CN114426295B - AFX type molecular sieve and synthetic method and application thereof - Google Patents
AFX type molecular sieve and synthetic method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 70
- 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 70
- 238000010189 synthetic method Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- 230000002093 peripheral effect Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical group CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 11
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- -1 pentyl cation Chemical class 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000269350 Anura Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910017119 AlPO Inorganic materials 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical class C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910006367 Si—P Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MPCVYAVDVXEPTK-UHFFFAOYSA-N butane Chemical compound CCC[CH2+] MPCVYAVDVXEPTK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an AFX type molecular sieve, a preparation method and application thereof. The AFX molecular sieve of the invention has a three-layer sandwich structure, and the thickness of each layer is about 8-12 mu m. The AFX type molecular sieve has a novel sandwich type layered structure, and when the molecular sieve with the specific morphology is used for the reaction of preparing olefin from methanol, the molecular sieve has good catalytic performance and high selectivity of low-carbon olefin.
Description
Technical Field
The invention belongs to the field of molecular sieves and preparation thereof, and particularly relates to an AFX type topological structure molecular sieve and a preparation method thereof, and application of the AFX type molecular sieve in the process of preparing low-carbon olefin from methanol.
Background
The United states United carbide company first reported AlPO 4 Synthesis of molecular sieves from AlO 4 - And PO (PO) 4 + Tetrahedra are alternately formed, and the whole skeleton is electrically neutral and has no ion exchange performance and strong acidity. SAPO molecular sieves can be regarded as silicon substitution into AlPO 4 The framework of the SAPO molecular sieve is electronegative and has exchangeable cations due to the intervention of silicon formed after the framework. SAPO molecular sieves can exhibit medium and strong acid properties depending on the synthesis conditions and the amount of silicon in the sample. The three-dimensional pore canal structure of the molecular sieve consists of a double six-membered ring, a gme cage and an aft cage, and the size of the pore opening of the eight-membered ring is 0.34nm multiplied by 0.36nm, and belongs to small pore zeolite with a large hole structure.
The Chinese energy source has the structural characteristics of more coal, lean oil and less gas, so the coal-to-olefin is most important. To date, the most successful route to light olefins is to use coal-based methanol to light olefins (MTO) technology, and research on methanol to light olefins catalysts has focused mainly on mesoporous and small pore acidic molecular sieves, of which the most representative are mesoporous ZSM-5 and small pore SAPO-34 molecular sieves. The mesoporous ZSM-5 molecular sieve has larger pore diameter and stronger surface acidity, so that the product is widened in the catalytic process, the low-carbon olefin selectivity is poor, and byproducts such as aromatic hydrocarbon, paraffin and the like are inevitably generated; the SAPO-34 molecular sieve has smaller pore diameter, effectively limits the generation of macromolecular substances in the MTO reaction, is beneficial to the improvement of the selectivity of the low-carbon olefin, and shows good shape-selective effect. The SAPO-34 is an excellent catalyst for the reaction of preparing the low-carbon olefin by converting methanol, the aperture of the AFX-type SAPO-56 molecular sieve is about 0.02nm smaller than that of the CHA-type SAPO-34 molecular sieve, and the catalyst is likely to show good low-carbon olefin selectivity in the MTO reaction and has extremely important significance for development of the catalyst.
CN108726529a discloses a preparation method for synthesizing SAPO-56 molecular sieve by adding polyethylene glycol, which comprises dissolving polyethylene glycol in deionized water, adding phosphoric acid, mixing thoroughly, adding aluminum source, stirring thoroughly to form a solution, adding silicon source and template agent into the solution successively, and obtaining the SAPO-56 molecular sieve with disc-shaped morphology structure after hydrothermal crystallization.
CN109071244a reports a method for preparing SAPO-56 (AFX) using a lower alkyl amine, preferably trimethyl amine, and a1, 4-diazabicyclo [2.2.2] octane derivative, preferably comprising a1, 4- (1, 4-diazabicyclo [2.2.2] octane) butyl cation or a1, 5- (1, 4-diazabicyclo [2.2.2] octane) pentyl cation, as Structure Directing Agent (SDA), lower alkyl ammonium hydroxides such as tetrabutylammonium hydroxide (TBAOH) can be used to control pH.
Tian Peng et Al (university journal of chemistry, 2001, 22, 991-994) studied the use of N, N, N ', N', -tetramethyl-1, 6-hexanediamine (TMHD) as a templating agent in Al by hydrothermal method 2 O 3 -P 2 O 5 -SiO 2 The SAPO-56 molecular sieve is synthesized in the system, the template agent and water are fixed, a phase diagram of an Al-Si-P ternary system is obtained, the synthesized molecular sieve crystal is in a plane hexagonal structure, and the catalytic performance of the synthesized molecular sieve crystal for preparing olefin by converting methanol is examined.
Disclosure of Invention
The invention provides an AFX type molecular sieve, a preparation method and application thereof. The AFX type molecular sieve has a novel sandwich type layered structure, and when the molecular sieve with the specific morphology is used for the reaction of preparing olefin from methanol, the molecular sieve has good catalytic performance and high selectivity of low-carbon olefin.
In a first aspect, the present invention provides an AFX-type molecular sieve having a three-layer sandwich structure, each layer having a thickness of about 8-12 μm.
Further, each layer of the AFX molecular sieve is hexagonal, preferably regular or quasi-regular hexagonal.
Further, the average side length of each layer of hexagons of the AFX molecular sieve is about 20-25 mu m.
Further, the outer peripheral surface of the middle sandwich layer of the AFX type molecular sieve is concave to the outer peripheral surfaces of the upper layer and the lower layer, preferably, the average side length of the middle sandwich layer is smaller than the average side length of the upper layer and smaller than the average side length of the lower layer, and preferably, the average side length of the middle sandwich layer is smaller than 0.1-3 μm.
Further, the specific surface of the AFX molecular sieve is 500-550 m 2 Per gram, the pore volume is 0.20-0.25 cm 3 /g。
Further, the AFX type molecular sieve is a SAPO-56 molecular sieve.
The second aspect of the invention provides a method for synthesizing an AFX-type molecular sieve, comprising the steps of:
(a) Mixing a phosphorus source, an aluminum source, and water to form a slurry;
(b) Uniformly stirring a silicon source and an organic template agent to form a mixed material;
(c) And (c) uniformly mixing the mixed material obtained in the step (b) with the slurry obtained in the step (a) to form a crystallization liquid, and performing two-stage crystallization to obtain the AFX type molecular sieve.
Further, the phosphorus source is P 2 O 5 The aluminum source is calculated as Al 2 O 3 The silicon source is represented by SiO 2 The organic template agent is represented by R, and the addition amount of the phosphorus source, the aluminum source, the water, the silicon source and the organic template agent is n (Al 2 O 3 )：n(P 2 O 5 )：n(SiO 2 )：n(R)：n(H 2 O)＝0.8～1.0：0.8～1.2：0.1～1.0：1.5～2.6：25～50。
Further, the phosphorus source is selected from at least one of phosphoric acid, phosphate or phosphorus oxide, preferably phosphoric acid; the aluminum source is selected from at least one of aluminum isopropoxide, activated alumina, pseudoboehmite or pseudo-boehmite, preferably pseudo-boehmite or aluminum isopropoxide; the water is preferably deionized water; the silicon source is at least one selected from silica sol, water glass, active silicon dioxide or tetraethoxysilane, and is preferably silica sol or tetraethoxysilane; the organic template agent (R) is at least one selected from N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD), tetraethylammonium hydroxide (TEAOH) and Triethylamine (TEA), preferably N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD) or a mixed template agent of N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD) and tetraethylammonium hydroxide, wherein the tetraethylammonium hydroxide in the mixed template agent accounts for 10-20% of the total mass of the mixed template agent.
Further, the two-stage thermal crystallization is preferably two-stage hydrothermal crystallization, including: crystallizing at a low temperature Duan Jinghua and a high temperature, wherein the temperature of the low temperature Duan Jinghua is 100-160 ℃ and the time is 2-48 h; the crystallization temperature of the high temperature section is 180-200 ℃ and the time is 8-90 h.
And after the crystallization is finished, washing, drying and optionally roasting to obtain the AFX type molecular sieve. The washing, drying and calcination may be carried out by conventional methods, for example, the washing may be carried out with distilled water, generally to a near neutral state, and the drying conditions are as follows: drying for 4-24 h at 80-110 ℃, wherein the roasting conditions are as follows: roasting for 4-10 h at 550-650 ℃.
The third aspect of the invention provides an application of the AFX type molecular sieve in preparing low-carbon olefin from methanol.
The application is that the methanol raw material is contacted with the AFX molecular sieve to react, so as to obtain the low-carbon olefin.
The reactor may be a fixed bed reactor. The reaction conditions are preferably as follows: the reaction temperature is 350-500 ℃, the reaction pressure is 0-1 MPa, and the weight airspeed is 1-6 h -1 . Wherein the raw material can be pure methanol, crude methanol containing water, and methanol containing inert gas.
The AFX molecular sieve provided by the invention has a specific novel morphology, has a proper pore structure, is applied to the reaction of preparing low-carbon olefin from methanol, and has excellent catalytic performance and high low-carbon olefin yield.
The preparation method of the AFX molecular sieve adopts a specific raw material mixing sequence and specific two-stage crystallization conditions, and the sandwich type layered structure which is different from the circular sheet-shaped or plane hexagonal structure of the traditional AFX molecular sieve can be prepared by adopting the method, so that the AFX molecular sieve has better catalytic performance.
Drawings
FIG. 1 is a scanning electron microscope image of an AFX-type molecular sieve obtained in comparative example 1;
FIG. 2 is a scanning electron microscope image of the AFX-type molecular sieve obtained in comparative example 2;
FIG. 3 is a scanning electron microscope image of the AFX-type molecular sieve obtained in example 1;
fig. 4 is an XRD diffractogram of the AFX-type molecular sieve obtained [ example 1 ].
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the examples.
In the invention, the morphology of the molecular sieve product is determined by Scanning Electron Microscopy (SEM). The Scanning Electron Microscope (SEM) picture of the molecular sieve is measured by a Nova NanoSEM 450 type scanning electron microscope, a sample is firstly ground to powder of 200-400 meshes, and after the powder is fixed by double-sided conductive adhesive, the test is carried out in a high vacuum state, and the emission voltage of the microscope is 200kV.
In the invention, XRD adopts a Bruker D8 advanced diffractometer, a Cu-K alpha ray source is used, the working voltage is 40kV, the current is 200mA, the scanning range is 5-50 degrees, the scanning step length is 0.02 degrees, and the scanning speed is 4 degrees/min.
In the present invention, the specific surface area and pore volume were measured on a Micromeritics TriStar model 3000 adsorber, and the calcined samples (A1, A2) were measured under a vacuum at 300 ℃ and calculated using the BET formula and BJH model.
[ comparative example 1 ]
Alumina, phosphoric acid, silica sol, N, N, N ', N', -tetramethyl-1, 6-hexamethylenediamine (TMHD) and polyethylene glycol 4000 (PEG) are respectively used as an aluminum source, a phosphorus source, a silicon source and a template agent (R), and the molar ratio of the PEG is: al (Al) 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=0.01: 0.8:1:1:2:45 weighing ingredients, uniformly mixing, putting the reaction mixture into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 90 hours at the autogenous pressure of 200 ℃, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying the solid in a drying oven at 100 ℃ for 12 hours, roasting the solid in the muffle for 8 hours at 550 ℃ to obtain a wafer-shaped AFX molecular sieve, wherein the average thickness of a wafer is about 4 mu m, the number is recorded as S1, and a scanning electron microscope is shown in figure 1.
[ comparative example 2]
In pseudo-boehmite formPhosphoric acid, silica sol, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD), an aluminum source, a phosphorus source, a silicon source and a template agent (R) respectively according to the mole ratio of Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=0.8: 1:0.6:2:50, weighing ingredients, uniformly mixing, putting the reaction mixture into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 48 hours at the autogenous pressure of 200 ℃, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying the solid in a 100 ℃ oven for 12 hours, roasting the solid in the muffle for 3 hours at 550 ℃ to obtain the planar hexagonal AFX molecular sieve, wherein the average thickness of a hexagon is about 3 mu m, the number is recorded as S2, and a scanning electron microscope is shown in figure 2.
[ comparative example 3 ]
Pseudo-boehmite, phosphoric acid, silica sol, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD), respectively an aluminum source, a phosphorus source, a silicon source and a template agent (R), according to the mole ratio of Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=0.8: 1:0.6:2:50 the ingredients are weighed out and mixed,
firstly, mixing phosphoric acid, pseudoboehmite and deionized water to form slurry; and uniformly stirring silica sol, N, N, N ', N', -tetramethyl-1, 6-hexamethylenediamine (TMHD) to form a mixed material, adding the mixed material into slurry, uniformly mixing, placing into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 90 hours at a self-generated pressure of 200 ℃, washing the crystallized product with deionized water to neutrality, separating to obtain a solid, drying in a 100 ℃ oven for 12 hours, roasting in the muffle furnace for 8 hours at 550 ℃ to obtain the planar hexagonal structure AFX molecular sieve, wherein the average thickness of hexagons is about 5 mu m, the number is marked as S3, and a scanning electron microscope is similar to that of FIG. 2.
[ example 1 ]
Pseudo-boehmite, phosphoric acid, silica sol, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD), respectively an aluminum source, a phosphorus source, a silicon source and a template agent (R), according to the mole ratio of Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=0.8: 1:0.6:2:50 the ingredients are weighed out and mixed,
firstly, phosphoric acid, pseudoboehmite and deionized waterMixing water to form slurry; and uniformly stirring silica sol, N, N, N ', N', -tetramethyl-1, 6-hexamethylenediamine (TMHD) to form a mixed material, adding the mixed material into slurry, uniformly mixing, placing into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 150 ℃ for 10 hours under the autogenous pressure of 200 ℃, and crystallizing at 200 ℃ for 80 hours to obtain the sandwich type layered AFX molecular sieve, wherein the serial number is recorded as S4, a scanning electron microscope is shown in figure 3, and an XRD (X) chart is shown in figure 4. S4 has a three-layer sandwich structure, each layer is hexagonal, the average side length of the hexagons of the upper layer and the lower layer is about 23 mu m, the average side length of the middle sandwich layer is about 22 mu m, the outer peripheral surface of the middle sandwich layer is concave on the outer peripheral surfaces of the upper layer and the lower layer, and the average thickness of each layer of hexagons is about 10 mu m. S4 has a specific surface of 539.6m 2 Per g, pore volume of 0.25cm 3 /g。
[ example 2]
Compared with example 1, the crystallization conditions were modified as follows: crystallizing at 160deg.C for 16 hr and then at 200deg.C for 32 hr to obtain sandwich type AFX molecular sieve with number of S5, scanning electron microscope similar to figure 3 and XRD similar to figure 4. S5 has a three-layer sandwich structure, each layer is hexagonal, the average side length of the hexagons of the upper layer and the lower layer is about 25 mu m, the average side length of the middle sandwich layer is about 23 mu m, the outer peripheral surface of the middle sandwich layer is concave on the outer peripheral surfaces of the upper layer and the lower layer, and the average thickness of each layer of hexagons is about 12 mu m. S5 has a specific surface of 509.1m 2 Per g, pore volume of 0.22cm 3 /g。
[ example 3 ]
Pseudo-boehmite, phosphoric acid, tetraethyl orthosilicate, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD), respectively an aluminum source, a phosphorus source, a silicon source and a template agent (R), according to the mole ratio of Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=1.0: 1:0.5:2.2:40, weighing ingredients;
firstly, mixing phosphoric acid, pseudo-boehmite and deionized water to form slurry; then tetraethyl orthosilicate, N, N, N ', N', -tetramethyl-1, 6-hexamethylenediamine (TMHD) are stirred uniformly to form a mixed material, and then the mixed material is added into slurry to be mixed uniformly and then is filled with the poly-tetra-diamineCrystallizing in a crystallization kettle of a fluoroethylene lining at 140 ℃ for 18 hours under autogenous pressure, crystallizing at 190 ℃ for 48 hours, washing the crystallized product to be neutral by deionized water, separating to obtain a solid, drying the solid in a drying oven at 100 ℃ for 12 hours, and roasting the solid in a muffle furnace for 5 hours at 550 ℃ to obtain the sandwich-type layered AFX molecular sieve, wherein the serial number is marked as S6, a scanning electron microscope is similar to that in FIG. 3, and an XRD pattern is similar to that in FIG. 4. S6 has a three-layer sandwich structure, each layer is hexagonal, the average side length of the hexagons of the upper layer and the lower layer is about 24 mu m, the average side length of the middle sandwich layer is about 23.5 mu m, the peripheral surface of the middle sandwich layer is concave on the peripheral surfaces of the upper layer and the lower layer, and the average thickness of each layer of hexagons is about 9 mu m. S6 has a specific surface of 526.5m 2 Per g, pore volume of 0.20cm 3 /g。
[ example 4 ]
Aluminum isopropoxide, phosphoric acid, tetraethyl orthosilicate, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD, R1) +tetraethylammonium hydroxide (TEAOH, R2), respectively an aluminum source, a phosphorus source, a silicon source and a mixed template agent (R), according to the mole ratio of Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R1：R2：H 2 O=1.0: 1:0.7:1.8:0.2:40, weighing ingredients;
firstly, mixing phosphoric acid, aluminum isopropoxide and deionized water to form slurry; tetraethyl orthosilicate, N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine (TMHD, R1) +tetraethylammonium hydroxide (TEAOH, R2) are stirred uniformly to form a mixed material, the mixed material is added into slurry and mixed uniformly, the mixed material is put into a crystallization kettle with a polytetrafluoroethylene lining, the crystallization is carried out for 24 hours at 120 ℃ under the autogenous pressure, the crystallization is carried out for 24 hours at 195 ℃, deionized water is used for washing the crystallization product to be neutral, the solid is obtained after separation, the solid is dried for 12 hours in a 100 ℃ oven, the solid is baked for 5 hours at 550 ℃ in a muffle furnace, the number is marked as S7, a scanning electron microscope is similar to FIG. 3, and the XRD pattern is similar to that of FIG. 4. S7 has a three-layer sandwich structure, each layer is hexagonal, the average side length of the hexagons of the upper layer and the lower layer is about 23 mu m, the average side length of the middle sandwich layer is about 22 mu m, the outer peripheral surface of the middle sandwich layer is concave on the outer peripheral surfaces of the upper layer and the lower layer, and the average thickness of each layer of hexagons is about 10 mu m. S7 has a specific surface of 518.5m 2 Per g, pore volume of 0.23cm 3 /g。
[ example 5 ]
Catalyst evaluation experiment
Samples S1 to S7 obtained in comparative examples 1 to 3 and examples 1 to 4 were respectively compressed and crushed, and then sieved to obtain 20 to 40 mesh fractions. And (3) adopting a fixed bed catalytic reaction device to respectively carry out catalyst evaluation experiments. The experimental conditions are as follows: the catalyst loading was 2.0g, the reaction temperature was 460℃and the normal pressure, the methanol weight space velocity was 4h -1 ，N 2 ：CH 3 OH is 1:1. The results are shown in Table 1, and compared with S1-S3, the catalyst provided by the invention has higher selectivity, and the selectivity of the low-carbon olefin of S4-S7 is higher than that of S1-S3.
TABLE 1 reaction results of methanol conversion to lower olefins
Claims (6)
1. An AFX-type molecular sieve, characterized in that: the AFX molecular sieve has a three-layer sandwich structure, and the thickness of each layer is 8-12 mu m; each layer of the AFX molecular sieve is hexagonal, and the average side length of each layer of hexagon is 20-25 mu m; the outer peripheral surface of the middle sandwich layer of the AFX type molecular sieve is concave on the outer peripheral surfaces of the upper layer and the lower layer, and the average side length of the middle sandwich layer is smaller than that of the upper layer and smaller than that of the lower layer;
the specific surface of the AFX type molecular sieve is 500-550 m 2 Per gram, the pore volume is 0.20-0.25 cm 3 /g。
2. The AFX-type molecular sieve according to claim 1, wherein: the AFX type molecular sieve is a SAPO-56 molecular sieve.
3. The method of synthesizing an AFX-type molecular sieve according to any one of claims 1-2, comprising the steps of:
(a) Mixing a phosphorus source, an aluminum source, and water to form a slurry;
(b) Uniformly stirring a silicon source and an organic template agent to form a mixed material;
(c) Uniformly mixing the mixed material obtained in the step (b) with the slurry obtained in the step (a) to form a crystallization liquid, and performing two-stage crystallization to obtain an AFX type molecular sieve;
the organic template agent is selected from N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine or a mixed template agent of N, N, N ', N' -tetramethyl-1, 6-hexamethylenediamine and tetraethylammonium hydroxide, wherein the tetraethylammonium hydroxide in the mixed template agent accounts for 10% -20% of the total mass of the mixed template agent;
the phosphorus source is P 2 O 5 The aluminum source is calculated as Al 2 O 3 The silicon source is represented by SiO 2 The organic template agent is represented by R, and the addition amount of the phosphorus source, the aluminum source, the water, the silicon source and the organic template agent is n (Al 2 O 3 ）：n（P 2 O 5 ）：n（SiO 2 ）：n（R）：n（H 2 O）＝0.8~1.0：0.8~1.2：0.1~1.0：1.5~2.6：25~50；
The two-stage crystallization is as follows: crystallizing at a low temperature Duan Jinghua and a high temperature, wherein the temperature of the low temperature Duan Jinghua is 100-160 ℃ and the time is 2-48 h; the crystallization temperature of the high-temperature section is 180-200 ℃ and the time is 8-90 h.
4. A method according to claim 3, characterized in that: the phosphorus source is selected from at least one of phosphoric acid, phosphate or phosphorus oxide; the aluminum source is at least one selected from aluminum isopropoxide, activated alumina, pseudoboehmite or pseudo-boehmite; the water is deionized water; the silicon source is selected from at least one of silica sol, water glass, active silicon dioxide or orthosilicate.
5. The method of claim 4, wherein: and after the two-stage crystallization is finished, washing, drying and optionally roasting to obtain the AFX molecular sieve.
6. Use of the AFX-type molecular sieve according to any one of claims 1-2 or prepared according to the method of any one of claims 3-5 in the preparation of lower olefins from methanol.
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| US8470293B2 (en) * | 2009-12-18 | 2013-06-25 | Exxonmobil Chemical Patents Inc. | Method of preparing a molecular sieve and its use in the conversion of oxygenates to olefins |
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| CN101857244A (en) * | 2010-06-22 | 2010-10-13 | 上海兖矿能源科技研发有限公司 | Silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN103058208A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of SAPO-56 molecular sieve |
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