CN110002461B - Rose-shaped SAPO-5 molecular sieve with pistils as well as preparation and application thereof - Google Patents
Rose-shaped SAPO-5 molecular sieve with pistils as well as preparation and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- 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 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 3
- 238000005538 encapsulation Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 34
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 241000628997 Flos Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 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
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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]
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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
- C01B32/00—Carbon; Compounds thereof
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- C01—INORGANIC CHEMISTRY
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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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- 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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Abstract
The invention relates to a rose-shaped SAPO-5 molecular sieve with multiple cores and a preparation method and an application thereof, wherein the preparation method mainly comprises the following steps: (1) adding a silicon source, a template agent and a cationic surfactant into deionized water, and stirring at room temperature to obtain a mixed solution; (2) adding an aluminum source and a phosphorus source into the mixed solution, stirring and aging to obtain sol; (3) transferring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180-220 ℃ for 24-48 h, cooling after the reaction is finished, and performing suction filtration and washing to obtain a solid substance; (4) drying at 80 deg.C for 8 h; then roasting for 6 hours in a muffle furnace at the temperature of 550-600 ℃. The average diameter of the prepared pistachio-rose SAPO-5 molecular sieve is less than 5um, the crystallinity is high, the molecular sieve crystal is composed of sheets, and a plurality of gaps are arranged among the sheet layers, so that the surface area of the molecular sieve is greatly improved, and the diffusion limitation is effectively reduced. Can be applied to catalysis, adsorption \ separation, encapsulation, preparation of carbon nano tubes and used as an active component carrier.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a rosette-shaped SAPO-5 molecular sieve with multiple cores, and preparation and application thereof.
Background
The AIPO (aluminum phosphate) series molecular sieves are isomorphously substituted with Si to form Silicoaluminophosphate (SAPOs) molecular sieves. Silicoaluminophosphate (SAPOs) molecular sieves have been widely used in isomerization, alkylation, hydrogenation, dehydrogenation and other reactions due to their tunable acidity and potential industrial prospects. The SAPO-5 molecular sieve is one member of the molecular sieve, an acidic framework is formed by isomorphously substituting phosphorus atoms or two silicon atoms in a single aluminum phosphate framework for a pair of phosphorus and aluminum atoms, the acidic framework has an AFI type structure, the framework is a one-dimensional channel structure of twelve-membered rings formed by four-membered rings and six-membered rings, the pore diameter is 0.73nm multiplied by 0.73nm, and the molecular sieve is a microporous molecular sieve. The SAPO-5 molecular sieve has moderate strong acidity and good hydrothermal stability, and is widely applied to reactions such as benzene alkylation, xylene isomerization, n-hexane cracking and the like.
At present, the application of SAPO-5 molecular sieves in the field of catalysis is mainly focused on the synthesis of multi-stage pore channels and the utilization of surface acidity, and researchers focus on the synthesis of molecular sieves with multi-stage pore structures due to the special pore channel structures of the molecular sieves. The molecular sieve with the multilevel structure has a mesoporous structure, so that on one hand, the diffusion rate of molecules in a pore channel can be effectively improved, and the generation of carbon deposition is slowed down; on the other hand, the presence of mesopores also provides a greater pore volume, increasing the reaction area. Such as Xiaohan, etc., the synthesis of multi-stage pore SAPO-5 molecular sieve and the application thereof in diesel oil hydrofining catalyst, petroleum refining and chemical engineering, 2013.1, Vol.44, No.1, pp.16-21.
The larger the specific surface area provided by the molecular sieve, the correspondingly larger the number of acid sites, and the synthesis of the SAPO-5 molecular sieve with a special morphology is an important aspect of improving the specific surface area. At present, most of the reported SAPO-5 molecular sieves are spherical solid particles with large sizes such as hexagonal prisms, and hollow shapes can be formed to help to improve the surface area of the solid particles.
Disclosure of Invention
The invention aims to provide a rosette-shaped SAPO-5 molecular sieve and a preparation method and application thereof, the rosette-shaped SAPO-5 molecular sieve is formed by assembling a plurality of thin layers, has small size, good stability and high specific surface area, and has a hierarchical pore structure, so that the problem of diffusion in the catalytic process can be remarkably reduced, and the problems in the prior art are solved.
A preparation method of a rose-shaped SAPO-5 molecular sieve with multiple cores mainly comprises the following steps:
(1) adding a silicon source, a template agent and a cationic surfactant into deionized water, and stirring at room temperature to obtain a mixed solution;
(2) adding an aluminum source and a phosphorus source into the mixed solution, stirring and aging to obtain sol;
(3) transferring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180-220 ℃ for 24-48 h, cooling after the reaction is finished, and performing suction filtration and washing to obtain a solid substance;
(4) drying at 80 deg.C for 8 h; and then roasting for 6 hours in a muffle furnace at the temperature of 550-600 ℃ to obtain the petal-shaped SAPO-5 molecular sieve.
Preferably, the cationic surfactant is cetyl trimethyl ammonium bromide; the template agent is triethylamine.
Preferably, the precursor materials of aluminum, silicon and phosphorus are Al 2 O 3 、SiO 2 And P 2 O 5 The feeding molar ratio of each component is as follows: al (aluminum) 2 O 3 :P 2 O 5 :SiO 2 :H 2 O:TEA:CTAB＝1:0.8～1.2:0.3～0.5:60～100:1.5～2.5:0.1～0.35。
Preferably, the silicon source is one of tetraethyl orthosilicate and gas-phase silicon dioxide; the aluminum source is one of aluminum isopropoxide and pseudo-boehmite; the phosphorus source is orthophosphoric acid solution.
Preferably, the stirring time in the step (2) is 4-7 hours, and the aging time is 6-10 hours.
Preferably, the cooling in step (3) is cooling in a natural state.
Preferably, the roasting condition in the step (4) is that the temperature of the muffle furnace is increased at the speed of 2 ℃/min.
The compound rose-shaped SAPO-5 molecular sieve prepared by the preparation method.
The application of the flos rosae rugosae-shaped SAPO-5 molecular sieve can be used as a catalyst, adsorption \ separation, encapsulation, preparation of a carbon nano tube and an active component carrier.
Preferably, the catalyst is used as a catalyst in solid acid catalyzed reactions. Mainly used as a catalyst for xylene isomerization reaction and the like and an active component carrier.
During the synthesis of the rose-shaped SAPO-5 molecular sieve with multiple cores, the added silicon sources (tetraethyl orthosilicate and fumed silica) are all substances with poor water solubility, and form a multiphase system with other substances, and during the hydrothermal synthesis, the synthesis of the molecular sieve is realized through a 'dissolution-crystallization' mechanism. Adding a surfactant CTAB, and improving the dispersibility of the silicon source in the solution by utilizing the solubilization performance of the surfactant CTAB; in addition, CTAB contains a long carbon chain, has the tendency of escaping from the solution, the hydrophilicity of a hydrophilic group limits the escaping of the hydrophilic group, the two processes compete to form a structure which takes a silicon source and part of triethylamine as centers and a hydrophobic group extends outwards, the rest most of triethylamine and part of dissolved silicon source are dispersed in the solution, after an aluminum source and a phosphorus source are added, crystals grow along the three-dimensional structure formed by CTAB under the conditions of a template agent triethylamine and hydrothermal reaction, and finally the apparent rosette-shaped SAPO-5 molecular sieve is formed.
The structure formed by the cationic surfactant is called micelle, and the core of the micelle can surround part of the silicon source and the triethylamine. After the aluminum source and the phosphorus source are added, the molecular sieve is gradually generated under the hydrothermal condition (crystallization process), and at the moment, the silicon source and triethylamine contained in the micelle can be released to participate in the growth of the molecular sieve.
Compared with the prior art, the composite rose-shaped SAPO-5 molecular sieve has the advantages that the average diameter is less than 5um, the crystallinity is high, compared with the SAPO-5 molecular sieve reported in the current literature, the composite rose-shaped SAPO-5 molecular sieve has a very unique structure, the molecular sieve crystal is composed of thin sheets, and a plurality of gaps are formed among the sheet layers, so that the surface area of the molecular sieve is greatly increased. The double-pistil rose-shaped SAPO-5 molecular sieve has the advantages that the pore diameter of micropores is short, and meanwhile, mesopores and even macropores exist, so that the diffusion distance in the micropores is short, and the diffusion limitation is effectively reduced. In addition, compared with the sheet shape, the sheet shape is formed, so that the sheet shape is loose in accumulation, diffusion is facilitated, pressure drop can be reduced, and reaction is facilitated.
Drawings
FIG. 1 is an X-ray powder diffraction XRD pattern of a sample of example 1;
FIG. 2 is a scanning electron micrograph of a sample of example 1;
FIG. 3 is N of the sample of example 1 2 Adsorption-desorption curve chart;
FIG. 4 is NH of a sample of example 1 3 -a TPD curve;
FIG. 5 is an X-ray powder diffraction XRD pattern of the sample of example 2;
FIG. 6 is a scanning electron micrograph of a sample of example 2;
FIG. 7 is a SEM image of a sample of example 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
12.6ml of deionized water was added to a beaker, 0.9ml of tetraethyl silicate was added dropwise thereto, 2.8ml of triethylamine was added thereto, and the mixture was stirred at room temperature, and then 1.08g of cetyltrimethylammonium bromide was weighed and added to the beaker, and the stirring was continued until the cetyltrimethylammonium bromide was dissolved, and the solution was colorless and transparent. Weighing 1.46g of pseudo-boehmite and 1.35ml of phosphoric acid solution, sequentially adding the mixed solution, continuously stirring for 6h, and aging for 6h to obtain gel. And transferring the gel into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an oven after the kettle is filled, and crystallizing for 48 hours at 220 ℃. After crystallization is finished, naturally cooling the reaction kettle to be close to room temperature, carrying out suction filtration on the sample, and washing until the filtrate at the last time is neutral. Collecting solid sample, drying in 80 deg.C blast drying oven for 8 hr, taking out dried sample, grinding into powder, placing in crucible, placing in muffle furnace, heating to 550 deg.C at a speed of 2 deg.C/min, roasting for 6 hr, and cooling to room temperature to obtain flos Rosae Rugosae with multiple pistilsSAPO-5 molecular sieve. The XRD spectrum of the sample is shown in figure 1, and the sample has typical SAPO-5 diffraction peaks and high crystallinity. The Scanning Electron Microscope (SEM) photograph is shown in FIG. 2, and the SEM photograph shows that the sample diameter is about 3um, the morphology is a rosette with multiple cores, and obvious gaps are formed among the lamellae. N is a radical of hydrogen 2 The adsorption-desorption results showed that the specific surface area was 400.6m 2 /g，N 2 The adsorption-desorption curve shows that the mesoporous material has an obvious mesoporous structure, and as shown in figure 3, the mesoporous volume is 0.3487cm 3 (ii) in terms of/g. The gaps between the sheets form mesopores (2-50 nm) and macropores (more than 50 nm).
Example 2
12.6ml of deionized water was added to a beaker, 0.9ml of tetraethyl silicate was added dropwise thereto, 2.8ml of triethylamine was added thereto, and the mixture was stirred at room temperature, and then 1.08g of cetyltrimethylammonium bromide was weighed and added to the beaker, and the stirring was continued until the cetyltrimethylammonium bromide was dissolved, and the solution was colorless and transparent. Weighing 1.46g of pseudo-boehmite and 1.35ml of phosphoric acid solution, sequentially adding the mixed solution, continuously stirring for 6h, and aging for 8h to obtain gel. And transferring the gel into a reaction kettle with a polytetrafluoroethylene lining, transferring the reaction kettle into an oven after the kettle is filled, and crystallizing for 24 hours at 180 ℃. After crystallization is finished, naturally cooling the reaction kettle to be close to room temperature, carrying out suction filtration on the sample, and washing until the filtrate at the last time is neutral. Collecting a solid sample, drying in a forced air drying oven at 80 ℃ for 8h, taking out the dried sample, grinding into powder, transferring into a crucible, placing in a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, roasting for 6h, and cooling to room temperature to obtain the pistachio-rosette SAPO-5 molecular sieve. The XRD spectrum of the sample is shown in figure 4, and the sample has typical SAPO-5 diffraction peaks and high crystallinity. The Scanning Electron Microscope (SEM) photograph is shown in FIG. 5, which shows that the sample diameter is about 5um, the morphology is a rosette with multiple cores, and obvious gaps are formed between the sheets.
Example 3
The procedure in this example is exactly the same as in example 1. Except that the amount of cetyltrimethylammonium bromide added was changed from 1.08g to 0.72 g. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rosea-shaped SAPO-5 molecular sieve.
Example 4
The procedure in this example is exactly the same as in example 1. Except that the amount of cetyltrimethylammonium bromide added was changed from 1.08g to 1.44 g. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rose SAPO-5 molecular sieve.
Example 5
The procedure in this example is exactly the same as in example 1. Except that the aluminum source used was changed from pseudoboehmite to aluminum isopropoxide. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rose SAPO-5 molecular sieve.
Example 6
The procedure in this example is exactly the same as in example 1. Except that the crystallization time was changed from 48h to 24 h. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rose SAPO-5 molecular sieve.
Example 7
The procedure in this example is exactly the same as in example 1. Except that the amount of tetraethyl silicate was changed from 0.9ml to 1.2 ml. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rose SAPO-5 molecular sieve.
Example 8
The procedure in this example is exactly the same as in example 1. Except that the amount of phosphoric acid used was changed from 1.35ml to 1.08 ml. The XRD spectrogram and SEM picture of the prepared sample show that the prepared sample is the pistachio-rose SAPO-5 molecular sieve.
Example 9
The procedure in this example is exactly the same as in example 1. Except that the amount of cetyltrimethylammonium bromide added was changed from 1.08g to 1.72 g. The XRD spectrum of the prepared sample shows SAPO-5 molecular sieve, but the SEM picture is shown in FIG. 7, which shows that the SAPO-5 molecular sieve is not rosette with double cores.
Example 10
The procedure in this example is exactly the same as in example 1. Except that the amount of pseudoboehmite added was changed from 1.46g to 2.92 g. The XRD spectrum of the prepared sample shows SAPO-5 molecular sieve, but the SEM picture shows that the SAPO-5 molecular sieve is not rosette-shaped.
Example 11
The procedure in this example is exactly the same as in example 1. Except that the surfactant added was octadecyl trimethyl ammonium chloride. The rosette SAPO-34 molecular sieve with pistil cannot be obtained.
Example 12
The procedure in this example is exactly the same as in example 1. Except that the templating agent was added without cetyltrimethylammonium bromide. The compound rose-shaped SAPO-5 molecular sieve cannot be obtained, and the traditional SAPO-34 structure is obtained.
Example 13
The procedure in this example is exactly the same as in example 1. Except that cetyltrimethylammonium bromide was added without the template triethylamine. The rosette SAPO-5 molecular sieve with double pistils cannot be obtained.
Example 14
The procedure in this example is exactly the same as in example 1. Except that the templating agent added was tetraethylammonium hydroxide. The compound rose-shaped SAPO-5 molecular sieve cannot be obtained, and the traditional SAPO-34 structure is obtained.
Although embodiments of the present invention have been shown and described, the present invention is not limited to these embodiments, and therefore, modifications or improvements made by those skilled in the art without departing from the scope of the present invention are within the scope of the claims.
Claims (8)
1. A preparation method of a rose-shaped SAPO-5 molecular sieve with pistils is characterized by mainly comprising the following steps:
(1) adding a silicon source, a template agent and a cationic surfactant into deionized water, and stirring at room temperature to obtain a mixed solution;
(2) adding an aluminum source and a phosphorus source into the mixed solution, stirring and aging to obtain sol;
(3) transferring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180-220 ℃ for 24-48 h, cooling after the reaction is finished, and performing suction filtration and washing to obtain a solid substance;
(4) drying at 80 deg.C for 8 h; then roasting for 6 hours in a muffle furnace at the temperature of 550-600 ℃ to obtain a petal-shaped SAPO-5 molecular sieve;
the cationic surfactant is cetyl trimethyl ammonium bromide; the template agent is triethylamine;
precursor materials of aluminum, silicon and phosphorus are respectively Al 2 O 3 、SiO 2 And P 2 O 5 The feeding molar ratio of each component is as follows: al (Al) 2 O 3 :P 2 O 5 :SiO 2 :H 2 O:TEA:CTAB＝1:0.8～1.2:0.3～0.5:60～100:1.5～2.5:0.1～0.35。
2. The preparation method according to claim 1, wherein the silicon source is one of tetraethyl orthosilicate and fumed silica; the aluminum source is one of aluminum isopropoxide and pseudo-boehmite; the phosphorus source is orthophosphoric acid solution.
3. The preparation method according to claim 1, wherein the stirring time in the step (2) is 4-7 hours, and the aging time is 6-10 hours.
4. The method according to claim 1, wherein the cooling in the step (3) is cooling in a natural state.
5. The method according to claim 1, wherein the roasting condition in the step (4) is that the temperature of the muffle furnace is increased at a rate of 2 ℃/min.
6. A pistachio-rose SAPO-5 molecular sieve prepared by the preparation method of any one of claims 1 to 5.
7. The application of the rosette SAPO-5 molecular sieve of claim 6, wherein the rosette SAPO-5 molecular sieve can be used as a catalyst, an adsorption/separation agent, an encapsulation agent, a carbon nanotube preparation agent and an active component carrier.
8. Use according to claim 7, wherein the catalyst is a catalyst for use in a solid acid catalysed reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| PL163309B1 (en) * | 1991-01-30 | 1994-03-31 | Inst Chemii Przemyslowej | Method of obtaining molecular sieves of sapo-5 type |
| CN101428819A (en) * | 2007-11-09 | 2009-05-13 | 汉能科技有限公司 | Process for producing SAPO-5 molecular sieve |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PL163309B1 (en) * | 1991-01-30 | 1994-03-31 | Inst Chemii Przemyslowej | Method of obtaining molecular sieves of sapo-5 type |
| CN101428819A (en) * | 2007-11-09 | 2009-05-13 | 汉能科技有限公司 | Process for producing SAPO-5 molecular sieve |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
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