CN116199239B - A low-silicon nano-sheet SAPO-34 molecular sieve and its preparation method and application - Google Patents
A low-silicon nano-sheet SAPO-34 molecular sieve and its preparation method and application Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 74
- 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 74
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 31
- 239000010703 silicon Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002135 nanosheet Substances 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000012265 solid product Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 20
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
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- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- 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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention discloses a low silicon slice-shaped SAPO-34 molecular sieve, preparation thereof and application thereof in preparing olefin from methanol. The molecular sieve is prepared by reducing the content of silica sol in a precursor, crystallizing at a low temperature and adopting a hydrothermal synthesis method with continuous rapid stirring in the crystallization process. The synthesized SAPO-34 product has low acidity and extremely small-sized nano-sheet morphology. The synthesis method is simple, efficient and controllable, does not need to add other solvents, surfactants and the like, and the molecular sieve has extremely high low-carbon olefin selectivity in the reaction of preparing olefin from methanol, particularly the total yield of ethylene and propylene can reach more than 88 percent, and has excellent stability, thus being very suitable for industrial amplification application.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a preparation method of a low silicon slice-shaped SAPO-34 molecular sieve and application of the low silicon slice-shaped SAPO-34 molecular sieve in a reaction for preparing olefin from methanol.
Background
Among several basic chemical products that are most produced and consumed worldwide, ethylene and propylene rank first and second, respectively. In industrial production, ethylene and propylene are mainly prepared by cracking petroleum products such as light oil, heavy oil, light diesel oil and the like. Based on the energy pattern that the coal-rich lean oil in China is low in gas content and the external dependence of petroleum is increased year by year, the utilization of a non-petroleum route for preparing low-carbon olefin is one of the feasible methods for solving the problem of energy shortage. Routes to lower olefins (MTO) from methanol are considered to be an ideal alternative process. Meanwhile, the MTO conversion route has the advantage of greater development by combining the characteristics of relatively abundant coal resource reserves, excessive methanol productivity and the like in China. Meanwhile, the MTO technology also promotes the diversification of domestic olefin production technology and sources, and provides a new opportunity for the adjustment of petrochemical industry structures in China.
Among the numerous MTO molecular sieve catalysts, SAP0-34 molecular sieve with topological structure has proper acid strength, unique pore structure, good thermal stability and hydrothermal stability, and shows excellent catalytic activity and low-carbon olefin selectivity in the reaction of preparing olefin from methanol. But the SAPO-34 molecular sieve is easily carbon-deposited during the reaction due to its narrow pore canal, thereby being rapidly deactivated. How to overcome the deactivation of carbon deposition caused by narrow pore channels and further improve the catalytic performance is the key point of current research.
The prior SAPO-34 molecular sieve has the size of micron level, the shape of cube, and longer mass transfer path, and the generated target product is easy to generate side reaction in the diffusion process.
The current method for synthesizing the nano SAPO-34 molecular sieve mainly comprises a mixed template agent method, a microwave synthesis method, an ultrasonic synthesis method, a recrystallization and seed crystal method and a xerogel conversion method, wherein the molecular sieve prepared by the methods mainly has the size of 100-500nm, has high silicon content, and is difficult to accurately and controllably synthesize the molecular sieves with low silicon and different sizes through regulating and controlling variables. There are very few prior reports of methods for synthesizing low acidity SAP0-34 molecular sieves. Therefore, research on developing nano flaky SAPO-34 molecular sieves with low silicon content and improving the catalytic performance thereof becomes an important research direction in the field.
Disclosure of Invention
The invention aims to provide a low-silicon nano flaky SAPO-34 molecular sieve and a preparation method thereof, and the molecular sieve is applied to the reaction of preparing low-carbon olefin from methanol, so that the problem of easy deactivation of the molecular sieve is solved, and meanwhile, the conversion rate and the selectivity of a catalyst are improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a low-silicon nano flaky SAPO-34 molecular sieve, which has low silicon content and small-size nano flaky morphology, wherein the silicon content is Si/(Si+A1+P) =0.0015-0.010 in terms of atomic ratio, the average grain diameter of the molecular sieve is 40-500nm, and the thickness is 10-30nm. The molecular sieve has extremely high low-carbon olefin selectivity in the reaction of preparing olefin from methanol, especially the total yield of ethylene and propylene can reach more than 88 percent, and the stability performance is excellent.
The invention provides a preparation method of the low-silicon nano flaky SAP0-34 molecular sieve, which comprises the following steps:
1) Adding an aluminum source into a mixed system of a template agent and water, and stirring for 1-4 hours at 20-40 ℃ to obtain a uniform mixture solution;
2) Adding a phosphorus source into the mixture solution, stirring for 4-6 hours at 40-65 ℃, then adding a silicon source, and continuing stirring for 2-4 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve;
3) Filling the gel mixture obtained in the step 2) into a polytetrafluoroethylene reaction kettle, and then fixing the gel mixture in a rotary oven for low-temperature crystallization;
4) After crystallization is finished, rapidly cooling the hydrothermal kettle, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, and then drying at 80-120 ℃ to obtain SAPO-34 molecular sieve raw powder;
5) And calcining the SAP0-34 molecular sieve raw powder at high temperature to remove the template agent contained in the raw powder, thereby obtaining the SAPO-34 molecular sieve with low-silicon and nano-size lamellar morphology.
Further, in the above technical scheme, in the steps 1) -2), the molar ratio of each component oxide, the template agent and the water in the initial gel mixture is SiO 2:Al2O3:P2O5, the template agent is H 2 O=0.01-0.2:1:0.8-1.2:1.5-2.5:20-60, the silicon source is calculated by SiO 2, the aluminum source is calculated by Al 2O3, and the phosphorus source is calculated by P 2O5.
Further, in the above technical scheme, in step 1) -2), the silicon source is at least one of silica sol, tetraethyl orthosilicate, sodium silicate, white carbon black and active silica, the aluminum source is at least one of aluminum oxide, pseudo-boehmite, aluminum isopropoxide and aluminum hydroxide, the template agent is at least one of tetraethyl ammonium hydroxide (TEAOH) aqueous solution, triethylamine (TEA) and Morpholine (MOR), and the phosphorus source is at least one of phosphoric acid, phosphate, phosphite and tributyl phosphate.
Further, in the above technical scheme, in the step 3), the rotational speed of the reactor is set to be 30-60r/min, the crystallization temperature is 100-115 ℃, and the crystallization time is 60-120h.
Further, in the above technical scheme, in step 5), the baking temperature is 500-650 ℃ and the baking time is 6-12h.
The invention provides application of the low-silicon nano sheet SAP0-34 molecular sieve prepared by the preparation method in a reaction for preparing low-carbon olefin from methanol.
Further, in the application scheme, the reaction pressure is 0.1-0.4MPa, the space velocity is 1-3h -1, and the reaction temperature is 400-550 ℃.
Advantageous effects
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1 the invention prepares the silicon sol with low acidity by reducing the content of the silicon sol in the precursor and adopting a hydrothermal synthesis method with low temperature crystallization and continuous rapid stirring in the crystallization process
Si/(Si+A1+P) =0.0015-0.010 and nano flaky SAPO-34 molecular sieve with extremely small size (average grain diameter of 40-500nm and thickness of 10-30 nm),
In the invention, under the condition of not affecting the catalytic activity, the SAPO-34 with low silicon content can reduce the carbon deposition generation and promote the stability of the catalyst, and the smaller size and the flaky morphology enable the molecular sieve to have a shorter mass transfer path, promote the selectivity of low-carbon olefin and promote the conversion rate and the stability, and the catalyst disclosed by the invention has the advantages that the performance is kept stable after 1000 minutes of reaction, and the stability is obviously promoted.
3 The SAPO-34 molecular sieve prepared by the invention has excellent catalytic performance in the reaction of preparing low-carbon olefin from methanol, wherein the total yield of ethylene and propylene can reach more than 88%.
Detailed Description
Example 1
Adding 16g of aluminum isopropoxide into a mixed system of 25g of TEAOH and 10g of water, stirring for 2 hours at 40 ℃ to obtain a uniform mixture solution, adding 10.9g of phosphoric acid into the mixture solution, stirring for 4 hours at 65 ℃ and then adding 0.77g of silica sol, and stirring for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, wherein the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.13:1:1.2:1.8:40, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 115 ℃ for 80 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.005, average particle size of 40-500nm and thickness of 10-30 nm.
Example 2
7.2G of pseudo-boehmite is added into a mixed system of 46.8g of TEAOH and 11g of water, stirred for 2 hours at 40 ℃ to obtain a uniform mixture solution, 13g of phosphoric acid is added into the mixture solution, stirred for 4 hours at 65 ℃, then 1.7g of silica sol is added, stirring is continued for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, and the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 115 ℃ for 80 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.007, average particle size of 40-500nm and thickness of 10-30 nm.
Example 3
Adding 8.4g of aluminum hydroxide into a mixed system of 46.8g of TEAOH and 10g of water, stirring at 40 ℃ for 2 hours to obtain a uniform mixture solution, adding 13g of phosphoric acid into the mixture solution, stirring at 65 ℃ for 4 hours, adding 1.7g of silica sol, and continuing stirring for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, wherein the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 115 ℃ for 80 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.003, average particle size of 40-500nm and thickness of 10-30 nm.
Example 4
7.2G of pseudo-boehmite is added into a mixed system of 46.8g of TEAOH and 11g of water, stirred for 2 hours at 40 ℃ to obtain a uniform mixture solution, 13g of phosphoric acid is added into the mixture solution, stirred for 4 hours at 65 ℃, then 2.4g of TEOS is added, stirring is continued for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, and the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 115 ℃ for 80 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.01, average particle size of 40-500nm and thickness of 10-30 nm.
Example 5
Adding 7.2g of pseudo-boehmite into a mixed system of 46.8g of TEAOH and 11g of water, stirring for 2 hours at 40 ℃ to obtain a uniform mixture solution, adding 13g of phosphoric acid into the mixture solution, stirring for 4 hours at 65 ℃, then adding 0.5g of white carbon black, and continuing stirring for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, wherein the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 115 ℃ for 80 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.002, average particle size of 40-500nm and thickness of 10-30 nm.
Example 6
7.2G of pseudo-boehmite is added into a mixed system of 23.4g of TEAOH and 35g of TEA, stirred for 2 hours at 40 ℃ to obtain a uniform mixture solution, 13g of phosphoric acid is added into the mixture solution, stirred for 4 hours at 65 ℃, then 1.7g of silica sol is added, stirring is continued for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, and the molar ratio of each component in the gel mixture is as follows
SiO2:Al2O3:P2O5:(TEAOH+TEA):H2O＝0.15:0.8:1:(1+1):50; Placing the gel mixture into a polytetrafluoroethylene reaction kettle, then fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing for 80 hours at 115 ℃, after crystallization, rapidly cooling the hydrothermal kettle, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, then drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano flaky SAPO-34 molecular sieve with Si/(Si+A1+P) =0.007, average particle size of 40-500nm and thickness of 10-30 nm.
Comparative example 1
7.2G of pseudo-boehmite is added into a mixed system of 46.8g of TEAOH and 11g of water, stirred for 2 hours at 40 ℃ to obtain a uniform mixture solution, 13g of phosphoric acid is added into the mixture solution, stirred for 4 hours at 65 ℃, then 2.4g of TEOS is added, stirring is continued for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, and the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, then fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 150 ℃ for 60 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano flaky SAPO-34 molecular sieve with Si/(Si+A1+P) =0.02, average particle size of 40-500nm and thickness of 10-30 nm.
Comparative example 2
7.2G of pseudo-boehmite is added into a mixed system of 46.8g of TEAOH and 11g of water, stirred for 2 hours at 40 ℃ to obtain a uniform mixture solution, 13g of phosphoric acid is added into the mixture solution, stirred for 4 hours at 65 ℃, then 2.4g of TEOS is added, stirring is continued for 2 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve, and the molar ratio of each component in the gel mixture is as follows
SiO 2:Al2O3:P2O5:TEAOH:H2 O=0.15:0.8:1:2.0:50, loading the gel mixture into a polytetrafluoroethylene reaction kettle, fixing the polytetrafluoroethylene reaction kettle in a rotary oven, crystallizing at 180 ℃ for 30 hours, rapidly cooling the hydrothermal kettle after crystallization, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, drying at 80 ℃ to obtain SAPO-34 molecular sieve raw powder, calcining the SAP0-34 molecular sieve raw powder at 650 ℃ for 10 hours to remove a template agent contained in the raw powder, and obtaining the nano sheet-shaped SAPO-34 molecular sieve with Si/(Si+A1+P) =0.03, average particle size of 40-500nm and thickness of 10-30 nm.
Example 7
We performed elemental analysis and nitrogen adsorption tests on 8 samples obtained in examples 1 to 6 and comparative examples 1 to 2, and the results are shown in table 1. It can be seen from table 1 that the 8 samples all have a higher specific surface area.
Meanwhile, 8 samples obtained in examples 1 to 6 and comparative examples 1 to 2 were tabletted and crushed to 20 to 40 mesh. 0.3g of the sample was weighed and placed in a stainless steel reaction tube with an inner diameter of 8mm, and the tube was fixed on a fixed bed reactor, and when the reaction was carried out, MTO evaluation was carried out by controlling the reaction temperature and the gas flow rate by a temperature programming device and a flow rate control device. Nitrogen is introduced at 500 ℃ for activation for 2.0 hours, then the temperature is reduced to 400 ℃, methanol is carried by nitrogen, the flow rate of the nitrogen is 15mL/min, the mass space velocity of the methanol is 2.0h -1, and the reaction pressure is 0.25MPa. The obtained product was analyzed by on-line gas chromatography (Agilcnt 7890,7890), and the results are shown in Table 1. It can be seen from table 1 that the samples of example 6 all had very high catalytic life with a total yield of ethylene and propylene exceeding 88%. Whereas the life of the comparative example 2 samples and the overall yield of ethylene and propylene were lower than in the examples. TABLE 1 skeleton element composition, specific surface area (BET) and MTO reaction test results of samples synthesized in examples and comparative examples
Note that the selectivities and yields in the tables are statistical results before the end of the reaction lifetime and at 100% conversion.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A preparation method of a low-silicon nano flaky SAPO-34 molecular sieve is characterized in that the low-silicon nano flaky SAPO-34 molecular sieve has low silicon content and small-size nano flaky morphology, wherein the silicon content is Si/(Si+A1+P) =0.0015-0.010, the average grain diameter of the molecular sieve is 40-500nm, and the thickness is 10-30nm, the molecular sieve shows extremely high low-carbon olefin selectivity in a methanol-to-olefin reaction, the total yield of ethylene and propylene reaches more than 88%, and the stability performance is excellent;
the preparation method of the low-silicon nano flaky SAPO-34 molecular sieve comprises the following steps:
1) Adding an aluminum source into a mixed system of a template agent and water, and stirring for 1-4 hours at 20-40 ℃ to obtain a uniform mixture solution;
2) Adding a phosphorus source into the mixture solution, stirring for 4-6 hours at 40-65 ℃, then adding a silicon source, and continuing stirring for 2-4 hours to obtain an initial gel mixture of the SAPO-34 molecular sieve;
3) Filling the gel mixture obtained in the step 2) into a polytetrafluoroethylene reaction kettle, and then fixing the mixture in a rotary oven for low-temperature crystallization, wherein the crystallization temperature is 100-115 ℃;
4) After crystallization is finished, rapidly cooling the hydrothermal kettle, centrifugally separating out a solid product, washing the solid product to be neutral by deionized water, and then drying at 80-120 ℃ to obtain SAPO-34 molecular sieve raw powder;
5) And (3) calcining the raw powder of the SAPO-34 molecular sieve at a high temperature to remove the template agent contained in the raw powder, thereby obtaining the SAPO-34 molecular sieve with low-silicon and nano-sized lamellar morphology.
2. The method according to claim 1, wherein the molar ratio of the oxide, the template and the water in the initial gel mixture is SiO 2:Al2O3:P2O5, the template is H 2 O=0.01-0.2:1:0.8-1.2:1.5-2.5:20-60, the silicon source is calculated as SiO 2, the aluminum source is calculated as Al 2O3, and the phosphorus source is calculated as P 2O5.
3. The method according to claim 1, wherein the silicon source is at least one of silica sol, ethyl orthosilicate, sodium silicate, white carbon black and active silica, the aluminum source is at least one of aluminum oxide, pseudo-boehmite, aluminum isopropoxide and aluminum hydroxide, the template agent is at least one of tetraethylammonium hydroxide (TEAOH) aqueous solution, triethylamine (TEA) and Morpholine (MOR), and the phosphorus source is at least one of phosphoric acid, phosphate, phosphite and tributyl phosphate.
4. The method of claim 1, wherein in step 3), the rotation speed of the oven is set to 30-60r/min, and the crystallization time is set to 60-120h.
5. The method according to claim 1, wherein in step 5), the calcination is carried out at a temperature of 500 to 650 ℃ for a calcination time of 6 to 12 hours.
6. The use of the low-silicon nano flaky SAPO-34 molecular sieve prepared by the preparation method of any one of claims 1-5 in a reaction for preparing low-carbon olefin from methanol.
7. The process according to claim 6, wherein the reaction pressure is from 0.1 to 0.4MPa, the space velocity is from 1 to 3h -1 and the reaction temperature is from 400 to 550 ℃.
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