CN107673370A - Synthetic method, the molecular sieve catalysts of SAPO 34 and its application of the nanometer molecular sieves of SAPO 34 - Google Patents
Synthetic method, the molecular sieve catalysts of SAPO 34 and its application of the nanometer molecular sieves of SAPO 34 Download PDFInfo
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- CN107673370A CN107673370A CN201610622095.XA CN201610622095A CN107673370A CN 107673370 A CN107673370 A CN 107673370A CN 201610622095 A CN201610622095 A CN 201610622095A CN 107673370 A CN107673370 A CN 107673370A
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- sapo
- nanometer
- molecular sieves
- molecular sieve
- silane
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- 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 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 241000269350 Anura Species 0.000 title abstract description 10
- 238000010189 synthetic method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 125000004193 piperazinyl group Chemical group 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002757 morpholinyl group Chemical group 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 5
- -1 aluminum alkoxide Chemical class 0.000 claims description 5
- 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 5
- 239000012265 solid product Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 241001502050 Acis Species 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000005496 eutectics Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- NYYGRSUHVRJFAO-UHFFFAOYSA-N [Cl-].C(CC)[NH3+].CO[Si](OC)OC Chemical compound [Cl-].C(CC)[NH3+].CO[Si](OC)OC NYYGRSUHVRJFAO-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The application is related to a kind of method, the molecular sieve catalysts of SAPO 34 and its application for synthesizing the molecular sieves of nanometer SAPO 34.By adding micropore template agent in being synthesized in hydro-thermal method and there is Formulas I (wherein R1~R3, x, y and n as defined herein) shown in structure functional organo-silane's template, synthesized the molecular sieves of nanometer SAPO 34.The molecular sieve catalysts of SAPO 34 are obtained after the molecular sieves of nanometer SAPO 34 are fired, the catalyst can be used in preparing low-carbon olefin from oxygen-containing compounds reaction.There is pure CHA crystalline phases by the molecular sieves of nanometer SAPO 34 obtained by the inventive method, and excellent catalytic performance is shown in MTO reactions by the molecular sieve catalysts of SAPO 34 obtained by the inventive method, catalyst life significantly extends, and selectivity of light olefin improves.
Description
Technical field
The present invention relates to molecular sieve art, relate more specifically to synthetic method, the SAPO-34 molecules of SAPO-34 molecular sieves
Sieve catalyst and its application.
Background technology
The skeleton structure species of silicoaluminophosphamolecular molecular sieves (SAPO-n) are various, and its three dimensional skeletal structure is by PO2 +、AlO2 -With
SiO2Tetrahedron is formed.Part P atoms in Si atom same order elements neutrality aluminum phosphate skeleton structures substitute P and Al former simultaneously
Son, skeleton is produced net negative electrical charge, cause Bronsted acidity, so as to assign SAPO molecular sieve acid catalytic property.
Among this, there is the SAPO-34 molecular sieves of CHA topological structures because it is in methanol to olefins reaction (MTO)
Excellent catalytic performance has been successfully applied to MTO commercialization process.However, microcellular structure intrinsic SAPO-34 limits mass transfer
Efficiency, cause SAPO-34 catalyst activities position utilization rate low, duct easily occurs and blocks and carbon distribution inactivation.Asked to solve this
Topic, people attempt SAPO-34 molecular sieve of the synthesis with mesoporous-microporous composite construction, by being introduced between intrinsic microcellular structure
Mesoporous or big hole path, or the little crystal grain of nano level molecular sieve is prepared to reduce the resistance to mass tranfer in reaction, intensified response
During molecule diffusion, lift reaction life-span and the selectivity of light olefin of catalytic reaction.
Triethylamine is a kind of structure directing agent or template of synthesis SAPO-34 molecular sieves cheap and easy to get, but is used
When triethylamine is as single template, the product for synthesizing to obtain is often the SAPO-34/-18 containing a small amount of SAPO-18
(CHA/AEI) eutectic.Silicone content is extremely low or during without silicon in synthesized gel rubber, or even can obtain SAPO-18 or AlPO-18
(Micorporous Mesoporous Materials, 2008,115,332-337).In addition, be oriented to using triethylamine
SAPO-34 molecular sieve particle diameters are larger (3~5 μm), can limit the molecular mass-transfer process in MTO reactions.These are all unfavorable for obtaining
Excellent MTO catalytic reaction results.
The content of the invention
In view of above-mentioned current condition, it is an object of the present invention to provide a kind of new synthesis nanometer SAPO-34 molecular sieves
Method to overcome one or more defects of the prior art.
Therefore, on the one hand, the present invention provides a kind of method for synthesizing nanometer SAPO-34 molecular sieves, its feature exists
In organic using the hydro-thermal method synthesis nanometer SAPO-34 molecular sieves, the functionalization in the presence of functional organo-silane
Silane has the structure shown in Formulas I：
Wherein, n is 1~16 integer；R1For the alkyl of C1~10；R2For the alkyl of C1~6；R3For diethylin, triethylamine
Base, piperazinyl, pyridine radicals or morpholinyl；X is 0~2 integer, and y is 1~3 integer, and x+y=3.
In a preferred embodiment, in the Formulas I, n is 3~8 integer；R1And R2It is each independently C1~4
Alkyl；R3For piperazinyl, pyridine radicals or morpholinyl.
In a preferred embodiment, methods described comprises the following steps：
A) it is the functional organo-silane is soluble in water, then sequentially add silicon source, phosphorus source, organic amine and extra silicon
Source, obtain the mixture with following mol ratio：
SiO2∶P2O5∶Al2O3: organic amine: H2O=0.2~1.2: 0.5~1.5: 0.6~1.4: 1.5~5.5: 50~
200；
B) mixture obtained by step a) is placed in crystallization 0.4~10 day at 150~220 DEG C；
C) after the completion of step b) crystallization, solid product is separated and washs and dries, that is, obtain the nanometer SAPO-
34 molecular sieves.
In a preferred embodiment, functional organo-silane described in the mixture obtained by step a) with it is described extra
Silicon source with SiO2Molal quantity meter mol ratio be 1~55: 10.
In a preferred embodiment, in step a), phosphorus source be selected from orthophosphoric acid, metaphosphoric acid, phosphate and
One or more in phosphite；Source of aluminium is one in aluminium salt, activated alumina, aluminum alkoxide and metakaolin
Kind is a variety of；The one kind or more of the extra silicon source in Ludox, active silica, positive esters of silicon acis and metakaolin
Kind.
In a preferred embodiment, in step a), the organic amine be triethylamine, tetraethyl ammonium hydroxide,
One or more in quinoline, diethylamine, di-n-propylamine and diisopropylamine.
In a preferred embodiment, in step a), the organic amine is triethylamine.
In a preferred embodiment, in step b), the time of the crystallization is 1~7 day.
On the other hand, the present invention provides a kind of SAPO-34 molecular sieve catalysts, it is characterised in that the SAPO-34 points
Sub- sieve catalyst is obtained by being calcined the nanometer SAPO-34 molecular sieves synthesized according to the above method in 400~700 DEG C of air
Arrive.
On the other hand, the present invention provides above-mentioned SAPO-34 molecular sieve catalysts in converting oxygen-containing compound to low-carbon alkene
Application in hydrocarbon, wherein the oxygenatedchemicals is the alcohol of C1~4, the low-carbon alkene is the alkene of C2~6.
Beneficial effect includes but is not limited to following aspect caused by the present invention：
(1) there is small primary particle size (about 50nm by the nanometer SAPO-34 molecular sieves obtained by the inventive method
~200nm), big external surface area (about 80-100m2/ g), big middle pore volume (about 0.10-0.25m3/g)；
(2) there is pure CHA crystalline phases by the nanometer SAPO-34 molecular sieves obtained by the inventive method；
(3) excellent urge is shown in MTO reactions by the SAPO-34 molecular sieve catalysts obtained by the inventive method
Change performance, catalyst life significantly extends, and selectivity of light olefin improves.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the nanometer SAPO-34 sieve samples obtained according to the embodiment of the present application 1.
Fig. 2 is the stereoscan photograph of the SAPO-34 sieve samples obtained according to the application comparative example 1.
Fig. 3 is the XRD diffraction spectras of the SAPO-34 sieve samples obtained according to the embodiment of the present application 1 and comparative example 1~3
Figure.
Embodiment
According to an aspect of the invention, there is provided a kind of received in the case where functional organo-silane aids in by hydro-thermal method synthesis
The method of rice SAPO-34 molecular sieves.Effect of the functional organo-silane in synthesis is at least that following three aspects：1)
As crystal growth inhibitor, crystal size is reduced；2) it is used as organic silicon source；3) functional group's tool of the functional organo-silane
There is part-structure guide effect, suppression uses such as triethylamine thus to succeed as SAPO-18 eutectics caused by micropore template agent
Synthesize the nanometer SAPO-34 molecular sieves with pure CHA crystalline phases.
In the present invention, the nanometer SAPO-34 molecular sieves of acquisition are usually the aggregation of nano particle.
In the present invention, the functional organo-silane is selected from containing diethylin, triethyamino, piperazinyl, pyridine radicals
Or at least one of alkoxyorganosilane compound of morpholinyl.Wherein, the alkoxyorganosilane can typically be seen
Make silicon atom and 1~4 alkoxy is joined directly together the organo-silicon compound of composition；The diethylin is nitrogen in diethyl amine molecule
The group obtained by hydrogen atom is lost on atom；The triethyamino is to be lost in triethylamine molecule on nitrogen-atoms obtained by hydrogen atom
The group arrived；The piperazinyl is to lose the group obtained by hydrogen atom in six-membered cyclic piperazine moieties on a certain nitrogen-atoms；Institute
Pyridine radicals is stated to lose the group obtained by hydrogen atom on nitrogen-atoms in six-membered cyclic piperazine moieties or any carbon atom；It is described
Quinoline base is to lose the group obtained by hydrogen atom in six-membered cyclic morpholine molecule on nitrogen-atoms or any carbon atom.
Preferably, the functional organo-silane has the structure shown in Formulas I：
Wherein, n is 1~16 integer；R1For the alkyl of C1~10；R2For the alkyl of C1~6；R3For diethylin, triethylamine
Base, piperazinyl, pyridine radicals or morpholinyl；X is 0~2 integer, and y is 1~3 integer, and x+y=3.It is further preferred that
N is 3~8 integer；R1And R2It is each independently the alkyl of C1~4；R3For piperazinyl, pyridine radicals or morpholinyl.
In the present invention, the alkyl loses any one hydrogen atom institute shape for any straight or branched saturated alkane molecule
Into group.
In the present invention, it is preferred to the synthetic method of the nanometer SAPO-34 molecular sieves includes following synthesis step：
A) by functional organo-silane it is soluble in water after, sequentially add silicon source, phosphorus source, organic amine and extra silicon source (i.e.
Organic silicon source or inorganic silicon source), the mixture that obtains there is following mol ratio (wherein described functional organo-silane with it is described
The addition of extra silicon source is with SiO2Molal quantity meter, the addition of phosphorus source is with P2O5Molal quantity meter, the addition of silicon source with
Al2O3Molal quantity meter)：
SiO2∶P2O5∶Al2O3: organic amine: H2O=0.2~1.2: 0.5~1.5: 0.6~1.4: 1.5~5.5: 50~
200；
B) mixture obtained by step a) is placed in crystallization 0.4~10 day at 150~220 DEG C；
C) after the completion for the treatment of the step b) crystallization, solid product separating, washing, drying, that is, the nanometer SAPO- is obtained
34 molecular sieves.
The above method can be carried out in the reactor such as crystallizing kettle of conventional hydrothermal synthesis of molecular sieve.
Preferably, in step a) mixture, there is functional organo-silane with extra silicon source with SiO2Molal quantity
Mol ratio (the functional organo-silane of meter：Extra silicon source) it is 1~55: 10.It is further preferred that functional organo-silane：
Extra silicon source is 1~15: 3.
Preferably, in step a), the inorganic phosphorous compound is selected from orthophosphoric acid, metaphosphoric acid, phosphate and phosphite
At least one of.
Preferably, in step a), source of aluminium in aluminium isopropoxide, boehmite and aluminium hydroxide at least one
Kind.
Preferably, in step a), the extra silicon source be selected from Ludox, active silica, positive esters of silicon acis and partially
At least one of kaolin.
Preferably, in step a), the organic amine is triethylamine, tetraethyl ammonium hydroxide, morpholine, diethylamine, two just
One or more in propylamine and diisopropylamine.It is further preferred that in step a), the organic amine is selected from triethylamine (letter
It is written as TEA).
Preferably, in step b), the time of crystallization is 1~7 day.
As a preferred embodiment mode, the method for the synthesis nanometer SAPO-34 molecular sieves comprises the following steps：
1) it is functional organo-silane is soluble in water, it is stirred at room temperature 4~24 hours；
2) silicon source, phosphorus source, organic amine and extra silicon source are sequentially added into the solution of step 1), is placed in and is stirred at room temperature 1
~24 hours, the molar ratio of each component was as follows in mixed solution：(0.2~1.2) SiO2: (0.5~1.5) P2O5∶(0.6
~1.4) Al2O3: (1.5~5.5) organic amine: (50~200) H2O；Wherein functional organo-silane and mole of extra silicon source
Than for 1~15: 3；
3) by the mixed solution of step 2) at 150~220 DEG C crystallization 0.4~10 day；
4) after the completion of the crystallization for treating step 3), solid product is centrifuged, is washed with deionized water to neutrality, 120
DEG C air drying, obtains a nanometer SAPO-34 molecular screen primary powders.
According to the another aspect of the application, there is provided a kind of SAPO-34 molecular sieve catalysts (or acid catalyst) are described
SAPO-34 molecular sieve catalysts pass through the nanometer SAPO-34 that will be synthesized in 400~700 DEG C of air according to any of the above-described method
Molecular sieve is calcined to obtain.
According to the another aspect of the application, there is provided a kind of above-mentioned SAPO-34 molecular sieve catalysts turn in oxygenatedchemicals
Change the application in olefine reaction processed.
Embodiment
The application is described in detail below by embodiment, but the application is not limited to these embodiments.
In the case where not doing specified otherwise, the test condition of the application is as follows：Element composition is using Philips companies
Magix-601 type ray fluorescence analysis instrument (XRF) determines.
X-ray powder diffraction material phase analysis (XRD) uses X ' the Pert PRO of Dutch PANalytical (PANalytical) company
X-ray diffractometer, Cu targets, K α radiation source (λ=0.15418nm), voltage 40KV, electric current 40mA.
SEM morphology analysis uses Scientific Instrument Factory of C.A.S SU8020 type SEM.
N2Physical absorption analysis is analyzed using the type physical absorptions of Micromeritics ASAP 2020 of Merck ＆ Co., Inc of the U.S.
Instrument determines.
Functional organo-silane and n-octyl trimethoxy silane employed in embodiment, buy in Shanghai flute cypress chemistry
Product Technology Co., Ltd..Octadecyldimethyl trimethoxy silicon propyl ammonium chloride is bought in Sigma-Aldrich (Shanghai) trade
Co., Ltd.As non-limiting examples, in the Formulas I, R1For methyl；R2For methyl；R3For piperazinyl, pyridine radicals, morpholine
It is any in base；X=1；Y=2；N=3~8；And by R3PiSi- is abbreviated as the functional organo-silane of piperazinyl
N, by R3BiSi-n is abbreviated as the functional organo-silane of pyridine radicals, by R3It is abbreviated as the functional organo-silane of morpholinyl
MoSi-n, n therein are corresponding n value.For example, " PiSi-3 " represents that chemical constitution is as n=3, R in Formulas I1For first
Base, R2For methyl, R3For functional organo-silane's compound of piperazinyl, x=1, y=2.
Embodiment 1
Each feed molar proportion scale, crystallization condition and sample element composition are shown in Table 1.Specific blending process is as follows：
9.28g PiSi-3 and 71.40g deionized water are mixed 1 hour, sequentially add 135.64g boehmites
(Al2O3Weight/mass percentage composition 72.5%), 34.58g phosphoric acid (H3PO4Weight/mass percentage composition 85%), 20.24g triethylamines and
8.33g tetraethyl orthosilicates, then gel mixture, is transferred in stainless steel cauldron by stirring ageing 24 hours afterwards.Synthesis
The mol ratio of system each component is 0.8SiO2∶1.5P2O5∶0.8Al2O3∶2TEA∶80H2O, PiSi-3 and tetraethyl orthosilicate
Mol ratio is 1: 1.
After reactor is put into baking oven, temperature programming is to 200 DEG C, static crystallization 48h.After reaction terminates, by solid product
Centrifugation, is washed repeatedly with deionized water, is dried in 120 DEG C of air and is obtained a nanometer SAPO-34 sieve samples.
The pattern of gained sample is characterized using ESEM, its electromicroscopic photograph is as shown in figure 1, gained sample is bar
Shape nanocrystal is gathered into spherical micron particles.The particle diameter distribution of strip nanocrystal is between 50nm~200nm.To gained sample
Product carry out XRD analysis, as a result see Fig. 3 and table 2, the results showed that synthetic product has pure SAPO-34 crystalline phases.
Elemental Composition analysis is carried out to gained sample using XRF, the results are shown in Table 1.
Comparative example 1
Proportion scale and building-up process are with embodiment 1, but no addition piperazinyl organosilan PiSi-3, and will implement
Piperazinyl organosilan PiSi-3 in example 1 is to contain same SiO2The tetraethyl orthosilicate of molal quantity substitutes.
The pattern of the sample obtained by comparative example is characterized using ESEM, its electromicroscopic photograph is as shown in Fig. 2 surface
The sample is the smooth cube big crystal grain in the surface of 5 μm or so of particle diameter.
The XRD diffraction spectrograms of the sample original powder of comparative example 1 are also as shown in Figure 3.The sample of comparative example 1 is in 16-17.5 °, 21-
22.5 °, 30-32 ° etc. there is obvious wide Bao Feng, and the sample of display comparison example 1 is the higher SAPO- of SAPO-34 contents
(specific each crystal content analysis refers to the website http of International Molecular sieve association to 34/-18 eutectics：//www.iza-
online.org/default.htm)。
Comparative example 2
Proportion scale and building-up process are with embodiment 1, but no addition piperazinyl organosilan PiSi-3, and will implement
Piperazinyl organosilan PiSi-3 in example 1 is to contain same SiO2The quaternary ammonium salt surface active agent octadecyl two of molal quantity
Methyl trimethoxy oxygen silicon propyl ammonium chloride (TPOAC) substitutes.
The XRD diffraction spectrograms of the sample original powder of comparative example 2 are as shown in Figure 3.The diffraction spectrogram shows, uses TPOAC contrast
Contain SAPO-18 eutectics in the sample of example 2.
Comparative example 3
Proportion scale and building-up process are with embodiment 1, but no addition piperazinyl organosilan PiSi-3, and will implement
Piperazinyl organosilan PiSi-3 in example 1 is to contain same P2OsThe n-octyl trimethoxy without organo-functional group of molal quantity
Base silane substitutes.
The XRD diffraction spectrograms of the sample original powder of comparative example 3 are as shown in Figure 3.The diffraction spectrogram shows, uses n-octyl trimethoxy
Contain SAPO-18 eutectics in the sample of the comparative example 3 of base.
Embodiment 2~12
Specific proportion scale and crystallization condition are shown in Table 1, and specific blending process is the same as embodiment 1.
XRD analysis are carried out to the gained sample of embodiment 2~12, data result is close with table 2, i.e. peak position and shape phase
Together, fluctuated according to the change of synthesis condition, the relative peak intensities at peak in the range of soil 10%, show that synthetic product has SAPO-34
The feature of structure.
XRF Elemental Composition analysis is carried out to the gained sample of embodiment 2~12, the results are shown in Table 1.
The pattern of the gained sample of embodiment 2~12 is analyzed using ESEM, gained electromicroscopic photograph with Fig. 1 phases
Seemingly.
Table 1：Zeolite synthesis dispensing, crystallization condition and element composition table
Table 2：The XRD results for the sample that embodiment 1 obtains
Wherein θ represents the XRD angles of diffraction, and d represents interplanar distance, and I represents relative diffraction peak intensity, I0Represent that relative maximum spreads out
Penetrate peak intensity.
Embodiment 13
Air roasting is passed through at 600 DEG C 4 hours to the sample of embodiment 1~4 and the gained of comparative example 1, then carries out N2
Physical absorption is analyzed, and the results are shown in Table 3.From the results shown in Table 3, compared with the data of comparative example 1, the gained of embodiment 1~4
Sample has obvious increased external surface area and mesoporous volume.
The specific surface area and pore volume of the sample of table 3
Wherein VMicroporeRepresent material Micropore volume, SBETRepresent material BET surface area, SMicroporeMaterial micropore specific area is represented,
SIt is mesoporousRepresent material mesopore surface area
Embodiment 14
The sample of embodiment 1~4 and the gained of comparative example 1 is passed through air roasting 4 hours at 600 DEG C, then tabletting, broken
It is broken to 40~60 mesh.Weigh 0.3g samples and load fixed bed reactors, carry out MTO reaction evaluatings.Lead to nitrogen activation at 550 DEG C
1 hour, then it is cooled to 450 DEG C and is reacted.Methanol is carried by nitrogen, nitrogen flow rate 42ml/min, methanol quality air speed
4h-1.Reaction product is analyzed (Varian3800, fid detector, capillary column PoraPLOT Q- by online gas-chromatography
HT).As a result it is shown in table 4.
Table 4：The preparing olefin by conversion of methanol reaction result of sample
A. methanol conversion is 100% reaction time.
B.100% during methanol conversion, highest (ethene+propylene) selectivity.
Although the application is disclosed as above with preferred embodiment, it is not used to limit the scope of the present invention, any ability
Field technique personnel without departing from the inventive concept of the premise, can make some possible variations and modification, therefore this Shen
Protection domain please should be defined by the scope that the application claim is defined.
Claims (10)
1. a kind of method for synthesizing nanometer SAPO-34 molecular sieves, methods described includes：Exist in functional organo-silane
Under, the nanometer SAPO-34 molecular sieves are synthesized using hydro-thermal method, the functional organo-silane has the structure shown in Formulas I：
Wherein, n is 1~16 integer；R1For the alkyl of C1~10；R2For the alkyl of C1~6；R3For diethylin, triethyamino,
Piperazinyl, pyridine radicals or morpholinyl；X is 0~2 integer, and y is 1~3 integer, and x+y=3.
2. according to the method for claim 1, it is characterised in that in the Formulas I, n is 3~8 integer；R1And R2Each
It independently is the alkyl of C1~4；R3For piperazinyl, pyridine radicals or morpholinyl.
3. method according to claim 1 or 2, it is characterised in that methods described comprises the following steps：
A) it is the functional organo-silane is soluble in water, silicon source, phosphorus source, organic amine and extra silicon source are then sequentially added,
Obtain the mixture with following mol ratio：
SiO2∶P2O5: Al2O3：Organic amine: H2O=0.2~1.2: 0.5~1.5: 0.6~1.4: 1.5~5.5: 50~200；
B) mixture obtained by step a) is placed in crystallization 0.4~10 day at 150~220 DEG C；
C) after the completion of step b) crystallization, solid product is separated and washs and dries, that is, obtain the nanometer SAPO-34 points
Son sieve.
4. according to the method for claim 3, it is characterised in that functionalization organosilicon described in the mixture obtained by step a)
Alkane is with the extra silicon source with SiO2Molal quantity meter mol ratio be 1~55：10.
5. according to the method for claim 3, it is characterised in that in step a), phosphorus source is selected from orthophosphoric acid, inclined phosphorus
One or more in acid, phosphate and phosphite；Source of aluminium be selected from aluminium salt, activated alumina, aluminum alkoxide and partially
One or more in kaolin；The extra silicon source is selected from Ludox, active silica, positive esters of silicon acis and metakaolin
In one or more.
6. according to the method for claim 3, it is characterised in that in step a), the organic amine is triethylamine, tetraethyl
One or more in ammonium hydroxide, morpholine, diethylamine, di-n-propylamine and diisopropylamine.
7. according to the method for claim 3, it is characterised in that in step a), the organic amine is triethylamine.
8. according to the method for claim 3, it is characterised in that in step b), the time of the crystallization is 1~7 day.
A kind of 9. SAPO-34 molecular sieve catalysts, it is characterised in that the SAPO-34 molecular sieve catalysts by 400~
The nanometer SAPO-34 molecular sieves that roasting synthesizes according to method according to any one of claims 1 to 8 in 700 DEG C of air obtain
Arrive.
10. SAPO-34 molecular sieve catalysts according to claim 9 answering in converting oxygen-containing compound to low-carbon olefins
With wherein the oxygenatedchemicals is the alcohol of C1~4, the low-carbon alkene is the alkene of C2~6.
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