CN114455605A - SFO structure molecular sieve and synthesis method and application thereof - Google Patents
SFO structure molecular sieve and synthesis method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 147
- 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 147
- 238000001308 synthesis method Methods 0.000 title claims abstract description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 108
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 claims abstract description 71
- 239000003292 glue Substances 0.000 claims abstract description 40
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000000614 phase inversion technique Methods 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005336 cracking Methods 0.000 claims abstract description 5
- 239000012188 paraffin wax Substances 0.000 claims abstract description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 61
- 238000002425 crystallisation Methods 0.000 claims description 58
- 230000008025 crystallization Effects 0.000 claims description 58
- 229910052593 corundum Inorganic materials 0.000 claims description 57
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 239000000499 gel Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007790 solid phase Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 235000011007 phosphoric acid Nutrition 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims 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 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 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
- 239000008096 xylene Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 239000001164 aluminium sulphate Substances 0.000 claims 1
- 235000011128 aluminium sulphate Nutrition 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 40
- 239000004810 polytetrafluoroethylene Substances 0.000 description 40
- 239000000523 sample Substances 0.000 description 39
- 239000000843 powder Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 18
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to the field of catalytic material synthesis, and discloses an SFO structure silicon-phosphorus-aluminum molecular sieve, a synthesis method and application thereofxAlyPz)O2Wherein, DMAP is template agent 4-dimethylamino pyridine, which is distributed in the pore canal of the molecular sieve; m is (Si) per molexAlyPz)O2Middle 4-dimethyl AmmoniaThe mole number of the pyridine, m is 0.1-0.2; x, y and z represent mole fractions of Si, Al and P respectively, and the ranges of x is 0.01-0.2, y is 0.4-0.6, z is 0.3-0.49, and x + y + z is 1. The molecular sieve is synthesized by adopting a phosphorus-aluminum dry glue solution phase inversion method, the template agent used for synthesis is 4-dimethylamino pyridine, HF is not introduced into a synthesis system, the production process is green and environment-friendly, and the synthesized molecular sieve has high crystallinity, regular appearance and stronger medium and strong acid centers. The synthesized SFO structure silicon-phosphorus-aluminum molecular sieve has potential catalytic application prospect in the processes of normal paraffin isomerization, dimethylbenzene isomerization, hydrotreatment/cracking and the like.
Description
Technical Field
The invention relates to the field of catalytic material synthesis, in particular to an SFO structure molecular sieve and a synthesis method and application thereof.
Background
The molecular sieve with the SFO structure is an important phosphorus-aluminum-based molecular sieve and is widely concerned and researched by researchers. The framework structure of the SFO structure molecular sieve belongs to a monoclinic system, the space group is C12/m1, and the unit cell parameter is
90.00 degrees alpha, 90.016 degrees beta, 90.00 degrees gamma, and a two-dimensional channel structure with interpenetrated twelve-membered and eight-membered rings along [001 ]]Twelve-membered ring pore size of 0.69X 0.71nm in the direction [ 010%]The aperture of the directional eight-membered ring is 0.39 multiplied by 0.31nm, and the directional eight-membered ring belongs to a large-pore molecular sieve. Due to the unique pore channel structure and the acidic characteristic, the catalyst has potential catalytic application prospect in the processes of normal paraffin isomerization, xylene isomerization, hydrotreating/cracking and the like.
In 2004, the literature (chemistry materials,2004(16): 2844-. The reaction system takes 4-N, N-dimethylaminopyridine (DMAP for short) as a template agent, pseudo-boehmite, orthophosphoric acid and hydrofluoric acid are added, and static crystallization is carried out for two days at 180 ℃ to synthesize inorganic microporous aluminum phosphate zeolite (Al)4(PO4)4F·C7N2H11·0.5H2And O. The synthesis of molecular sieves was studied in the literature (journal of oxygen atoms materials,2009,16(2):119-Inducing the generation of a precursor of a molecular sieve with an SFO structure (known as AlPO)45 and unknown molecular sieves such as BPC-1 and EMM-8) which can be converted into molecular sieves of SFO structure after high-temperature roasting. The document (Microporousanophorous materials,2008,112(1-3):357-367) adopts a microwave synthesis method to successfully synthesize the SFO structure silicon-phosphorus-aluminum molecular sieve. The reaction system respectively takes DMAP as a template agent and gas-phase silicon dioxide as silicon sources, and pseudo-boehmite, orthophosphoric acid and hydrofluoric acid are added. The synthesis process is carried out according to the ratio of xDMAP to 1.0Al2O3:0.9P2O5:0.1SiO2:0.5HF:50H2The molar ratio of O, wherein x is between 1.33 and 2.5. In 2010, the document (catalysis communications,2010,11(7): 638:642) adopts a microwave synthesis method and an impregnation method to synthesize the SFO structure cobalt-phosphorus-aluminum molecular sieve, and explores the catalytic performance of the SFO structure cobalt-phosphorus-aluminum molecular sieve in the epoxidation reaction of styrene. The molecular sieve synthesis respectively uses DMAP as a template agent and cobalt nitrate as a metal source, and pseudo-boehmite, orthophosphoric acid and hydrofluoric acid are added. The synthesis process is carried out according to 2.5DMAP (1-x) Al2O3:xCo2O3:1.0P2O5:0.5HF:50H2The molar ratio of O, wherein x is 0.1, 0.05 or 0.01.
In summary, the SFO structure molecular sieve is synthesized using 4-Dimethylaminopyridine (DMAP) as a template. At present, molecular sieves consisting of three different elements, namely phosphorus aluminum, silicon phosphorus aluminum and cobalt phosphorus aluminum, have been successfully synthesized. But the mineralizer HF is required to be added in the synthesis system. However, HF has strong corrosivity and toxicity, is not beneficial to the protection of ecological environment, and hinders the synthesis and catalytic application of the molecular sieve with the SFO structure.
Disclosure of Invention
The invention aims to overcome the problem that the synthesis and catalytic application of the SFO structure molecular sieve are hindered due to the fact that a mineralizer HF is required to be added in a synthesis system of the SFO structure molecular sieve in the prior art, and provides a novel SFO structure silicoaluminophosphate molecular sieve and a synthesis method thereof.
In order to achieve the above object, the present invention provides an SFO molecular sieve, wherein the anhydrous chemical composition of the SFO molecular sieve is mDMAP (Si)xAlyPz)O2Wherein, DMAP is template agent 4-dimethylamino pyridine, which is distributed in the pore canal of the molecular sieve; m is (Si) per molexAlyPz)O2The mole number of the 4-dimethylamino pyridine is 0.1-0.2; x, y and z represent mole fractions of Si, Al and P respectively, and the ranges of x is 0.01-0.2, y is 0.4-0.6, z is 0.3-0.49, and x + y + z is 1.
The second aspect of the invention provides a synthesis method of an SFO structure silicon-phosphorus-aluminum molecular sieve, wherein the SFO structure molecular sieve is a silicon-phosphorus-aluminum molecular sieve synthesized by adopting a phosphorus-aluminum dry glue solution phase inversion method, and a template agent used for synthesis is 4-dimethylaminopyridine.
Preferably, the synthesis method comprises the following steps:
(1) providing a mixture A, wherein the mixture A contains a phosphorus source, an aluminum source and water;
(2) aging the mixture A, and then drying to obtain the phosphorus-aluminum dry glue;
(3) providing an initial gel mixture B, wherein the initial gel mixture B contains the phosphorus-aluminum dry glue prepared in the step (2), a silicon source, a template agent and water;
(4) crystallizing the initial gel mixture B;
(5) carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase;
wherein the template agent is 4-dimethylaminopyridine.
Through the technical scheme of the invention:
(1) obtaining the molecular sieve with the SFO structure, wherein the anhydrous chemical composition of the molecular sieve with the SFO structure is mDMAP (Si)xAlyPz)O2The SFO structure silicon-phosphorus-aluminum molecular sieve does not contain fluorine elements, wherein DMAP is template agent 4-dimethylamino pyridine and is distributed in the pore channel of the molecular sieve; m is (Si) per molexAlyPz)O2Meso-4-dimethylaminopyridineM is 0.1-0.2; x, y and z represent mole fractions of Si, Al and P respectively, and the ranges of x is 0.01-0.2, y is 0.4-0.6, z is 0.3-0.49, and x + y + z is 1.
(2) The preparation method for synthesizing the SFO structure silicon-phosphorus-aluminum molecular sieve by using 4-dimethylaminopyridine as a template agent and adopting a phosphorus-aluminum dry glue solution phase inversion method is obtained. No mineralizer HF is added in the synthesis system, the production process is green and environment-friendly, and the industrial scale-up production is easy.
(3) The SFO structure silicon-phosphorus-aluminum molecular sieve synthesized by the method has the characteristics of high crystallinity and regular appearance.
(4) The SFO structure silicon-phosphorus-aluminum molecular sieve synthesized by the method has a medium-strong acid center and higher acid strength.
(5) The SFO structure silicon-phosphorus-aluminum molecular sieve synthesized by the method has potential catalytic application prospect in normal paraffin isomerization, xylene isomerization, hydrotreating/cracking and other processes.
Drawings
FIG. 1 is an XRD spectrum of a sample of the molecular sieve synthesized in example 1;
FIG. 2 is an SEM photograph of a sample of the molecular sieve synthesized in example 1;
FIG. 3 is NH of a sample of the molecular sieve synthesized in example 33-a TPD spectrum;
FIG. 4 shows a sample of the molecular sieve synthesized in example 329A SiMASNMR spectrum;
FIG. 5 is an SEM photograph of a sample of the molecular sieve synthesized in example 6;
FIG. 6 is an SEM photograph of a sample of the molecular sieve synthesized in example 8;
FIG. 7 is an SEM photograph of a sample of the molecular sieve synthesized in example 10;
FIG. 8 is an SEM photograph of a sample of the molecular sieve synthesized in example 12;
figure 9 is an XRD spectrum of a sample of the molecular sieve synthesized in comparative example 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Technical terms in the present invention are defined in the following, and terms not defined are understood in the ordinary sense in the art.
The templating agent in the present invention is also referred to in the art as a structure directing agent or an organic structure directing agent.
According to the invention, the molecular sieve with the SFO structure has an anhydrous chemical composition of mDMAP (Si)xAlyPz)O2The silicoaluminophosphate molecular sieve of (1). The SFO structure silicon-phosphorus-aluminum molecular sieve obtained by the synthesis method does not contain F element. Specifically, the SFO structure silicon-phosphorus-aluminum molecular sieve has anhydrous chemical composition of mDMAP (Si)xAlyPz)O2Wherein, DMAP is template agent 4-dimethylamino pyridine, which is distributed in the pore canal of the molecular sieve; m is (Si) per molexAlyPz)O2The mole number of the 4-dimethylamino pyridine is 0.1-0.2; x, y and z represent mole fractions of Si, Al and P respectively, and the ranges of x is 0.01-0.2, y is 0.4-0.6, z is 0.3-0.49, and x + y + z is 1.
The invention provides a silicon-phosphorus-aluminum molecular sieve with an SFO structure, which is a silicon-phosphorus-aluminum molecular sieve synthesized by adopting a phosphorus-aluminum dry glue solution phase inversion method, wherein a template agent used for synthesis is 4-dimethylaminopyridine.
Specifically, the synthesis method comprises the following steps:
(1) providing a mixture A, wherein the mixture A contains a phosphorus source, an aluminum source and water;
(2) aging the mixture A, and then drying to obtain the phosphorus-aluminum dry glue;
(3) providing an initial gel mixture B, wherein the initial gel mixture B contains the phosphorus-aluminum dry glue prepared in the step (2), a silicon source, a template agent and water;
(4) crystallizing the initial gel mixture B;
(5) and (3) carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase.
According to the above synthesis method of the present invention, the template agent is 4-dimethylaminopyridine.
Herein, "at least one" means one or two or more.
According to the invention, in the method for synthesizing the molecular sieve by adopting a phosphorus-aluminum dry glue solution phase inversion method, when the mixture A is prepared, the mixture A contains a phosphorus source, an aluminum source and water, and the phosphorus source is represented by P2O5The aluminum source is calculated as Al2O3The molar ratio of the phosphorus source to the aluminum source to the water is 0.6-1.2:1:30-70, preferably 0.8-1.2:1: 35-65. In preparing the mixture a, the water is the total amount of water, for example, including added water, and also including water in a phosphorus source and an aluminum source. In the preparation of the initial gel mixture B, the initial gel mixture B contains the phosphorus-aluminum dry glue prepared in the step (2), a silicon source, a template agent and water, and the phosphorus-aluminum dry glue is prepared from Al2O3The silicon source is SiO2The molar ratio of the phosphorus-aluminum dry glue to the silicon source to the template to the water is as follows: 1:0.1-1:1-10:10-200, preferably 1:0.3-0.8:2-5: 20-120. In preparing the initial gel mixture B, the water is the total amount of water, including, for example, the added water, as well as the amount of water in the phosphor-aluminum xerogel, the silicon source, and the templating agent.
According to the invention, in the synthesis of the molecular sieve by adopting a phosphorus-aluminum dry glue solution phase inversion method, the phosphorus-aluminum dry glue can be prepared by adopting a conventional method, and the phosphorus-aluminum dry glue, a silicon source, a template agent and water are mixed, so that the initial gel mixture B is obtained. Specifically, an aluminum source is mixed with water, then a phosphorus source is added with stirring to obtain a mixture A, the mixture A is aged with stirring, the aging temperature can be 50-80 ℃, preferably 60-70 ℃, the aging time can be 6-20 hours, preferably 10-18 hours, then the aged mixture A is dried, the drying temperature can be 80-110 ℃, preferably 80-100 ℃, and the drying time can be 15-35 hours, preferably 20-30 hours, and the phosphorus-aluminum dry glue is prepared. Preferably, the phosphorus aluminum dry glue, the silicon source, the water and the template agent are sequentially added and uniformly mixed, so as to obtain the initial gel mixture B.
In the present invention, the types of the phosphorus source, the silicon source, and the aluminum source are not particularly limited and may be selected conventionally.
Generally, the phosphorus source may be selected from at least one of orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and an organic phosphide.
Preferably, the organophosphate is at least one of trimethylphosphorus and triethylphosphorous.
The aluminum source may be at least one selected from the group consisting of aluminum salt, pseudoboehmite, aluminum isopropoxide, aluminum hydroxide dry gel and activated alumina.
Preferably, the aluminum salt is at least one of aluminum chloride and aluminum sulfate.
The silicon source can be at least one selected from silica sol, active silica, solid silica gel, silicon-containing compound shown in formula I and white carbon black,
in the formula I, R1、R2、R3And R4Each is C1-C4Such as methyl, ethyl, propyl and isomers thereof and butyl and isomers thereof.
Preferably, the silicon-containing compound is at least one of silica sol, active silica, solid silica gel, ethyl orthosilicate and white carbon black.
According to the invention, the crystallization process can be carried out at a single-stage temperature, and the crystallization is generally carried out under the autogenous pressure and at the temperature of 170-210 ℃ for 30-92 hours; preferably, the crystallization is carried out for 40-85 hours under the autogenous pressure and at the temperature of 170-200 ℃; more preferably, the crystallization is carried out under autogenous pressure at 190 ℃ for 50-81 hours.
According to the present invention, preferably, the crystallization process employs two-stage temperature-variable crystallization, that is, a first stage crystallization and a second stage crystallization, where the first stage crystallization temperature is lower than the second stage crystallization temperature, and the crystallization conditions of each stage are, independently: the first section of crystallization is carried out for 25 to 45 hours under the autogenous pressure and the temperature of 130-170 ℃, and the second section of crystallization is carried out for 30 to 55 hours under the autogenous pressure and the temperature of 170-200 ℃; preferably, the first-stage crystallization is performed at the autogenous pressure and the temperature of 135-165 ℃ for 25-40 hours, and the second-stage crystallization is performed at the autogenous pressure and the temperature of 170-195 ℃ for 35-50 hours; more preferably, the first-stage crystallization is performed at the autogenous pressure and the temperature of 140 ℃ and 160 ℃ for 30-40 hours, and the second-stage crystallization is performed at the autogenous pressure and the temperature of 175 ℃ and 190 ℃ for 40-50 hours.
According to the invention, the solid phase obtained by solid-liquid separation and washing of the crystallized product (mixture) can be dried and optionally calcined under conventional conditions to obtain the molecular sieve. In the present invention, "optional" means unnecessary, and may be understood as either included or excluded. Specifically, the drying may be performed at a temperature of 90 to 120 ℃, and the drying time may be selected according to the drying temperature, and may be generally 6 to 14 hours. The roasting aims to remove the template agent remained in the molecular sieve pore channel in the molecular sieve synthesis process, and whether the roasting is carried out can be determined according to specific use requirements. It is preferable to perform the calcination after the completion of the drying. The calcination may be carried out at a temperature of 400-700 ℃, and the duration of the calcination may be selected according to the calcination temperature, and may be generally 3 to 6 hours. The calcination is generally carried out in an air atmosphere. In addition, the solid phase obtained by solid-liquid separation is washed before drying, namely, the crystallized product obtained by hydrothermal crystallization is subjected to solid-liquid separation, washed to be neutral by deionized water and dried to obtain the molecular sieve raw powder; or, carrying out solid-liquid separation on a crystallization product obtained by hydrothermal crystallization, washing the crystallization product to be neutral by using deionized water, drying and roasting to obtain the roasted hydrogen type molecular sieve. The solid-liquid separation method can be carried out by a conventional method such as filtration, centrifugal separation, etc.
According to the invention, the temperature rising mode of any step in the SFO structure molecular sieve synthesis method is not particularly limited, and a temperature programming mode can be adopted, for example, 0.5-5 ℃/min.
According to the invention, the crystallization in the SFO structure molecular sieve synthesis method is carried out in a closed environment, and a reaction vessel for crystallization is a stainless steel reaction kettle with a polytetrafluoroethylene lining.
According to the invention, the invention provides the application of the molecular sieve with the SFO structure in normal paraffin isomerization, xylene isomerization and hydrotreating/cracking, and the molecular sieve has good application prospect.
The present invention will be described in detail below by way of examples.
In the following examples, X-ray powder diffraction phase analysis (XRD) was carried out using an Empyrean type diffractometer of the Parnake, the Netherlands, equipped with PIXcel3DA detector. And (3) testing conditions are as follows: cu target, Ka radiation, Ni filter, tube voltage 40kV, tube current 40mA, and scanning range 5-50 deg.
In the following examples, the analysis of the inorganic elemental composition (XRF) of a sample of a molecular sieve was determined using a Philips Magix type fluorescence spectrometer, and the analysis of the organic elemental Composition (CHN) of a molecular sieve was determined using an elementarivaroELCUBE type elemental analyzer.
In the following examples, scanning electron microscopy morphology analysis (SEM) was performed using a scanning electron microscope, type S4800 Hitachi, Japan. And (3) testing conditions are as follows: after the sample was dried and ground, it was stuck on a conductive gel. The accelerating voltage of the analysis electron microscope is 5.0kV, and the magnification is 20-800000 times.
In the following examples, NH3Temperature programmed desorption analysis (NH)3TPD) the determination of the total acid content was carried out using an instrument Micro-meriticAutochem II 2920. And (3) testing conditions are as follows: purging the sample with helium at high temperature to remove impurities, cooling to 100 ℃, and switching the gas path to NH3-He gas to adsorb ammonia gas (w (NH)3) 10.02%) and then continuing to purge the physisorbed ammonia molecules with helium. When the baseline is stable, the solution is desorbed at high temperature (600 ℃), and the TCD is adopted to detect NH3And (4) automatically obtaining the total acid amount by changing.
In the following examples of the present invention,29the testing instrument for SiMASNMR analysis was a Bruker AvananceIII model 500MHz nuclear magnetic resonance spectrometer. And (3) testing conditions are as follows: adopting a 7mm double resonance probe; the resonance frequency is 99.28 MHz; the sampling time is 17.3 ms; the delay time is 4 s; the pulse width is 2.1 mus; the sampling times are 5000 times; the rotation speed is 5000 Hz. In the following examples, DMAP is used as a template, and 4-dimethylaminopyridine is used as the template.
Examples 1-12 are presented to illustrate the synthesis of SFO structured silicoaluminophosphate molecular sieves of the present invention using the phase inversion of a dry liquid aluminophosphate gel.
Example 1
4.91 g of pseudo-boehmite (Al)2O383 percent of mass fraction) and 33.88 g of deionized water are stirred and mixed until uniform, and 8.76 g of orthophosphoric acid (H) is slowly added in a trickle manner under the stirring state3PO485% by mass), stirring thoroughly at 70 ℃ and aging for 12 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 80 ℃ for 24 hours to obtain the phosphorus-aluminum dry glue.
5.43 g of the dry aluminum phosphate gel (87.22% solids) are added to a polytetrafluoroethylene liner, and 0.65 g of solid silica gel (SiO)293% by mass), 13.60 g of deionized water, 7.40 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.95、SiO2/Al2O3＝0.5、DMAP/Al2O3＝3.0、H2O/Al2O3＝40。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 170 deg.C for 72 hr, cooling to room temperature, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and an XRD spectrogram is shown in figure 1, so that the molecular sieve is proved to be a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM picture is shown in figure 2 and is in a regular blocky appearance. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.16DMAP (Si)0.11Al0.47P0.43)O2。
Example 2
4.16 gActivated alumina (Al)2O398% by mass) and 33.32 g of deionized water were mixed with stirring until homogeneous, and 12.47 g of phosphorous acid (H) were slowly added in a trickle under stirring3 PO 350% by mass), stirring thoroughly at 70 ℃ and aging for 12 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 85 ℃ for 28 hours to obtain the phosphorus-aluminum dry adhesive.
5.68 g of the dry aluminum phosphate gel (83.34% solids) are added to a polytetrafluoroethylene liner, and 1.20 g of silica Sol (SiO)230 percent by mass), 5.36 g of deionized water, 6.17 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.95、SiO2/Al2O3＝0.3、DMAP/Al2O3＝2.5、H2O/Al2O3＝20。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 150 ℃ for 36 hours, heating to 180 ℃ again, and carrying out second-stage crystallization: crystallizing at 180 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.14DMAP (Si)0.07Al0.48P0.45)O2。
Example 3
5.44 g of aluminum hydroxide dry glue (Al)2O375 percent of mass fraction) and 29.68 g of deionized water are stirred and mixed until uniform, and the mixture is slowly added under the stirring state9.22 g of orthophosphoric acid (H) are added3PO485% by mass), stirring thoroughly at 60 ℃ and aging for 18 hours to give a mixture A. And pouring the mixture A into a tray, and drying at 110 ℃ for 15 hours to obtain the aluminum phosphate dry glue.
5.70 g of the prepared dry aluminum phosphate gel (85.55% solids) were added to a polytetrafluoroethylene liner, followed by 0.65 g of solid silica gel (SiO)293% by mass), 17.07 g of deionized water, 7.40 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.00、SiO2/Al2O3＝0.5、DMAP/Al2O3＝3、H2O/Al2O3＝50。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 180 deg.C for 60 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.17DMAP (Si)0.10Al0.46P0.44)O2. And subjecting the molecular sieve to acid analysis, NH thereof3The TPD results are shown in FIG. 3, and it can be seen that the molecular sieve has more weak acid centers and medium acid centers (desorption temperature of 310 ℃, namely 583K), and the acid strength is obviously enhanced compared with the medium acid centers (desorption temperature of 530K) reported in the literature (Microporous and Mesonous Materials,2008,112(1-3): 357-367). Bound to molecular sieves29Si MAS NMR spectrum, as shown in FIG. 4, the coordination form of silicon is mainlySi (4Al) at chemical shift-88 and Si (1Al) at chemical shift-110, and small amounts of Si (3Al), Si (2Al), etc. The molecular sieve silicon coordination reported in the literature (Microporous and Mesoporous Materials,2008,112(1-3):357-367) is mainly Si (1Al) at-108.3 and Si (2Al) at-105.6. The molecular sieve has more strong acid centers, and silicon atoms in a framework of the molecular sieve mainly exist in the form of four-coordinate silicon, namely Si (4 Al).
Example 4
4.91 g of pseudo-boehmite (Al)2O383 percent by mass) and 27.76 g of deionized water are stirred and mixed until uniform, and 11.32 g of ammonium hydrogen phosphate ((NH) is slowly added in a trickle manner under the stirring state4)2HPO498% by mass), and aging at 70 ℃ for 18 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 100 ℃ for 18 hours to obtain the phosphorus-aluminum dry glue.
6.02 g of the prepared phosphorus-aluminum dry glue (solid content 83.40%) were added to a polytetrafluoroethylene lining, and 0.8 g of silica Sol (SiO)230 percent by mass), 9.15 grams of deionized water, 9.87 grams of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.05、SiO2/Al2O3＝0.2、DMAP/Al2O3＝4.0、H2O/Al2O3＝30。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 170 ℃ for 26 hours, then heating to 190 ℃ to carry out second-stage crystallization: crystallizing at 190 deg.C for 40 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
Carrying out X-ray diffraction analysis on the obtained molecular sieve and adopting SEM to carry out shape analysis on the molecular sieveAnd (4) observing, wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve, and the sample is in a blocky shape. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.14DMAP (Si)0.04Al0.49P0.47)O2。
Example 5
4.16 activated alumina (Al)2O398 percent of mass fraction) and 45.30 g of deionized water are stirred and mixed until uniform, and 9.68 g of orthophosphoric acid (H) is slowly added under stirring3PO485% by mass), stirring thoroughly at 65 ℃ and aging for 18 hours to give a mixture A. And pouring the mixture A into a tray, and drying at 95 ℃ for 22 hours to obtain the aluminum phosphate dry glue.
6.11 g of the dry aluminum phosphate gel (82.11% solids) are added to a polytetrafluoroethylene liner, followed by 0.19 g of solid silica gel (SiO)293% by mass, 27.67 g of deionized water, 4.94 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.05、SiO2/Al2O3＝0.15、DMAP/Al2O3＝2.0、H2O/Al2O3＝80。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 175 deg.C for 75 hr, cooling to room temperature in high pressure kettle, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.14DMAP (Si)0.04Al0.50P0.46)O2。
Example 6
16.67 aluminum isopropoxide (C)9H21AlO398 percent of mass fraction) and 50.03 g of deionized water are stirred and mixed until uniform, and 7.44 g of ammonium dihydrogen phosphate (NH) is slowly added into the mixture in a trickle manner under the stirring state4H2PO499% by mass), stirring thoroughly at 50 ℃ and aging for 20 hours to give a mixture A. And pouring the mixture A into a tray, and drying at 105 ℃ for 20 hours to obtain the aluminum phosphate dry glue.
5.16 g of the prepared phosphorus-aluminum dry glue (solid content 83.45%) is added into a polytetrafluoroethylene lining, and 0.98 g of white carbon black (SiO)298% by mass), 35.08 g of deionized water, 7.4 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.8、SiO2/Al2O3＝0.8、DMAP/Al2O3＝3、H2O/Al2O3＝100。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 200 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and is proved to be a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM photo is shown in figure 5 and is in a regular blocky appearance. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.19DMAP (Si)0.13Al0.48P0.39)O2。
Example 7
10.78 g of aluminum chloride (AlCl)399% mass fractionStirred and mixed with 36.90 g of deionized water until uniform, and 12.47 g of phosphorous acid (H) was added slowly in a trickle under stirring3 PO 350% by mass), stirring thoroughly at 80 ℃ and aging for 8 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 110 ℃ for 15 hours to obtain the aluminum phosphate dry glue.
5.50 g of the prepared phosphorus-aluminum dry glue (solid content 86.15%) was added to a polytetrafluoroethylene lining, and 1.29 g of solid silica gel (SiO) was added in sequence293% by mass), 4.52 g of deionized water, 3.70 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.95、SiO2/Al2O3＝1.0、DMAP/Al2O3＝1.5、H2O/Al2O3＝15。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 160 ℃ for 32 hours, heating to 190 ℃, and carrying out second-stage crystallization: crystallizing at 180 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.11DMAP (Si)0.15Al0.49P0.36)O2。
Example 8
4.91 g of pseudo-boehmite (Al)2O383 percent of mass fraction) and 29.62 g of deionized water are stirred and mixed until uniform, and 11.15 g of phosphorous acid (H) is slowly added in the stirring state3PO3The mass fraction is 50 percent) Then, the mixture was stirred sufficiently at 70 ℃ and aged for 10 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 90 ℃ for 27 hours to obtain the phosphorus-aluminum dry glue.
5.16 g of the prepared dry aluminum phosphate glue (86.20% of solid content) is added into a polytetrafluoroethylene lining, and 0.25 g of active silicon dioxide (SiO) is added in turn295% by mass), 9.98 g of deionized water, 9.87 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.85、SiO2/Al2O3＝0.2、DMAP/Al2O3＝4.0、H2O/Al2O3＝30。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 145 ℃ for 35 hours, then heating to 185 ℃, and carrying out second-stage crystallization: crystallizing at 185 deg.C for 45 hr, cooling to room temperature, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and is proved to be a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM photo is shown in figure 6 and is in a regular blocky appearance. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.15DMAP (Si)0.05Al0.53P0.42)O2。
Example 9
16.67 aluminum isopropoxide (C)9H21AlO398 percent of mass fraction) and 23.50 g of deionized water are stirred and mixed until uniform, and 9.22 g of orthophosphoric acid (H) is slowly added in a trickle manner under the stirring state3PO485% by mass), stirring thoroughly at 65 ℃ and aging for 15 hours to obtain a mixture A. The mixture A was poured into a tray and dried at 85 ℃ for 26 hoursAnd preparing the phosphorus-aluminum dry glue.
6.01 g of the dry aluminum phosphate gel (81.11% solids) are added to a polytetrafluoroethylene liner, followed by 2.11 g of ethyl orthosilicate (C)8H20O499% of Si by mass), 31.22 g of deionized water, 4.94 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.0、SiO2/Al2O3＝0.5、DMAP/Al2O3＝2.0、H2O/Al2O3＝90。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 190 deg.C for 55 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.14DMAP (Si)0.11Al0.50P0.40)O2。
Example 10
4.91 g of pseudo-boehmite (Al)2O383 percent of mass fraction) and 44.97 g of deionized water are stirred and mixed until uniform, and 6.92 g of orthophosphoric acid (H) is slowly added in the stirring state3PO485% by mass), stirring thoroughly at 55 ℃ and aging for 20 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 90 ℃ for 24 hours to obtain the phosphorus-aluminum dry glue.
4.94 g of the prepared phosphorus-aluminum dry glue (solid content: 84.45%) is added into a polytetrafluoroethylene lining, and 0.74 g of white carbon black (SiO) is sequentially added298% by mass), 24.36 g of deionized water, 7.40 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.75、SiO2/Al2O3＝0.6、DMAP/Al2O3＝3、H2O/Al2O3＝70。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 155 ℃ for 38 hours, heating to 185 ℃, and performing second-stage crystallization: crystallizing at 185 deg.C for 45 hr, cooling to room temperature, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and is proved to be a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM photo is shown in figure 7 and is in a regular blocky appearance. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.17DMAP (Si)0.13Al0.51P0.36)O2。
Example 11
5.44 g of aluminum hydroxide dry glue (Al)2O375 percent by mass) and 38.01 g of deionized water are stirred and mixed until uniform, and 12.94 g of ammonium hydrogen phosphate ((NH) is slowly added in a trickle manner under the stirring state4)2HPO498% by mass), and aging at 75 ℃ for 10 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 105 ℃ for 20 hours to obtain the aluminum phosphate dry glue.
6.23 g of the dry aluminum phosphate gel (87.42% solids) are added to a polytetrafluoroethylene liner, followed by 0.52 g of solid silica gel (SiO)293% by mass), 17.11 g of deionized water, 8.64 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.2、SiO2/Al2O3＝0.4、DMAP/Al2O3＝3.5、H2O/Al2O3＝50。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 165 ℃ for 25 hours, heating to 190 ℃, and performing second-stage crystallization: crystallizing at 190 deg.C for 50 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve and the morphology of the sample is a blocky morphology. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.17DMAP (Si)0.09Al0.48P0.43)O2。
Example 12
16.67 aluminum isopropoxide (C)9H21AlO398 percent of mass fraction) and 28.40 g of deionized water are stirred and mixed until uniform, and 9.30 g of ammonium dihydrogen phosphate (NH) is slowly added into the mixture in a trickle way under the stirring state4H2PO499% by mass), stirring thoroughly at 70 ℃ and aging for 14 hours to give a mixture A. And pouring the mixture A into a tray, and drying at 80 ℃ for 32 hours to obtain the aluminum phosphate dry glue.
5.71 g of the prepared dry aluminum phosphate gel (85.35% solids) were added to a polytetrafluoroethylene liner, followed by 0.38 g of activated Silica (SiO)295% by mass), 15.23 g of deionized water, 12.34 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.0、SiO2/Al2O3＝0.3、DMAP/Al2O3＝5、H2O/Al2O3＝45。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing single-stage crystallization under the autogenous pressure: crystallizing at 170 deg.C for 80 hr, cooling to room temperature in high pressure kettle, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and is proved to be a pure-phase SFO structure silicon-phosphorus-aluminum molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM picture is shown in figure 8 and is in a regular blocky appearance. XRF and CHN elemental analysis is carried out on the obtained molecular sieve raw powder sample, and the chemical composition is 0.19DMAP (Si)0.07Al0.50P0.43)O2。
Comparative example 1
A molecular sieve was synthesized according to the procedure of example 1, except that the comparative example employed a hydrothermal synthesis.
2.46 g of pseudo-boehmite (Al)2O383% by mass), 13.22 g of deionized water, 4.38 g of orthophosphoric acid (H)3PO485% by mass), 0.65 g of solid silica gel (SiO)293% by mass), 7.4 g of 4-dimethylaminopyridine (C)7H10N299 percent of mass fraction) are sequentially added into the polytetrafluoroethylene lining and stirred uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.95、SiO2/Al2O3＝0.5、DMAP/Al2O3＝3.0、H2O/Al2O3＝40。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel high-pressure autoclave for sealing, putting the high-pressure autoclave into a rotating convection oven, setting the rotating speed to be 20r/min, and performing single-stage crystallization under autogenous pressure: crystallizing at 170 deg.C for 72 hr, cooling to room temperature, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The X-ray diffraction analysis of the obtained solid revealed that it was a mixed phase of a small amount of SFO structure and a large amount of hetero-crystalline phase, and the X-ray diffraction peak intensity was weak, as shown in fig. 9, and it was found that a pure-phase SFO-structure silicoaluminophosphate molecular sieve could not be synthesized without adding HF.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. The molecular sieve with the SFO structure is characterized in that the anhydrous chemical composition of the molecular sieve with the SFO structure, namely the silicoaluminophosphate molecular sieve is mDMAP (Si)xAlyPz)O2Wherein, DMAP is template agent 4-dimethylamino pyridine, which is distributed in the pore canal of the molecular sieve; m is (Si) per molexAlyPz)O2The mole number of the 4-dimethylamino pyridine is 0.1-0.2; x, y and z represent mole fractions of Si, Al and P respectively, and the ranges of x is 0.01-0.2, y is 0.4-0.6, z is 0.3-0.49, and x + y + z is 1.
2. The synthesis method of the SFO structure molecular sieve of claim 1, wherein the SFO structure molecular sieve is a silicon-phosphorus-aluminum molecular sieve synthesized by a phosphorus-aluminum dry glue solution phase inversion method, and a template agent used for the synthesis is 4-dimethylaminopyridine.
3. The method of synthesis of claim 2, wherein the method of synthesis comprises the steps of:
(1) providing a mixture A, wherein the mixture A contains a phosphorus source, an aluminum source and water;
(2) aging the mixture A, and then drying to obtain the phosphorus-aluminum dry glue;
(3) providing an initial gel mixture B, wherein the initial gel mixture B contains the phosphorus-aluminum dry glue prepared in the step (2), a silicon source, a template agent and water;
(4) crystallizing the initial gel mixture B;
(5) carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase;
wherein the template agent is 4-dimethylaminopyridine.
4. The synthetic method according to claim 3, wherein,
the phosphorus source is P2O5The aluminum source is calculated as Al2O3The molar ratio of the phosphorus source to the aluminum source to the water in the mixture A is 0.6-1.2:1:30-70, preferably 0.8-1.2:1: 35-65;
the phosphorus-aluminum dry glue is Al2O3The silicon source is SiO2The mol ratio of the phosphorus-aluminum dry glue, the silicon source, the template agent and the water in the initial gel mixture B is 1:0.1-1:1-10:10-200, preferably 1:0.3-0.8:2-5: 20-100.
5. The synthesis method according to claim 3 or 4, wherein the crystallization in step (4) is a two-stage crystallization process comprising a first stage crystallization and a second stage crystallization, and the first stage crystallization temperature is lower than the second stage crystallization temperature;
the first section of crystallization is carried out for 25 to 45 hours under the autogenous pressure and the temperature of 130-170 ℃, and the second section of crystallization is carried out for 30 to 55 hours under the autogenous pressure and the temperature of 170-200 ℃;
preferably, the first-stage crystallization is performed at the autogenous pressure and the temperature of 135-165 ℃ for 25-40 hours, and the second-stage crystallization is performed at the autogenous pressure and the temperature of 170-195 ℃ for 35-50 hours;
more preferably, the first-stage crystallization is performed at the autogenous pressure and the temperature of 140-160 ℃ for 30-40 hours, and the second-stage crystallization is performed at the autogenous pressure and the temperature of 175-190 ℃ for 40-50 hours.
6. The synthesis method according to claim 3 or 4, wherein the crystallization in step (4) is a single-stage crystallization process, and the crystallization is performed under autogenous pressure at 170 ℃ and 210 ℃ for 30-92 hours; preferably, the crystallization is carried out for 40-85 hours under the autogenous pressure and at the temperature of 170-200 ℃; more preferably, the crystallization is carried out under autogenous pressure at 190 ℃ for 50-81 hours.
7. The synthesis method according to claim 3 or 4, wherein the phosphorus source is selected from at least one of orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and an organic phosphide; the organic phosphide is preferably trimethyl phosphorus and/or triethyl phosphorus.
8. The synthesis method according to claim 3 or 4, wherein the aluminum source is selected from at least one of aluminum salt, pseudoboehmite, aluminum isopropoxide, aluminum hydroxide dry gel and activated alumina; the aluminium salt is preferably aluminium chloride and/or aluminium sulphate.
9. The synthesis method according to claim 3 or 4, wherein the silicon source is at least one selected from silica sol, active silica, solid silica gel, silicon-containing compound represented by formula I and white carbon black,
in the formula I, R1、R2、R3And R4Each is C1-C4Preferably, the silicon-containing compound is ethyl orthosilicate.
10. The synthesis process according to claim 3, wherein in step (2) mixture A is subjected to aging under stirring at a temperature of 50-80 ℃, preferably 60-70 ℃, for a time of 6-20 hours, preferably 10-18 hours; the drying temperature is 80-110 deg.C, preferably 80-100 deg.C, and the drying time is 15-35 hr, preferably 20-30 hr.
11. The synthesis method according to claim 3, wherein the temperature for drying the solid phase obtained in step (5) is 90-120 ℃ and the temperature for calcining is 400-700 ℃.
12. Use of the SFO structured molecular sieve according to claim 1 or obtained by the synthesis process according to any one of claims 2 to 11 for n-paraffin isomerisation, xylene isomerisation and hydrotreating/cracking.
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