WO2014047800A1 - 一种sapo-34分子筛的合成方法及由其制备的催化剂 - Google Patents
一种sapo-34分子筛的合成方法及由其制备的催化剂 Download PDFInfo
- Publication number
- WO2014047800A1 WO2014047800A1 PCT/CN2012/081992 CN2012081992W WO2014047800A1 WO 2014047800 A1 WO2014047800 A1 WO 2014047800A1 CN 2012081992 W CN2012081992 W CN 2012081992W WO 2014047800 A1 WO2014047800 A1 WO 2014047800A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- molecular sieve
- sapo
- crystallization
- diisopropylamine
- Prior art date
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- 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 43
- 238000000034 method Methods 0.000 title claims description 33
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 title claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical group CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940043279 diisopropylamine Drugs 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims abstract description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 carbon olefins Chemical class 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 8
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims abstract description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 37
- 230000008025 crystallization Effects 0.000 claims description 37
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- KKFGZKBFBZYLJH-UHFFFAOYSA-N N-ethyl-N-propan-2-ylpropan-2-amine hydrazine Chemical group C(C)(C)N(CC)C(C)C.NN KKFGZKBFBZYLJH-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002927 oxygen compounds Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 6
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 5
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 5
- 241000269350 Anura Species 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CPXNLEJOHUVOOS-UHFFFAOYSA-N OP(O)(O)=O.O.P Chemical compound OP(O)(O)=O.O.P CPXNLEJOHUVOOS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910001586 aluminite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- QVFWZNCVPCJQOP-UHFFFAOYSA-N chloralodol Chemical compound CC(O)(C)CC(C)OC(O)C(Cl)(Cl)Cl QVFWZNCVPCJQOP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KVAKUTBXRCXYLC-UHFFFAOYSA-N dodecane trimethylazanium chloride Chemical compound [Cl-].C[NH+](C)C.CCCCCCCCCCCC KVAKUTBXRCXYLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- 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
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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)
Definitions
- the present invention relates to a SAP0-34 molecular sieve synthesized by diisopropylamine as a host templating agent.
- the invention relates to a hydrothermal synthesis method for obtaining the SAP0-34 molecular sieve with high yield and high crystallinity.
- the invention further relates to the catalytic use of the above materials in the conversion of oxygenates to low carbon 'olefins. Background technique
- SAPO-34 is a chabazite-type (CHA) molecular sieve with an eight-membered ring ellipsoidal cage and a three-dimensional cross-cell structure formed by a double six-membered ring stacked in an ABC manner.
- the pore size is 0.38 ⁇ 0.38 nm, and the cage size is 1.0 ⁇ 0.67 nm.
- SAPO-34 belongs to small pore molecular sieve. Its spatial symmetry group is R3m, which belongs to the trigonal system (J. Phys. Chem., 1990, 94: 2730).
- SAPO-34 is composed of four elements of Si, Al, P and O, and its composition can be varied within a certain range, generally n(Si) ⁇ n(P;) ⁇ n(;A.
- SAPO-34 molecular sieves are generally hydrothermally synthesized using water as a solvent in a closed autoclave.
- the synthetic components include an aluminum source, a silicon source, a phosphorus source, a structure directing agent, and deionized water.
- silicon source with silica sol, active silica and orthosilicate, aluminum source with activated alumina, pseudoboehmite and alkoxy aluminum.
- the ideal source of silicon and aluminum is silica sol and pseudo-thin water.
- Aluminite; Phosphorus source generally uses 85% phosphoric acid.
- the choice of structure-directing agent will have some influence on the microstructure, element composition and morphology of the synthetic molecular sieve, and then affect its catalytic performance.
- Cisoka Patent CN1131845C discloses a method for synthesizing SAPO-34 molecular sieves using a multi-template agent containing diisopropylamine.
- a method for synthesizing SAPO molecular sieves by dry synthesis using a solid precursor is reported in the international patent WO 03/040037 A1, the structure directing agent of which covers diisopropylamine, but the product is vaguely expressed as comprising one of SAPO-34 molecular sieves.
- Series of SAPO molecular sieves It is worth noting that although the range of templating agents in the above literature reports include diisopropylamine, this has not been done in the examples. Moreover, the schemes in these patents have been confirmed by experiments, and all have defects such as low product yield and poor crystallinity. Summary of the invention
- the present invention provides a SAP0-34 molecular sieve synthesized by diisopropylamine as a host templating agent.
- An object of the present invention is to provide a hydrothermal synthesis method for obtaining the SAPO-34 molecular sieve with high yield and high crystallinity.
- the present invention adopts diisopropylamine as a main template, and after low temperature aging treatment, with the aid of a crystallization accelerator, a high yield of a conventional silicon-aluminum source using a synthetic SAPO molecular sieve is obtained.
- SAPO-34 molecular sieve is obtained.
- the present invention provides a SAPO-34 molecular sieve characterized in that the chemical composition is - m - nT - (Si x Al y P z ) 0 2
- R is diisopropylamine distributed in the molecular sieve cage and in the pores; m is per mole
- the X-ray diffraction pattern has diffraction peaks at the following positions: No. 2 ⁇
- the present invention reports a synthetic method for obtaining high crystallinity SAPO-34 molecular sieve in high yield, which is characterized in that the preparation process is as follows:
- Si0 2 /Al 2 0 3 0.05-1.5;
- step b) aging the initial gel mixture obtained in step a) at 20 ⁇ 60 ° C, the aging time is 0.5 to 12 hours;
- step b) The gel mixture after the step b) is charged into a synthesis kettle, sealed, heated to 150-220 ° C and crystallized under autogenous pressure for 0.5 to 72 h;
- SDA is a mixture of diisopropylamine or diisopropylamine and other organic amine/ammonium T; T is preferably triethylamine, morpholine, diethylamine, di-n-propylamine, hydrazine, hydrazine-diisopropylethylamine, A mixture of one or both of sec-butylamine, tert-butylamine, isobutylamine or tetraethylammonium hydroxide.
- the SDA in the step a) is a mixture of diisopropylamine and other organic amine/ammonium T
- the molar ratio of diisopropylamine to T is not less than 2.
- the silicon source used in the step a) is a mixture of silicon sol, active silica, orthosilicate, metakaolin or a mixture of any of the following; aluminum source is aluminum salt, activated alumina, alkoxy a mixture of one or any of aluminum, metakaolin; the phosphorus source is one or a mixture of any of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide or phosphorus oxide.
- the crystallization promoter CGP is an alkyl ammonium halide; preferably dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, octadecyl Trimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide Any one or a mixture of any of several.
- the molar ratio of H 2 0/A1 2 0 3 in the initial gel mixture in the step a) is preferably in the range of from 26 to 120, and further preferably in the range of from 31 to 100.
- the step a) the molar ratio of SDA/A1 2 0 3 in the initial gel mixture preferably ranges from 1.2 to 5.0.
- the step a) the molar ratio of CGP/A1 2 0 3 in the initial gel mixture preferably ranges from 0.001 to 0.03.
- the aging conditions in the step b) are as follows: the aging temperature is 40 to 60 ° C, and the aging time is 2 to 8 h.
- the crystallization is preferably carried out in the step c): the crystallization temperature is 170 to 210 ° C, and the crystallization time is 1 to 60 h; further preferred conditions are: the crystallization temperature is 180 to 210 ° C, and the crystallization time is 1 to 24 h.
- the preferred conditions for one step are as follows: the crystallization temperature is 190 to 210 ° C, and the crystallization time is 1 to 12 h.
- step c) The crystallization process in step c) can be carried out either statically or dynamically.
- the synthesized SAPO-34 molecular sieve can be used as a catalyst for acid-catalyzed reaction after being calcined in air at 400 to 700 °C.
- the synthesized SAPO-34 molecular sieve can be used as a catalyst for the conversion of an olefin to an olefin reaction after being calcined in air at 400 to 700 °C.
- the present invention emphasizes that the synthetic gel is subjected to a low temperature aging treatment before hydrothermal crystallization, and the purpose of this step is to increase the yield of the synthetic product.
- the present invention emphasizes the addition of a small amount of a crystallization promoter to the synthesis system.
- the main function of the addition of the crystallization promoter is to increase the crystallinity of the synthetic product.
- SAPO-34 molecular sieve was obtained in a high yield by low temperature aging treatment.
- SAPO-34 has a very excellent methanol-to-olefin catalytic reaction performance.
- DIPA Diisopropylamine
- triethylamine abbreviated as TEA
- morpholine abbreviated as MOR
- diethylamine abbreviated as DEA
- di-n-propylamine abbreviated as DPA
- hydrazine hydrazine-diisopropylethylamine
- DIEA diisopropylethylamine
- sec-butylamine abbreviated as SBA
- tert-butylamine abbreviated as hydrazine
- isobutylamine abbreviated as hydrazine
- tetraethylammonium hydroxide abbreviated as hydrazine
- dodecyltrimethylammonium bromide referred to as DTAB
- tetradecyltrimethylammonium bromide abbreviated as hydrazine
- cetyltrimethylammonium bromide abbreviated as
- Example 1 The amount of ingredients and crystallization conditions are shown in Table 1.
- the specific batching process is as follows. 14.06 g of pseudo-boehmite (A1 2 0 3 mass percent 72.5%) and 90 g of deionized water are mixed and mixed, and then 23.0 g of phosphoric acid (H 3 P0 4 mass percent 85%) Add dropwise, stir well, then add 6.4g silica sol (Si ⁇ 2 mass% 30%) and 1.09g cetyltrimethylammonium bromide as crystallization accelerator, and finally 30.4g diiso Propylamine (DIPA, 99% by mass) was added to the mixture and aged for 2 h at 25 ° C in a constant temperature water bath.
- DIPA diiso Propylamine
- the molar ratio of each component of the synthesis system was 3.0 DIPA: 0.30 SiO 2 : 1 Al 2 O 3 : 1P 2 O 5 : 0.03 CTAB: 50H 2 O.
- the synthesis kettle was heated to 200 Q C for 24 h. After the completion of the crystallization, the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain 27.6 g of the original powder. The sample was subjected to XRD analysis, and the results showed that the synthesized product had the characteristics of SAPO-34 structure, and the XRD data are shown in Table 2.
- Example 1 The solid yield was 90.5% (calculation method: product dry basis mass / total amount of feed oxide base ⁇ 100%).
- Example 1 The obtained sample was measured by a nitrogen physical adsorption experiment to have a BET specific surface area of 700 m 2 /go.
- the specific proportion of ingredients and crystallization conditions are shown in Table 1.
- the specific batching process is the same as in Example 1. Only the organic amine is changed to a mixture of DIPA and TEA, and the crystallization accelerator is replaced by a mixture of CTAB and CTAC and DTAB.
- the XRD analysis of the synthesized samples showed that the XRD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks fluctuated within ⁇ 10%, indicating that the synthesized products have the characteristics of SAPO-34 structure.
- Example 22 The synthesis was carried out under static conditions, and other conditions were the same as in Example 1.
- the XRD analysis of the synthesized samples showed that the XRD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks fluctuated within ⁇ 10%, indicating that the synthesized products have the characteristics of SAPO-34 structure.
- Example 22 The XRD analysis of the synthesized samples showed that the XRD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks fluctuated within ⁇ 10%, indicating that the synthesized products have the characteristics of SAPO-34 structure.
- the crystallization accelerator was changed to a mixture of CTAB (0.0015 mol) and OTAB (0.0015 mol), and the other conditions were the same as in Example 1.
- the XD analysis of the synthesized samples showed that the XRD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks fluctuated within ⁇ 10%, indicating that the synthesized products have the characteristics of SAPO-34 structure.
- the crystallization accelerator was changed to a mixture of CTAB (0.01 mol), DTAB (0.001 mol) and ⁇ ( ⁇ . ⁇ ), and the other conditions were the same as in Example 1.
- the XRD analysis of the synthesized samples showed that the XD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks fluctuated within ⁇ 10%, indicating that the synthesized products have the characteristics of SAPO-34 structure. Comparative Example 1 (no crystallization accelerator added)
- Example 1 The specific proportion of ingredients, the batching process and the crystallization conditions were the same as in Example 1. No CTAB was added to the synthetic gel. The synthetic sample weighed 25.4 g. The XRD analysis of the sample showed that the XRD results of the product were close to those of Table 2, that is, the peak position and peak shape were the same, indicating that the synthesized product has the CHA structure. The relative crystallinity of the sample was 70% as compared with the sample of Example 1 (the crystallinity of the sample of Example 1 was defined as 100%).
- Relative crystallinity (Ii +1 2 + + + ⁇ 3 ') ( ⁇ ⁇ 1 2 and 1 3 are the strongest three diffraction peak heights in the XRD spectrum of the sample of Comparative Example 1, 1 , 1 2 ' and 1 3 ' are the XRD spectra of the sample of Example 1 The strongest three diffraction peaks are high.)
- Comparative Example 1 The sample obtained in Comparative Example 1 was measured by a nitrogen physical adsorption test to have a BET specific surface area of 460 m 2 /g, which was significantly lower than that of the sample of Example 1. Comparative Example 2 (no low temperature aging process)
- the specific batch ratio, batching process and crystallization conditions were the same as in Example 1, but the low temperature aging process was omitted.
- the synthetic sample weighed 20.0 g.
- the XRD analysis of the sample showed that the XRD results of the product were close to those of Table 2, that is, the peak position and the peak shape were the same, indicating that the synthesized product had the characteristics of SAPO-34 structure.
- the relative crystallinity of the sample was 90% as compared with the sample of Example 1 (the crystallinity of the sample of Example 1 was defined as 100%).
- Example 1 The sample obtained in Example 1 was calcined at 600 ° C for 4 hours, and then tableted and crushed to 20 to 40 mesh.
- the l.Og sample was weighed into a fixed bed reactor for MTO reaction evaluation. The reaction was carried out by a nitrogen gas activation at 55 CTC for 1 hour, followed by cooling to 45 CTC. The methanol was carried by nitrogen, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity was 2.0 h.
- the reaction product was analyzed by on-line gas chromatography (Varian 3800, FID detector, capillary column PoraPLOT Q-HT). The results are shown in Table 3. Table 3 sample methanol conversion to olefin' hydrocarbon reaction results
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Abstract
本发明公开了一种SAPO-34分子筛,其特征在于,化学组成为:mR.nT.(SixAlyPz)O2。其中,R为二异丙胺,分布于分子筛笼及孔道中;m为每摩尔(SixAlyPz)O2中二异丙胺模板剂的摩尔数,m=0.01〜0.3;T为三乙胺、吗啉、二乙胺、二正丙胺、Ν,Ν-二异丙基乙胺、仲丁胺、叔丁胺、异丁胺或四乙基氢氧化铵中的一种或任意两者的混合物,分布于分子筛笼及孔道中,n为每摩尔(SixAlyPz)O2中T的摩尔数,n=0.01-0.10;m/n>2;x、y、z分别表示Si、Al、P的摩尔分数,其范围分别是x=0.01~0.30,y=0.01-0.60,z=0.01~0.52,且x+y+z=1。本发明涉及高收率、高结晶度获取该SAPO-34分子筛的合成制备方法。本发明还涉及该SAPO-34分子筛在含氧化合物转化制低碳烯烃反应中的催化应用。
Description
一种 SAPO-34分子筛的合成方法及由其制备的催化剂 技术领域
本发明涉及一种二异丙胺作为主体模板剂合成的 SAP0-34分子筛。 本发明涉及高收率、 高结晶度获取该 SAP0-34 分子筛的水热合成方 法。
本发明还涉及上述材料在含氧化合物转化制低碳 '烯烃反应中的催化 应用。 背景技术
自从 1982年, 美国联碳公司申请的专利 US 4310440中, 成功的合成 出一系列的磷酸铝分子筛及其衍生物以来,磷酸铝分子筛及其杂原子取代 衍生物一直是材料界和催化领域的研究热点之一。 其中, 具有 CHA拓扑 结构的硅磷铝分子筛 SAPO-34, 由于其适宜的孔道结构和酸性质,在甲醇 制'烯烃(MTO)反应中呈现出优异的催化性能(Applied Catalysis, 1988, 40: 316)。
SAPO-34是菱沸石型 (CHA)分子筛, 具有由双六元环按照 ABC方 式堆积而成的八元环椭球形笼和三维交叉孔道结构,孔径为 0.38x0.38nm, 笼大小 1.0x0.67nm, 属于小孔分子筛。 其空间对称群为 R3m, 属三方晶 系 (J. Phys. Chem., 1990, 94: 2730)。 SAPO-34由 Si、 Al、 P和 O四种元素 构成, 其组成可在一定范围内变化, 一般 n(Si)<n(P;)<n(;A 。
SAPO-34分子筛一般采用水热合成法, 以水为溶剂,在密闭高压釜内 进行。 合成组分包括铝源、 硅源、 磷源、 结构导向剂和去离子水。 可选作 硅源的有硅溶胶、活性二氧化硅和正硅酸酯, 铝源有活性氧化铝、拟薄水 铝石和烷氧基铝, 理想的硅源与铝源是硅溶胶和拟薄水铝石; 磷源一般采 用 85%的磷酸。结构导向剂的选择对于合成分子筛的微结构、元素组成和 形貌会产生一定影响, 并进而影响其催化性能。 美国专利 US 4310440 和 US 4440871中报道了多种 SAPO分子筛的制备, 其公布的合成 SAPO-34 的模板剂四乙基氢氧化铵、异丙胺、 以及四乙基氢氧化铵及二正丙胺的混
合物。中国专利 ZL93112230公开了以三乙胺为模板剂合成 SAPO-34的方 法, 该模板剂价格低廉, 可以降低 SAPO-34的合成成本。 此后, 中国专 利 ZL93112015和 ZL94110059又分别公开了以二乙胺为模板剂或以三乙 胺和二乙胺双模板剂合成 SAPO-34的方法, 进一步降低了合成成本。
中国专利 CN1131845C 公布了一种含二异丙胺的多模板剂合成 SAPO-34分子筛的方法。国际专利 WO 03/040037A1中报道了一种利用固 体前驱体通过干法合成 SAPO分子筛的方法,其结构导向剂范围涵盖了二 异丙胺,但是其产品模糊的表述为包含为 SAPO-34分子筛的一系列 SAPO 分子筛。 值得注意的是, 以上文献报道中模板剂范围虽然都包括二异丙 胺, 但在实施例中都未这样做。 而且这些专利中的方案, 经过实验证实, 均存在产品收率低、 结晶度差等缺陷。 发明内容
本发明提供一种二异丙胺作为主体模板剂合成的 SAP0-34分子筛。 本发明的目的在于提供一种高收率、 高结晶度获取该 SAPO-34分子 筛的水热合成方法。
为实现上述目的, 本发明采用有二异丙胺作为主体模板剂,经过低温 老化处理,在结晶促进剂的辅助下,采用合成 SAPO分子筛的常规硅铝源 高收率的获取了结晶度较高的 SAPO-34分子筛。
本发明提供了一种 SAPO-34分子筛, 其特征在于,化学组成为- m -nT- (SixAlyPz)02
其中, R为二异丙胺, 分布于分子筛笼及孔道中; m为每摩尔
(SixAlyPz)〇2中二异丙胺模板剂的摩尔数, m=0.01〜0.3 ; T为三乙胺、 吗啉、 二乙胺、 二正丙胺、 Ν,Ν-二异丙基乙胺、 仲丁胺、 叔丁胺、 异 丁胺或四乙基氢氧化铵中的一种或任意两者的混合物, 分布于分子筛 笼及孔道中, η为每摩尔 (SixAlyPz)02中 Τ的摩尔数, n=0.01~0.10; m/n>2;
x、 y、 z分别表示 Si、 Al、 P的摩尔分数, 其范围分别是 x=0.01~0.30, y=0.01〜0.60, z=0.01~0.52, 且 x+y+z=l。
根据本发明 SAPO-34分子筛的一个优选实施方案, X射线衍射图谱在 以下位置具有衍射峰:
No. 2Θ
1 9.5177
2 12.7987
3 14.1388
4 15.9829
5 18.1242
6 20.5413
7 22.278
8 23.0981
9 25.3853
10 25.7835
11 27.5448
12 28.5382
13 29.5454
14 30.4947
15 31.3812
16 34.3501
17 36.4789
18 39.6546
19 43.4168
20 47.4822
21 49.1405
22 50.4542
23 51.1735
24 53.0514
25 53.9912
26 54.7895
27 55.7846
28 56.4017
29 59.6235
30 60.8263 本发明报道一种高收率获取高结晶度 SAPO-34 分子筛的合成方法, 该方法的特点在于制备过程如下:
a) 将硅源、 铝源、 磷源、 结晶促进剂 (CGP)、 去离子水和结构导向 剂 (SDA) 混合, 形成具有如下摩尔配比的初始凝胶混合物:
Si02/Al203 =0.05-1.5;
Ρ2Ο5/Α12Ο3 = 0.5~1.5;
H20/A1203= 16- 150;
SDA/Al2O3 = 0.5〜5.9;
CGP/ A1203 = 0.001-0.05;
b) 将步骤 a)所得初始凝胶混合物在 20^60 °C下进行老化处理, 老化 时间为 0.5〜12小时;
c) 将步骤 b ) 处理后的凝胶混合物装入合成釜, 密闭, 升温到 150-220 °C在自生压力下晶化 0.5~72h;
d) 待晶化完全后, 固体产物经离心分离, 用去离子水洗搽至中性, 干燥后即得到 SAPO-34分子筛。
其中, SDA为二异丙胺或二异丙胺与其他有机胺 /铵 T的混合物; T 优选为三乙胺、 吗啉、 二乙胺、 二正丙胺、 Ν,Ν-二异丙基乙胺、 仲丁胺、 叔丁胺、 异丁胺或四乙基氢氧化铵中的一种或任意两者的混合。
所述步骤 a) 中的 SDA为二异丙胺与其他有机胺 /铵 T的混合物时, 二异丙胺与 T的摩尔比不小于 2。
所述步骤 a) 中所用的硅源为硅溶胶、 活性二氧化硅、 正硅酸酯、 偏 高岭土中的一种或任意几种的混合物; 铝源为铝盐、活性氧化铝、烷氧基 铝、 偏高岭土中的一种或任意几种的混合物; 磷源为正磷酸、 磷酸氢铵、 磷酸二氢铵、 有机磷化物或磷氧化物中的一种或任意几种的混合物。
所述结晶促进剂 CGP为烷基卤化铵; 优选十二烷基三甲基氯化铵、 十四烷基三甲基氯化铵、十六烷基三甲基氯化铵、十八烷基三甲基氯化铵、 十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、 十八烷基三甲基溴化铵中的任意一种或任意几种的混合物。
所述步骤 a ) 初始凝胶混合物中 H20/A1203的摩尔比优选范围为 26-120, 进一步的优选范围为 31-100。
所述步骤 a ) 初始凝胶混合物中 SDA/A1203的摩尔比优选范围为 1.2-5.0。
所述步骤 a) 初始凝胶混合物中 CGP/A1203的摩尔比优选范围为 0.001-0.03。
步骤 b)中的老化优选条件为:老化温度为 40〜60°C,老化时间为 2〜8h。 步骤 c)中的晶化优选条件为:晶化温度 170~210°C,晶化时间 1 ~ 60h; 进一步的优选条件为: 晶化温度为 180〜210°C, 晶化时间为 l ~ 24h; 再进
一步的优选条件为: 晶化温度为 190〜210°C, 晶化时间为 l ~ 12h。
步骤 c )中的晶化过程可以在静态进行, 也可以在动态进行。
合成的 SAPO-34分子筛经 400 ~ 700°C空气中焙烧后, 可用做酸催化 反应的催化剂。
合成的 SAPO-34分子筛经 400 ~ 700°C空气中焙烧后, 可用做含氧化 合物转化制'烯烃反应的催化剂。
本发明强调水热晶化前, 将合成凝胶进行低温老化处理, 该步骤的目 的是提高合成产品的收率。
本发明强调在合成体系中加入少量结晶促进剂,加入结晶促进剂的主 要作用是提高合成产品的结晶度。
本发明能产生的有益效果包括:
( 1 ) 以二异丙胺为主体结构导向剂, 通过低温老化处理, 高收率的获 得了 SAPO-34分子筛。
(2) 通过向体系中添加结晶促进剂, SAPO-34的结晶度明显提高。
(3 ) 通过本发明得到 SAPO-34具有非常优异的甲醇转化制 '烯烃催化 反应性能。 具体实施方式
下面通过实施例详述本发明, 但本发明并不局限于这些实施例。
实施例中, 下列物质采用英文縮写简称:
二异丙胺, 简称为 DIPA; 三乙胺,简称为 TEA; 吗啉, 简称为 MOR; 二乙胺, 简称为 DEA; 二正丙胺, 简称为 DPA; Ν,Ν-二异丙基乙胺, 简 称为 DIEA; 仲丁胺, 简称为 SBA; 叔丁胺, 简称为 ΤΒΑ; 异丁胺, 简称 为 ΙΡΑ; 四乙基氢氧化铵, 简称为 ΤΕΑΟΗ; 十二烷基三甲基溴化铵, 简 称为 DTAB; 十四烷基三甲基溴化铵, 简称为 ΤΤΑΒ; 十六烷基三甲基溴 化铵, 简称为 CTAB; 十八烷基三甲基溴化铵, 简称为 ΟΤΑΒ; 十二烷基 三甲基氯化铵, 简称为 DTAC; 十四烷基三甲基氯化铵, 简称为 TTAC; 十六烷基三甲基氯化铵, 简称为 CTAC; 十八烷基三甲基氯化铵, 简称为 OTAC。
实施例 1
配料用量和晶化条件见表 1。具体配料过程如下, 将 14.06g拟薄水铝 石(A1203质量百分含量 72.5%)和 90g去离子水混合搅匀, 然后将 23.0g 磷酸 (H3P04质量百分含量 85%) 滴加进入, 搅拌均匀, 然后加入 6.4g 硅溶胶(Si〇2质量百分含量 30%)和 1.09g作为结晶促进剂的十六烷基三 甲基溴化铵, 最后将 30.4g 二异丙胺 (简称 DIPA, 质量百分含量 99%) 加入该混合物中, 并在 25 °C恒温水浴搅拌状态下老化 2h。 老化结束后, 将凝胶转移到不锈钢反应釜中。 合成体系各组分的摩尔配比为 3.0DIPA: 0.30SiO2:lAl2O3:lP2O5:0.03CTAB:50H2O。
将合成釜升温到 200QC动态下晶化 24h。 晶化结束后, 将固体产物离 心, 洗涤, 在 100°C空气中烘干后, 得原粉 27.6g。 样品做 XRD分析, 结 果表明合成产物具有 SAPO-34结构的特征, XRD数据见表 2。
实施例 1固体收率为 90.5% (计算方法:产品干基质量 /投料氧化物干 基总量 χ100% )。
实施例 1 所得样品利用氮气物理吸附实验测得其 BET 比表面积为 700m2/g o
表 1 分子筛合成配料及晶化条件表 *
04mol 土 i O. l Omol 0.15mol ol 0.001
DEAO.O mol mol
lmol
DIPAO. Y氧 正磷酸 硅溶胶 8.3 TTAB 20°C 3h 200°C 24h 87.6
12mol 化铝 O. l Omol 0.12mol mol 0.005
TEA 0.1 mol
0. lmol mol
DIPAO. 硫 酸 正磷酸 活性二 2.6 CTAC 20°C 8h 190°C 12h 86.2
5mol 铝 0.05mol 氧化硅 mol 0.002
0.1 mol
DEAO. l 0.03mol mol
mol
TEAO. l
mol
DIPAO. 氯化 正磷酸 正硅酸 12m DTACO 20°C 8h 200°C 24h 90.3
3mol 铝 i 0.12mol 乙酯 ol 0.003
DEAO.O mol 0.08mol mol
5mol
IPA0.1
mol
DIPAO. 拟薄 正磷酸 硅溶胶 3.1 OTAC 30°C 3h 200°C 24h 90.1
033mol 水铝 0.09mol 0.03mol mol 0.004
DEAO.O 石 0.1 mol
17mol mol
DIPAO. 偏尚 正磷酸 硅溶胶 10m TTAC 30°C 4h 200°C 24h 89.5
08mol 岭土 0.15mol 0.05mol ol 0.002
DEAO.O 0.1 mol
4mol mol
DIPAO. 拟薄 磷酸氢 硅溶胶 6.6 OTAC 30°C 2.5h 220°C 0.5h 86.2
26mol 水铝 胺 0.06mol mol 0.001
TEAO. l 石 0.1 O. l Omol mol
3mol mol
DIPAO. 拟薄 磷酸氢 偏高岭 5.2 CTAC 60°C 2h 200°C 24h 90.2
2mol 水铝 二胺 土 mol 0.0009
MORO.1 石 0.1 O. l Omol 0.06mol mol
mol mol
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DIPAO. 拟薄 正磷酸 硅溶胶 5.0 CTAB 25°C 2h 200°C 24h 90.8
25mol 水铝 O. l Omol 0.03mol mol 0.001m
TEAO.O 石 ι ol+CTA
5mol mol CO.001
mol+D
TABO.O
01 mol
H十算方法: 产品干基质量 /投料氧化物干基总量 χ 100 %。 表 2实施例 1样品的 XRD结果
1 9.5177 9.29267 100
2 12.7987 6.91689 19.92
3 14.1388 6.26416 13.11
4 15.9829 5.5453 50.04
5 18.1242 4.89469 22.4
6 20.5413 4.32386 84.84
7 22.278 3.99057 6.09
8 23.0981 3.85071 4.97
9 25.3853 3.50871 23.15
10 25.7835 3.45542 18.75
11 27.5448 3.23834 3.71
12 28.5382 3.12783 2.09
13 29.5454 3.02346 5.07
14 30.4947 2.93147 25.16
15 31.3812 2.85065 18.51
16 34.3501 2.61076 6.33
17 36.4789 2.46314 2.67
18 39.6546 2.2729 3.18
19 43.4168 2.08427 5.1
20 47.4822 1.91487 2.79
21 49.1405 1.85407 5.48
22 50.4542 1.80883 3.22
23 51.1735 1.78508 3.43
24 53.0514 1.72624 2.25
25 53.9912 1.69839 1.01
26 54.7895 1.67552 1.62
27 55.7846 1.64797 2.24
28 56.4017 1.63139 1.57
29 59.6235 1.55071 0.97
30 60.8263 1.52163 1.28
实施例 2-17
具体配料比例和晶化条件见表 1, 具体配料过程同实施例 1。
合成样品做 XRD分析,数据结果与表 2接近, 即峰位置和形状相同, 依合成条件的变化峰相对峰强度在 ±10%范围内波动, 表明合成产物具有
SAPO-34结构的特征。 实施例 18
具体配料比例和晶化条件见表 1, 具体配料过程同实施例 1。 只将有 机胺变为 DIPA和 IPA的混合物,结晶促进剂换成 CTAB与 OTAB的混合, 另外, 合成过程在静态进行。 合成样品做 XRD分析, 结果表明合成产物 XRD结果与表 2接近, 即峰位置和形状相同, 各峰相对峰强度在 ±10%范 围内波动, 表明合成产物具有 SAPO-34结构的特征。 实施例 19
具体配料比例和晶化条件见表 1, 具体配料过程同实施例 1。 只将有 机胺变为 DIPA和 TEA的混合物,结晶促进剂换成 CTAB与 CTAC和 DTAB 的混合。 合成样品做 XRD分析, 结果表明合成产物 XRD结果与表 2接 近, 即峰位置和形状相同, 各峰相对峰强度在 ±10%范围内波动, 表明合 成产物具有 SAPO-34结构的特征。
实施例 20
对实施例 2-19原粉样品进行 13C MAS NM 分析,并对分析结果进行 拟合, 结合 TG分析, 将拟合结果与 XRF测定得到的无机元素组成归一 化, 得到分子筛原粉的无水化学组成依次为
0.25DIPA-0.1DEA.(Sio.o8Alo.5oPo.42) 2;
0.30DIPA-0.15DEA.(Si0.oiAlo.5oPo.49) 2,
0.06DIPA-0.03DEA.(Sio.3oAlo.45Po.25) 2,
0.20DIPA-0.05TEA.(Sio.25Al0.4oPo.3o)02,
0.30DIPA-0.05DEAO.06TEA.(Si009Al0 47P0 44)O2,
0.30DIPA-0.05DEA.0.06IPA Sio.i5Alo.45Po.4o)02,
0.05DIPA-0.017DEA.(Sio.ioAlo.48Po.42)02,
0.12DIPA-0.04DEA.(Si0 13Al 45P0 42)O2,
0.09DIPA-0.03TEA.(Sio.ioAlo.49Po.4i)02,
0.07DIPA-0.03MO .(Si0.15Alo.5oPo.35)02,
0.08DIPA-0.02DPA.(Sio.o7Alo.6oPo.33)02,
0.08DIPA-0.03DIEA.(Sio.o8Alo.49Po.43)02;
0.12DIPA-0.02SBA.(Sio.o9Alo.49Po.42)02,
0.09DIPA-0.01TBA.(Sio.o9Alo.47Po.44)02,
0.20DIPA-0.10IPA.(Si 07Al 50P 43)O2,
0.15DIPA-0.05IPA.(Sio.o8Alo.5oPo.42)02,
0.20DIPA-0.07TEAOH.(Si 08Al 48P0.44)O2,
0.12DIPA-0.06IPA.(Sio.o7Alo.5oPo.43)02,
0.16DIPA'0.06TEA.(Si0.08Al 49P0.39)O2。 实施例 21
将合成改为静止条件下进行,其他条件同实施例 1。合成样品做 XRD 分析, 结果表明合成产物 XRD结果与表 2接近, 即峰位置和形状相同, 各峰相对峰强度在 ±10%范围内波动, 表明合成产物具有 SAPO-34结构的 特征。 实施例 22
将结晶促进剂改成 CTAB(0.0015mol)和 OTAB(0.0015mol)的混合物, 其他条件同实施例 1。合成样品做 X D分析, 结果表明合成产物 XRD结 果与表 2接近, 即峰位置和形状相同, 各峰相对峰强度在 ±10%范围内波 动, 表明合成产物具有 SAPO-34结构的特征。
实施例 23
将结 晶促进剂改成 CTAB(O.OOlmol) 、 DTAB(O.OOlmol) 和 ΟΤΑΒ(Ο.ΟΟΙιηοΓ)的混合物, 其他条件同实施例 1。合成样品做 XRD分析, 结果表明合成产物 X D结果与表 2接近, 即峰位置和形状相同, 各峰相 对峰强度在 ±10%范围内波动, 表明合成产物具有 SAPO-34结构的特征。
对比例 1 (无结晶促进剂添加)
具体配料比例、 配料过程和晶化条件同实施例 1, 合成凝胶中不再添 加 CTAB。合成样品称重为 25.4g。样品经 XRD分析,结果表明产物 XRD 结果与表 2接近, 即峰位置和峰形状相同, 表明合成产物具有 CHA结构 的特征。样品的相对结晶度与实施例 1样品相比为 70% (实施例 1样品结 晶度定义为 100%)。
相对结晶度 =(Ii +12 +
+ +Ι3') (ΙΙ Λ 12和 13为对比例 1样 品 XRD谱图中最强的三个衍射峰高 , 1 、 12' 和 13 ' 为实施例 1 样品 XRD谱图中最强的三个衍射峰高。 )
对比例 1 所得样品利用氮气物理吸附实验测得其 BET 比表面积为 460m2/g, 与实施例 1样品的结果相比明显偏低。 对比例 2 (无低温老化过程)
具体配料比例、 配料过程和晶化条件同实施例 1, 但省去低温老化过 程。 合成样品称重为 20.0g。 样品经 XRD分析, 结果表明产物 XRD结果 与表 2接近, 即峰位置和峰形状相同, 表明合成产物具有 SAPO-34结构 的特征。样品的相对结晶度与实施例 1样品相比为 90% (实施例 1样品结 晶度定义为 100%)。
对比例 2固体收率为 65.5%, 与实施例 1的结果相比明显偏低。 实施例 24
将实施例 1得到的样品于 600°C下通入空气焙烧 4小时,然后压片、 破碎至 20〜40目。 称取 l .Og样品装入固定床反应器, 进行 MTO反应 评价。 在 55CTC下通氮气活化 1小时, 然后降温至 45CTC进行反应。 甲醇 由氮气携带, 氮气流速为 40ml/min, 甲醇重量空速 2.0h— 反应产物由 在线气相色谱进行分析(Varian3800, FID检测器, 毛细管柱 PoraPLOT Q-HT ) 。 结果示于表 3。
表 3样品的甲醇转化制烯'烃反应结果
寿命 选择性(质量%) *
样品
(mill) CH4 C2H4 C2 C3H C3H8 c4 + c5 + C2H4+C3H6 实施
240 1.6 50.5 0.64 36.5 0.64 7.9 1.7 87.0 例 1
* 100%甲醇转化率时最高 (乙烯 +丙烯)选择性
Claims
1 . 一种 SAPO-34分子筛, 其特征在于,化学组成为:
m -nT- (SixAlyPz)02
其中, R为二异丙胺, 分布于分子筛笼及孔道中; m为每摩尔
(SixAlyPz)〇2中二异丙胺模板剂的摩尔数, m=0.01〜0.3 ; T为三乙胺、 吗啉、 二乙胺、 二正丙胺、 Ν,Ν-二异丙基乙胺、 仲丁胺、 叔丁胺、 异 丁胺或四乙基氢氧化铵中的一种或任意两者的混合物, 分布于分子筛 笼及孔道中, η为每摩尔 (81;^1^ 02中 Τ的摩尔数, η=0.01〜0.10 ; m/n>2 ; x、 y、 z分别表示 Si、 Al、 P的摩尔分数, 其范围分别是 x=0.01~0.30 , y=0.01-0.60 , z=0.01-0.52 , 且 x+y+z=l。
2. 根据权利要求 1所述的 SAPO-34分子筛, 其特征在于, X射线衍射 图谱在以下位置具有衍射峰-
No. 2Θ
1 9.5177
2 12.7987
3 14.1388
4 15.9829
5 18.1242
6 20.5413
7 22.278
8 23.0981
9 25.3853
10 25.7835
11 27.5448
12 28.5382
13 29.5454
14 30.4947
15 31.3812
16 34.3501
17 36.4789
18 39.6546
19 43.4168
20 47.4822
21 49.1405
22 50.4542
23 51. 1735
24 53.0514
25 53.9912
26 54.7895
27 55.7846
28 56.4017
29 59.6235
30 60.8263
3. 一种权利要求 1所述 SAPO-34分子筛的合成方法, 其特征在于, 合成 步骤如下- a) 将硅源、 铝源、 磷源、 结晶促进剂 CGP、 去离子水和结构导向剂 SDA 混合, 形成具有如下摩尔配比的初始凝胶混合物:
Si02/Al203 =0.05 - 1.5;
Η20/Α1203 = 16 - 150;
SDA/Al2O3 = 0.5 ~ 5.9;
CGP/ A1203 = 0.001-0.05;
b) 将步骤 a)所得初始凝胶混合物在 20^60 °C下进行老化处理, 老化时间 为 0.5〜12小时;
c) 将步骤 b) 处理后的凝胶混合物装入合成釜, 密闭, 升温到 150~22(TC 在自生压力下晶化 0.5~72小时;
d)待晶化完全后, 固体产物经分离、 洗搽、 干燥后即得到 SAPO-34分子 其中,所述结构导向剂 SDA为二异丙胺或二异丙胺与其他有机胺 /铵 T的 混合物; 所述结晶促进剂 CGP为烷基卤化铵。
4. 按照权利要求 3所述的方法, 其特征在于, 所述 T为三乙胺、 吗啉、 二乙胺、 二正丙胺、 Ν,Ν-二异丙基乙胺、 仲丁胺、 叔丁胺、 异丁胺或 四乙基氢氧化铵中的一种或任意两者的混合物。
5. 按照权利要求 3所述的方法, 其特征在于, 所述步骤 a)初始凝胶混合 物中 SDA为二异丙胺与其他有机胺 /铵 T的混合物时, 二异丙胺与 T 的摩尔比不小于 2。
6. 按照权利要求 3所述的方法, 其特征在于, 所述步骤 a)中的硅源为硅 溶胶、 活性二氧化硅、 正硅酸酯、 偏高岭土中的一种或任意几种的混 合物; 铝源为铝盐、 活性氧化铝、 烷氧基铝、 偏高岭土中的一种或任 意几种的混合物; 磷源为正磷酸、 磷酸氢铵、 磷酸二氢铵、 有机磷化 物或磷氧化物中的一种或任意几种的混合物。
7. 按照权利要求 3所述的方法, 其特征在于, 所述步骤 a) 初始凝胶混合 物中的结晶促进剂 CGP为十二烷基三甲基氯化铵、十四烷基三甲基氯 化铵、 十六烷基三甲基氯化铵、 十八烷基三甲基氯化铵、 十二烷基三 甲基溴化铵、 十四烷基三甲基溴化铵、 十六烷基三甲基溴化铵、 十八 烷基三甲基溴化铵中的任意一种或任意几种的混合物。
8. 按照权利要求 3所述的方法, 其特征在于, 所述步骤 a) 初始凝胶混合 物中 H20/A1203的摩尔比为 26-120, 优选为 31-100。
9. 按照权利要求 3所述的方法, 其特征在于, 所述步骤 a) 初始凝胶混合 物中 SDA/A1203的摩尔比为 1.2-5.0。
10.按照权利要求 3所述的方法, 其特征在于, 所述步骤 a) 初始凝胶混合 物中 CGP/A12〇3的摩尔比为 0.001-0.03。
11.按照权利要求 3所述的方法, 其特征在于, 所述步骤 b) 中的老化温 度为 40~60 °C, 老化时间为 2~8小时。
12.按照权利要求 3所述的方法, 其特征在于, 所述步骤 c)中的晶化温度 为 170〜210°C, 优选为 180〜210°C, 更优选为 190〜210°C, 晶化时间为 1 〜60小时, 优选为 1 ~ 24小时, 更优选为 1 〜 12小时。
13.按照权利要求 3所述的方法, 其特征在于, 所述步骤 c) 中的晶化过 程在静态进行。
14.按照权利要求 3所述的方法, 其特征在于, 所述步骤 0中的晶化过程 在动态进行。
15.—种酸催化反应的催化剂, 其特征在于, 根据权利要求 3-14所述任一 方法合成的 SAPO-34分子筛经 400 ~ 700°C空气中焙烧得到。
16. 一种含氧化合物转化制烯烃反应的催化剂, 其特征在于, 根据权利 要求 3-14所述任一方法合成的 SAPO-34分子筛经 400〜 700 °C空气中 焙烧得到。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460956A (zh) * | 2015-12-22 | 2016-04-06 | 天津众智科技有限公司 | 一种制备规则立方颗粒sapo-34分子筛的方法及其应用 |
EP3495320A4 (en) * | 2016-08-02 | 2020-05-27 | Dalian Institute Of Chemical Physics Chinese Academy of Sciences | SYNTHESIS METHOD OF A NANO SAPO-34 MOLECULAR SIEVE, AND SAPO-34 MOLECULAR SIEVE CATALYST AND ITS APPLICATION |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1088483A (zh) * | 1992-12-19 | 1994-06-29 | 中国科学院大连化学物理研究所 | 一种以三乙胺为模板剂的合成硅磷铝分子筛及其制备 |
CN1299776A (zh) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | 一种双模板剂或多模板剂合成磷酸硅铝分子筛的方法 |
-
2012
- 2012-09-26 WO PCT/CN2012/081992 patent/WO2014047800A1/zh active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1088483A (zh) * | 1992-12-19 | 1994-06-29 | 中国科学院大连化学物理研究所 | 一种以三乙胺为模板剂的合成硅磷铝分子筛及其制备 |
CN1299776A (zh) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | 一种双模板剂或多模板剂合成磷酸硅铝分子筛的方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460956A (zh) * | 2015-12-22 | 2016-04-06 | 天津众智科技有限公司 | 一种制备规则立方颗粒sapo-34分子筛的方法及其应用 |
CN105460956B (zh) * | 2015-12-22 | 2021-05-11 | 天津众智科技有限公司 | 一种制备规则立方颗粒sapo-34分子筛的方法及其应用 |
EP3495320A4 (en) * | 2016-08-02 | 2020-05-27 | Dalian Institute Of Chemical Physics Chinese Academy of Sciences | SYNTHESIS METHOD OF A NANO SAPO-34 MOLECULAR SIEVE, AND SAPO-34 MOLECULAR SIEVE CATALYST AND ITS APPLICATION |
US10822244B2 (en) | 2016-08-02 | 2020-11-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for synthesizing nano SAPO-34 molecular sieve, and SAPO-34 molecular sieve catalyst and application thereof |
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