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), the type of the zeolite molecular sieve, the silicon-aluminum ratio of the zeolite molecular sieve, the aging temperature and the aging time, the molar ratio of the components of the mixed slurry, the type of the organic template agent, the type of the silicon source, the adding amount of seed crystal, the type of the added acid, the type of the metal salt M, the crystallization temperature and the crystallization time in the step 2), 50.0g of the H-type SSZ-13 molecular sieve is taken in the step 4), different types, concentrations, solution volumes and metal load amounts of soluble metal salts are adopted, 40g of the copper modified CHA-type SSZ-13 molecular sieve is taken in the step 5), and 30.0g of aluminum sol (Al) 2 O 3 The contents are as follows: 20.0 wt%) and 75.40g deionized water, and the catalyst slurry with the solid content of 33.7wt% is prepared and coated on the cordierite regular material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 6
The process for synthesizing the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except thatThe molar ratio of the components of the slurry in the step 1) (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), zeolite molecular sieve type, zeolite molecular sieve Si/Al ratio, aging temperature and aging time, and the mixed slurry component molar ratio, organic template agent type, silicon source type, seed crystal addition amount, acid addition type, metal salt M type, crystallization temperature and crystallization time in the step 2), taking 50.0g of H-type SSZ-13 molecular sieve in the step 4), adopting different soluble metal salt types, concentrations, solution volumes and metal loading amounts, and taking 40g of copper modified CHA-type SSZ-13 molecular sieve in the step 5), and 30.0g of aluminum sol (Al) 2 O 3 The contents are as follows: 20.0 wt%) and 68.97g deionized water, and the catalyst slurry with the solid content of 33.1wt% is prepared and coated on the cordierite regular material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 7
The process for synthesizing the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that the slurry components in step 1) are present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), zeolite molecular sieve type, zeolite molecular sieve Si/Al ratio, aging temperature and aging time, and the mixed slurry component molar ratio, organic template agent type, silicon source type, seed crystal addition amount, acid addition type, metal salt M type, crystallization temperature and crystallization time in the step 2), taking 50.0g of H-type SSZ-13 molecular sieve in the step 4), adopting different soluble metal salt types, concentrations, solution volumes and metal loading amounts, and taking 40g of copper modified CHA-type SSZ-13 molecular sieve in the step 5), and 30.0g of aluminum sol (Al) 2 O 3 The content is as follows: 20.0 wt%) and 52.67g of deionized water were uniformly mixed to prepare a catalyst slurry having a solid content of 37.5wt%, and the catalyst slurry was coated on a cordierite structured material by a dipping method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
Example 8
The process for the synthesis of the CHA-type SSZ-13 molecular sieve is similar to that of example 1, except that in step 1) the slurry composition is present in a molar ratio (nNa) 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O), the type of the zeolite molecular sieve, the silicon-aluminum ratio of the zeolite molecular sieve, the aging temperature and the aging time, the molar ratio of the components of the mixed slurry, the type of the organic template agent, the type of the silicon source, the adding amount of seed crystal, the type of the added acid, the type of the metal salt M, the crystallization temperature and the crystallization time in the step 2), 50.0g of the H-type SSZ-13 molecular sieve is taken in the step 4), different types, concentrations, solution volumes and metal load amounts of soluble metal salts are adopted, 40g of the copper modified CHA-type SSZ-13 molecular sieve is taken in the step 5), and 30.0g of aluminum sol (Al) 2 O 3 The content is as follows: 20.0 wt%) and 55.00g of deionized water, and the catalyst slurry with the solid content of 36.8wt% is prepared and coated on the cordierite regular material by an impregnation method. Specific parameters in this example are shown in tables 1, 2, 3 and 4.
TABLE 1 selection of parameters in the Synthesis of the molecular sieves step 1)
Examples | nNa2O:nSiO 2 :nAl 2 O 3 :nH 2 O | Zeolite molecular sieve species | Zeolite molecular sieve silica-alumina ratio | Ageing temperature/. Degree.C | Aging time/h |
Example 1 | 0.75:1.0:0.192:10 | HY | 5.20 | 85 | 36 |
Example 2 | 1.25:1.0:0.189:10 | NaY | 5.29 | 120 | 8 |
Example 3 | 1.05:1.0:0.417:6 | NaX | 2.40 | 100 | 24 |
Example 4 | 2.45:1.0:0.040:20 | ZSM-5 | 22.0 | 110 | 40 |
Example 5 | 1.35:1.0:0.139:15 | USY | 7.20 | 85 | 48 |
Example 6 | 2.05:1.0:0.085:20 | MOR | 11.8 | 105 | 36 |
Example 7 | 1.15:1.0:0.208:12 | NaY | 4.80 | 90 | 16 |
Example 8 | 1.85:1.0:0.074:18 | USY | 12.1 | 105 | 12 |
TABLE 2 selection of parameters in molecular Sieve Synthesis step 2)
TABLE 3 table of the molecular sieves obtained in examples 1 to 8
* : the sample is used after the hydrothermal treatment for 16 hours by saturated water vapor at 800 DEG C 27 And testing the aluminum proportioning ratio by Al MAS NMR solid nuclear magnetic resonance.
Table 4 SCR catalyst metal ion parameters and metal loadings prepared in examples 1-8
Comparative example 1
17.0g of SB powder was dissolved in 50.0g of a 50wt% NaOH aqueous solution, and 200.0g of white carbon was added thereto and mixed well. An aqueous solution of N, N, N-trimethyladamantane ammonium hydroxide (TMADA +) (25 wt% concentration) was slowly added to the mixture while mixing. 80.0g of deionized water was slowly added and the resulting mixture was mixed well for 1 hour. The molar composition of the synthesis mixture was:
0.21Na 2 O:SiO 2 :0.0286Al 2 O 3 :0.18TMADa + :26.8H 2 O
and then transferring the obtained gel into a stainless steel reaction kettle to crystallize at 170 ℃ for 168 hours, after the reaction is finished, washing the product with deionized water, drying at 120 ℃ for 12h, and roasting at 540 ℃ for 4 hours to obtain the SSZ-13 molecular sieve raw powder. And (2) carrying out ion exchange on the molecular sieve raw powder and an ammonium nitrate solution with the concentration of 1.0mol/L for 2 hours at 80 ℃ according to the solid-liquid mass ratio of 1. The filter cake obtained by subsequent filtration is dried at 110 ℃ overnight to obtain ammonium type molecular sieve NH 4 Heating to 450 ℃ and roasting for 16 hours to obtain the H-type SSZ-13 molecular sieve.
10g of SSZ-13 molecular sieve raw powder was added to 100g of Cu (NO) of 0.3mol/L concentration 3 ) 2 ·3H 2 And (3) dripping dilute nitric acid into the O aqueous solution to adjust the pH value to 5.8, and uniformly stirring. After stirring was stopped for 1 hour, the supernatant was siphoned off when SSZ-13 zeolite settled. The exchange with fresh copper nitrate solution was repeated once, and finally the exchanged SSZ-13 zeolite was filtered and washed with deionized water. Drying at 90 ℃ for 12 hours under the low pressure of 10Torr, and then roasting at 500 ℃ for 4 hours under normal atmospheric pressure to obtain the copper modified SSZ-13 molecular sieve powder. According to XRF analysis, copper (II) ions accounted for 2.9% of the total weight of the molecular sieve catalyst.
Taking 15g of the obtained copper modified SSZ-13 molecular sieve, and5.56g of silica sol (30wt%; siO) 2 ) And 22.80g of deionized water are uniformly mixed to prepare catalyst slurry with the solid content of 38.44wt%, the catalyst slurry is coated on a honeycomb-shaped porous regular material (400 cpsi, the diameter of 20mm and the length of 40 mm) made of cordierite through an impregnation method, redundant slurry drops are blown off by compressed air, the drying is carried out for 12 hours at 110 ℃, then, the slurry is coated again, the SCR catalyst is prepared after the calcination is carried out for 2 hours at 500 ℃, and the catalyst loading capacity on the regular material is 228.4g/L and is marked as VS-1.
Comparative example 2
The SSZ-13 molecular sieve is synthesized and the SCR catalyst is prepared according to the method in CN 103328385:
to 13.9g of N, N-trimethyladamantanamine hydroxide solution (TMADAOH, 25%), 31.4g of pure water, 2.5g of an aqueous potassium hydroxide solution (concentration: 48%), and 9.0g of an amorphous aluminosilicate gel prepared from sodium silicate and aluminum sulfate were added and sufficiently mixed to obtain a raw material composition. The raw material composition is SiO2:0.048Al2O3:0.124TMADAOH:0.054Na2O:0.081k2o:18H2O. The raw material composition was sealed in an 80ml stainless steel autoclave and crystallized at 150 ℃ for 72 hours at a rotation speed of 55 rpm. And (3) carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with deionized water to be nearly neutral, and drying the product at 110 ℃ to obtain an SSZ-13 molecular sieve product, wherein the SiO2/Al2O3 molar ratio of the product is 14.9, and the particle size of the product is 1.0-3.0 mu m.
And (2) performing ion exchange on the SSZ-13 molecular sieve raw powder and an ammonium nitrate solution with the concentration of 1.0mol/L for 2 hours at 90 ℃ according to the solid-liquid mass ratio of 1. The filter cake obtained by subsequent filtration is dried at 110 ℃ overnight to obtain ammonium type molecular sieve NH 4 Heating to 450 ℃ and roasting for 16 hours to obtain the H-type SSZ-13 molecular sieve.
10g of SSZ-13 molecular sieve raw powder was added to 100g of Cu (NO) having a concentration of 0.3mol/L 3 ) 2 ·3H 2 And (3) dripping dilute nitric acid into the O aqueous solution to adjust the pH value to 5.8, and uniformly stirring. After stirring was stopped for 1 hour, the supernatant was siphoned off when SSZ-13 zeolite settled. Repetition ofThe exchange was performed once with fresh copper nitrate solution and finally the exchanged SSZ-13 zeolite was filtered, washed with deionized water. Drying at 90 ℃ for 12 hours under the low pressure of 10Torr, and then roasting at 500 ℃ for 4 hours under normal atmospheric pressure to obtain the copper modified SSZ-13 molecular sieve powder. According to XRF analysis, copper (II) ions accounted for 3.0% of the total weight of the molecular sieve catalyst.
15g of the resulting copper-modified SSZ-13 molecular sieve was taken and mixed with 5.56g of silica sol (30wt% SiO) 2 ) And 22.80g of deionized water are uniformly mixed to prepare catalyst slurry with the solid content of 38.44wt%, the catalyst slurry is coated on a honeycomb-shaped porous regular material (400 cpsi, the diameter of 20mm and the length of 40 mm) made of cordierite through a dipping method, redundant slurry drops are blown off by compressed air, the drying is carried out for 12 hours at 110 ℃, then, the slurry is coated again, the SCR catalyst is prepared after the calcination is carried out for 2 hours at 500 ℃, and the catalyst loading capacity on the regular material is 216.6g/L and is marked as VS-2.
Examples 9 to 14
Testing of the SCR catalyst:
SCR catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 were placed in a reactor160mL/min of a mixed gas stream containing 500ppm of NO, 500ppm of NH3, 10 vol% of O2, 5 vol% of steam and Ar as an equilibrium gas first passes through a preheater (set at 250 ℃) and then enters an SCR reactor. At a reaction temperature of 150-650 ℃ for 48000h -1 The test specimens were tested at a volumetric gas hourly space velocity. The temperature is monitored by an internal thermocouple located at the sample site.
The used fresh SCR catalysts of the above examples and comparative examples were subjected to a hydrothermal durability treatment under the conditions of the hydrothermal durability treatment test to obtain aged SCR catalysts:
space velocity SV:30000/h, temperature: 800 ℃, time: 16 hours, water concentration: 10%, oxygen concentration: 10%, nitrogen concentration: and (4) balancing.
After hydrothermal aging treatment is carried out according to the parameters, the catalyst is continuously used as an SCR catalyst for NOx catalytic reduction reaction evaluation test:
the NO conversion or "denox" activity was determined under steady state conditions by measuring NOx, NH3 and N2O concentrations at the outlet using a Bruker EQUINOX model 55 FT-IR spectrometer.
The SCR catalyst activity laboratory evaluation device described above was used to evaluate the selective catalytic reduction performance of NOx on the Cu-supported SCR catalysts prepared in examples and comparative examples, and the results are shown in table 5.
TABLE 5 evaluation index for NOx Selective reduction Performance of catalysts prepared in examples 1 to 6 and comparative examples 1 to 2
* 800 ℃ in an atmosphere of 10% water concentration +10% oxygen concentration, at a space velocity of 30000/h, for 16 hours.
As can be seen from Table 5, the evaluation of the Cu-SSZ-13 or Fe-SSZ-13 catalysts obtained in examples 1 to 6 in examples 9 to 14 shows that they have better low-temperature ignition properties and high-temperature activity, the SCR activity being significantly better than the catalytic performance of the catalysts VS-1 and VS-2 obtained in comparative example 1 in examples 15 to 16, whether in the "fresh" state or in the "aged" state. Thus, the results obtained from examples 9-14 clearly show that the Cu-SSZ-13 or Fe-SSZ-13 catalyst materials of the present invention and the catalysts obtained therewith have improved SCR catalytic activity, especially at low conversion temperatures characteristic of cold start conditions when treating NOx, for example, in diesel locomotive applications. For other SCR applications, the Cu-SSZ-13 or Fe-SSZ-13 catalyst material of the present invention allows for higher conversion at lower temperatures, thus allowing for higher efficiency and thus, at comparable conversion, for high energy efficiency treatment of NOx-containing exhaust gases, such as exhaust gases obtained from industrial processes.
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (13)
1. A novel structure template agent synthesized CHA molecular sieve is characterized in that: the CHA molecular sieve is synthesized by adopting an organic template agent, wherein the organic template agent is one or more than two of N, N, N-trialkyl- (indan-5-yl) quaternary ammonium onium, N, N, N-trialkyl- (indan-1-yl) quaternary ammonium onium or N, N, N-trialkyl- (indan-4-yl) quaternary ammonium onium compounds which are mixed in any proportion, the mole ratio of silicon dioxide to aluminum oxide of the CHA molecular sieve is 6-80, the average grain diameter is less than or equal to 500nm, and the total specific surface area is more than or equal to 400m 2 The total pore volume is more than or equal to 0.20ml/g, and the micropore volume is more than or equal to 0.10ml/g; the molecular sieve has a CHA topological structure, the range of the half-value width (FWHM) of a crystal face of X-ray crystal diffraction (-210) is 0.1-0.2 degrees, and the diameter size of crystal grains in the direction of the crystal face (-210) is 50-160 nm; after the molecular sieve is treated by saturated steam at 600-850 ℃, the four-coordinate aluminum accounts for more than or equal to 90 percent of the total aluminum content, and the six-coordinate aluminum accounts for less than or equal to 10 percent of the total aluminum content;
the organic template agent is N, N, N-trialkyl- (indan-5-yl) quaternary ammonium shown as a formula I, N, N, N-trialkyl- (indan-1-yl) quaternary ammonium shown as a formula II, and N, N, N-trialkyl- (indan-4-yl) quaternary ammonium shown as a formula III:
wherein R1 and R2 are independently selected from methyl or deuterated methyl, C2-C4 straight-chain or branched-chain alkyl, and R3 is selected from C1-C5 straight-chain or branched-chain alkyl; x - A counter anion which is a quaternary ammonium onium ion, including any one of hydroxide, halide, sulfate, bisulfate, carbonate, bicarbonate, oxalate, phosphate, carboxylate, alkyl-substituted sulfate, carbonate, or oxalate;
the molecular sieve has at least one XRD diffraction peak in each of the following tables in the range of 4 to 40 DEG 2 theta and has the characteristics set forth in the following table:
* The relative intensity is an intensity relative to a peak intensity of 2 θ =20.40 to 20.90;
the synthesis method of the CHA molecular sieve comprises the following steps:
1) Fully dissolving and dispersing zeolite molecular sieve with the molar ratio of silicon dioxide to aluminum oxide of 2-30, naOH and deionized water to obtain slurry with the molar ratio of nNa 2 O:nSiO 2 :nAl 2 O 3 :nH 2 O = (0.5-2.5): 1, (0.0333-0.5): 5-20), and aging is carried out in a crystallization kettle at 60-120 ℃ for 6-48 hours to obtain silicon-aluminum gel;
2) Adding a silicon source, an organic template agent OSDA, a metal salt M and deionized water into the silicon-aluminum gel obtained in the step 1), fully and uniformly mixing, supplementing NaOH according to the alkalinity requirement of a system, and mixing the components of the slurry according to the molar ratio nNa 2 O:nSiO 2 :nA1 2 O 3 :nOSDA:nM:nH 2 O = (0.05-0.5) 1, (0.0125-0.20), (0.01-0.5), (0.05-0.5) and (10-100); adding acid solution to control alkali hydroxyl OH in mixed slurry - With SiO 2 In a molar ratio of nOH - /nSiO 2 =0.1 to 1.0; adding CHA molecular sieve seed crystal with SiO in the slurry 2 And A1 2 O 3 0.5-15% of the total mass;
3) Stirring the mixture obtained in the step 2), transferring the mixture into a hydrothermal crystallization reaction kettle, crystallizing for 8-120 hours at the autogenous pressure and the temperature of 125-200 ℃, and filtering, washing, drying and roasting the obtained crystallized product to obtain molecular sieve raw powder;
4) Mixing the molecular sieve raw powder obtained in the step 3) with an ammonium salt solution with the concentration of 0.1-5.0 mol/L according to the solid-liquid mass ratio of 1: (5-50) carrying out ion exchange at 60-100 ℃, wherein each time of exchange is 0.5-6 hours, and repeatedly exchanging the obtained filter cake with an ammonium ion solution for 1-3 times until the Na ion content in the molecular sieve sample is lower than 500ppm; then filtering and separating out a solid product, repeatedly washing the solid product by using deionized water until the solid product is neutral, drying a filter cake at the temperature of between 100 and 130 ℃ for 12 to 48 hours, and roasting the filter cake at the temperature of between 400 and 600 ℃ for 2 to 16 hours to obtain the CHA molecular sieve.
2. The novel structural templating agent synthetic CHA molecular sieve of claim 1, characterized by: the halide comprises chloride, bromide or iodide; carboxylates include formate, acetate, propionate; alkyl substituted sulphate, carbonate or oxalate includes methyl sulphate, ethyl sulphate, methyl carbonate, ethyl carbonate, methyl oxalate or ethyl oxalate.
3. The CHA molecular sieve of claim 1, characterized in that: the zeolite molecular sieve with the mole ratio of the silicon dioxide to the aluminum oxide of 2-30 in the step 1) is any one of FAU type zeolite, MFI type zeolite, BEA type zeolite, MOR type zeolite, LTA type zeolite and EMT type zeolite, the silicon source in the step 2) is selected from one or more of silica sol, water glass, white carbon black, sodium metasilicate, column chromatography silica gel, macroporous silica gel, coarse pore silica gel, fine pore silica gel, amorphous silica, B type silica gel, methyl silicate, ethyl silicate, propyl silicate, butyl silicate, ultrafine silica powder, activated clay, organic silicon, kieselguhr and gas phase method silica gel, and the metal salt M is NaCl, naNO 3 、Na 2 SO 4 、Na 3 PO 4 、NaBr、NaF、KCl、KNO 3 、K 2 SO 4 、KBr、KF、K 3 PO 4 The acid solution is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, citric acid, carbolic acid, oxalic acid and benzoic acid.
4. The CHA molecular sieve of claim 1, characterized in that: the zeolite molecular sieve with the mole ratio of the silicon dioxide to the aluminum oxide of 2-30 in the step 1) is any one of FAU type zeolite, MFI type zeolite, BEA type zeolite and MOR type zeolite.
5. The CHA molecular sieve of claim 1, wherein: the zeolite molecular sieve with the mole ratio of the silicon dioxide to the aluminum oxide of 2-30 in the step 1) has any one of an X molecular sieve, a Y molecular sieve and a USY molecular sieve with an FAU-type structure.
6. The CHA molecular sieve of claim 1, characterized in that: in the step 2), the silicon source is selected from any one or more of silica sol, water glass, column chromatography silica gel, white carbon black, macroporous silica gel, coarse porous silica gel, fine porous silica gel, amorphous silica, B-type silica gel, methyl silicate and ethyl silicate.
7. The CHA molecular sieve of claim 1, characterized in that: the metal salt M is NaCl and NaNO 3 、Na 2 SO 4 、Na 3 PO 4 Any of the above.
8. The CHA molecular sieve of claim 1, characterized in that: and 4) the ammonium salt in the step 4) comprises a mixture formed by mixing any one, two or more than two of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium acetate in any proportion.
9. An SCR catalyst for denitration, characterized in that: carrying out ion exchange on the CHA molecular sieve of any one of claims 1 to 8 and a soluble metal salt solution, forming slurry with the solid content of 25.0-48.0 wt% with a binder and deionized water, and coating the slurry on a carrier of a porous regular material or an integral filter substrate to form a proper coating layer to obtain the SCR catalyst of the metal-promoted CHA molecular sieve;
the soluble metal salt is selected from one or more of soluble salts of copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold or silver.
10. The SCR catalyst of claim 9, wherein: the soluble metal salt is selected from one or two of copper salt and iron salt.
11. The SCR catalyst of claim 9, wherein: the soluble metal salt is selected from copper salt; the copper salt is one or more of copper nitrate, copper chloride, copper acetate or copper sulfate; the concentration of copper ions in the water solution of the soluble salt of copper is 0.1-0.5 mol/L.
12. The SCR catalyst of claim 9, wherein: the binder is selected from any one or mixture of silica sol, aluminum sol or pseudo-boehmite; the porous regular material or the monolithic filter base material is prepared from any one of cordierite, alpha-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate.
13. Use of the SCR catalyst of any one of claims 9 to 12, characterized in that: the method is applied to the reduction process of nitrogen oxide selective catalyst in the tail gas of internal combustion engine, the purification of gas containing nitrogen oxide generated in the industrial process of refining, and the purification treatment of gas containing nitrogen oxide from refining heaters and boilers, chemical processing industry, coke ovens, municipal waste treatment devices and incinerators.
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