CN116081638A - Preparation method of nano sheet AFN structure molecular sieve - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 104
- 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 104
- 239000002135 nanosheet Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000002243 precursor Substances 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 31
- -1 polypropylene Polymers 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 239000011521 glass Substances 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
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- 238000007789 sealing Methods 0.000 description 10
- 239000008399 tap water Substances 0.000 description 10
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- 238000005406 washing Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 244000282866 Euchlaena mexicana Species 0.000 description 5
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 101100059320 Mus musculus Ccdc85b gene Proteins 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- CCDBCHAQIXKJCG-UHFFFAOYSA-N 1-propan-2-ylpiperidin-4-one Chemical compound CC(C)N1CCC(=O)CC1 CCDBCHAQIXKJCG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- NGHMEZWZOZEZOH-UHFFFAOYSA-N silicic acid;hydrate Chemical compound O.O[Si](O)(O)O NGHMEZWZOZEZOH-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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]
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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Abstract
The invention discloses a preparation method of a nano sheet AFN structure molecular sieve, which comprises the steps of adding an aluminum source into water, adding a phosphorus source and a template agent, adding a silicon source, drying and grinding to obtain an SAPO-14 molecular sieve xerogel precursor; adding an aluminum source into water, uniformly mixing, adding a phosphorus source and a template agent, uniformly mixing, drying, and grinding to obtain an AlPO-14 molecular sieve xerogel precursor; adding water into a SAPO-14 molecular sieve xerogel precursor or an AlPO-14 molecular sieve xerogel precursor reaction kettle, isolating the xerogel precursor from the water, and maintaining the temperature at 150-180 ℃ for 4-8h to obtain the molecular sieve with the nano sheet AFN structure. The precursor is in a dry gel form before being crystallized in a kettle, the solvent content is extremely low, the close contact between materials with different components is facilitated, the nucleation rate is high, the synthesis time is greatly shortened, the crystallinity is slightly different, and the crystallinity is increased along with the time extension.
Description
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and relates to a preparation method of a nano sheet AFN structure molecular sieve.
Background
Propylene is an important chemical basic raw material, is widely applied to the fields of modern petrochemical industry and fine chemical industry, plays a role in the chemical industry, and is an important raw material for producing chemicals such as polypropylene, acrylonitrile, propylene oxide and the like. At present, the production process of propylene in China mainly comprises catalytic cracking, steam cracking, preparing olefin from coal/methanol (CTO/MTO) and preparing olefin from Propane Dehydrogenation (PDH).
Crude catalytic cracking and naphtha steam cracking are traditional propylene production routes, but propylene is only a byproduct in the two routes, the yield is low, and the propylene purity is low. The propane dehydrogenation is to take propane as a raw material and obtain propylene through dehydrogenation treatment, the route has the characteristics of low investment, high yield, short process flow, high purity of the obtained propylene, few byproducts and the like, but the economy of the propane dehydrogenation process mainly depends on the price difference of raw materials propane and propylene and stable acquisition of the propane, the supply of the propane raw material has uncertainty, in addition, the future productivity will intensively burst, and certain risk exists in the economy of the propane dehydrogenation process. The coal-to-olefin (MTO) reaction has the advantages of high methanol conversion rate and high low-carbon olefin selectivity, the coal-to-methanol technology is mature, the methanol supply is greater than the market current situation, and the MTO reaction has wide development prospect and huge application space.
The research and development of the high-performance catalyst is the core for controlling the reaction of preparing olefin from methanol, and the molecular sieve has a uniform pore canal structure, good hydrothermal stability, controllable acid property and unique shape-selective effect, and is the main catalyst for the reaction of preparing olefin from methanol. The existing common catalyst for preparing olefin from methanol mainly comprises two molecular sieves, namely ZSM-5 and SAPO-34. ZSM-5 is a silicon-aluminum molecular sieve with an MFI topological structure, and the molecular sieve has relatively excellent anti-carbon property due to a special pore canal structure, is relatively slow in deactivation in MTO (Methanol to Olefins, methanol-to-olefin) reaction, can keep long-time catalysis, and has more advantages on propylene and aromatic hydrocarbon in product selectivity due to relatively strong acidity. SAPO-34 is a silicon-aluminum-phosphorus molecular sieve with a CHA topological structure, and is the most widely applied catalyst for the industrial MTO reaction at present. The pore size formed by the special pore structure and proper acidity make the catalyst have the advantage of high total olefin selectivity in the MTO reaction, but the selectivity of the product of the MTO reaction catalyzed by the SAPO-34 molecular sieve is difficult to regulate and control, and the propylene/ethylene ratio is low.
Patent CN108147423 discloses a synthetic method of an AFN structure silicon aluminum phosphorus SAPO-14 molecular sieve, which takes 1-isopropyl-4-piperidone as a template agent. Comprises the steps of adopting a hydrothermal method to prepare the AFN structure silicon-aluminum-phosphorus molecular sieve: carrying out hydrothermal crystallization on a mixed solution containing a phosphorus source, an aluminum source, a silicon source, a template agent R and water, and then carrying out solid-liquid separation and drying; and preparing the AFN structure silicon-phosphorus-aluminum molecular sieve by adopting a phosphorus-aluminum dry glue solution phase inversion method, aging the mixed solution A containing a phosphorus source, an aluminum source and water, then drying to prepare phosphorus-aluminum dry glue, carrying out hydrothermal crystallization on the raw material mixture B containing the phosphorus-aluminum dry glue, the silicon source, the template agent R and the water, and then carrying out solid-liquid separation and drying.
In the literature (YangM, liB, gaoM, et al, high propylene selectivity in methanol conversion over a small-pore SAPO molecular sieve with ultra-smallage [ J ]. ACSCatalysis,2020,10 (6): 3741-3749.), pseudo-boehmite, phosphoric acid, TEOS, isopropylamine and water are used as raw materials, the SAPO-14 molecular sieve is prepared by rotary hydrothermal crystallization for 48 hours at 200 ℃, and the molecular sieve is used in MTO reaction, wherein the highest diene selectivity can reach 87.5%, and the propylene selectivity can reach 77.3%, which is the highest record of single-pass propylene selectivity reported in the literature at present.
The same hydrothermal synthesis method is used in literature (ZhouY, zhangJ, maW, et al small pore SAPO-14-based zeolites with improved propylene selectivity in the methanol toolefins process [ J ]. Inorganic chemistry front, 2022,9 (8): 1752-1760.) to prepare SAPO-14 molecular sieves by crystallization at 200℃for 24 hours using pseudo-boehmite, phosphoric acid, TEOS, isopropylamine and water as raw materials.
In summary, the existing synthesis method of the AFN structure molecular sieve is single, mainly comprises a hydrothermal synthesis method, and has the advantages of higher crystallization temperature, longer crystallization time, and usually more than 24 hours at 200 ℃. In addition, the AFN molecular sieve synthesized by hydrothermal method has the defects of low raw material utilization rate, complex subsequent separation procedures of products and the like.
Therefore, there is a need to develop a simple, green, economical and efficient AFN structure molecular sieve synthesis technology.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a preparation method of a nano sheet AFN structure molecular sieve, which has the advantages of low reaction temperature, short preparation time, high raw material utilization rate and simple subsequent separation process.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
1) Adding an aluminum source into water, uniformly mixing, adding a phosphorus source and a template agent, uniformly mixing, adding a silicon source, uniformly mixing, drying and grinding to obtain a SAPO-14 molecular sieve xerogel precursor; adding an aluminum source into water, uniformly mixing, adding a phosphorus source and a template agent, uniformly mixing, drying, and grinding to obtain an AlPO-14 molecular sieve xerogel precursor;
2) Adding water into a reaction kettle of an SAPO-14 molecular sieve xerogel precursor or an AlPO-14 molecular sieve xerogel precursor, isolating the xerogel precursor from the water, then keeping the mixture at 150-180 ℃ for 4-8 hours, quenching, and removing a template agent to obtain the molecular sieve with the nano sheet AFN structure.
Further, the silicon source is tetraethoxysilane, silica sol Ludox-40, silicon powder or hydrated silicic acid.
Further, the template agent is isopropylamine.
Further, the aluminum source is pseudo-boehmite or aluminum isopropoxide.
Further, the phosphorus source is phosphoric acid.
Further, the SAPO-14 molecular sieve xerogel precursor is prepared according to SiO in a silicon source 2 Al in aluminum source 2 O 3 P in phosphorus Source 2 O 5 Molar ratio of isopropylamine to water, (0.1-1.5) SiO 2 :(0.4-3)Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O; the AlPO-14 molecular sieve xerogel precursor is prepared by mixing Al in an aluminum source 2 O 3 P in phosphorus Source 2 O 5 Mole ratio of isopropylamine to water, (0.4-3) Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O。
Further, the dosage ratio of the SAPO-14 molecular sieve xerogel precursor or the AlPO-14 molecular sieve xerogel precursor to water in the step 2) is 1:0.5-24g.
Further, the temperature for removing the template agent is 550-650 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a mode of combining a xerogel method and a steam-assisted crystallization technology is adopted to efficiently prepare the nano-sheet molecular sieve phosphorus aluminum AlPO-14 molecular sieve and the silicon aluminum phosphorus SAPO-14 molecular sieve with AFN structures, the molecular sieve has good crystallinity and good hydrothermal stability, the nano-sheet particle morphology is adopted, the silicon aluminum phosphorus SAPO-14 molecular sieve has moderate acid strength and adjustable acid quantity. According to the invention, the SAPO-14 molecular sieve xerogel precursor and the AlPO-14 molecular sieve xerogel precursor are in a dry gel form before entering a kettle for crystallization, the solvent content is extremely low, so that close contact between materials with different components is facilitated, the nucleation rate is high, the synthesis time is greatly shortened, the crystallization time is 4-8 hours, the crystallinity is slightly different, the crystallinity is increased along with the time extension, and the problems that the materials are required to interact under the self-pressure of the solvent and the nucleation rate is slower in the hydrothermal preparation technology in the prior art are solved. The invention has low synthesis temperature, can crystallize at 150-180 ℃ and is easy to operate.
Furthermore, the SAPO-14 molecular sieve of the invention is applied to MTP reaction, wherein the selectivity of diene (ethylene and propylene) is up to 86.57%, the selectivity of propylene is up to 79.98%, and the P/E is up to 9.08.
Furthermore, the silicon-aluminum source of the invention has wide sources, the silicon source can be TEOS, ludox-40, fumed silica hydrate, and the aluminum source can be pseudo-boehmite or aluminum isopropoxide.
Furthermore, the xerogel is crystallized in a kettle, the solvent consumption is low, and the product is easy to separate.
Drawings
Fig. 1 is an X-ray diffraction pattern of comparative example 1 and example 1.
Fig. 2 is a scanning electron microscope picture of comparative example 1.
Fig. 3 is a scanning electron microscope picture of example 1.
FIG. 4 is NH of comparative example 1 and example 1 3 -TPD profile.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention adopts a method combining a xerogel method and a steam-assisted crystallization technology to efficiently prepare the silicoaluminophosphate molecular sieve SAPO-14 and the phosphoaluminophosphate molecular sieve AlPO-14 with the nano-sheet AFN structure, and the preparation process is as follows:
1) Raw materials: silicon source (TEOS (Tetraethoxysilane), ludox-40 (i.e. silica sol), fumeslica (i.e. silica powder) or hydrated silicic acid), templating agent (isopropylamine, IPA), aluminum source (pseudo-boehmite or aluminum isopropoxide), phosphorus source (phosphoric acid) and water.
2) Synthesizing proportion, the SAPO-14 molecular sieve is prepared according to SiO in a silicon source 2 Al in aluminum source 2 O 3 P in phosphorus Source 2 O 5 Mole ratio of isopropylamine to water; alPO-14 molecular sieves are based on Al in an aluminum source 2 O 3 P in phosphorus Source 2 O 5 The mole ratio of isopropylamine to water is as follows:
SAPO-14 molecular sieves:(0.1-1.5)SiO 2 :(0.4-3)Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O。
AlPO-14 molecular sieves: (0.4-3) Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O。
3) Preparation steps
Preparation of xerogel of SAPO-14 molecular sieve: adding an aluminum source into water according to a synthesis ratio, and uniformly stirring for 1h; then adding a phosphorus source and a template agent in sequence, and uniformly stirring for 1h; and finally adding a silicon source to obtain a solvent, transferring the solution to a shaking table, shaking until the solution is uniform and layering does not occur, transferring the solution to an evaporation dish, drying at 60-80 ℃ to obtain xerogel, and crushing and grinding the hard cake-shaped xerogel into powder to obtain the SAPO-14 molecular sieve xerogel precursor.
Xerogel preparation of AlPO-14 molecular sieves: adding an aluminum source into water according to a synthesis ratio, and uniformly stirring for 1h; and sequentially adding a phosphorus source and a template agent, uniformly stirring for 1h to obtain a solvent, transferring the solution into an evaporation dish, drying at 80 ℃ to obtain xerogel, and crushing and grinding the hard cake-shaped xerogel into powder to obtain an AlPO-14 molecular sieve xerogel precursor.
Steam assisted reforming (SAC): putting 1g of prepared SAPO-14 molecular sieve xerogel precursor or AlPO-14 molecular sieve xerogel precursor into a glass vessel, adding 0.5-24g of water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting the glass vessel into the lining to ensure that the xerogel precursor cannot be directly contacted with liquid water, sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle into an oven preheated to 150-180 ℃, quenching the high-pressure reaction kettle by using tap water after keeping for 4-8 hours, condensing steam during high-temperature water absorption and quenching, recovering a sample by centrifuging, washing and drying products in the glass vessel, and calcining at 550-650 ℃ to remove a template agent to obtain the nano sheet-shaped AFN structural silicon-aluminum-phosphorus molecular sieve SAPO-14 or phosphorus-aluminum molecular sieve AlPO-14.
4) Use of SAPO-14 molecular sieves in MTP (methanol to propylene) reactions: the MTP catalytic reaction experiment is carried out on a two-stage fixed bed reactor, the device is divided into a preheating stage and a reaction stage, the preheating stage is used for preheating reaction materials to 150 ℃, the reaction stage is filled with 0.25g of SAPO-14 molecular sieve, argon is used as carrier gas in the whole device, and the flow is controlled to be 30mL/min. The catalyst was activated at 600 ℃ for 2 hours, then the reaction section temperature was maintained at 400 ℃, the device sample injection was performed by batch injection, and the product components were detected by on-line chromatography, sampling was performed at the time when the reaction proceeded for 2 minutes, 6 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, respectively.
Wherein the raw materials comprise the following components in percentage by weight:
silicon source (TEOS, ludox-40, silicic acid hydrate, fumed silica), aluminum source (pseudo-boehmite), phosphorus source (phosphoric acid), template agent (isopropylamine) and deionized water, wherein the silicon source is SiO 2 The aluminum source is Al 2 O 3 Phosphorus source P 2 O 5 The mole ratio of each material of the SAPO-14 molecular sieve is as follows: aSiO (al-Si-O) 2 :bAl 2 O 3 :cP 2 O 5 :dIPA:eH 2 O, wherein a: b: c: d: e=0.1-1.5: 0.4-3:1:1.5-3:20-50; the mole ratio of the materials of the AlPO-14 molecular sieve is as follows: aAl (al) 2 O 3 :bP 2 O 5 :cIPA:dH 2 O, wherein a: b: c: d=0.4-3:1:1.5-3:20-50.
The molecular sieve prepared by the invention has good crystallinity, good hydrothermal stability, nano-sheet particle morphology, the acid property of the SAPO-14 molecular sieve, moderate acid strength and adjustable acid quantity, and the AlPO-14 molecular sieve has no acid property because of no silicon.
Comparative example 1 (Synthesis of SAPO-14 by hydrothermal method)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 0.26g of TEOS into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Placing the solution obtained in the step (3) into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, sealing the high-pressure reaction kettle, transferring the high-pressure reaction kettle into an oven preheated to 200 ℃, keeping the temperature for 24 hours, quenching the high-pressure reaction kettle by tap water, centrifuging, washing, drying and recovering a sample, and calcining at 650 ℃ for 12 hours to remove a template agent to obtain a final product.
Example 1 (TEOS, 0.8 SiO) 2 ,8H-SAPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 2.08g of TEOS into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining the sample at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 2 (AlPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour to obtain a solution;
(3) Transferring the solution obtained in the step (2) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(4) Putting 1g of the solid precursor obtained in the step (3) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(5) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by tap water, centrifuging, washing, drying and recovering a sample, and calcining at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 3 (3 Al) 2 O 3 ，1.5SiO 2 -SAPO-14)
(1) Under the stirring condition, 5.10g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 3.91g of TEOS into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 60 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 4 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining at 550 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 4 (0.4 Al) 2 O 3 ，1SiO 2 -SAPO-14)
(1) Under the stirring condition, 0.68g of pseudo-boehmite is added into 11.26g of deionized water, and the mixture is stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 2.60g of TEOS into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 70 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 6 hours, quenching the high-pressure reaction kettle by tap water, recovering a sample by centrifugation, washing and drying, and calcining at 600 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 5 (1.5 SDA-SAPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 1.11g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 1.04g of TEOS into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 160 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining the sample at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 6 (Ludox-40-SAPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Slowly dripping 0.75g of Ludox-40 into the solution in the step (2), transferring the solution onto a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining the sample at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 7 (Fumed iica-SAPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Adding 0.30g Fumed iica to the solution in the step (2), transferring the solution to a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining the sample at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 8 (hydrous silicic acid-SAPO-14)
(1) Under the stirring condition, 1.70g of pseudo-boehmite is added into 11.26g of deionized water, and stirred for 1h to form a uniform solution A;
(2) 2.88g of phosphoric acid and 2.22g of isopropylamine are slowly added into the solution A in sequence under the stirring condition, and the mixture is stirred for 1 hour;
(3) Adding 0.075g of hydrated silicic acid into the solution in the step (2), transferring the solution to a shaking table, and shaking until the solution is uniform and has no layering phenomenon;
(4) Transferring the solution obtained in the step (3) into an evaporation dish, drying at 80 ℃ for 5 hours, and grinding into powder to obtain a solid precursor.
(5) Putting 1g of the solid precursor obtained in the step (4) into a glass bottle, adding 4g of deionized water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting a glass vessel into the lining to enable xerogel not to be in direct contact with liquid water, and sealing the high-pressure reaction kettle;
(6) Transferring the high-pressure reaction kettle into an oven preheated to 180 ℃, keeping the temperature for 8 hours, quenching the high-pressure reaction kettle by using tap water, recovering a sample by centrifugation, washing and drying, and calcining the sample at 650 ℃ for 12 hours to remove the template agent, thus obtaining the final product.
Example 9
1) Adding an aluminum source into water, uniformly mixing, sequentially adding a phosphorus source and a template agent, uniformly mixing, adding a silicon source, shaking on a shaking table until the solution is uniform and layering phenomenon does not exist, drying to obtain xerogel, and crushing and grinding the xerogel into powder to obtain a SAPO-14 molecular sieve xerogel precursor; the silicon source is silicon powder, the template agent is isopropylamine, the aluminum source is pseudo-boehmite, and the phosphorus source is phosphoric acid. SAPO-14 molecular sieve xerogel precursor is prepared according to SiO in silicon source 2 Al in aluminum source 2 O 3 P in phosphorus Source 2 O 5 The mole ratio of isopropylamine to water, aSiO 2 :bAl 2 O 3 :cP 2 O 5 :dIPA:eH 2 O, wherein a: b: c: d: e=0.1: 3:1:3:20;
2) Putting the SAPO-14 molecular sieve xerogel precursor into a glassware, adding water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting the glassware into the lining to isolate the xerogel precursor from water, then keeping the xerogel precursor at 170 ℃ for 5 hours, quenching, calcining at 580 ℃ for 12 hours to remove a template agent, and obtaining the molecular sieve with a nano sheet AFN structure. The dosage ratio of the SAPO-14 molecular sieve xerogel precursor to water is 1:0.5g.
Example 10
1) Adding an aluminum source into water, uniformly mixing, sequentially adding a phosphorus source and a template agent, uniformly mixing, adding a silicon source, shaking on a shaking table until the solution is uniform and layering phenomenon does not exist, drying to obtain xerogel, and crushing and grinding the xerogel into powder to obtain a SAPO-14 molecular sieve xerogel precursor; the silicon source is silicon powder, the template agent is isopropylamine, the aluminum source is pseudo-boehmite, and the phosphorus source is phosphoric acid. SAPO-14 molecular sieve xerogel precursor is prepared according to SiO in silicon source 2 Al in aluminum source 2 O 3 P in phosphorus Source 2 O 5 The mole ratio of isopropylamine to water, aSiO 2 :bAl 2 O 3 :cP 2 O 5 :dIPA:eH 2 O, wherein a: b: c: d: e=1.5: 0.4:1:1.5:50;
2) Putting the SAPO-14 molecular sieve xerogel precursor into a glassware, adding water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting the glassware into the lining to isolate the xerogel precursor from water, then keeping the xerogel precursor at 170 ℃ for 5 hours, quenching, and calcining at 620 ℃ for 12 hours to remove a template agent, thereby obtaining the molecular sieve with a nano sheet AFN structure. The dosage ratio of the SAPO-14 molecular sieve xerogel precursor to water is 1:24g.
Example 11
1) Adding an aluminum source into water, uniformly mixing, sequentially adding a phosphorus source and a template agent, uniformly mixing, then drying to obtain xerogel, crushing and grinding the xerogel into powder to obtain an AlPO-14 molecular sieve xerogel precursor; the silicon source is silica sol Ludox-40, the template agent is isopropylamine, the aluminum source is aluminum isopropoxide, and the phosphorus source is phosphoric acid.
The AlPO-14 molecular sieve xerogel precursor is prepared by mixing Al in an aluminum source 2 O 3 P in phosphorus Source 2 O 5 Based on the mole ratio of isopropylamine to water, aAl 2 O 3 :bP 2 O 5 :cIPA:dH 2 O, wherein a: b: c: d=1:1:2:30.
2) Putting an AlPO-14 molecular sieve xerogel precursor into a glassware, adding water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting the glassware into the lining to isolate the xerogel precursor from water, keeping the xerogel precursor at 150 ℃ for 8 hours, quenching, calcining at 600 ℃ for 12 hours to remove a template agent, and obtaining the molecular sieve with a nano sheet AFN structure. The dosage ratio of AlPO-14 molecular sieve xerogel precursor to water is 1:15g.
Example 12
1) Adding an aluminum source into water, uniformly mixing, sequentially adding a phosphorus source and a template agent, uniformly mixing, then drying to obtain xerogel, crushing and grinding the xerogel into powder to obtain an AlPO-14 molecular sieve xerogel precursor; the silicon source is silica sol Ludox-40, the template agent is isopropylamine, the aluminum source is aluminum isopropoxide, and the phosphorus source is phosphoric acid.
The AlPO-14 molecular sieve xerogel precursor is prepared by mixing Al in an aluminum source 2 O 3 P in phosphorus Source 2 O 5 Based on the mole ratio of isopropylamine to water, aAl 2 O 3 :bP 2 O 5 :cIPA:dH 2 O, wherein a: b: c: d=2:1:2.5:40.
2) Putting an AlPO-14 molecular sieve xerogel precursor into a glassware, adding water into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, putting the glassware into the lining to isolate the xerogel precursor from water, keeping the xerogel precursor at 165 ℃ for 5 hours, quenching, calcining at 550 ℃ for 12 hours to remove a template agent, and obtaining the molecular sieve with a nano sheet AFN structure. The dosage ratio of the AlPO-14 molecular sieve xerogel precursor to water is 1:5g.
Application of SAPO-14 prepared by xerogel method in MTP reaction:
use of SAPO-14 molecular sieves in MTP reactions: the MTP catalytic reaction experiment is carried out on a two-stage fixed bed reactor, the device is divided into a preheating stage and a reaction stage, the preheating stage is used for preheating reaction materials to 150 ℃, the reaction stage is filled with 0.25g of the SAPO-14 comparative example 1 or the molecular sieve of example 1, argon is used as carrier gas in the whole device, and the flow is controlled to be 30mL/min. The catalyst was activated at 600 ℃ for 2 hours, then the reaction section temperature was maintained at 400 ℃, the device sample injection was performed by batch injection, and samples were taken at the time when the reaction proceeded to 2 minutes, 6 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, respectively, and the product components were detected by on-line chromatography, with the highest propylene selectivity as shown in table 1.
Table 1 summary of data for comparative example 1 and example 1
Referring to fig. 1 and table 1, it can be seen that the crystallinity and yield of the product of example 1 are greatly improved compared to the products of comparative example 1 and example 1.
Referring to fig. 2 and 3, it can be seen that the products of comparative example 1 and example 1 have similar particle morphology, both of which are nanosheet particle morphology.
Referring to FIG. 4, it can be seen that the weak acid duty cycle of the example 1 product is higher at similar total acid levels compared to the product of comparative example 1 and example 1, resulting in improved propylene selectivity when the example 1 product is used in an MTP reaction.
Claims (8)
1. The preparation method of the nano sheet AFN structure molecular sieve is characterized by comprising the following steps:
1) Adding an aluminum source into water, uniformly mixing, adding a phosphorus source and a template agent, uniformly mixing, adding a silicon source, uniformly mixing, drying and grinding to obtain a SAPO-14 molecular sieve xerogel precursor; adding an aluminum source into water, uniformly mixing, adding a phosphorus source and a template agent, uniformly mixing, drying, and grinding to obtain an AlPO-14 molecular sieve xerogel precursor;
2) Adding water into a reaction kettle of an SAPO-14 molecular sieve xerogel precursor or an AlPO-14 molecular sieve xerogel precursor, isolating the xerogel precursor from the water, then keeping the mixture at 150-180 ℃ for 4-8 hours, quenching, and removing a template agent to obtain the molecular sieve with the nano sheet AFN structure.
2. The method for preparing a nano-sheet AFN structure molecular sieve according to claim 1, wherein the silicon source is tetraethoxysilane, silica sol Ludox-40, silica powder or silicic hydrate.
3. The method for preparing a nano-sheet AFN structure molecular sieve according to claim 1, wherein the template agent is isopropylamine.
4. The method for preparing a molecular sieve with a nano-sheet AFN structure according to claim 1, wherein the aluminum source is pseudo-boehmite or aluminum isopropoxide.
5. The method for preparing a molecular sieve with a nano-sheet AFN structure according to claim 1, wherein the phosphorus source is phosphoric acid.
6. The method for preparing nano-sheet AFN structure molecular sieve according to claim 1, wherein the SAPO-14 molecular sieve xerogel precursor is prepared from SiO in silicon source 2 Al in aluminum source 2 O 3 P in phosphorus Source 2 O 5 Molar ratio of isopropylamine to water, (0.1-1.5) SiO 2 :(0.4-3)Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O; the AlPO-14 molecular sieve xerogel precursor is prepared by mixing Al in an aluminum source 2 O 3 P in phosphorus Source 2 O 5 Mole ratio of isopropylamine to water, (0.4-3) Al 2 O 3 :1P 2 O 5 :(1.5-3)IPA:(20-50)H 2 O。
7. The method for preparing a nano-sheet AFN structure molecular sieve according to claim 1, wherein the dosage ratio of the SAPO-14 molecular sieve xerogel precursor or the AlPO-14 molecular sieve xerogel precursor to water in the step 2) is 1:0.5-24g.
8. The method for preparing a molecular sieve with a nano-sheet AFN structure according to claim 1, wherein the temperature for removing the template agent is 550-650 ℃.
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