WO2008022532A1 - A method for rapidly synthesizing a silicoaluminophosphate sapo-34 molecular sieve - Google Patents
A method for rapidly synthesizing a silicoaluminophosphate sapo-34 molecular sieve Download PDFInfo
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- WO2008022532A1 WO2008022532A1 PCT/CN2007/002375 CN2007002375W WO2008022532A1 WO 2008022532 A1 WO2008022532 A1 WO 2008022532A1 CN 2007002375 W CN2007002375 W CN 2007002375W WO 2008022532 A1 WO2008022532 A1 WO 2008022532A1
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- Prior art keywords
- molecular sieve
- sapo
- synthesis method
- organic amine
- rapid synthesis
- Prior art date
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 52
- 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 52
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 29
- 238000001308 synthesis method Methods 0.000 claims description 20
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- -1 activated aluminas Chemical class 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- USJRHIYLKAMMSO-UHFFFAOYSA-M hexadecanoyl(trimethyl)azanium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC(=O)[N+](C)(C)C USJRHIYLKAMMSO-UHFFFAOYSA-M 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the invention relates to a rapid synthesis method of a phosphorous silicon aluminum SAPO-34 molecular sieve. ⁇ This synthesis method can synthesize high crystallinity SAPO-34 molecular sieves in a shorter crystallization time. Background technique
- the phosphosilicate aluminum SAPO-34 molecular sieve is a molecular sieve having a chabazite-like structure composed of phosphorus, silicon, aluminum and oxygen. Its structural unit is composed of P0 2 + , Si0 2 and ⁇ 10 2 ⁇ tetrahedron.
- the anhydrous chemical composition can be expressed as: mM- (Si x -Al y -P z ) 0 2 , where M is present in the molecular sieve crystal
- M is present in the molecular sieve crystal
- European Patent EP 0 103 117 discloses a hydrothermal synthesis process for SAPO-34 molecular sieves using tetraethylammonium hydroxide, isopropylamine or a mixture of tetraethylammonium hydroxide and di-n-propylamine as a templating agent.
- UCC United States Carbide Corporation
- SAPO-n silica-alumina series molecular sieves
- Their pore sizes are approximately 0.43 nm is a good type of shape-selective catalyst.
- SAPO-34 molecular sieve exhibits excellent catalytic performance in MTO reaction due to its suitable acidity and pore structure.
- Chinese researchers reported for the first time that SAPO-34 molecular sieves have excellent performance in the conversion of methanol to ethylene and propylene (Applied Catalysis, Vol. 40, No 1-2, 1988, p316).
- the object of the present invention is to provide a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, which adopts three
- the amine and/or diethylamine is used as a templating agent, and an organic amine promoter is added to the initial gel, and the gel mixture is optionally subjected to aging treatment, followed by crystallization, which can be synthesized in a shorter crystallization time.
- High crystallinity SAPO-34 molecular sieve is used as a templating agent, and an organic amine promoter is added to the initial gel, and the gel mixture is optionally subjected to aging treatment, followed by crystallization, which can be synthesized in a shorter crystallization time.
- the present invention provides a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, which comprises mixing a phosphorus source, a silicon source, an aluminum source, a water and an organic amine template into a gel, and then adding an organic amine promoter.
- a uniform SAPO-34 molecular sieve to synthesize the initial gel mixture, optionally aging the gel mixture, and then crystallization, in the 180 ⁇ 250 crystallization conditions
- the crystallization time can be shortened to 0.5 to 12 hours, and a high crystallinity SAPO-34 molecular sieve can be synthesized.
- the molar ratio of each oxide in the initial gel mixture is:
- Mj is a template agent
- M 2 is an organic amine promoter.
- the crystallization time is 1 to 6 hours.
- the templating agent is one or a mixture of two of triethylamine and diethylamine.
- the silicon source is at least one selected from the group consisting of silica sol, silicone gel, water glass, active silica or orthosilicate;
- the aluminum source is selected from the group consisting of aluminum salts and alumina acids. At least one of a salt, an activated alumina, an aluminum alkoxide, a pseudo-boehmite or a pseudoboehmite;
- the phosphorus source being at least one selected from the group consisting of orthophosphoric acid, phosphate, organic phosphide or phosphorus oxide One. '
- the organic amine promoter is a quaternary ammonium salt, and its structural formula is:
- R] R 2, R 3 is alkyl with the ⁇ C 5, R 'is C 5 ⁇ C 24 alkyl group; X is Cl, Br or I.
- the aging treatment temperature is room temperature to 180 ° C, and the aging time is 1 to 12 hours.
- the SAPO-34 molecular sieve prepared by the above synthesis method can be used as a catalyst for the reaction of methanol or dimethyl ether to produce a low-carbon olefin.
- the templating agent triethylamine and/or diethylamine can be promoted by the addition of an organic amine promoter.
- the dissolution in the gel reduces the amount of the templating agent used on the one hand, and on the other hand, it can effectively shorten the crystallization time and reduce the energy consumption.
- the synthetic gel mixture is optionally subjected to an aging treatment followed by crystallization.
- the SAPO-34 molecular sieve catalyst synthesized by the present invention can be used for the reaction of methanol and dimethyl ether to produce a low-carbon olefin, which can effectively improve the selectivity of ethylene and propylene.
- the invention provides a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, the method comprising: a) mixing an organic amine template, a phosphorus source, an aluminum source, a silicon source and water to provide an initial gel mixture; b) adding an organic amine promoter to the initial gel mixture obtained in step a) to obtain a uniform initial gel mixture;
- step b) optionally aging the homogeneous initial gel mixture obtained in step b);
- Mi is a template
- M 2 is an organic amine promoter.
- the templating agent used in the present invention is a mixture of one or both of triethylamine and diethylamine
- the silicon source used is selected from the group consisting of silica sol, silicone gel, water glass, active silica or orthosilicate.
- the esters; the aluminum source is at least one selected from the group consisting of aluminum salts, aluminates, activated aluminas, aluminum alkoxides, pseudoboehmite or pseudoboehmite; It is at least one selected from the group consisting of orthophosphoric acid, phosphate, organic phosphide or phosphorus oxide.
- the organic amine promoter used in the present invention is a quaternary ammonium salt, and its structural formula is:
- the method for rapidly synthesizing a phosphosilica SAPO-34 molecular sieve of the present invention comprises: a) prototyping a mold, a phosphorus source, an aluminum source, a silicon source and water into an initial gel of a SAPO-34 molecular sieve Mixture
- step b) adding a metered organic amine promoter to the initial gel mixture obtained in step a), stirring to obtain a homogenous initial gel mixture;
- step b) The uniform initial gel mixture obtained in the step b) is placed in a stainless steel synthetic kettle lined with polytetrafluoroethylene, sealed, and aged at room temperature to 180 ° C, and the aging time is 1 to 12 hours;
- the crystallization temperature is 180 to 250 ⁇
- the crystallization time is 0.5 to 12 hours, preferably the crystallization time. For 1 to 6 hours;
- step d centrifuging the solid product obtained from step d), washing it to neutral with deionized water, and drying in 120 Torr of air to obtain a raw powder of SAPO-34 molecular sieve;
- the SAPO-34 molecular sieve raw powder obtained in the step e) is calcined in air at 500-600 ° C for 3 to 8 hours to obtain a SAPO-34 molecular sieve catalyst.
- the SAPO-34 molecular sieve catalyst synthesized by the invention can be used for the reaction of methanol or dimethyl ether to produce a low-carbon olefin, the reaction temperature is 300-600 ° C, the preferred reaction temperature is 400-500 ° C, and the weight of the raw material methanol or dimethyl ether is empty.
- the rate is from 1 to 40 h- ] , and the selectivity of the C 2 -C 3 low-carbon olefin in the product is about 90%.
- the invention is described in detail below by way of examples.
- Example 1 SAPO-34 molecular sieve synthesis
- the initial gel ratio is 2.5 TEA: 0.6 SiO 2 : P 2 0 5 : A1 2 0 3 : 50H 2 O: 0.1 CTAB (TEA is a triethylamine template, CTAB is cetyltrimethyl).
- TC polytetrafluoroethylene
- I8 TC, at autogenous pressure
- the crystal was separated by constant temperature for 2 hours.
- the solid product was separated by centrifugation, washed with deionized water until neutral, and dried in 120 Torr air.
- the XRD analysis was as shown in Table 2, and the synthesized product was the original powder of SAPO-34 molecular sieve.
- Example 2 X-ray diffraction analysis results of synthetic samples
- the initial gel ratio is 2.0 DEA on a molar basis: 0.2 SiO 2 : P 2 0 5 : A1 2 0 3 : 50H 2 O: 0.05CTAB (DEA is a diethylamine template, CTAB is cetyltrimethylammonium bromide), the metering materials are mixed, fully stirred into a gel, aged at 100 ° C for 4 hours, and then placed in the liner In a stainless steel autoclave made of polytetrafluoroethylene, it was hermetically heated to 220 Torr and crystallized at autogenous pressure for 2 hours. The solid product was centrifuged, washed with deionized water to neutrality, and dried in air at 120 ° C. The XRD analysis was as shown in Table 3, and the synthesized product was a raw powder of SAPO-34 molecular sieve. Table 3 X-ray diffraction analysis results of the synthesized sample of Example 3
- the initial gel ratio is 1.0 TEA on a molar basis: 1.0 DEA: 0.2 SiO 2 : P 2 0 5 : A1 2 0 3 : 503 ⁇ 40:
- CTAB hexadecanoyltrimethylammonium bromide
- the four SAPO-34 molecular sieve raw powders obtained in Examples 1, 2, 3, and 4 were calcined at 350 ° C for 2 hours, 45 (TC calcined for 1 hour, and 55 CTC was calcined for 4 hours to obtain four SAPO-34 molecular sieve catalysts.
- the numbers are SP-01, SP-02, SP-03 and SP-04.
- Example 6 catalytic reaction experiment
- the four SAPO-34 molecular sieve catalysts obtained in Example 5 were separately tableted and sieved. 0.6 g of 20-40 mesh granule catalyst samples were respectively charged into the reactor for methanol olefin catalytic reaction. Each was activated by a nitrogen gas at 550 ° C for 1 hour, and then cooled to 450 ° C to carry out a reaction. The raw material methanol was carried with nitrogen as a diluent gas, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity ⁇ . ⁇ reaction product composition was analyzed by on-line gas chromatography, and the results are shown in Table 5. Table 5 Results of methanol conversion reaction of synthetic molecular sieve catalyst
- the four SAPO-34 molecular sieve catalysts obtained in Example 5 were separately tableted and sieved. 0.6 g of 20-40 mesh particle catalyst samples were respectively charged into the reactor for dimethylene to olefin catalytic reaction. Each was activated by a nitrogen gas at 550 ° C for 1 hour, and then cooled to 45 CTC for reaction. Nitrogen was used as the diluent gas, and the dimethyl ether gas was fed. The weight of the dimethyl ether was 2.0 h. The composition of the reaction product was analyzed by on-line gas chromatography. The results are shown in Table 6. Table 6 Results of dimethyl ether conversion reaction of synthetic molecular sieve catalyst No. SP-01 SP-02 SP-03 SP-04
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Abstract
Provided is a method for rapidly synthesizing a silicoaluminophosphate SAPO-34 molecular sieve, wherein triethylamine and/or diethylamine are/is used as templating agents, an organic amine accelerator is added to the initial gel for synthesis at the same time, and the gel mixture is optionally subjected to aging treatment. The method could give SAPO-34 molecular sieves with high crystallization degree in a relative short crystallization period. The SAPO-34 molecular sieve catalysts synthesized by the method can be used in the MTO or DTO reaction, the selectivity of C2~C3 olefins in the product could be up to about 90%.
Description
一种磷硅铝 SAPO-34分子筛的快速合成方法 Rapid synthesis method of phosphorus silicon aluminum SAPO-34 molecular sieve
技术领域 Technical field
本发明涉及一种磷硅铝 SAPO-34分子筛的快速合成方法。 釆用该合成方法可在 较短的晶化时间内合成高结晶度的 SAPO-34分子筛。 背景技术 The invention relates to a rapid synthesis method of a phosphorous silicon aluminum SAPO-34 molecular sieve.合成This synthesis method can synthesize high crystallinity SAPO-34 molecular sieves in a shorter crystallization time. Background technique
磷硅铝 SAPO-34分子筛是一种由磷、 硅、 铝和氧组成的具有类菱沸石结构的分 子筛。 其结构单元由 P02 + 、 Si02和 Α102·四面体构成, 无水化学组成可表示为: mM- (Six-Aly-Pz) 02, 上式中 M为存在于分子筛晶体微孔中的模板剂, m为 M的摩尔 数, x、 y、 z分另 iJ Si、 Al、 P的摩尔分数, 并满足 x+y+z= l。 欧洲专利 EP0103117 公开了一种 SAPO-34分子筛的水热合成方法, 该方法使用四乙基氢氧化铵、异丙胺或 以四乙基氢氧化铵和二正丙胺的混合物为模板剂。 1984年, 美国联合碳化物公司 (UCC)幵发了系列新型磷酸硅铝系列分子筛(SAPO-n) (USP 4,440,871),在 SAPO-34 的合成中使用了相同的模板剂。 随着磷酸硅铝系列分子筛的问世, 人们开始将这种小 孔的酸性适中的分子筛用于 MTO反应, 如 SAPO-17, SAPO-18, SAPO-34, SAPO-44 等, 它们的孔径大约为 0.43nm,是一类较好的择形催化剂。 其中 SAPO-34分子筛由于 具有适宜的酸性和孔道结构在 MTO反应中呈现出优异的催化性能。 1988年, 中国的 研究者首次报道了 SAPO-34分子筛在甲醇转化制乙烯、 丙烯反应中具有优异的性能 (Applied Catalysis, Vol. 40, No 1-2, 1988, p316)。 The phosphosilicate aluminum SAPO-34 molecular sieve is a molecular sieve having a chabazite-like structure composed of phosphorus, silicon, aluminum and oxygen. Its structural unit is composed of P0 2 + , Si0 2 and Α10 2 · tetrahedron. The anhydrous chemical composition can be expressed as: mM- (Si x -Al y -P z ) 0 2 , where M is present in the molecular sieve crystal The templating agent in the micropores, m is the number of moles of M, x, y, z are the molar fractions of iJ Si, Al, P, and satisfy x + y + z = l. European Patent EP 0 103 117 discloses a hydrothermal synthesis process for SAPO-34 molecular sieves using tetraethylammonium hydroxide, isopropylamine or a mixture of tetraethylammonium hydroxide and di-n-propylamine as a templating agent. In 1984, the United States Carbide Corporation (UCC) issued a series of new silica-alumina series molecular sieves (SAPO-n) (USP 4,440,871), using the same templating agent in the synthesis of SAPO-34. With the advent of the silicoaluminophosphate series of molecular sieves, it has begun to use such small pores of moderately acidic molecular sieves for MTO reactions such as SAPO-17, SAPO-18, SAPO-34, SAPO-44, etc. Their pore sizes are approximately 0.43 nm is a good type of shape-selective catalyst. Among them, SAPO-34 molecular sieve exhibits excellent catalytic performance in MTO reaction due to its suitable acidity and pore structure. In 1988, Chinese researchers reported for the first time that SAPO-34 molecular sieves have excellent performance in the conversion of methanol to ethylene and propylene (Applied Catalysis, Vol. 40, No 1-2, 1988, p316).
由于四乙基氢氧化铵价格昂贵, 合成 SAPO-34分子筛成本较高, 不利于工业化 生产。 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 剂较廉价, 可以降低 SAPO-34分子筛的合成成本。 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分子筛的方法, 使合成成本进一步降低。 但是, 这些专利中模板剂使用较多 且晶化时间较长, 能耗较大。 发明内容 Due to the high price of tetraethylammonium hydroxide, the high cost of synthesizing SAPO-34 molecular sieve is not conducive to industrial production. Chinese Patent ZL93112230 discloses a method for synthesizing SAPO-34 using triethylamine as a template, which is relatively inexpensive and can reduce the synthesis cost of SAPO-34 molecular sieve. Since then, Chinese patents ZL93112015 and ZL94110059 have respectively disclosed a method of synthesizing SAPO-34 molecular sieve with diethylamine as a template or a combination of triethylamine and diethylamine to reduce the synthesis cost. However, in these patents, the templating agent is used in a large amount and has a long crystallization time and a large energy consumption. Summary of the invention
本发明的目的是提供一种磷硅铝 SAPO-34分子筛的快速合成方法, 其采用三乙
胺和 /或二乙胺为模板剂, 在合成初始凝胶中加入有机胺促进剂, )f得凝胶混合物任选 经过老化处理, 然后进行晶化, 可在较短的晶化时间内合成高结晶度的 SAPO-34分子 筛。 The object of the present invention is to provide a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, which adopts three The amine and/or diethylamine is used as a templating agent, and an organic amine promoter is added to the initial gel, and the gel mixture is optionally subjected to aging treatment, followed by crystallization, which can be synthesized in a shorter crystallization time. High crystallinity SAPO-34 molecular sieve.
为达到上述目的, 本发明提供一种磷硅铝 SAPO-34分子筛的快速合成方法, 将磷 源、 硅源、 铝源、 水和有机胺模板剂混合成凝胶后, 再加入有机胺促进剂, 提高有机 胺模板剂在凝胶中的溶解度, 可制备出均匀的 SAPO-34分子筛合成初始凝胶混合物, 任选将凝胶混合物进行老化处理, 然后进行晶化, 在 180〜250Ό晶化条件下, 可将晶 化时间缩短为 0.5〜12小时, 同时合成出高结晶度的 SAPO-34分子筛, In order to achieve the above object, the present invention provides a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, which comprises mixing a phosphorus source, a silicon source, an aluminum source, a water and an organic amine template into a gel, and then adding an organic amine promoter. , to improve the solubility of the organic amine template in the gel, can prepare a uniform SAPO-34 molecular sieve to synthesize the initial gel mixture, optionally aging the gel mixture, and then crystallization, in the 180~250 crystallization conditions The crystallization time can be shortened to 0.5 to 12 hours, and a high crystallinity SAPO-34 molecular sieve can be synthesized.
其中, 初始凝胶混合物中各氧化物的摩尔比为: Wherein, the molar ratio of each oxide in the initial gel mixture is:
SiO2/Al2O3 = 0.1〜2.0; SiO2/Al 2 O 3 = 0.1~2.0;
Ρ2Ο5/ Α12Ο3 = 0.5〜15; Ρ 2 Ο 5 / Α1 2 Ο 3 = 0.5~15;
H20/ A1203 = 10- 100; H 2 0/ A1 2 0 3 = 10- 100;
Mj/ A1203 = 1〜5, Mj为模板剂; Mj/ A1 2 0 3 = 1~5, Mj is a template agent;
M2/ A1203 = 0.01〜 1, M2为有机胺促进剂。 M 2 / A1 2 0 3 = 0.01 〜 1, M 2 is an organic amine promoter.
在上述合成方法中, 所述晶化时间为 1〜6小时。 In the above synthesis method, the crystallization time is 1 to 6 hours.
在上述合成方法中, 所述模板剂为三乙胺和二乙胺中的一种或二者的混合物。 在上述合成方法中, 所述硅源为选自硅溶胶、硅凝胶、水玻璃、活性二氧化硅或 正硅酸酯中的至少一种; 所述铝源为选自铝盐、 铝酸盐、 活性氧化铝、 烷氧基铝、 假 勃母石或拟薄水铝石中的至少一种; 所述磷源为选自正磷酸、 磷酸盐、 有机磷化物或 磷氧化物中的至少一种。 ' In the above synthesis method, the templating agent is one or a mixture of two of triethylamine and diethylamine. In the above synthesis method, the silicon source is at least one selected from the group consisting of silica sol, silicone gel, water glass, active silica or orthosilicate; the aluminum source is selected from the group consisting of aluminum salts and alumina acids. At least one of a salt, an activated alumina, an aluminum alkoxide, a pseudo-boehmite or a pseudoboehmite; the phosphorus source being at least one selected from the group consisting of orthophosphoric acid, phosphate, organic phosphide or phosphorus oxide One. '
在上述合成方法中, 所述有机胺促进剂为季胺盐, 其结构式为: In the above synthesis method, the organic amine promoter is a quaternary ammonium salt, and its structural formula is:
其中 R】、 R2、 R3为 〜C5的垸基, R'为 C5〜C24的烷基; X为 Cl、 Br或 I。 在上述合成方法中, 所述老化处理温度为室温〜 180°C, 老化时间为 1〜12小时。 采用上述合成方法制得的 SAPO-34分子筛可用作甲醇或二甲醚制低碳烯烃反应 的催化剂。 Wherein R], R 2, R 3 is alkyl with the ~C 5, R 'is C 5 ~C 24 alkyl group; X is Cl, Br or I. In the above synthesis method, the aging treatment temperature is room temperature to 180 ° C, and the aging time is 1 to 12 hours. The SAPO-34 molecular sieve prepared by the above synthesis method can be used as a catalyst for the reaction of methanol or dimethyl ether to produce a low-carbon olefin.
在本发明的方法中,通过加入有机胺促进剂,可以促进模板剂三乙胺和 /或二乙胺
在凝胶中的溶解, 一方面降低模板剂的使用量, 另一方面, 可以有效缩短晶化时间, 减少能耗。 In the process of the invention, the templating agent triethylamine and/or diethylamine can be promoted by the addition of an organic amine promoter. The dissolution in the gel reduces the amount of the templating agent used on the one hand, and on the other hand, it can effectively shorten the crystallization time and reduce the energy consumption.
在本发明的方法中, 任选对合成的凝胶混合物迸行老化处理, 然后进行晶化。 本发明合成的 SAPO-34分子筛催化剂用于甲醇和二甲醚制低碳烯烃反应中, 可 以有效地提高乙烯和丙烯的选择性。 具体实施方式 In the process of the invention, the synthetic gel mixture is optionally subjected to an aging treatment followed by crystallization. The SAPO-34 molecular sieve catalyst synthesized by the present invention can be used for the reaction of methanol and dimethyl ether to produce a low-carbon olefin, which can effectively improve the selectivity of ethylene and propylene. detailed description
本发明提供一种磷硅铝 SAPO-34分子筛的快速合成方法, 该方法包括: a)将有机胺模板剂、 磷源、 铝源、 硅源和水混合, 以提供一种初始凝胶混合物; b) 向步骤 a) 中得到的初始凝胶混合物中加入有机胺促进剂, 得到均匀的初始凝 胶混合物; The invention provides a rapid synthesis method of a phosphosilicate aluminum SAPO-34 molecular sieve, the method comprising: a) mixing an organic amine template, a phosphorus source, an aluminum source, a silicon source and water to provide an initial gel mixture; b) adding an organic amine promoter to the initial gel mixture obtained in step a) to obtain a uniform initial gel mixture;
c)任选将步骤 b) 中得到的均匀初始凝胶混合物老化; c) optionally aging the homogeneous initial gel mixture obtained in step b);
d)进行晶化, 以得到分子筛产物。 d) crystallization is carried out to obtain a molecular sieve product.
本发明方法中初始凝胶混合物中各氧化物摩尔比为 - SiO2/Al2O3 = 0.1〜2.0; The molar ratio of each oxide in the initial gel mixture in the method of the invention is - SiO 2 /Al 2 O 3 = 0.1~2.0;
P205/ A1203 = 0.5-15; P 2 0 5 / A1 2 0 3 = 0.5-15;
H20/ A1203 = 10〜 100; H 2 0/ A1 2 0 3 = 10~ 100;
Μ!/ Α1203 = 1〜5, Mi为模板剂; Μ!/ Α1 2 0 3 = 1~5, Mi is a template;
Μ2/ Α12Ο3 = 0.01〜1, M2为有机胺促进剂。 Μ 2 / Α1 2 Ο 3 = 0.01~1, M 2 is an organic amine promoter.
本发明所使用的模板剂为三乙胺和二乙胺中的一种或二者的混合物,使用的硅源 为选自硅溶胶、 硅凝胶、 水玻璃、 活性二氧化硅或正硅酸酯中的至少一种; 所述铝源 为选自铝盐、铝酸盐、活性氧化铝、烷氧基铝、假勃母石或拟薄水铝石中的至少一种; 所述磷源为选自正磷酸、 磷酸盐、 有机磷化物或磷氧化物中的至少一种。 The templating agent used in the present invention is a mixture of one or both of triethylamine and diethylamine, and the silicon source used is selected from the group consisting of silica sol, silicone gel, water glass, active silica or orthosilicate. At least one of the esters; the aluminum source is at least one selected from the group consisting of aluminum salts, aluminates, activated aluminas, aluminum alkoxides, pseudoboehmite or pseudoboehmite; It is at least one selected from the group consisting of orthophosphoric acid, phosphate, organic phosphide or phosphorus oxide.
本发明使用的有机胺促进剂为季胺盐, 其结构式为: The organic amine promoter used in the present invention is a quaternary ammonium salt, and its structural formula is:
其中 Ri、 R2、 为 〜¾的烷基, R'为 C5-C24的烷基; X为 Cl、 Br或 I。 按照一个优选实施方案,本发明快速合成磷硅铝 SAPO-34分子筛的方法包括: a)按比例将模扳剂、 磷源、 铝源、 硅源和水配制成 SAPO-34分子筛的初始凝胶
混合物; Wherein Ri, R 2 is an alkyl group of 〜3⁄4, R' is a C 5 -C 24 alkyl group; and X is Cl, Br or I. According to a preferred embodiment, the method for rapidly synthesizing a phosphosilica SAPO-34 molecular sieve of the present invention comprises: a) prototyping a mold, a phosphorus source, an aluminum source, a silicon source and water into an initial gel of a SAPO-34 molecular sieve Mixture
b)在步骤 a) 中得到的初始凝胶混合物中加入计量有机胺促进剂, 搅拌得到均勾 的初始凝胶混合物; b) adding a metered organic amine promoter to the initial gel mixture obtained in step a), stirring to obtain a homogenous initial gel mixture;
C)将步骤 b) 中得到的均匀初始凝胶混合物装入内衬聚四氟乙烯的不锈钢合成釜 中, 密闭, 在室温〜 180°C进行老化, 老化时间为 1〜12小时; C) The uniform initial gel mixture obtained in the step b) is placed in a stainless steel synthetic kettle lined with polytetrafluoroethylene, sealed, and aged at room temperature to 180 ° C, and the aging time is 1 to 12 hours;
d)进一步将步骤 c)得到的老化混合物, 密闭加热到晶化温度, 在自生压力下, 进行恒温晶化, 晶化温度为 180〜250Ό , 晶化时间为 0.5〜12小时, 优选晶化时间为 1〜6小时; d) further heating the aged mixture obtained in the step c) to a crystallization temperature, and performing isothermal crystallization under autogenous pressure, the crystallization temperature is 180 to 250 Å, and the crystallization time is 0.5 to 12 hours, preferably the crystallization time. For 1 to 6 hours;
e)离心分离得自步骤 d)的固体产物, 用去离子水洗涤至中性, 在 120Ό空气中干 燥, 得到 SAPO-34分子筛原粉; e) centrifuging the solid product obtained from step d), washing it to neutral with deionized water, and drying in 120 Torr of air to obtain a raw powder of SAPO-34 molecular sieve;
ί)将步骤 e)得到的 SAPO-34分子筛原粉在 500-600°C空气中焙烧 3〜8小时, 得 到 SAPO-34分子筛催化剂。 )) The SAPO-34 molecular sieve raw powder obtained in the step e) is calcined in air at 500-600 ° C for 3 to 8 hours to obtain a SAPO-34 molecular sieve catalyst.
本发明合成的 SAPO-34分子筛催化剂可用于甲醇或二甲醚制低碳烯烃反应, 反 应温度为 300〜600°C,较佳反应温度为 400〜500°C,原料甲醇或二甲醚重量空速为 1〜 40h-], 产物中 C2-C3低碳烯烃选择性达到 90%左右。 下面通过实施例详述本发明。 实施例 1 ( SAPO-34分子筛合成) The SAPO-34 molecular sieve catalyst synthesized by the invention can be used for the reaction of methanol or dimethyl ether to produce a low-carbon olefin, the reaction temperature is 300-600 ° C, the preferred reaction temperature is 400-500 ° C, and the weight of the raw material methanol or dimethyl ether is empty. The rate is from 1 to 40 h- ] , and the selectivity of the C 2 -C 3 low-carbon olefin in the product is about 90%. The invention is described in detail below by way of examples. Example 1 (SAPO-34 molecular sieve synthesis)
以摩尔计, 将初始凝胶比例为 3.0TEA: 0.6SiO2: P205: A1203: 50H2O (TEA为 三乙胺模板剂)的计量原料混合, 充分搅拌成凝胶, 在 80°C条件下老化 5小时, 然后装 入内衬聚四氟乙烯的不锈钢髙压釜中, 密闭加热到 200°C, 在自生压力下, 恒温晶化 5 小时。 固体产物经离心分离, 用去离子水洗涤至中性, 在 120°C空气中干燥后, XRD 分析如表 1所示, 合成产物为 SAPO-34分子筛原粉。 表 1 实施例 1合成样品 X射线衍射分析结果 Mixing the metering materials with an initial gel ratio of 3.0 TEA: 0.6 SiO 2 : P 2 0 5 : A1 2 0 3 : 50H 2 O (TEA is a triethylamine templating agent) on a molar basis, and fully stirring into a gel. After aging at 80 ° C for 5 hours, it was placed in a stainless steel autoclave lined with polytetrafluoroethylene, sealed and heated to 200 ° C, and crystallized at autogenous pressure for 5 hours. The solid product was centrifuged, washed with deionized water to neutrality, and dried in air at 120 ° C. The XRD analysis was as shown in Table 1, and the synthesized product was a SAPO-34 molecular sieve raw powder. Table 1 X-ray diffraction analysis results of the synthesized sample of Example 1
2Θ D(A) IOQXI/IQ 2Θ D(A) IOQXI/IQ
9.43 9.37 100 9.43 9.37 100
12.78 6.92 1512.78 6.92 15
15.96 .55 44
07 002375 15.96 .55 44 07 002375
20.52 4.32 5920.52 4.32 59
21.07 4.21 1221.07 4.21 12
25.17 3.55 1125.17 3.55 11
25.81 3.45 1625.81 3.45 16
30.49 2.93 1830.49 2.93 18
31.07 2.88 18 实施例 2 (SAPO-34分子筛合成) 31.07 2.88 18 Example 2 (Synthesis of SAPO-34 molecular sieve)
以摩尔计, 将初始凝胶比例为 2.5TEA: 0.6SiO2: P205: A1203: 50H2O: 0.1CTAB (TEA 为三乙胺模板剂, CTAB 为十六烷基三甲基溴化铵)的计量原料混合, 充分搅拌 成凝胶, 在 100Ό条件下老化 8小时, 然后装入内衬聚四氟乙烯的不锈钢髙压釜中, 密闭加热到 I8(TC, 在自生压力下, 恒温晶化 2小时。 固体产物经离心分离, 用去离 子水洗涤至中性,在 120Ό空气中干燥后, XRD分析如表 2所示,合成产物为 SAPO-34 分子筛原粉。 表 2实施例 2合成样品 X射线衍射分析结果 On a molar basis, the initial gel ratio is 2.5 TEA: 0.6 SiO 2 : P 2 0 5 : A1 2 0 3 : 50H 2 O: 0.1 CTAB (TEA is a triethylamine template, CTAB is cetyltrimethyl The metering raw materials of ammonium bromide were mixed, fully stirred into a gel, aged under 100 Torr for 8 hours, and then placed in a stainless steel autoclave lined with polytetrafluoroethylene, and sealed to I8 (TC, at autogenous pressure). The crystal was separated by constant temperature for 2 hours. The solid product was separated by centrifugation, washed with deionized water until neutral, and dried in 120 Torr air. The XRD analysis was as shown in Table 2, and the synthesized product was the original powder of SAPO-34 molecular sieve. Example 2 X-ray diffraction analysis results of synthetic samples
2Θ D(A) ΙΟΟχΙ/Ιο 2Θ D(A) ΙΟΟχΙ/Ιο
9.40 9.40 100 9.40 9.40 100
12.76 6.93 1712.76 6.93 17
13.90 6.37 913.90 6.37 9
15.92 5.56 4515.92 5.56 45
17.71 5.00 1217.71 5.00 12
20.48 4.33 7420.48 4.33 74
24.84 3.58 1624.84 3.58 16
25.77 3.45 2025.77 3.45 20
30.45 2.93 2630.45 2.93 26
31.01 2.88 18 实施例 3 ( SAPO-34分子筛合成) 31.01 2.88 18 Example 3 (Synthesis of SAPO-34 molecular sieve)
以摩尔计, 将初始凝胶比例为 2.0DEA : 0.2SiO2 : P205 : A1203: 50H2O:
0.05CTAB(DEA为二乙胺模板剂, CTAB为十六烷基三甲基溴化铵)的计量原料混合, 充分搅拌成凝胶, 在 100°C条件下老化 4小时, 然后装入内衬聚四氟乙烯的不锈钢高 压釜中, 密闭加热到 220Ό , 在自生压力下, 恒温晶化 2小时。 固体产物经离心分离, 用去离子水洗涤至中性, 在 120°C空气中干燥后, XRD分析如表 3所示, 合成产物为 SAPO-34分子筛原粉。 表 3 实施例 3合成样品 X射线衍射分析结果
The initial gel ratio is 2.0 DEA on a molar basis: 0.2 SiO 2 : P 2 0 5 : A1 2 0 3 : 50H 2 O: 0.05CTAB (DEA is a diethylamine template, CTAB is cetyltrimethylammonium bromide), the metering materials are mixed, fully stirred into a gel, aged at 100 ° C for 4 hours, and then placed in the liner In a stainless steel autoclave made of polytetrafluoroethylene, it was hermetically heated to 220 Torr and crystallized at autogenous pressure for 2 hours. The solid product was centrifuged, washed with deionized water to neutrality, and dried in air at 120 ° C. The XRD analysis was as shown in Table 3, and the synthesized product was a raw powder of SAPO-34 molecular sieve. Table 3 X-ray diffraction analysis results of the synthesized sample of Example 3
9.42 9.38 100 9.42 9.38 100
12.75 6.94 2012.75 6.94 20
15.93 5.56 5015.93 5.56 50
17.87 4.96 1217.87 4.96 12
20.48 4.33 7320.48 4.33 73
21.18 4.19 1421.18 4.19 14
25.12 3.54 1625.12 3.54 16
25.78 3.45 2125.78 3.45 21
30.48 2.93 2430.48 2.93 24
31.04 2.88 20 实施例 4 ( SAPO-34分子筛合成) 31.04 2.88 20 Example 4 (Synthesis of SAPO-34 molecular sieve)
以摩尔计, 将初始凝胶比例为 1.0TEA: 1.0DEA: 0.2SiO2: P205: A1203: 50¾0:The initial gel ratio is 1.0 TEA on a molar basis: 1.0 DEA: 0.2 SiO 2 : P 2 0 5 : A1 2 0 3 : 503⁄40:
0.02CTAB(TEA为三乙胺模板剂, DEA为二乙胺模板剂, CTAB为十六垸基三甲基溴 化铵)的计量原料混合, 充分搅拌成凝胶, 在 120°C条件下老化 5小时, 然后装入内衬 聚四氟乙烯的不锈钢髙压釜中, 密闭加热到 200Ό , 在自生压力下, 恒温晶化 2小时。 固体产物经离心分离, 用去离子水洗涤至中性, 在 120Ό空气中干燥后, XRD分析如 表 4所示, 合成产物为 SAPO-34分子筛原粉。
表 4 实施例 4合成样品 X射线衍射分析结果 Mixing 0.02CTAB (TEA is a triethylamine template, DEA is a diethylamine template, CTAB is hexadecanoyltrimethylammonium bromide), fully stirred into a gel, aged at 120 ° C After 5 hours, it was placed in a stainless steel autoclave lined with polytetrafluoroethylene, sealed to 200 Torr, and crystallized at autogenous pressure for 2 hours. The solid product was centrifuged, washed with deionized water until neutral, and dried in 120 Torr air. The XRD analysis was as shown in Table 4, and the synthesized product was a SAPO-34 molecular sieve original powder. Table 4 X-ray diffraction analysis results of the synthesized sample of Example 4
2Θ D(A) 100xI/Io 2Θ D(A) 100xI/Io
9.46 9.34 100 9.46 9.34 100
12.80 6.91 2012.80 6.91 20
15.96 5.55 5115.96 5.55 51
17.91 4.95 1317.91 4.95 13
20.53 4.32 8020.53 4.32 80
23.06 3.85 1123.06 3.85 11
25.15 3.54 1925.15 3.54 19
25.81 , 3.45 2125.81, 3.45 21
30.51 2.93 2630.51 2.93 26
31.19 2.87 21 实施例 5 ( SAPO-34分子筛催化剂制备 ) 31.19 2.87 21 Example 5 (Preparation of SAPO-34 molecular sieve catalyst)
将实施例 1、 2、 3、 4得到的四种 SAPO-34分子筛原粉, 分别在 350°C焙烧 2小 时, 45(TC焙烧 1小时, 55CTC焙烧 4小时, 得到四种 SAPO-34分子筛催化剂。 编号分 别为 SP-01 , SP-02, SP-03和 SP-04。 实施例 6 (催化反应实验) The four SAPO-34 molecular sieve raw powders obtained in Examples 1, 2, 3, and 4 were calcined at 350 ° C for 2 hours, 45 (TC calcined for 1 hour, and 55 CTC was calcined for 4 hours to obtain four SAPO-34 molecular sieve catalysts. The numbers are SP-01, SP-02, SP-03 and SP-04. Example 6 (catalytic reaction experiment)
将实施例 5得到的四种 SAPO-34分子筛催化剂分别压片、过筛。各取 0.6克 20-40 目的颗粒催化剂样品,分别先后装入反应器中,用于甲醇制烯烃催化反应。各在 550°C 下通氮气活化 1 小时, 然后降温至 450°C进行反应。 以氮气为稀释气携带原料甲醇, 氮气流速为 40ml/min, 甲醇重量空速 Ζ.ΟΙιΛ 反应产物组成采用在线气相色谱分析, 结果如表 5所示。
表 5 合成分子筛催化剂甲醇转化反应结果 The four SAPO-34 molecular sieve catalysts obtained in Example 5 were separately tableted and sieved. 0.6 g of 20-40 mesh granule catalyst samples were respectively charged into the reactor for methanol olefin catalytic reaction. Each was activated by a nitrogen gas at 550 ° C for 1 hour, and then cooled to 450 ° C to carry out a reaction. The raw material methanol was carried with nitrogen as a diluent gas, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity Ζ.ΟΙιΛ reaction product composition was analyzed by on-line gas chromatography, and the results are shown in Table 5. Table 5 Results of methanol conversion reaction of synthetic molecular sieve catalyst
编号 SP-01 SP-02 SP-03 SP-04 No. SP-01 SP-02 SP-03 SP-04
CH4 1.34 1.75 1.66 1.48 CH 4 1.34 1.75 1.66 1.48
C2H4 50.67 55.29 54.98 55.80 C 2 H 4 50.67 55.29 54.98 55.80
C2H6 0.09 0.08 0.05 0.06 C 2 H 6 0.09 0.08 0.05 0.06
C3H6 36.85 34.98 35.44 34.77 C 3 H 6 36.85 34.98 35.44 34.77
C3H8 1.72 1.37 0.45 0.41 C 3 H 8 1.72 1.37 0.45 0.41
C4 + 7.02 5.61 6.21 6.09 C 4 + 7.02 5.61 6.21 6.09
C5+ 2.31 0.92 1.21 1.39 C 5 + 2.31 0.92 1.21 1.39
∑C2 =-C3 = 87.53 90.28 90.42 90.58 实施例 7 (催化反应实验) ∑C 2 = -C 3 = 87.53 90.28 90.42 90.58 Example 7 (catalytic reaction experiment)
将实施例 5得到的四种 SAPO-34分子筛催化剂分别压片、过筛。各取 0.6克 20-40 目的颗粒催化剂样品,分别先后装入反应器中,用于二甲醚制烯烃催化反应。各在 550°C 下通氮气活化 1 小时, 然后降温至 45CTC进行反应。 以氮气为稀释气, 二甲醚气体进 料, 二甲醚重量空速 2.0h— 反应产物组成采用在线气相色谱分析, 结果如表 6所示。 表 6合成分子筛催化剂二甲醚转化反应结果 编号 SP-01 SP-02 SP-03 SP-04 The four SAPO-34 molecular sieve catalysts obtained in Example 5 were separately tableted and sieved. 0.6 g of 20-40 mesh particle catalyst samples were respectively charged into the reactor for dimethylene to olefin catalytic reaction. Each was activated by a nitrogen gas at 550 ° C for 1 hour, and then cooled to 45 CTC for reaction. Nitrogen was used as the diluent gas, and the dimethyl ether gas was fed. The weight of the dimethyl ether was 2.0 h. The composition of the reaction product was analyzed by on-line gas chromatography. The results are shown in Table 6. Table 6 Results of dimethyl ether conversion reaction of synthetic molecular sieve catalyst No. SP-01 SP-02 SP-03 SP-04
CH4 1.15 1.40 1.32 1.33 CH 4 1.15 1.40 1.32 1.33
C2H4 50.24 55.08 55.52 55.33 C2H4 50.24 55.08 55.52 55.33
C2H6 0.11 0.05 0.05 0.05 C 2 H 6 0.11 0.05 0.05
C3H6 35.79 35.51 35.43 35.89 C3H6 35.79 35.51 35.43 35.89
C4 + 8.35 6.15 5.97 5.86 C 4 + 8.35 6.15 5.97 5.86
C5 + 2.20 1.51 1.40 1.28 C 5 + 2.20 1.51 1.40 1.28
∑C2 =-C3 = 86.04 90.60 90.95 91.22
∑C 2 = -C 3 = 86.04 90.60 90.95 91.22
Claims
1、 一种磷硅铝 SAPO-34分子筛的快速合成方法, 该方法包括: 1. A rapid synthesis method of a phosphorous silicon aluminum SAPO-34 molecular sieve, the method comprising:
a) 将有机胺模板剂、磷源、铝源、硅源和水混合, 以提供一种 初始凝 胶混合物; a) mixing an organic amine templating agent, a phosphorus source, an aluminum source, a silicon source, and water to provide an initial gel mixture;
b) 向步骤 a) 中得到的初始凝胶混合物中加入有机胺促进剂, 得到均匀 的初始凝胶混合物; b) adding an organic amine promoter to the initial gel mixture obtained in step a) to obtain a uniform initial gel mixture;
c) 任选将步骤 b) 中得到的均匀初始凝胶混合物老化; c) optionally aging the homogeneous initial gel mixture obtained in step b);
d) 进行晶化, 以得到分子筛产物, d) performing crystallization to obtain a molecular sieve product,
其中步骤 a)中初始凝胶混合物中各氧化物摩尔比为: Wherein the molar ratio of each oxide in the initial gel mixture in step a) is:
Si02/Al203 = 0.1 -2.0; Si0 2 /Al 2 0 3 = 0.1 -2.0;
Ρ2θ5/ Α12θ3 = 0.5〜15; Ρ 2 θ5/ Α1 2 θ3 = 0.5~15;
Η2Ο/ Α12Ο3 = 10 〜100; Η 2 Ο / Α 1 2 Ο 3 = 10 ~100;
M^ Al.Os ^ l 〜5, Mi为有机胺模板剂; M^ Al.Os ^ l 〜5, Mi is an organic amine template;
Μ2/ Α12Ο3 = 0.01〜1, M2为有机胺促进剂。 Μ 2 / Α1 2 Ο 3 = 0.01~1, M 2 is an organic amine promoter.
2、 按照权利要求 1所述的快速合成方法, 其中晶化温度为 180〜250°C, 晶化时 间为 0.5〜12小时。 The rapid synthesis method according to claim 1, wherein the crystallization temperature is 180 to 250 ° C and the crystallization time is 0.5 to 12 hours.
3、 按照权利要求 2所述的快速合成方法, 其中所述晶化时间为 1〜6小时。 3. The rapid synthesis method according to claim 2, wherein said crystallization time is from 1 to 6 hours.
4、 按照权利要求 1所述的快速合成方法, 其中所述有机胺模板剂为三乙胺和二 乙胺中的一种或二者的混合物。 4. The rapid synthesis method according to claim 1, wherein the organic amine templating agent is one or a mixture of two of triethylamine and diethylamine.
5、 按照权利要求 1所述的快速合成方法, 其中所述有机胺促进剂为季胺盐, 其 结构式为: 5. The rapid synthesis method according to claim 1, wherein the organic amine promoter is a quaternary ammonium salt, and the structural formula is:
6、 按照权利要求 1 所述的快速合成方法, 其中所述老化处理温度为室温 180。C, 老化时间为 1〜12小时。
6. The rapid synthesis method according to claim 1, wherein the aging treatment temperature is room temperature 180. C, the aging time is 1 to 12 hours.
7. 按照权利要求 1所述的快速合成方法, 其中所述硅源为选自硅溶胶、 硅凝 胶、水玻璃、活性二氧化硅或正硅酸酯中的至少一种; 所述铝源为选自铝盐、铝酸盐、 活性氧化铝、 烷氧基铝、 假勃母石或拟薄水铝石中的至少一种; 所述磷源为选自正磷 酸、 磷酸盐、 有机磷化物或磷氧化物中的至少一种。 7. The rapid synthesis method according to claim 1, wherein the silicon source is at least one selected from the group consisting of silica sol, silicone gel, water glass, active silica or orthosilicate; Is at least one selected from the group consisting of aluminum salts, aluminates, activated aluminas, aluminum alkoxides, pseudo-boehmite or pseudoboehmite; the phosphorus source is selected from the group consisting of orthophosphoric acid, phosphate, and organic phosphorus. At least one of a compound or a phosphorus oxide.
8、 按照权利要求 1-7任何一项所述的快速合成方法, 其中合成的 SAPO-34分 子筛在焙烧后应用在甲醇或二甲醚制低碳烯烃反应中。
A rapid synthesis method according to any one of claims 1 to 7, wherein the synthesized SAPO-34 molecular sieve is used in a reaction of methanol or dimethyl ether to produce a low-carbon olefin after calcination.
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Cited By (6)
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
CN1088483A (en) * | 1992-12-19 | 1994-06-29 | 中国科学院大连化学物理研究所 | A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine |
CN1096496A (en) * | 1993-06-18 | 1994-12-21 | 中国科学院大连化学物理研究所 | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve |
CN1106715A (en) * | 1994-02-05 | 1995-08-16 | 中国科学院大连化学物理研究所 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
US20040082466A1 (en) * | 2001-11-30 | 2004-04-29 | Guang Cao | Method of synthesizing molecular sieves |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5227151A (en) * | 1991-11-15 | 1993-07-13 | Mobil Oil Corporation | Method of preparing silicoaluminophosphate compositions using a reagent containing both quaternary ammonium and silicon reactive sites in the same molecule |
US20040064008A1 (en) * | 2002-09-30 | 2004-04-01 | Torsten Maurer | Molecular sieve catalyst composition |
-
2006
- 2006-09-27 CN CN200610152273A patent/CN100584758C/en active Active
-
2007
- 2007-08-08 WO PCT/CN2007/002375 patent/WO2008022532A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
CN1088483A (en) * | 1992-12-19 | 1994-06-29 | 中国科学院大连化学物理研究所 | A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine |
CN1096496A (en) * | 1993-06-18 | 1994-12-21 | 中国科学院大连化学物理研究所 | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve |
CN1106715A (en) * | 1994-02-05 | 1995-08-16 | 中国科学院大连化学物理研究所 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
US20040082466A1 (en) * | 2001-11-30 | 2004-04-29 | Guang Cao | Method of synthesizing molecular sieves |
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