WO2018152829A1 - Cu-SAPO分子筛、合成方法及其催化应用 - Google Patents
Cu-SAPO分子筛、合成方法及其催化应用 Download PDFInfo
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- WO2018152829A1 WO2018152829A1 PCT/CN2017/074985 CN2017074985W WO2018152829A1 WO 2018152829 A1 WO2018152829 A1 WO 2018152829A1 CN 2017074985 W CN2017074985 W CN 2017074985W WO 2018152829 A1 WO2018152829 A1 WO 2018152829A1
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 51
- 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 51
- 230000003197 catalytic effect Effects 0.000 title description 7
- 238000001308 synthesis method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 28
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical group CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 9
- 229940043276 diisopropanolamine Drugs 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 6
- -1 alkoxy aluminum Chemical compound 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 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
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 238000002156 mixing Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000013385 inorganic framework Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 50
- 239000007789 gas Substances 0.000 description 25
- 239000002994 raw material Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 241000269350 Anura Species 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006069 physical mixture Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange 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
- 238000007254 oxidation reaction Methods 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
- F01N2370/04—Zeolitic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/14—Nitrogen oxides
Definitions
- the invention relates to a novel copper-containing SAPO molecular sieve, a synthesis method and the application thereof in denitration reaction.
- Nitrogen oxide pollution mainly comes from the emission of mobile source vehicle exhaust gas and the emission of fixed source factory exhaust gas, NOx.
- the treatment of pollution is carried out by selective catalytic reduction of NH 3 , urea or hydrocarbon as a reducing agent, which is converted into harmless nitrogen.
- the traditional denitration catalyst is mainly V-Ti-W system.
- the exhaust gas emission temperature of the lean-burn exhaust gas is lowered, and the narrower temperature range of the catalyst of the V-Ti-W system cannot meet the requirements. And its potential for environmental pollution limits its application.
- the copper-based catalyst and the iron-based catalyst are two representative systems, and the copper-based catalyst exhibits excellent low-temperature activity, but an excessively high load causes a severe NH 3 oxidation reaction in the high temperature section.
- Iron-based catalysts have excellent high temperature activity, but their lower conversion rate in the low temperature range limits their use in certain fields.
- Small pore molecular sieves such as SSZ-13 and SAPO-34 can effectively improve the high temperature hydrothermal stability of the catalyst, and when loaded with copper as the active metal, it has high NO conversion activity in a wide temperature range. High N 2 selectivity. Although it has problems such as sensitivity to sulfur, this problem has gradually been resolved with the improvement of oil quality.
- the invention provides a one-step synthesis method of Cu-SAPO molecular sieve catalyst with controlled Cu content, and exhibits excellent deNOx catalytic activity, and has potential application value.
- the novel molecular sieve synthesized by the invention exhibits the characteristics of coexistence of broad peaks and peaks, and its XRD diffraction spectrum and literature (Microporous and Mesoporous Materials, 30 (1999) 335-346; official website of the International Molecular Sieve Association http://www .iza-structure.org/databases/Catalog/ABC_6.pdf )
- the spectra of silicoalulites with GME/CHA symbiotic structure are similar.
- We analyzed this type of molecular sieve as a novel SAPO molecular sieve with a GME/CHA symbiotic structure.
- a Cu-SAPO molecular sieve having a CHA and a GME symbiotic crystal phase, characterized in that the X-ray diffraction pattern of the molecular sieve contains at least the following diffraction peaks:
- m can be from 0.02 to 0.15; n can be from 0.01 to 0.09; x can be from 0.05 to 0.28; y can be from 0.40 to 0.50; z can be from 0.30 to 0.50; and w can be from 0.005 to 0.100.
- Another object of the present invention is to provide a method for synthesizing the above Cu-SAPO molecular sieve, which comprises the following steps:
- SiO 2 /Al 2 O 3 0.05 to 2.0;
- R1 is diisopropanolamine (DIPA) or diethanolamine (DEOA);
- R2 is trimethylamine (TMA), benzyltrimethylammonium chloride (BTACl), benzyltrimethylammonium hydroxide (BTAOH) Any one or a mixture of any of several.
- the specific batching sequence can be as follows: the copper source is first dissolved in water, then R1 and R2 are added, and stirred at room temperature for 0.5-5 h. Subsequently, an aluminum source, a silicon source and a phosphorus source were sequentially added to the mixed solution, and the mixed gel was stirred at room temperature for 1-5 h.
- step b) The initial gel mixture obtained in the step a) is placed in a high pressure synthesis reactor, sealed, heated to 160 to 220 ° C, and crystallized for 5 to 72 hours.
- the silicon source in step a) is selected from one or more of silica sol, active silica, orthosilicate, metakaolin;
- the aluminum source is selected from the group consisting of aluminum salt, activated alumina, and thin One or more of diaspore, alkoxy aluminum, metakaolin;
- the phosphorus source is selected from one or more of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide, and phosphorus oxide.
- the copper source is one or more selected from the group consisting of Cu(OAc) 2 , CuSO 4 , Cu(NO 3 ) 2 , CuCl 2 and the like.
- step b) The crystallization process in step b) is carried out either statically or dynamically.
- said step a) initially in the gel mixture P 2 O 5 /Al 2 O 3 0.8 to 1.5.
- the organic templating agent benzyltrimethylammonium chloride (BTACl) and benzyltrimethylammonium hydroxide (BTAOH) in R2 are decomposed in the molecular sieve synthesis to form trimethylamine and enter the pore cage of the molecular sieve.
- the R1/R2 molar ratio preferably ranges from 16 to 60; and when R1 is diisopropanolamine, the preferred crystallization temperature is from 195 to 220 °C.
- a further object of the present application is to provide a catalyst for removing NO x selective reduction reaction, it was 550 ⁇ 700 °C was air calcined in the above-described molecular sieves and / or molecular sieve synthesized according to the method described above.
- a novel Cu-SAPO molecular sieve is provided.
- the prepared molecular sieve can be used as a catalyst for catalytic removal of nitrogen oxides and exhibits good catalytic performance.
- Figure 1 is an XRD pattern of the synthesized product in Example 1.
- Example 2 is a scanning electron micrograph (SEM) of the synthesized product of Example 1.
- Figure 4 is a comparison of NH 3 -SCR reaction evaluation results for catalysts with different copper contents (Examples 11-13)
- Figure 5 is a comparison of the evaluation results of NH 3 -SCR reaction before and after high temperature hydrothermal treatment of the sample of Example 1 (Example 11 and Example 14)
- Figure 6 is an XRD result of a sample corresponding to Comparative Example 3-8.
- test conditions of this application are as follows:
- the elemental composition was determined using a Philips Magix 2424X ray fluorescence analyzer (XRF).
- the FT-IR is collected using the German BRUKER TENSOR 27 instrument.
- the specific surface area and pore size distribution of the samples were determined using a Micromeritics ASAP Model 2020 physical adsorber. Before the analysis, the sample was preheated at 350 ° C for 6 h, and the free volume of the sample tube was measured with He as the medium. When the sample was analyzed, the adsorption and desorption measurements were carried out at a liquid nitrogen temperature (77 K) using nitrogen as an adsorption gas. The specific surface area of the material was determined using the BET formula; the total pore volume of the material was calculated using the adsorption amount of N 2 at a relative pressure (P/P 0 ) of 0.99. The micropore surface area and micropore volume were calculated by the t-plot method. When calculated, the cross-sectional area of the N 2 molecule was taken to be 0.162 nm 2 .
- the SEM morphology analysis was performed using a Hitachi (SU8020) type scanning electron microscope.
- Carbon nuclear magnetic resonance ( 13 C MAS NMR) analysis was performed using a Varian Infinity plus 400 WB solid-state nuclear magnetic spectrum analyzer with a BBO MAS probe operating at a magnetic field strength of 9.4T.
- the CHN elemental analysis was performed using a Vario EL Cube elemental analyzer made in Germany.
- the molar ratio of each raw material and the crystallization conditions are shown in Table 2.
- the specific batching process is as follows: the copper source is first dissolved in water, then R1 and R2 are added, and stirred at room temperature for 2 h. Subsequently, an aluminum source, a silicon source and a phosphorus source were sequentially added to the mixed solution, and the mixed gel was stirred at room temperature for 5 hours to form a gel, and the gel was transferred to a stainless steel reaction vessel. After the reactor was placed in an oven, it was heated at a rate of 2 ° C/min to 200 ° C for crystallization for 36 h.
- the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain a sample of the molecular sieve raw powder.
- the sample was subjected to XRD analysis, and the peak shape exhibited characteristics of broad peaks and peaks.
- the XRD diffraction pattern is shown in Fig. 1, and the XRD diffraction data is shown in Table 3.
- the specific surface area and pore volume were measured.
- the sample had a high BET specific surface area of 602 m 2 g -1 and a large pore volume of 0.27 cm 3 g -1 , which was calculated according to the t-plot method.
- the specific pore surface area and micropore volume were 533 m 2 g -1 and 0.26 cm 3 g -1 , respectively .
- the scanning electron micrograph of the obtained sample is shown in Fig. 2. It can be seen that the morphology of the obtained sample is a layered stacked disc having a particle size ranging from 3 to 5 ⁇ m.
- Example 2 The specific proportion of ingredients and crystallization conditions are shown in Table 2, and the specific batching process is the same as in Example 1.
- the synthesized samples were subjected to XRD analysis.
- the results of XRD data of Examples 4 and 9 were similar to those of Table 3.
- the results of XRD data of Examples 5 and 6 were similar to those of Table 4, and the results of XRD data of Examples 7 and 8 were close to Table 5.
- CHA crystal phase in the silicon-phosphorus aluminum molecular sieve provided in Examples 1-9 is obvious by comparison with the diffraction spectrum of the different proportions of GME/CHA symbiotic silicoaluminosilicate crystal phase given on the official website of the International Molecular Sieve Association. Higher than the GME crystal phase.
- the CHN elemental analysis of the original powder samples of Examples 1-9 was carried out by XRF analysis of the bulk elemental composition of the molecular sieve product.
- the composition of the molecular sieve raw powder obtained by comprehensive CHN elemental analysis, XRF and 13 C MAS NMR analysis is shown in Table 6.
- Example Sample raw powder composition 1 0.038Cu0.07DEOA0.02TMA(Si 0.203 Al 0.470 P 0.327 )O 2 2 0.008Cu0.04DEOA0.01TMA(Si 0.032 Al 0.490 P 0.478 )O 2 3 0.029Cu0.081DIPA0.058TMA (Si 0.205 Al 0.488 P 0.307 )O 2 4 0.040Cu0.13DEOA0.048TMA(Si 0.165 Al 0.488 P 0.347 )O 2 5 0.018Cu0.07DEOA0.02TMA(Si 0.072 Al 0.470 P 0.458 )O 2 6 0.035Cu0.11DEOA0.034TMA(Si 0.155 Al 0.488 P 0.357 )O 2 7 0.020Cu0.12DEOA0.038TMA(Si 0.100 Al 0.488 P 0.412 )O 2
- the raw powder samples of Examples 1-9 were separately mixed with potassium bromide and ground and pressed, and subjected to FT-IR characterization. Both of them showed a characteristic vibration absorption peak attributed to the double six-membered ring at 637 cm -1 . There is a double six-membered ring in the sample.
- Samples obtained in Example 1 was calcined temperature 650 °C 2h, after removal of the template agent for selective reduction of NH 3 reacts with NO x removal catalyst properties were characterized.
- the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
- the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
- the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The results are shown in Figures 3 and 4. It can be seen that the conversion of NO at the reaction temperature is 77% at 150 ° C, and the conversion of NO is greater than 90% over a wide temperature range of 180 - 450 ° C. Similarly, the samples obtained in Example 2-8 after the same as in Example 1, treated sample also showed a better removal of NO x selective reduction of catalytic performance.
- Example 3 The sample obtained in Example 3 at 650 °C calcination temperature 2h, after removal of the template agent for selective reduction of NH2 3 reacts with NO x removal catalyst properties were characterized.
- the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
- the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
- the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The results are shown in Figure 4.
- Example 8 The sample obtained in Example 8 at 650 °C calcination temperature 2h, after removal of the template agent for selective reduction of NH 3 reacts with NO x removal catalyst properties were characterized.
- the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
- the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
- the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The reaction results are shown in Figure 4.
- Example 1 The sample obtained in Example 1 was calcined at 650 ° C for 2 h, and after removing the templating agent, hydrothermal aging treatment was carried out at 800 ° C, the water vapor content was 100%, the treatment time was 24 h, and after the treatment, it was dried at 100 ° C.
- the relative crystallinity of the sample was determined by XRD method, and the crystallinity of the sample was 95% of the sample of Example 1, indicating that the sample prepared in Example 1 has high hydrothermal stability and can be well maintained after water treatment. Its structural integrity.
- Example 9 10 g of the sample molecular sieve raw powder obtained in Example 9 was used as a precursor, and was heated at a rate of 2 ° C/min to a constant temperature of 600 ° C for 4 hours to remove the organic templating agent and water contained therein.
- the calcined sample was placed in a 3.66 mol/L ammonium nitrate aqueous solution at a solid-liquid ratio (mass ratio) of 1:10, stirred for five minutes, and then heated to 80 ° C for ion exchange for 2 hours. It was then separated by centrifugation and washed three times with deionized water and dried at 80 ° C to obtain a NH 4 + type molecular sieve.
- Example 9 Samples of the microporous surface area and pore volume were 559m 2 g -1 and 0.28cm 3 g -1, porous Cu-9 / T samples of specific surface area and pore volume of 520m 2 g -1, respectively, And 0.25cm 3 g -1 . These results show that the catalyst prepared according to the method of Example 1 can better maintain the regularity of the sample skeleton structure.
- the sample obtained in Comparative Example 1 was calcined at a high temperature of 650 ° C for 2 h, and used as a catalyst for selective reduction of NOx by NH 3 .
- the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
- the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 was a balance gas, and the total gas flow rate was 300 mL/min.
- the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The specific results are shown in Figure 3.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 1, except that the diethanolamine in the raw material was replaced with triethylamine.
- the synthetic sample was SAPO-34 molecular sieve, and the XRD analysis results are shown in Fig. 6.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 2 except that the benzyltrimethylammonium hydroxide in the raw material was replaced with 1,6-hexanediamine.
- the synthesized sample is a layered phase.
- the XRD results are shown in Figure 6.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 3, except that the addition of trimethylamine in the raw materials was omitted.
- the synthetic sample was a physical mixture of SAPO-34 and SAPO-5, and the XRD results are shown in Figure 6.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 4, except that the diethanolamine in the raw material was replaced with diethylamine.
- the synthesized sample was a physical mixture of a small amount of SAPO-34 DNL-6 (SAPO molecular sieve with RHO structure), and the XRD results are shown in Fig. 6.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 5 except that the trimethylamine in the raw material was replaced with triethanolamine.
- the synthetic sample was a physical mixture of SAPO-5 and SAPO-34, and the XRD results are shown in Figure 6.
- the molar ratio of the specific ingredients, the raw materials and the crystallization conditions were the same as in Example 5, except that the addition of trimethylamine in the raw materials was omitted.
- the synthesized sample was amorphous, and the XRD analysis results are shown in Fig. 6.
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Abstract
Description
实施例 | 样品原粉组成 |
1 | 0.038Cu0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2 |
2 | 0.008Cu0.04DEOA0.01TMA(Si0.032Al0.490P0.478)O2 |
3 | 0.029Cu0.081DIPA0.058TMA(Si0.205Al0.488P0.307)O2 |
4 | 0.040Cu0.13DEOA0.048TMA(Si0.165Al0.488P0.347)O2 |
5 | 0.018Cu0.07DEOA0.02TMA(Si0.072Al0.470P0.458)O2 |
6 | 0.035Cu0.11DEOA0.034TMA(Si0.155Al0.488P0.357)O2 |
7 | 0.020Cu0.12DEOA0.038TMA(Si0.100Al0.488P0.412)O2 |
8 | 0.09Cu0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2 |
9 | 0.07DEOA0.02TMA(Si0.203Al0.470P0.327)O2 |
Claims (10)
- 根据权利要求1中所述的分子筛,其特征在于,分子筛的无机骨架具有如下的化学组成:wCu-(SixAlyPz)O2,其中:x、y、z分别表示Si、Al、P的摩尔分数,其范围分别是x=0.01~0.28,y=0.35~0.55,z=0.28~0.50,且x+y+z=1,w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数,w=0.001~0.124。
- 根据权利要求1所述的分子筛,其特征在于,分子筛包含模板剂的无水化学组成可表示为:wCu·mR1·nR3·(SixAlyPz)O2,其中:R1为二异丙醇胺或二乙醇胺,R3为三甲胺;m为每摩尔(SixAlyPz)O2中R1模板剂的摩尔数,n为每摩尔(SixAlyPz)O2中R3模板剂的摩尔数,m=0.01~0.20,n=0.01~0.10;x、y、z分别表示Si、Al、P的摩尔分数,其范围分别是x=0.01~0.28,y=0.35~0.55,z=0.28~0.50,且x+y+z=1;w为每摩尔(SixAlyPz)O2对应的Cu的摩尔数,w=0.001~0.124。
- 一种合成权利要求1-3中任一项所述的分子筛的方法,其特征在于,包括如下步骤:a)将铜源,去离子水、模板剂R1和R2,硅源、铝源和磷源按比例混合,得到具有如下摩尔配比的初始凝胶混合物: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;其中,R1为二异丙醇胺(DIPA)或二乙醇胺(DEOA);R2为三甲胺(TMA)、苄基三甲基氯化铵(BTACl)、苄基三甲基氢氧化铵(BTAOH)中的任意一种或任意几种的混合物;b)将步骤a)所得初始凝胶混合物装入高压合成釜,密闭,升温到160~220℃,晶化5~72小时;c)晶化完成后,固体产物经分离、洗涤、干燥后,即得所述的分子筛。
- 根据权利要求4所述的方法,其特征在于,步骤a)的配料过程如下:铜源首先与水混合,然后加入R1和R2,并在室温搅拌0.5-5h,随后依次向混合液中加入铝源,硅源和磷源,并将混合凝胶在室温搅拌1-5h。
- 根据权利要求4所述的方法,其特征在于,步骤a)中所述硅源选自硅溶胶、活性二氧化硅、正硅酸酯、偏高岭土中的一种或几种;所述铝源选自铝盐、活性氧化铝、拟薄水铝石、烷氧基铝、偏高岭土中的一种或几种;所述磷源选自正磷酸、磷酸氢铵、磷酸二氢铵、有机磷化物、磷氧化物中的一种或几种;所述铜源选自Cu(OAc)2,CuSO4,Cu(NO3)2,CuCl2中的一种或几种。
- 根据权利要求4所述的方法,其特征在于,所述步骤b)中的晶化过程在静态或动态下进行。
- 根据权利要求4所述的方法,其特征在于,所述步骤a)初始凝胶混合物中R1/Al2O3=5.0~10。
- 根据权利要求4所述的方法,其特征在于,所述步骤a)初始凝胶混合物中R2/Al2O3=0.25~1.0。
- 一种用于NOx选择还原脱除反应的催化剂,其由根据权利要求1-3中任一项所述的分子筛或根据权利要求4-9中任一项所述的方 法合成的分子筛经550~700℃空气中焙烧得到。
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JP2019543950A JP6990712B2 (ja) | 2017-02-27 | 2017-02-27 | Cu-SAPO分子篩、合成方法及びその触媒としての使用 |
MYPI2019004880A MY192640A (en) | 2017-02-27 | 2017-02-27 | Cu-sapo molecular sieve, synthesis method therefor and catalytic use thereof |
PCT/CN2017/074985 WO2018152829A1 (zh) | 2017-02-27 | 2017-02-27 | Cu-SAPO分子筛、合成方法及其催化应用 |
EP17897284.0A EP3586960B1 (en) | 2017-02-27 | 2017-02-27 | Cu-sapo molecular sieve, synthesis method therefor and catalytic use thereof |
US16/488,732 US20210130179A1 (en) | 2017-02-27 | 2017-02-27 | Cu-sapo molecular sieve, synthesis method therefor and catalytic use thereof |
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US11806696B2 (en) | 2018-10-25 | 2023-11-07 | China Petroleum & Chemical Corporation | Silicoaluminophosphate molecular sieve, its preparation and application thereof |
RU2811839C2 (ru) * | 2018-10-25 | 2024-01-18 | Чайна Петролеум Энд Кемикал Корпорейшн | Силикоалюмофосфатное молекулярное сито, его получение и применение |
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JP2020511382A (ja) | 2020-04-16 |
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US20210130179A1 (en) | 2021-05-06 |
EP3586960A4 (en) | 2020-11-18 |
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