CN107915237A - A kind of 34 molecular sieves of twin SAPO and its synthetic method and a kind of method of methanol-to-olefins - Google Patents
A kind of 34 molecular sieves of twin SAPO and its synthetic method and a kind of method of methanol-to-olefins Download PDFInfo
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- CN107915237A CN107915237A CN201610887406.5A CN201610887406A CN107915237A CN 107915237 A CN107915237 A CN 107915237A CN 201610887406 A CN201610887406 A CN 201610887406A CN 107915237 A CN107915237 A CN 107915237A
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- sapo
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- phosphorus
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 119
- 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 119
- 238000010189 synthetic method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 29
- 241000269350 Anura Species 0.000 title abstract 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 81
- 239000011574 phosphorus Substances 0.000 claims abstract description 81
- 239000007787 solid Substances 0.000 claims abstract description 64
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 63
- 239000004411 aluminium Substances 0.000 claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910001868 water Inorganic materials 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000003292 glue Substances 0.000 claims abstract description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 49
- 239000010703 silicon Substances 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 18
- 150000003235 pyrrolidines Chemical class 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims description 122
- 230000008025 crystallization Effects 0.000 claims description 122
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 93
- 229910052593 corundum Inorganic materials 0.000 claims description 90
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 75
- 239000000377 silicon dioxide Substances 0.000 claims description 44
- 229910052681 coesite Inorganic materials 0.000 claims description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims description 40
- 229910052682 stishovite Inorganic materials 0.000 claims description 40
- 229910052905 tridymite Inorganic materials 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 25
- 235000011007 phosphoric acid Nutrition 0.000 claims description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 10
- 239000000806 elastomer Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical group 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 35
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 238000003756 stirring Methods 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 29
- 239000003643 water by type Substances 0.000 description 27
- 239000012071 phase Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 20
- 238000010792 warming Methods 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000005119 centrifugation Methods 0.000 description 18
- 206010013786 Dry skin Diseases 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 238000012876 topography Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229910019142 PO4 Inorganic materials 0.000 description 12
- PFCBHFDNVFQUJI-UHFFFAOYSA-N 3-methylbut-2-en-1-amine Chemical compound CC(C)=CCN PFCBHFDNVFQUJI-UHFFFAOYSA-N 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- -1 3- crassitudes Chemical class 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000002445 carbon-13 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007430 reference method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PXHHIBMOFPCBJQ-UHFFFAOYSA-N 1,2-dimethylpyrrolidine Chemical compound CC1CCCN1C PXHHIBMOFPCBJQ-UHFFFAOYSA-N 0.000 description 2
- 150000008382 2,5-dimethylpyrrolidines Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004410 13C MAS NMR Methods 0.000 description 1
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical class CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- 238000002050 diffraction method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000725 suspension 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]
-
- 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
- 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
-
- 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
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to catalysis material to synthesize field, disclose a kind of 34 molecular sieves of twin SAPO and its synthetic method, including synthesizing 34 molecular sieves of twin SAPO using hydro-thermal method, hydrothermal crystallizing, then separation of solid and liquid, drying will be carried out containing the mixed liquor of phosphorus source, silicon source, silicon source, template and water；And including using 34 molecular sieves of phosphorus aluminium dry glue liquid phase conversion synthesis twin SAPO, aging will be carried out containing the mixed liquor A of phosphorus source, silicon source and water, then dry, phosphorus aluminium dry glue is made, and hydrothermal crystallizing will be carried out containing the raw mixture B of phosphorus aluminium dry glue, silicon source, template and water, then separation of solid and liquid, drying, the template are pyrrolidines.34 molecular sieve crystal patterns of present invention synthesis twin SAPO are the cube that a triangular pyramid is respectively provided with the center of six faces.34 molecular sieves of twin SAPO synthesized by the present invention can be used for converting oxygen-containing compound to low-carbon olefins reaction, especially in methanol-to-olefins reaction reaction, have the selectivity of light olefin of preferable ethene and propylene.
Description
Technical field
The present invention relates to a kind of SAPO-34 molecular sieves and its synthetic method, and the invention further relates to a kind of side of methanol-to-olefins
Method.
Background technology
SAPO-34 molecular sieves are U.S. combinating carbide companies in a kind of new aluminium silicophosphate molecular sieve of exploitation in 1984.
Since SAPO-34 molecular sieves are steady with suitable pore size, pore passage structure, acid strength and good heat endurance, hydro-thermal
The advantages that qualitative, make it show good application feature in gas absorption separation, all kinds of hydrocarbon conversion catalyst fields, especially exist
There is very high selectivity to ethene, propylene in methanol-to-olefins reaction (MTO), show excellent catalytic performance, mesh
Before have become the preferred catalyst of MTO technical process.
The topological structure of SAPO-34 molecular sieves is Chabazite-type (CHA), and space group R-3m, belongs to trigonal system, structure cell ginseng
Numberα=94.47 °, β=94.47 °, γ=94.47 °, have and are pressed by double hexatomic rings
The octatomic ring elliposoidal cage (CHA cages) and three dimensional intersection pore passage structure accumulated according to ABC modes, pore size for 0.38nm ×
0.38nm, cage size are 1.0nm × 0.67nm × 0.67nm, belong to small pore molecular sieve.
The typical crystal morphology of SAPO-34 molecular sieves is cube pattern, this CN103663490A,
In numerous patents such as CN103818928A, CN103896305A, CN102336413A, CN104418358A, CN102464338A
All have been reported that.In recent years, researcher both domestic and external has done substantial amounts of research to SAPO-34 molecular sieves, existing a variety of differences
It is synthesized in the SAPO-34 molecular sieves of normal cubic pattern, such as sheet-like morphology, spherical morphology.
For example, CN103011188A has opened a kind of synthetic method with SAPO-34 molecular sieves, this method will contain aluminium
Source, silicon source, phosphorus source, the mixed solution of organic amine template and water are placed in autoclave, by the way of microwave heating, are led to
Control microwave synthesis condition is crossed, has synthesized the SAPO-34 molecular sieves of nanometer spherical and sheet-like morphology.Wherein, the organic formwork
Agent is diethylamine, one or more of mixtures in triethylamine, tetraethyl ammonium hydroxide, morpholine, dipropylamine.
And for example, CN104986780A discloses a kind of synthetic method of SAPO-34 molecular sieves, and this method uses Hydrothermal Synthesiss
Method, use for by the first template triethylamine be and the second template cetyl trimethylammonium bromide, cetyl front three
The composite mould plate agent of base ammonium hydroxide or hexadecyltrimethylammonium chloride composition, is 180-200 DEG C in crystallization temperature, during crystallization
Between be 10-50h under conditions of, synthesized the SAPO-34 molecular sieves of nanoscale twins crystal morphology.
And for example, CN103936027A discloses a kind of method of SAPO-34 molecular sieves, and this method adds in crystallization process
Biomass suspension, is 180-200 DEG C in crystallization temperature, under conditions of crystallization time is 24-72h, has synthesized flower-like microsphere shape
The SAPO-34 molecular sieves of looks.Used template is triethylamine, diethylamine or tetraethyl ammonium hydroxide.
Though above-mentioned SAPO-34 molecular sieves because synthesis condition and template change and caused by pattern it is different, be normal life
Long SAPO-34 molecular sieve crystals.In addition, also there are it is a kind of because molecular sieve itself crystal growth produce defect formed it is twin
It is brilliant.From crystallography, twin refers to two crystal (or two parts of a crystal) along a public crystal face (i.e. specific orientation
Relation) mirror-symmetrical orientation relationship is formed, the two crystal are known as " twin ".
On molecular sieve twin growth phenomenon and reason in document (Mineralogical Magazine, 2000,64 (1):
Reported in 1-8.).The document describes the SEM patterns that there is A type molecular sieve two independent cubic grains to interpenetrate.From
From the point of view of pattern, the twin of A type molecular sieve is to rotate 180 ° around triad by a single cubic grain to be formed.From structure
From the point of view of, the formation of A type molecular sieve twin be on the one of face of crystal recurring structure failure and produce.The twin structure of formation
Two sodalite cages of A type molecular sieve may be made to connect together by hexatomic ring, cause 3 D pore canal to stress in twin plane two
New arrangement.Therefore, the appearance of molecular sieve twin is changed its structure and pattern, so as to can cause the materialization of molecular sieve
Matter is different from routine.
Document (Crystal Growth＆Design, 2010,10 (7):2824-2828.) report and be in crystallization temperature
200 DEG C, under conditions of crystallization time is 48h, hydrofluoric acid (HF) is used as mineralizer, morpholine synthesizes SAPO-34 points for template
During son sieve, its crystal morphology is the twin growth thing that some small protrusions are grown on the Sharp edge of normal cubic crystal grain.
The content of the invention
It is an object of the invention on the basis of existing technology, there is provided one kind has is respectively provided with one at the center of six faces
The twin SAPO-34 molecular sieves of the cube pattern of triangular pyramid and its synthetic method and application.The molecular sieve can be used for oxygen-containing
Compound converts reaction for preparing light olefins, especially in methanol-to-olefins reaction reaction, has preferable ethene and third
The selectivity of light olefin of alkene.
Therefore, according to the first aspect of the invention, the present invention provides a kind of twin SAPO-34 molecular sieves, wherein, institute
The crystal morphology for stating twin SAPO-34 molecular sieves is the cube that a triangular pyramid is respectively provided with the center of six faces.
According to the second aspect of the invention, present invention also offers a kind of synthesis of the twin SAPO-34 molecular sieves
Method, wherein, the synthetic method includes：
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water, phosphorus source with
P2O5Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, the molar ratio of template and water are
0.6-1.2:0.05-1.2:1:1.5-10:3-100, is preferably 0.8-1.2:0.1-1:1:1.5-5:5-50；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid phase is dried and optionally
Roasting；
Wherein, the template is pyrrolidines, N- crassitudes, 2- crassitudes, 3- crassitudes and 2,5-
At least one of dimethyl pyrrolidine.
According to the third aspect of the present invention, present invention also offers the conjunction of another twin SAPO-34 molecular sieves
Into method, wherein, the synthetic method includes：
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water, and phosphorus source is with P2O5Meter, source of aluminium
With Al2O3Meter, the molar ratio of phosphorus source, silicon source and water is 0.6-1.2:1:20-70, is preferably 0.8-1.2:1:20-60；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) raw mixture B, the raw mixture B are provided and contains phosphorus aluminium dry glue, silicon source, template made from step (2)
Agent and water, the phosphorus aluminium dry glue is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water
For：1:0.05-1.2:1.5-10:3-100, is preferably 1:0.1-1:1.5-5:5-50；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid phase is dried and optionally
Roasting；
Wherein, the template is pyrrolidines, N- crassitudes, 2- crassitudes, 3- crassitudes and 2,5-
At least one of dimethyl pyrrolidine.
The present invention has synthesized the pure phase twin SAPO- with regular morphology by template of pyrrolidines first
34 molecular sieves.The SAPO-34 molecular sieves synthesized using hydrothermal synthesis method or phosphorus aluminium dry glue liquid phase conversion have regular twin
Brilliant crystal morphology, twin pattern are the cube that a triangular pyramid is respectively provided with six faces center of normal cubic crystal grain.
It is different from traditional SAPO- on pore passage structure by twin SAPO-34 molecular sieves prepared by template of pyrrolidines
34 molecular sieves, there are octatomic ring duct to intersect connection phenomenon, it is can be used for converting oxygen-containing compound to low-carbon olefins reaction,
Excellent catalytic performance is especially shown in MTO catalytic reactions, there is preferable ethene (C2Alkene) and propylene (C3Alkene)
Selectivity of light olefin.
In addition, the template such as common triethylamine, tetraethyl ammonium hydroxide exists in SAPO-34 molecular sieve industrial productions
It is heated to decompose in the building-up process of SAPO-34, it is impossible to recycle, cause production cost high, and can not realize
The clean manufacturing that template recycles, pollutes environment.Pyrrolidines template stable structure of the present invention,
In sieve synthesis procedure, do not decompose, it is possible to achieve the industrial clean manufacturing that template recycles, advantageously reduces
Production cost, and reduce environmental pollution.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the XRD spectra for the sieve sample that embodiment 1 synthesizes；
Fig. 2 is the SEM photograph for the sieve sample that embodiment 1 synthesizes；
Fig. 3 is the liquid of template used dose of embodiment 313C MAS NMR spectras；
Fig. 4 is the liquid of 3 molecular sieve synthesis mother liquid of embodiment13C MAS NMR spectras；
Fig. 5 is the XRD spectra for the sieve sample that embodiment 8 synthesizes；
Fig. 6 is the SEM photograph for the sieve sample that embodiment 8 synthesizes；
Fig. 7 is the XRD spectra for the sieve sample that embodiment 10 synthesizes；
Fig. 8 is the SEM photograph for the sieve sample that embodiment 10 synthesizes；
Fig. 9 is the XRD spectra for the sieve sample that embodiment 14 synthesizes；
Figure 10 is the SEM photograph for the sieve sample that embodiment 14 synthesizes；
Figure 11 is the XRD spectra for the sieve sample that embodiment 15 synthesizes；
Figure 12 is the SEM photograph for the sieve sample that embodiment 15 synthesizes；
Figure 13 is the SEM photograph for the sieve sample that comparative example 1 synthesizes；
Figure 14 is the XRD spectra for the sieve sample that comparative example 2 synthesizes；
Figure 15 is the SEM photograph for the sieve sample that comparative example 2 synthesizes.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Technical term in the present invention, provides being defined from it for definition, does not provide then usually the containing by this area of definition
Reason and good sense solution.
Template in the present invention, in the art also referred to as structure directing agent or Organic structure directing agent.
According to the first aspect of the invention, the SAPO-34 molecular sieves provided by the invention are pure phase twin SAPO-34
Molecular sieve, has regular twin crystal morphology, and has higher crystallinity, and there are octatomic ring duct to intersect connection phenomenon,
Crystal morphology is the cube that a triangular pyramid is respectively provided with the center of six faces.Importantly, synthesized by the method for the present invention
Twin SAPO-34 molecular sieves in the reaction of methanol-to-olefins have show excellent catalytic performance, there is preferable second
The selectivity of light olefin of alkene and propylene.
According to the second aspect of the invention, should the present invention provides a kind of synthetic method of twin SAPO-34 molecular sieves
Synthetic method is hydro-thermal method, wherein, the synthetic method includes：
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid phase is dried and optionally
Roasting.
Present invention also offers the synthetic method of another twin SAPO-34 molecular sieves, which is phosphorus aluminium
Dry glue liquid phase conversion, wherein, the synthetic method includes：
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) raw mixture B, the raw mixture B are provided and contains phosphorus aluminium dry glue, silicon source, template made from step (2)
Agent and water；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture obtained hydrothermal crystallizing carries out separation of solid and liquid, obtained solid phase is dried and optionally
Roasting.
Above-mentioned synthetic method according to the present invention, the template is pyrrolidines, N- crassitudes, 2- methylpyrroles
At least one of alkane, 3- crassitudes, 2,5- dimethyl pyrrolidines.
Herein, " at least one " represents one or more kinds of.
According to the present invention, it is described mixed preparing in twin SAPO-34 molecular sieves of the present invention are synthesized using hydro-thermal method
When closing liquid, phosphorus source is with P2O5Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, template
The molar ratio of agent and water is 0.6-1.2:0.05-1.2:1:1.5-10:3-100, is preferably 0.8-1.2:0.1-1:1:1.5-5:
5-50.Wherein, when preparing the mixed liquor, the water is total Water, it may for example comprise the water of addition, further includes phosphorus source, silicon
Water in source, silicon source and template.
According to the present invention, in twin SAPO-34 molecular sieves of the present invention are synthesized using phosphorus aluminium dry glue liquid phase conversion,
When preparing phosphorus aluminium dry glue, phosphorus source is with P2O5Meter, source of aluminium is with Al2O3Meter, the molar ratio of phosphorus source, silicon source and water are
0.6-1.2:1:20-70, is preferably 0.8-1.2:1:20-60；In preparing raw material mixture B, the phosphorus aluminium dry glue is with Al2O3
Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water are：1:0.05-1.2:1.5-10:3-
100, it is preferably 1:0.1-1:1.5-5:5-50.Wherein, when preparing the mixed liquor A, the water is total Water, for example,
Water including addition, further includes the water in phosphorus source, silicon source.In preparing raw material mixture B, the water is total Water, example
Such as, include the water of addition, further include the water in phosphorus aluminium dry glue, silicon source and template.
The present invention is not particularly limited for the species of phosphorus source, silicon source and silicon source, can be conventional selection.
Usually, phosphorus source can be selected from orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphorus compound
At least one of.
Preferably, the organic phosphorus compound are at least one of trimethyl phosphorus and triethyl phosphine.
Source of aluminium can be in aluminium salt, boehmite, aluminium isopropoxide, aluminum hydroxide solid elastomer and activated alumina
It is at least one.
Preferably, the aluminium salt is at least one of aluminium chloride and aluminum sulfate.
The silicon source can be selected from Ludox, active silica, solid silicone, the silicon-containing compound shown in Formulas I and white
At least one of carbon black,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, such as methyl, ethyl, propyl group and its isomers and butyl and
Its isomers.
Preferably, the silicon-containing compound is Ludox, active silica, solid silicone, ethyl orthosilicate and hard charcoal
It is at least one of black.
According to the present invention, in twin SAPO-34 molecular sieves of the present invention are synthesized using hydro-thermal method, can use conventional
Method mixes phosphorus source, silicon source, silicon source, template and water, so as to obtain the mixed liquor.Specifically, can by silicon source, water,
Phosphorus source, silicon source and template are sequentially added and are uniformly mixed, so as to obtain the mixed liquor.
According to the present invention, in twin SAPO-34 molecular sieves of the present invention are synthesized using phosphorus aluminium dry glue liquid phase conversion,
Phosphorus aluminium dry glue can be prepared using conventional method, and phosphorus aluminium dry glue, silicon source, template and water are mixed, so as to obtain the original
Expect mixture B.Specifically, silicon source is mixed with water, then with stirring addition phosphorus source, obtains mixed liquor A, mixed liquor A is existed
Stirring is lower to carry out aging, and aging temperature can be 50-80 DEG C, be preferably 60-70 DEG C, excellent when ageing time can be 6-20 small
Elect as 10-18 it is small when, then the mixed liquor A after aging is dried, dry temperature can be 80-120 DEG C, be preferably
80-100 DEG C, when the dry time can be 12-36 small, when being preferably 20-30 small, phosphorus aluminium dry glue is made.By phosphorus aluminium dry glue, silicon
Source, water and template are sequentially added and are uniformly mixed, so as to obtain the raw mixture B.
According to the present invention, the hydrothermal crystallizing can carry out at conventional temperatures, such as at a temperature of 100-200 DEG C into
OK.The time of the hydrothermal crystallizing can also be conventional selection.
However, the method according to the invention, using previously described template, while uses two sections of variable temperature crystallizations, also can
Twin SAPO-34 molecular sieves with more high-crystallinity and more preferable MTO catalytic performances, preferable case are prepared with the yield of higher
Under, the hydrothermal crystallizing uses two sections of variable temperature crystallizations, i.e., including first segment crystallization and second segment crystallization, the temperature of first segment crystallization
It can be 100-180 DEG C, the temperature of second segment crystallization can be 140-200 DEG C, it is further preferred that the temperature of first segment crystallization is 130-
170 DEG C, the temperature of second segment crystallization is 150-195 DEG C, and most preferably, the temperature of first segment crystallization is 140-160 DEG C, and second segment is brilliant
The temperature of change is 160-190 DEG C.
It is more excellent when the time of second segment crystallization can be 3-80 small when the time of first segment crystallization can be 10-70 small
Choosing, when the time of first segment crystallization is 20-60 small, when the time of second segment crystallization is 4-60 small, most preferably, first segment crystallization
When time is 30-45 small, when the time of second segment crystallization is 5-50 small.
According to the present invention, the solid phase mixture progress separation of solid and liquid that hydrothermal crystallizing obtains obtained can be in normal condition
Under be dried and optionally roast, so as to obtain twin SAPO-34 molecular sieves.It is " optional " to represent inessential in the present invention,
It can be understood as including or do not include.Specifically, the drying can carry out at a temperature of 80-120 DEG C, the drying when
Between can be made choice according to dry temperature, generally can be 2-12 it is small when.The purpose of the roasting essentially consists in removing point
The template in molecular sieve pore passage is remained in son sieve building-up process, can determine whether to be roasted according to specifically used requirement
Burn.It is preferred that roasted after the completion of drying.The roasting can carry out at a temperature of 400-700 DEG C, and the roasting is held
The continuous time can make choice according to the temperature of roasting, when generally can be 2-8 small.It is described roasting generally in air atmosphere into
OK.Further, it is also possible to the solid phase that separation of solid and liquid is obtained is washed before the drying, i.e. the mixing for obtaining hydrothermal crystallizing
Thing carries out separation of solid and liquid, washing (optional) and drying, can obtain molecular screen primary powder；Alternatively, by the mixture that hydrothermal crystallizing obtains into
Row separation of solid and liquid, washing (optional), dry (optional) and roasting, the molecular sieve after must can roasting.Washing is generally in room temperature to 50
Mixed or eluted with water at DEG C, water is generally 1-20 times of hydrothermal crystallizing product quality.The method of the separation of solid and liquid
Conventional method can be used to carry out, such as filtering, centrifugation etc..
According to the present invention, to the heating mode of either step in the twin SAPO-34 Zeolite synthesis methods without spy
Other limitation, can be by the way of temperature programming, such as 0.5 DEG C -1 DEG C/min.
According to the present invention, it is not special to the hydrothermal crystallizing pressure in the twin SAPO-34 Zeolite synthesis methods
Limitation, can be the self-generated pressure of crystallization system.
According to the third aspect of the present invention, the present invention provides a kind of method of methanol-to-olefins, this method to be included in
Under the conditions of methanol to olefins reaction, methanol is contacted with twin SAPO-34 molecular sieves provided by the invention.
Methanol-to-olefins method according to the present invention, can carry out under the conditions of conventional methanol to olefins reaction, as long as
Use twin SAPO-34 molecular sieves provided by the invention.Usually, can at a temperature of 400-500 DEG C by methanol with
SAPO-34 molecular sieves contact.The weight space velocity of methanol can be 1-9h-1。
The present invention will be described in detail by way of examples below.
In following embodiments and comparative example, X-ray powder diffraction material phase analysis (XRD) is using Dutch Panaco Empyrean
Type diffractometer, it is equipped with PIXcel3DDetector.Test condition：Cu targets, K α radiation, Ni filter plates, tube voltage 40kV, pipe electricity
Flow 40mA, 5 ° -50 ° of scanning range.
In following embodiments and comparative example, scanning electron microscope morphology analysis (SEM) is swept using Hitachi, Japan S4800 types
Retouch Electronic Speculum.Test condition：After sample drying milled processed, it is sticked on conducting resinl.Analytic electron microscope accelerating potential is 5.0kV,
20-800000 times of amplification factor.
Template is represented with R in following embodiments.
Embodiment 1-12 is used to illustrate to synthesize twin SAPO-34 molecules of the present invention using phosphorus aluminium dry glue liquid phase conversion
Sieve.
Embodiment 1
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 18.86 grams of deionized waters to equal
Even, slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always
Change 12 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 20 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 79.5%) made from 7.67 grams to add in polytetrafluoroethyllining lining, and sequentially add
0.16 gram of solid silicone (SiO2Mass fraction 93%), 0.58 gram of deionized water, 4.34 grams of N- crassitudes (C5H11N mass
Fraction>98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.1, R/
Al2O3=2.0, H2O/Al2O3=5.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 30 it is small when, then be warming up to 160 DEG C, carry out second segment crystallization：When 160 DEG C of crystallization 15 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 1, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is twin pattern, is given birth at cubical six faces center
A triangular pyramid is grown, SEM photograph is shown in Fig. 2.
Embodiment 2
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 11.66 grams of deionized waters to equal
Even, slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, always
Change 12 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 24 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 83.3%) made from 7.32 grams to add in polytetrafluoroethyllining lining, sequentially add 0.24
Gram solid silicone (SiO2Mass fraction 93%), 3.17 grams of deionized waters, 4.34 grams of 2- crassitudes (C5H11N mass fractions
98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.15, R/Al2O3
=2.0, H2O/Al2O3=10.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 160 DEG C, carry out second segment crystallization：When 160 DEG C of crystallization 10 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 3
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 26.06 grams of deionized waters to equal
Even, slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always
Change 12 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 24 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 81.4%) made from 7.49 grams to add in polytetrafluoroethyllining lining, sequentially add 1.50
Gram Ludox (SiO2Mass fraction 30%), 6.49 grams of deionized waters, 3.26 grams of N- crassitudes (C5H11N mass fractions>
98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/Al2O3
=1.5, H2O/Al2O3=20.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 40 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 5 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Template used dose of N- crassitude is synthesized to the present embodiment and molecular sieve synthesis mother liquid carries out liquid13C MAS
NMR is analyzed, the liquid of template N- crassitudes13C MAS NMR spectras are shown in Fig. 3, the liquid of molecular sieve synthesis mother liquid13C
MAS NMR spectras are shown in Fig. 4.Contrast is as it can be seen that used pyrrolidines template stable structure, in Zeolite synthesis mistake
Cheng Zhong, does not decompose.
Embodiment 4
By 4.91 boehmite (Al2O3Mass fraction 83%) it is stirred with 33.78 grams of deionized waters to uniform,
Slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, aging 12
Hour obtained mixture A.Mixture A is poured into pallet, is placed in when drying 20 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 79.5%) made from 7.67 grams to add in polytetrafluoroethyllining lining, sequentially add 0.81
Gram solid silicone (SiO2Mass fraction 93%), 11.84 grams of deionized waters, 2.69 grams of pyrrolidines (C4H9N mass fractions 99%),
Stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.5, R/Al2O3=1.5,
H2O/Al2O3=30.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 20 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 5
By 4.91 grams of boehmite (Al2O3Mass fraction 83%) it is stirred with 41.12 grams of deionized waters to uniform,
Slow thread adds 8.30 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, aging
16 are made mixture A when small.Mixture A is poured into pallet, is placed in when drying 30 is small at 90 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 85.6%) made from 6.71 grams to add in polytetrafluoroethyllining lining, sequentially add 4.00
Gram Ludox (SiO2Mass fraction 30%), 18.60 grams of deionized waters, 6.52 grams of 2- crassitudes (C5H11N mass fractions
98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=0.9, SiO2/Al2O3=0.8, R/Al2O3
=3.0, H2O/Al2O3=50.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：160 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 25 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 6
By 16.67 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%) it is stirred with 34.28 grams of deionized waters to equal
Even, slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, always
Change 16 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 24 is small at 100 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 92.6%) made from 7.38 grams to add in polytetrafluoroethyllining lining, sequentially add 1.58
Gram ethyl orthosilicate (SiO2Mass fraction>28%), 16.20 grams of deionized waters, 10.08 grams of 3- crassitudes (C5H11N mass
Fraction 95%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/
Al2O3=4.5, H2O/Al2O3=40.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 40 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 7
By 4.16 grams of activated alumina (Al2O3Mass fraction 98%) it is stirred with 34.39 grams of deionized waters to uniform,
Slow thread adds 10.15 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, aging
16 are made mixture A when small.Mixture A is poured into pallet, is placed in when drying 24 is small at 90 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 89.7%) made from 7.19 grams to add in polytetrafluoroethyllining lining, sequentially add 0.47
Gram active silica (SiO2Mass fraction 95%), 7.48 grams of deionized waters, 10.77 grams of 2,5- dimethyl pyrrolidines (C6H14N
Mass fraction 93%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.1, SiO2/Al2O3=
0.3、R/Al2O3=4.0, H2O/Al2O3=20.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：140 DEG C of crystalline substances
Change 40 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 45 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 8
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 35.94 grams of deionized waters to equal
Even, slow thread adds 11.81 grams of phosphorous acid (H under stirring3PO3Mass fraction 50%), it is sufficiently stirred at 70 DEG C,
Mixture A is made in aging 10 when small.Mixture A is poured into pallet, is placed in when drying 24 is small at 100 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 93.1%) made from 6.17 grams to add in polytetrafluoroethyllining lining, sequentially add 0.79
Gram ethyl orthosilicate (SiO2Mass fraction>28%), 6.25 grams of deionized waters, 3.26 grams of N- crassitudes (C5H11N mass point
Number>98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=0.9, SiO2/Al2O3=0.15, R/
Al2O3=1.5, H2O/Al2O3=15.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 40 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 40 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 5, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is twin pattern, is given birth at cubical six faces center
A triangular pyramid is grown, SEM photograph is shown in Fig. 6.
Embodiment 9
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 27.22 grams of deionized waters to equal
It is even, 10.78 grams of ammonium hydrogen phosphate ((NH are slowly added under stirring4)2HPO4Mass fraction 98%), fully stirred at 60 DEG C
Mix, mixture A is made in aging 18 when small.Mixture A is poured into pallet, be placed at 90 DEG C dry 30 it is small when phosphorus aluminium be made do
Glue.
Take phosphorus aluminium dry glue (solid content 88.9%) made from 6.86 grams to add in polytetrafluoroethyllining lining, sequentially add 0.31
Gram white carbon (SiO2Mass fraction 98%), 3.67 grams of deionized waters, 3.26 grams of 2- crassitudes (C5H11N mass fractions
98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.2, R/Al2O3
=1.5, H2O/Al2O3=10.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：140 DEG C of crystalline substances
Change 45 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 50 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 10
By 16.67 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%) it is stirred with 35.45 grams of deionized waters to equal
It is even, 10.78 grams of ammonium hydrogen phosphate ((NH are slowly added under stirring4)2HPO4Mass fraction 98%), fully stirred at 70 DEG C
Mix, mixture A is made in aging 14 when small.Mixture A is poured into pallet, be placed at 80 DEG C dry 24 it is small when phosphorus aluminium be made do
Glue.
Take phosphorus aluminium dry glue (solid content 76.6%) made from 7.96 grams to add in polytetrafluoroethyllining lining, sequentially add 0.65
Gram solid silicone (SiO2Mass fraction 93%), 9.28 grams of deionized waters, 3.26 grams of N- crassitudes (C5H11N mass fractions>
98%), stir evenly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3
=1.5, H2O/Al2O3=25.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 36 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 45 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 7, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is twin pattern, is given birth at cubical six faces center
A triangular pyramid is grown, SEM photograph is shown in Fig. 8.
Embodiment 11
By 4.91 grams of boehmite (Al2O3Mass fraction 83%) it is stirred with 35.09 grams of deionized waters to uniform,
7.44 grams of ammonium dihydrogen phosphate (NH are slowly added under stirring4H2PO4Mass fraction 99%), it is sufficiently stirred at 70 DEG C, always
Change 14 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 24 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 80.2%) made from 6.72 grams to add in polytetrafluoroethyllining lining, sequentially add 0.48
Gram solid silicone (SiO2Mass fraction 93%), 7.57 grams of deionized waters, 6.29 grams of pyrrolidines (C4H9N mass fractions 99%), stir
Mix uniformly, the addition molar ratio of wherein each component is：P2O5/Al2O3=0.8, SiO2/Al2O3=0.3, R/Al2O3=3.5,
H2O/Al2O3=20.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：160 DEG C of crystalline substances
Change 30 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 20 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 12
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) and 34.53 grams of deionized waters, it is stirred to equal
It is even, 11.15 grams of ammonium dihydrogen phosphate (NH are slowly added under stirring4H2PO4Mass fraction 99%), fully stirred at 70 DEG C
Mix, mixture A is made in aging 12 when small.Mixture A is poured into pallet, be placed at 90 DEG C dry 24 it is small when phosphorus aluminium be made do
Glue.
Take phosphorus aluminium dry glue (solid content 83.7%) made from 8.13 grams to add in polytetrafluoroethyllining lining, sequentially add 0.16
Gram solid silicone (SiO2Mass fraction 93%), 5.37 grams of deionized waters, 4.49 grams of pyrrolidines (C4H9N mass fractions 99%), stir
Mix uniformly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.2, SiO2/Al2O3=0.1, R/Al2O3=2.5,
H2O/Al2O3=15.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 10 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 13-15 is used to illustrate to synthesize twin SAPO-34 molecular sieves of the present invention using hydro-thermal method.
Embodiment 13
By 3.40 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%), 0.44 gram of deionized water, 5.76 grams of orthophosphoric acid
(H3PO4Mass fraction 85%), 0.16 gram of solid silicone (SiO2Mass fraction 93%), 4.34 grams of N- crassitudes (C5H11N
Mass fraction>98%) sequentially add in polytetrafluoroethyllining lining, stir evenly, the addition molar ratio of wherein each component is：P2O5/
Al2O3=1.0, SiO2/Al2O3=0.1, R/Al2O3=2.0, H2O/Al2O3=5.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 36 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 45 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, sample topography is twin pattern, is grown at cubical six faces center
Go out a triangular pyramid.
Embodiment 14
By 3.07 grams of boehmite (Al2O3Mass fraction 83%), 18.27 grams of deionized waters, 5.19 grams of orthophosphoric acid
(H3PO4Mass fraction 85%), 4.00 grams of Ludox (SiO2Mass fraction 30%), 6.52 grams of 2- crassitudes (C5H11N matter
Amount fraction 98%) sequentially add in polytetrafluoroethyllining lining, stir evenly, the addition molar ratio of wherein each component is：P2O5/
Al2O3=0.9, SiO2/Al2O3=0.8, R/Al2O3=3.0, H2O/Al2O3=50.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：160 DEG C of crystalline substances
Change 35 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 25 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 9, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is twin pattern, is given birth at cubical six faces center
A triangular pyramid is grown, SEM photograph is shown in Figure 10.
Embodiment 15
By 10.42 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%), 10.80 grams of deionized waters, 6.74 grams of phosphoric acid hydrogen
Ammonium ((NH4)2HPO4Mass fraction 98%), 0.65 gram of solid silicone (SiO2Mass fraction 93%), 3.26 grams of N- crassitudes
(C5H11N mass fractions>98%) sequentially add in polytetrafluoroethyllining lining, stir evenly, wherein the addition molar ratio of each component
For：P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3=1.5, H2O/Al2O3=25.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 36 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 45 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Figure 11, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is twin pattern, is given birth at cubical six faces center
A triangular pyramid is grown, SEM photograph is shown in Figure 12.
Comparative example 1
This comparative example explanation is using reference method synthesis SAPO-34 molecular sieves.
Method according to embodiment 3 synthesizes SAPO-34 molecular sieves, difference lies in this comparative example without using N- crassitudes
Make template, but synthesize most commonly used triethylamine using SAPO-34 and make template.
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 26.06 grams of deionized waters to equal
Even, slow thread adds 9.22 grams of orthophosphoric acid (H under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always
Change 12 it is small when mixture A is made.Mixture A is poured into pallet, is placed in when drying 25 is small at 80 DEG C and phosphorus aluminium dry glue is made.
Take phosphorus aluminium dry glue (solid content 81.4%) made from 7.49 grams to add in polytetrafluoroethyllining lining, sequentially add 1.50
Gram Ludox (SiO2Mass fraction 30%), 6.52 grams of deionized waters, 3.83 grams of triethylamine (C6H15N mass fractions 99%), stir
Mix uniformly, the addition molar ratio of wherein each component is：P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/Al2O3=1.5,
H2O/Al2O3=20.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 40 it is small when, then be warming up to 170 DEG C, carry out second segment crystallization：When 170 DEG C of crystallization 5 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized
The result shows that sample is pure phase SAPO-34 molecular sieves, SEM photograph is shown in Figure 13, and display sample topography is conventional cube pattern.
Comparative example 2
This comparative example explanation is using reference method synthesis SAPO-34 molecular sieves.
Method according to embodiment 15 synthesizes SAPO-34 molecular sieves, difference lies in this comparative example without using N- methylpyrroles
Alkane makees template, but synthesizes most commonly used tetraethyl ammonium hydroxide using SAPO-34 and make template.
By 10.42 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%), 0.61 gram of deionized water, 6.74 grams of ammonium hydrogen phosphates
((NH4)2HPO4Mass fraction 98%), 0.65 gram of solid silicone (SiO2Mass fraction 93%), 15.78 grams of tetraethyl hydroxides
Ammonium (C8H21NO mass fractions 35%) sequentially add in polytetrafluoroethyllining lining, stir evenly, wherein the addition mole of each component
Than for：P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3=1.5, H2O/Al2O3=25.
It will be capped equipped with the polytetrafluoroethyllining lining of above-mentioned reaction mixture, be put into stainless steel autoclave and seal, by this
Autoclave, which is placed in, to be rotated in convection oven, and speed setting 20r/min, carries out first segment crystallization at autogenous pressures：150 DEG C of crystalline substances
Change 36 it is small when, then be warming up to 180 DEG C, carry out second segment crystallization：When 180 DEG C of crystallization 45 are small, treat that crystallization is completed, autoclave temp drop
Crystallization product is taken out during to room temperature, filtered or centrifugation, is washed with deionized, 110 DEG C of dryings 12 obtain solid when small
Product, is molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Figure 14, it was demonstrated that is pure phase SAPO-34 molecules
Sieve.The pattern of molecular sieve is observed using SEM, sample topography is conventional cube pattern, and SEM photograph is shown in Figure 15.
Embodiment 16-19
Embodiment 16-19 is used for the methanol-to-olefins method for illustrating the present invention.
Embodiment 16-19 illustrates anti-in methanol-to-olefins using embodiment 8,10,14 and 15 gained sieve samples respectively
Catalytic performance result in answering.
The molecular screen primary powder of the gained of embodiment 8,10,14 and 15 is placed in Muffle furnace Program respectively and is warming up to 550 DEG C of roastings
Burn 3 it is small when roasted after sample, sieve through tabletting, choose 20-40 mesh sample, be respectively labeled as S-1, S-2, S-3 and
S-4。
It is put into respectively using 3g sieve samples S-1, S-2, S-3 and S-4 as catalyst in fixed bed reactors, 500
At DEG C lead to nitrogen activation 0.5 it is small when, be then cooled to 450 DEG C, reaction pressure 0.1MPa.The pure methanol of raw material passes through flow measurement
Enter preheating furnace after pump under the carrying as the nitrogen of carrier gas, and gas is vaporized into preheating furnace, subsequently into fixed bed
Reacted in reactor.Wherein, nitrogen flow 350mL/min, the weight space velocity of methanol is 1h-1。
Reaction product is with ethene (C2=) and propylene (C3=) it is target product, reaction product is by Agilent GC7890A gas phases
On-line chromatographic analysis, the results are shown in Table 1 for MTO catalytic performances.
Comparative example 3
Comparative example 3 is used for the reference method for illustrating methanol-to-olefins.
The explanation of comparative example 3 uses catalytic performance result of the 2 gained sieve sample of comparative example in methanol to olefins reaction.
By the molecular screen primary powder of the gained of comparative example 2 be placed in Muffle furnace Program be warming up to 550 DEG C of roastings 3 it is small when roasted
Sample afterwards, sieves through tabletting, the sample of 20-40 mesh is chosen, labeled as D-1.Evaluation method and condition and embodiment 16-19 phases
Together, the results are shown in Table 1 for MTO catalytic performances.
Table 1
As seen from Table 1, the zeolite product that the present invention synthesizes has a longer life expectancy and higher pair
Alkene selectivity, the wherein diene selective of S-1 are up to 86.63%, illustrate the twin pattern SAPO-34 molecular sieves that the present invention synthesizes
With preferable MTO catalytic performances.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of twin SAPO-34 molecular sieves, it is characterised in that the crystal morphology of the twin SAPO-34 molecular sieves is six
The cube of a triangular pyramid is respectively provided with the center of face.
2. the synthetic method of twin SAPO-34 molecular sieves described in claim 1, it is characterised in that the synthetic method includes：
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water, and phosphorus source is with P2O5
Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, the molar ratio of template and water are 0.6-
1.2:0.05-1.2:1:1.5-10:3-100, is preferably 0.8-1.2:0.1-1:1:1.5-5:5-50；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture for obtaining hydrothermal crystallizing carries out separation of solid and liquid, and obtained solid phase is dried and is optionally roasted；
Wherein, the template is pyrrolidines, N- crassitudes, 2- crassitudes, 3- crassitudes and 2,5- diformazan
At least one of base pyrrolidines.
3. the synthetic method of twin SAPO-34 molecular sieves described in claim 1, it is characterised in that the synthetic method includes：
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water, and phosphorus source is with P2O5Meter, source of aluminium with
Al2O3Meter, the molar ratio of phosphorus source, silicon source and water is 0.6-1.2:1:20-70, is preferably 0.8-1.2:1:20-60；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) raw mixture B is provided, the raw mixture B contain phosphorus aluminium dry glue made from step (2), silicon source, template and
Water, the phosphorus aluminium dry glue is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water are：
1:0.05-1.2:1.5-10:3-100, is preferably 1:0.1-1:1.5-5:5-50；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture for obtaining hydrothermal crystallizing carries out separation of solid and liquid, and obtained solid phase is dried and is optionally roasted；
Wherein, the template is pyrrolidines, N- crassitudes, 2- crassitudes, 3- crassitudes and 2,5- diformazan
At least one of base pyrrolidines.
4. the synthetic method according to Claims 2 or 3, wherein, the hydrothermal crystallizing includes first segment crystallization and second segment
Crystallization, for first segment crystallization when crystallization 10-70 is small at 100-180 DEG C, second segment crystallization crystallization 3-80 at 140-200 DEG C is small
When；
It is preferred that first segment crystallization is when crystallization 20-60 is small at 130-170 DEG C, second segment crystallization crystallization 4-60 at 150-195 DEG C
Hour；
More preferably first segment crystallization is when crystallization 30-45 is small at 140-160 DEG C, second segment crystallization crystallization 5- at 160-190 DEG C
50 it is small when.
5. the synthetic method according to Claims 2 or 3, wherein, phosphorus source be selected from orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate,
At least one of ammonium dihydrogen phosphate and organic phosphorus compound,
The organic phosphorus compound are preferably at least one of trimethyl phosphorus and triethyl phosphine.
6. the synthetic method according to Claims 2 or 3, wherein, source of aluminium is selected from aluminium salt, boehmite, isopropanol
At least one of aluminium, aluminum hydroxide solid elastomer and activated alumina,
The aluminium salt is preferably at least one of aluminium chloride and aluminum sulfate.
7. the synthetic method according to Claims 2 or 3, wherein, the silicon source is selected from Ludox, active silica, consolidates
At least one of silicon-containing compound and white carbon shown in body silica gel, Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl,
The silicon-containing compound is preferably ethyl orthosilicate.
8. synthetic method according to claim 3, wherein, in step (2) by mixed liquor A carry out aging under agitation into
OK, aging temperature is 50-80 DEG C, is preferably 60-70 DEG C, when ageing time is 6-20 small, when being preferably 10-18 small；Dry
Temperature is 80-120 DEG C, is preferably 80-100 DEG C, when the dry time is 12-36 small, when being preferably 20-30 small.
9. the synthetic method according to Claims 2 or 3, wherein, the temperature that obtained solid phase is dried is 80-120
DEG C, the temperature of the roasting is 400-700 DEG C.
10. a kind of method of methanol-to-olefins, this method are included under the conditions of methanol to olefins reaction, by methanol and claim
The 1 twin SAPO-34 molecular sieves or the twin obtained as the synthetic method described in any one in claim 2-9
SAPO-34 molecular sieves contact.
11. according to the method described in claim 10, wherein, the contact carries out at a temperature of 400-500 DEG C, the weight of methanol
Amount air speed is 1-9h-1。
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