CN108502900A - Cu-SAPO molecular sieves, synthetic method and its catalytic applications - Google Patents
Cu-SAPO molecular sieves, synthetic method and its catalytic applications Download PDFInfo
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- CN108502900A CN108502900A CN201710108084.4A CN201710108084A CN108502900A CN 108502900 A CN108502900 A CN 108502900A CN 201710108084 A CN201710108084 A CN 201710108084A CN 108502900 A CN108502900 A CN 108502900A
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- molecular sieve
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- sapo
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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 44
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 230000003197 catalytic effect Effects 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 claims abstract description 5
- 238000003379 elimination reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical group CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 18
- 229940043276 diisopropanolamine Drugs 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 229940043237 diethanolamine Drugs 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- -1 template R1 and R2 Chemical compound 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 241001502050 Acis Species 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 125000003636 chemical group Chemical group 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 241000269350 Anura Species 0.000 abstract description 7
- 239000000523 sample Substances 0.000 description 53
- 239000007789 gas Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 238000004410 13C MAS NMR Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000006069 physical mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ONWIUHATKXRGRY-UADPMFFRSA-N (2r)-6-amino-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r)-2-[[(2r,3s)-2-amino-3-hydroxybutanoyl]amino]propanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-3-phenylpropanoyl]amino]-4-methylpentanoyl]amino]-4-methylpentanoyl]amino]-n-[(2r)-1-[[(2r)-1-[[2-[[ Chemical compound C([C@H](C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCCCN)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](C)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(N)=O)NC(=O)[C@@H](CC=1C=CC(O)=CC=1)NC(=O)[C@@H](C)NC(=O)[C@H](N)[C@H](C)O)C1=CC=CC=C1 ONWIUHATKXRGRY-UADPMFFRSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of Cu SAPO molecular sieves with CHA and GME symbiosis crystalline phases and its synthetic method and the applications in denitration reaction.The Cu SAPO molecular sieves of the present invention are characterized in that the feature that broad peak and spike coexist is presented in the XRD diffraction spectrograms of the molecular sieve analog, and inorganic skeleton has following chemical composition：wCu‑(SixAlyPz)O2, wherein：X, y, z indicates that the molar fraction of Si, Al, P, range are that x=0.01~0.28, y=0.35~0.55, z=0.28~0.50, and x+y+z=1, w are every mole of (Si respectively respectivelyxAlyPz)O2The molal quantity of corresponding Cu, w=0.001~0.124.The molecular sieve that the present invention synthesizes can be used as NOxThe catalyst of selective reduction elimination reaction.
Description
Technical field
The present invention relates to a kind of novel cupric SAPO molecular sieve, synthetic method and its applications in denitration reaction.
Background technology
NOx can cause acid rain as one of Air Pollutants, many environmental problems such as photochemical fog, and to people
Body health, which is constituted, to be seriously endangered, and nitrogen oxides pollution is mainly derived from discharge and the stationary source plant gas of moving source vehicle exhaust
Discharge, NOx pollution processing method be with NH3, urea or hydrocarbon are that reducing agent carries out selective catalysis reduction instead
It answers, is translated into harmless nitrogen.Traditional denitrating catalyst is mainly V-Ti-W systems, but in engine technology
Lean burn technology it is widely used, lean-burn tail gas exhaust temperature reduce, the relatively narrow temperature applicable range of catalyst of V-Ti-W systems is not
It can meet the requirements, and its possibility potentially polluted the environment also limits its application.Molecular sieve catalytic system by
Gradually become current research hotspot.In the catalyst of molecular sieve system, Cu-series catalyst and Fe-series catalyst, which are two classes, to be had
Representative system, Cu-series catalyst shows excellent low temperature active, but excessively high load capacity can cause high temperature section serious
NH3Oxidation reaction.Ferrum-based catalyst has an excellent high temperature active, but its lower conversion ratio of low-temperature zone limit its
The application in certain fields.
1986, Iwamoto et al. reported Cu for the first time2+The ZSM-5 of exchange has catalysis NO to be directly decomposed into N2And O2's
Ability is reacted since researcher more pays close attention to by the SCR of reducing agent of hydrocarbon, Fe-ZSM-5 in research later
It is increasingly becoming next research hotspot.Compared with oxide catalyst, with wider the advantages of molecular sieve series catalysts
Reaction temperature window, good thermal stability, and sulfur poisoning resistance is stronger at high temperature, still, there is also some to ask for they
Topic, for example, high-temperature hydrothermal stability is poor, and low temperature sulfur resistance is poor etc..
Small pore molecular sieve such as SSZ-13 and SAPO-34 can effectively promote the high temperature hydro-thermal of catalyst as carrier material
Stability, and when supported copper is as active metal, high NO activity of conversion and height are possessed within the scope of wider temperature
N2Selectivity.Although the problems such as there is to sulfur sensitive, this problem is also gradually obtained with the promotion of oil quality
To solution.
The synthesis of usual SAPO molecular sieve needs organic amine/ammonium as structure directing agent, passes through hydro-thermal or the side of solvent heat
Method synthesizes to obtain.The innovation of synthetic method and the selection of template have the control of product structure and performance most important
Influence.It can be with one-step synthesis method Cu-SAPO-18 and Cu-SAPO-34 by template of copper-amine complex.This one-step method is closed
At Cu-SAPO catalyst simplify the preparation process of catalyst, have great importance.And the Cu- of this one-step synthesis method
SAPO type catalyst shows excellent NH3- SCR catalytic activity, and composition adjustable denaturation, have certain industry answer
Foreground.
The present invention provides a kind of method for the one-step synthesis method Cu-SAPO molecular sieve catalysts that Cu contents are controllable, and table
Reveal excellent deNOx catalytic activity, has potential application.
Invention content
The purpose of the present invention is to provide a kind of Cu-SAPO molecular sieves with GME and CHA eutectic structures.
The feature that broad peak and spike coexist, XRD diffraction spectrograms and document is presented in novel molecular sieve synthesized by the present invention
In (Microporous and Mesoporous Materials, 30 (1999) 335-346；International Molecular sieves the official of association
Websitehttp://www.iza-structure.org/databases/Catalog/ABC_6.pdf) there is GME/CHA symbiosis
The spectrogram of the Si-Al zeolite of structure has similitude.It is have GME/CHA symbiotic structures novel that we, which analyze the molecular sieve analog,
SAPO molecular sieve.
Embodiment according to the present invention provides a kind of Cu-SAPO molecular sieves with CHA and GME symbiosis crystalline phases, special
Sign is that the X ray diffracting spectrum of the molecular sieve at least contains following diffraction maximum：
Table 1
The inorganic skeleton of molecular sieve has following chemical composition：wCu-(SixAlyPz)O2, wherein：X, y, z indicates respectively
The molar fraction of Si, Al, P, range are x=0.01~0.28, y=0.35~0.55, z=0.28~0.50, and x+y respectively
+ z=1, w are every mole of (SixAlyPz)O2The molal quantity of corresponding Cu, w=0.001~0.124.
Molecular sieve includes that the anhydrous chemical composition of template is represented by：wCu mR1 nR3(SixAlyPz)O2, wherein：R1
For diisopropanolamine (DIPA) or diethanol amine, R3 is trimethylamine；M is every mole of (SixAlyPz)O2The molal quantity of middle R1 templates, n are
Every mole of (SixAlyPz)O2The molal quantity of middle R3 templates, m=0.01~0.20, n=0.01~0.10；X, y, z indicates respectively
The molar fraction of Si, Al, P, range are x=0.01~0.28, y=0.35~0.55, z=0.28~0.50, and x+y respectively
+ z=1；W is every mole of (SixAlyPz)O2The molal quantity of corresponding Cu, w=0.001~0.124.In certain embodiments, m
Can be 0.02~0.15；N can be 0.01~0.09；X can be 0.05~0.28；Y can be 0.40~0.50；Z can be with
It is 0.30~0.50；W can be 0.005~0.100.
Another object of the present invention is to provide the synthetic method of above-mentioned Cu-SAPO molecular sieves, which is characterized in that including such as
Lower step：
A) by copper source, deionized water, template R1 and R2, silicon source, silicon source and phosphorus source mix, obtain having as follows in proportion
The initial gel mixture of mol ratio：
Cu/Al2O3=0.01~0.25；
SiO2/Al2O3=0.05~2.0；
P2O5/Al2O3=0.5~1.5；
H2O/Al2O3=8~40；
R1/Al2O3=5~20；
R2/Al2O3=0.1~1.5；
Wherein, R1 is diisopropanolamine (DIPA) (DIPA) or diethanol amine (DEOA)；R2 is trimethylamine (TMA), benzyl trimethyl
Any one in ammonium chloride (BTACl), benzyltrimethylammonium hydroxide (BTAOH) or arbitrary several mixture.
Specific dispensing sequence can be as follows：Copper source with water mixed dissolution, then adds R1 and R2, and stir in room temperature first
Mix 0.5-5h.Then, silicon source, silicon source and phosphorus source is added into mixed liquor successively, and 1-5h is stirred at room temperature in mixed gel.
B) initial gel mixture obtained by step a) is packed into Autoclaves for synthesis, it is closed, 160~220 DEG C are warming up to, crystallization
5~72 hours.
C) after the completion of waiting for crystallization, to get the molecular sieve after solid product separating, washing, drying.
Wherein, silicon source described in step a) in Ludox, active silica, positive esters of silicon acis, metakaolin one
Kind is several；The one kind or several of source of aluminium in aluminium salt, activated alumina, boehmite, aluminum alkoxide, metakaolin
Kind；Phosphorus source is selected from one or more of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphorus compound, phosphorous oxides；
Copper source is selected from Cu (OAc)2,CuSO4,Cu(NO3)2,CuCl2One or more of the inorganic salts of equal cuprics.
Crystallization process in the step b) is carried out either statically or dynamically lower.
Preferably, SiO in the step a) initial gel mixtures2/Al2O3=0.20~1.8.
Preferably, P in the step a) initial gel mixtures2O5/Al2O3=0.8~1.5.
Preferably, R1/Al in the step a) initial gel mixtures2O3=5.0~10.
Preferably, R2/Al in the step a) initial gel mixtures2O3=0.25~1.0.
Organic formwork agent benzyltrimethylammonium chloride (BTACl) and benzyltrimethylammonium hydroxide (BTAOH) in R2 exist
It can decompose in Zeolite synthesis, trimethylamine be generated, into the hole cage of molecular sieve.
In the method for above-mentioned synthesis of molecular sieve, when R1 is diethanol amine, R1/R2 molar ratio preferred scopes are 16-
60；When R1 is diisopropanolamine (DIPA), preferred crystallization temperature is 195-220 DEG C.
The further object of the application is to provide a kind of NOxThe catalyst of selective reduction elimination reaction, it is by above-mentioned
Molecular sieve and/or according to the above method synthesize molecular sieve obtained through being roasted in 550~700 DEG C of air.
The advantageous effect that can generate of the present invention includes：
(1) a kind of novel C u-SAPO molecular sieves are provided.
(2) molecular sieve prepared by can be used as the catalytic eliminating reaction of catalyst nitrogen oxides, and show good
Catalytic performance.
Description of the drawings
Fig. 1 is the XRD spectrum of synthetic product in embodiment 1
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of 1 synthetic product of embodiment
Fig. 3 is the NH of embodiment 11 and comparative example 23- SCR reaction evaluating results
Fig. 4 is the NH of different Cu content (embodiment 11-13) catalyst3- SCR reaction evaluating Comparative results
Fig. 5 is (embodiment 11 and embodiment 14) NH before and after 1 high-temperature sample hydro-thermal process of embodiment3- SCR reaction evaluating knots
Fruit compares
Fig. 6 is the XRD results of comparative example 3-8 counter samples
Specific implementation mode
With reference to embodiment, the present invention is further explained.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or
According to the normal condition proposed by manufacturer.In the case of not doing specified otherwise, raw material used in this application passes through commercial sources
Purchase, not specially treated direct use.
In the case of not doing specified otherwise, the test condition of the application is as follows：
Element composition is measured using the 2424 X-type ray fluorescence analysis instrument (XRF) of Magix of Philips companies.
FT-IR is acquired using 27 instruments of Germany BRUKER TENSOR.
X-ray powder diffraction material phase analysis (XRD) uses X ' the Pert PRO of Dutch Panaco (PANalytical) company
X-ray diffractometer, Cu targets, K α radiation source (λ=0.15418nm), voltage 40KV, electric current 40mA.
Specific surface area using 2020 type physical adsorption appearance determination samples of Micromeritics companies of U.S. ASAP and hole
Diameter is distributed.Before analysis, sample vacuumizes heat pre-treatment 6h at 350 DEG C, using He as Medium Measurement sample cell free volume.Point
When analysing sample, using nitrogen as adsorbed gas, physical absorption is carried out under liquid nitrogen temperature (77K) and desorption measures.Using BET formula
Determine the specific surface area of material；Use relative pressure (P/P0) be 0.99 when N2Adsorbance calculate material total pore volume.Use t-
Plot methods calculate micro pore surface area and Micropore volume.When calculating, N2Molecular cross-sectional area takes 0.162nm2。
SEM morphology analysis uses Hitachi (SU8020) type scanning electron microscope.
Nuclear magnetic resonance of carbon (13C MAS NMR) analyze the Infinityplus 400WB solids for using Varian companies of the U.S.
Magnetic resonance spectroscopy analyzer, with BBO MAS probes, magnetic manipulation field intensity is 9.4T.
The Vario EL Cube elemental analysers that CHN elemental analyses are manufactured using Germany.
The present invention is described in detail below by embodiment, but the invention is not limited in these embodiments.
Embodiment 1
Each feed molar ratio and crystallization condition are shown in Table 2.Specific blending process is as follows：Copper source first with water mixed dissolution,
Then R1 and R2 are added, and 2h is stirred at room temperature.Then, silicon source, silicon source and phosphorus source is added into mixed liquor successively, and will mix
It closes gel and 5h is stirred at room temperature, gel is made, gel is transferred in stainless steel cauldron.After reaction kettle is put into baking oven, with 2
DEG C/min rates are warming up to crystallization 36h under 200 DEG C of rotation conditions.After crystallization, solid product is centrifuged, is washed, at 100 DEG C
After being dried in air, the molecular screen primary powder sample is obtained.Sample does XRD analysis, and the spy that broad peak and spike coexist is presented in peak shape
Sign, XRD diffraction patterns are shown in that Fig. 1, XRD diffraction datas are shown in Table 3.After sample is roasted removed template method, its specific surface area and Kong Rong are surveyed,
Sample has high BET specific surface area 602m2g-1And big pore volume 0.27cm3g-1, wherein being calculated according to t-plot methods
To micropore specific area and micropore volume be respectively 533m2g-1And 0.26cm3g-1。
The stereoscan photograph of gained sample is as shown in fig. 2, it can be seen that the pattern of gained sample is the circle of stratiform accumulation
Sheet, particle size range are 3~5 μm.
Table 2：Zeolite synthesis dispensing and crystallization condition table
The XRD results of 3 embodiment of table, 1 sample
Embodiment 2
Specific proportion scale and crystallization condition are shown in Table 2, and specific blending process is the same as embodiment 1.
Synthetic sample does XRD analysis, and representative data result is shown in Table 4.
Stereoscan photograph shows that the pattern of gained sample is similar with 1 sample of embodiment.
The XRD results of 4 embodiment of table, 2 sample
Embodiment 3
Specific proportion scale and crystallization condition are shown in Table 2, and specific blending process is the same as embodiment 1.
Synthetic sample does XRD analysis, and representative data result is shown in Table 5.
Stereoscan photograph shows that the pattern of gained sample is similar with 1 sample of embodiment.
The XRD results of 5 embodiment of table, 3 sample
Embodiment 4-9
Specific proportion scale and crystallization condition are shown in Table 2, and specific blending process is the same as embodiment 1.
Synthetic sample does XRD analysis, and the XRD data results and table 3 of embodiment 4,9 are close, the XRD data of embodiment 5,6
As a result close with table 4, the XRD data results and table 5 of embodiment 7,8 are close.
By sieving the different proportion GME/CHA symbiosis Si-Al zeolite crystalline phases provided in official website of association with International Molecular
Diffraction spectrogram compares, and the content of CHA crystalline phases will be apparently higher than GME crystalline phases in the aluminium silicophosphate molecular sieve provided in embodiment 1-9.
Embodiment 10
Embodiment 1-9 powder samples are carried out13C MAS NMR analysis, by with diisopropanolamine (DIPA), diethanol amine and trimethylamine
's13C MAS NMR standard spectrograms compare, find using diisopropanolamine (DIPA) be the sample that synthesize of solvent have simultaneously diisopropanolamine (DIPA) with
The formant of trimethylamine has the formant of diethanol amine and trimethylamine using diethanol amine as the sample that solvent synthesizes simultaneously.According to
Quantitative analysis is carried out according to the peculiar misaligned peaks NMR of two kinds of substances, determines the ratio of the two.
It is formed using XRF analysis zeolite product body phase element, CHN elemental analyses is carried out to embodiment 1-9 original powder samples.
Comprehensive CHN elemental analyses, XRF and13C MAS NMR analysis results, the composition for obtaining molecular screen primary powder are shown in Table 6.
The composition of the original powder sample of 6 embodiment 1-9 of table
By the original powder sample of embodiment 1-9 respectively with potassium bromide mixed grinding tabletting, FT-IR characterizations are carried out, they exist
637cm-1Place occurs obviously belonging to the eigen vibration absorption peak of double hexatomic rings, shows in sample there are double hexatomic rings.
Embodiment 11
The sample that embodiment 1 is obtained is in 650 DEG C of high-temperature roasting 2h, after removing template, is used for NH3Selective reduction is de-
Except NOxThe catalytic performance of reaction is characterized.Specific experiment process and condition are as follows：Sample tabletting is sieved after roasting, is weighed
60 to 80 mesh samples of 0.1g are mixed with 0.4g quartz sands (60 to 80 mesh), are packed into fixed bed reactors.Lead to nitrogen at 600 DEG C
40min is activated, 120 DEG C is then cooled to and starts to react, and temperature programming is to 550 DEG C.Reactor feed gas is：NO：500ppm,
NH3：500ppm, O2：5%, H2O：5%, N2As Balance Air, gas flow rate 300mL/min.Reaction end gas is public using Bruker
The 27 type instruments of Tensor of department, carry out online FTIR analyses, as a result see Fig. 3 and Fig. 4.It can be seen that reaction NO at 150 DEG C
Conversion ratio up to 77%, within the scope of 180-450 DEG C of wider temperature, the conversion ratio of NO is more than 90%.Similarly, embodiment 2-
8 obtained samples also present preferable selective reduction removing NO after processing identical with 1 sample of embodimentxCatalytic
Energy.
Embodiment 12
The sample that embodiment 3 is obtained is in 650 DEG C of high-temperature roasting 2h, after removing template, is used for NH3Selective reduction is de-
Except NOxThe catalytic performance of reaction is characterized.Specific experiment process and condition are as follows：Sample tabletting is sieved after roasting, is weighed
60 to 80 mesh samples of 0.1g are mixed with 0.4g quartz sands (60 to 80 mesh), are packed into fixed bed reactors.Lead to nitrogen at 600 DEG C
40min is activated, 120 DEG C is then cooled to and starts to react, and temperature programming is to 550 DEG C.Reactor feed gas is：NO：500ppm,
NH3：500ppm, O2：5%, H2O：5%, N2As Balance Air, gas flow rate 300mL/min.Reaction end gas is public using Bruker
The 27 type instruments of Tensor of department, carry out online FTIR analyses, reaction result is shown in Fig. 4.
Embodiment 13
The sample that embodiment 8 is obtained is in 650 DEG C of high-temperature roasting 2h, after removing template, is used for NH3Selective reduction is de-
Except NOxThe catalytic performance of reaction is characterized.Specific experiment process and condition are as follows：Sample tabletting is sieved after roasting, is weighed
60 to 80 mesh samples of 0.1g are mixed with 0.4g quartz sands (60 to 80 mesh), are packed into fixed bed reactors.Lead to nitrogen at 600 DEG C
40min is activated, 120 DEG C is then cooled to and starts to react, and temperature programming is to 550 DEG C.Reactor feed gas is：NO：500ppm,
NH3：500ppm, O2：5%, H2O：5%, N2As Balance Air, gas flow rate 300mL/min.Reaction end gas is public using Bruker
The 27 type instruments of Tensor of department, carry out online FTIR analyses.Reaction result is shown in Fig. 4.
Embodiment 14
The sample that embodiment 1 is obtained is in 650 DEG C of high-temperature roasting 2h, and after removing template, hydrothermal aging is carried out in 800 DEG C
Processing, water vapour content 100%, processing time is after treatment for 24 hours, in 100 DEG C of drying.
With the relative crystallinity of XRD method determination sample, the crystallinity of sample is the 95% of 1 sample of embodiment, shows reality
Applying the sample prepared by example 1 has higher hydrothermal stability, after aqueous workup, can preferably keep the complete of its structure
Property.
For NH3Selective reduction removes NOxThe catalytic performance of reaction is characterized.Specific experiment process and condition are as follows：
Sample tabletting is sieved, and is weighed 60 to 80 mesh samples of 0.1g and is mixed with 0.4g quartz sands (60 to 80 mesh), and fixed bed reaction is packed into
Device.Lead to nitrogen activation 40min at 600 DEG C, is then cooled to 120 DEG C and starts to react, and temperature programming is to 550 DEG C.Reaction is former
Expect that gas is：NO：500ppm, NH3：500ppm, O2：5%, H2O：5%, N2As Balance Air, gas flow rate 300mL/min.Reaction
Tail gas uses the 27 type instruments of Tensor of Bruker companies, carries out online FTIR analyses.Reaction result is shown in Fig. 5.
Comparative example 1：
The sample molecule obtained using 10g embodiments 9 sieves original powder as precursor, and 600 DEG C of perseverances are warming up to the speed of 2 DEG C/min
Temperature roasting 4h, removes organic formwork agent and water contained therein.
According to 1:Baked sample is put into the aqueous ammonium nitrate solution of 3.66mol/L by 10 solid-to-liquid ratio (mass ratio), is stirred
After mixing five minutes, it is warming up to 80 DEG C of ion exchange 2h.It is then centrifuged for detaching, and is washed with deionized three times, 80 DEG C of drying, i.e.,
Obtain NH4 +Type molecular sieve.
By 7g NH4 +Type molecular sieve is according to 1:Cu (the CH of 25 solid-to-liquid ratio input 0.03mol/L3COO)2·H2O solution, is stirred
It mixes 5 minutes, is warming up to 50 DEG C of ion exchange 4h.It is then centrifuged for detaching, and is washed with deionized 3 times, 80 DEG C of drying, gained sample
Product are denoted as Cu-9/T.XRF elemental analyses the results show that product oxidation copper content 3.2%, it is close with embodiment 1.Using N2Object
The specific surface area and Kong Rong for managing 9 sample of determining adsorption roasting type embodiment and Cu-9/T samples, calculate according to t-plot methods
The micropore specific area and micropore volume arrived.The micropore specific area and micropore volume of 9 sample of embodiment are respectively 559m2g-1With
0.28cm3g-1, the micropore specific area and micropore volume of Cu-9/T samples are respectively 520m2g-1And 0.25cm3g-1.These results
The regularity of sample skeleton structure can be preferably kept by being shown as the catalyst of 1 method of embodiment preparation.
Comparative example 2
The sample that comparative example 1 is obtained is used as NH in 650 DEG C of high-temperature roasting 2h3Selective reduction removes NOxReaction is urged
Agent.Specific experiment process and condition are as follows：Sample tabletting is sieved after roasting, weighs 60 to 80 mesh samples of 0.1g and 0.4g stones
Sand (60 to 80 mesh) mixes, and is packed into fixed bed reactors.Lead to nitrogen activation 40min at 600 DEG C, is then cooled to 120 DEG C
Start to react, and temperature programming is to 550 DEG C.Reactor feed gas is：NO：500ppm, NH3：500ppm, O2：5%, H2O：5%, N2
For Balance Air, gas overall flow rate 300mL/min.Total air speed GHSV=180000h of reaction-1.Reaction end gas is public using Bruker
The Tensor27 type instruments of department, carry out online FTIR analyses.Concrete outcome is shown in Fig. 3.
Comparative example 3
Specific dispensing molar ratio, raw material and crystallization condition are with embodiment 1, the difference is that the diethanol amine in raw material is used
Triethylamine substitutes.Synthetic sample is SAPO-34 molecular sieves, and XRD analysis result is shown in Fig. 6.
Comparative example 4
Specific dispensing molar ratio, raw material and crystallization condition are with embodiment 2, the difference is that by the benzyl trimethyl in raw material
Ammonium hydroxide is substituted with 1,6- hexamethylene diamines.Synthetic sample is lamellar phase, and XRD results are shown in Fig. 6.
Comparative example 5
Specific dispensing molar ratio, raw material and crystallization condition are with embodiment 3, the difference is that saving the trimethylamine in raw material
Addition.Synthetic sample is the physical mixture of SAPO-34 and SAPO-5, and XRD results are shown in Fig. 6.
Comparative example 6
Specific dispensing molar ratio, raw material and crystallization condition are with embodiment 4, the difference is that the diethanol amine in raw material is used
Diethylamine substitutes.The physical mixture for the DNL-6 (SAPO molecular sieve with RHO structures) that synthetic sample is a small amount of SAPO-34,
XRD results are shown in Fig. 6.
Comparative example 7
Specific dispensing molar ratio, raw material and crystallization condition with embodiment 5, unlike by the trimethylamine in raw material with three
Ethanol amine substitutes.Synthetic sample is the physical mixture of SAPO-5 and SAPO-34, and XRD results are shown in Fig. 6.
Comparative example 8
Specific dispensing molar ratio, raw material and crystallization condition are with embodiment 5, the difference is that saving the trimethylamine in raw material
Addition.Synthetic sample is amorphous, and XRD analysis result is shown in Fig. 6.
The composite result of comparative example 3-8 shows the Cu-SAPO molecular sieves with GME and CHA eutectics of present patent application, only
Having can just access under the combination of specific template and suitable crystallization condition.
Although the application is disclosed as above with preferred embodiment, it is not used to limit claim, any art technology
Personnel can make several possible variations and modification, therefore the guarantor of the application under the premise of not departing from the application design
Shield range should be subject to the range that the application claim defined.
Claims (10)
1. a kind of silicoaluminophosphate (SAPO) molecular sieve of the cupric with CHA and GME symbiosis crystalline phases, which is characterized in that described point
The X ray diffracting spectrum of son sieve at least contains following diffraction maximum：
2. according to the molecular sieve described in claim 1, which is characterized in that the inorganic skeleton of molecular sieve has following chemical group
At：wCu-(SixAlyPz)O2, wherein：X, y, z indicates the molar fraction of Si, Al, P respectively, range be respectively x=0.01~
0.28, y=0.35~0.55, z=0.28~0.50, and x+y+z=1, w are every mole of (SixAlyPz)O2Corresponding Cu's rubs
That number, w=0.001~0.124.
3. molecular sieve according to claim 1, which is characterized in that molecular sieve includes the anhydrous chemical composition of template can table
It is shown as：wCu·mR1·nR3·(SixAlyPz)O2, wherein：R1 is diisopropanolamine (DIPA) or diethanol amine, and R3 is trimethylamine；M is
Every mole of (SixAlyPz)O2The molal quantity of middle R1 templates, n are every mole of (SixAlyPz)O2The molal quantity of middle R3 templates, m=
0.01~0.20, n=0.01~0.10；X, y, z indicates the molar fraction of Si, Al, P respectively, range be respectively x=0.01~
0.28, y=0.35~0.55, z=0.28~0.50, and x+y+z=1；W is every mole of (SixAlyPz)O2Corresponding Cu's rubs
That number, w=0.001~0.124.
4. the method for the molecular sieve described in a kind of any one of synthesis claim 1-3, which is characterized in that include the following steps：
A) by copper source, deionized water, template R1 and R2, silicon source, silicon source and phosphorus source mix in proportion, obtain having following mole
The initial gel mixture of proportioning：
Cu/Al2O3=0.01~0.25；
SiO2/Al2O3=0.05~2.0；
P2O5/Al2O3=0.5~1.5；
H2O/Al2O3=8~40；
R1/Al2O3=5~20；
R2/Al2O3=0.1~1.5；
Wherein, R1 is diisopropanolamine (DIPA) (DIPA) or diethanol amine (DEOA)；R2 is trimethylamine (TMA), benzyl trimethyl chlorination
Any one in ammonium (BTACl), benzyltrimethylammonium hydroxide (BTAOH) or arbitrary several mixture；
B) initial gel mixture obtained by step a) is packed into Autoclaves for synthesis, it is closed, it is warming up to 160~220 DEG C, crystallization 5~
72 hours；
C) after the completion of crystallization, to get the molecular sieve after solid product separating, washing, drying.
5. according to the method described in claim 4, it is characterized in that, the blending process of step a) is as follows：Copper source is mixed with water first
It closes, R1 and R2 is then added, and 0.5-5h is stirred at room temperature, silicon source, silicon source and phosphorus source is then added into mixed liquor successively, and
1-5h is stirred at room temperature in mixed gel.
6. according to the method described in claim 4, it is characterized in that, silicon source described in step a) is selected from Ludox, active dioxy
One or more of SiClx, positive esters of silicon acis, metakaolin；Source of aluminium be selected from aluminium salt, activated alumina, boehmite,
One or more of aluminum alkoxide, metakaolin；Phosphorus source is selected from orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organophosphor
One or more of compound, phosphorous oxides；Copper source is selected from Cu (OAc)2, CuSO4,Cu(NO3)2, CuCl2In one kind or
It is several.
7. according to the method described in claim 4, it is characterized in that, the crystallization process in the step b) is under either statically or dynamically
It carries out.
8. according to the method described in claim 4, it is characterized in that, R1/Al in the step a) initial gel mixtures2O3=
5.0~10.
9. according to the method described in claim 4, it is characterized in that, R2/Al in the step a) initial gel mixtures2O3=
0.25~1.0.
10. one kind being used for NOxThe catalyst of selective reduction elimination reaction, by according to any one of claim 1-3 point
Son sieve or the molecular sieve of the method synthesis according to any one of claim 4-9 in 550~700 DEG C of air through roasting
It arrives.
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