CN116409798A - ZSM-5 molecular sieve and synthesis method thereof - Google Patents
ZSM-5 molecular sieve and synthesis method thereof Download PDFInfo
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- CN116409798A CN116409798A CN202111680553.2A CN202111680553A CN116409798A CN 116409798 A CN116409798 A CN 116409798A CN 202111680553 A CN202111680553 A CN 202111680553A CN 116409798 A CN116409798 A CN 116409798A
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- 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 78
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 77
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 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 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000002149 hierarchical pore Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- -1 benzene and the like Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthesis method of ZSM-5 molecular sieve, the mole ratio of raw materials of the adopted synthetic solution is SiO 2 ：Al 2 O 3 ：Na 2 O: template agent: h 2 O=1: (0.01-0.04): (0.01-0.04): (0.1-0.4): (30-80), and crystallizing the synthetic solution for 15-60min under the ultrasonic condition. The invention also relates to a ZSM-5 molecular sieve synthesized by the synthesis method, wherein the ZSM-5 molecular sieve is a multi-stage pore canal ZSM-5 zeolite molecular sieve and has an intergranular mesoporous and intragranular microporous structure. The method does not need to add extra mesoporous pore-forming agent and has extremely short crystallization time, and the obtained ZSM-5 zeolite molecular sieve has regular morphology and micropores and abundant mesopores, so the method has important application prospect in the fields of shape selective catalysis and the like.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieves, and particularly relates to a method for synthesizing a hierarchical pore ZSM-5 molecular sieve in an ultrafast manner and a synthesized ZSM-5 molecular sieve.
Background
ZSM-5 is a medium pore zeolite molecular sieve with a cross ten-membered ring pore structure, and pore channels of the medium pore zeolite molecular sieve are respectively ten-membered ring straight pore channels along the direction of a b axis
And a ten-membered ring positive dazzle channel in the a-c plane +.>
As the aperture of the ZSM-5 zeolite molecular sieve is similar to the molecular diameter of important compounds such as benzene and the like, and the silicon-aluminum ratio of the ZSM-5 zeolite molecular sieve is continuously adjustable in a very wide range, the ZSM-5 zeolite molecular sieve has very wide application in the fields of shape selective catalysis, adsorption separation and the like.
The multistage pore ZSM-5 molecular sieve catalyst is an important research hotspot in the industry and academia. Because the catalyst has two pore channels of micropores and mesopores, the mass transfer diffusion of guest molecules in the molecular sieve can be effectively enhanced while the shape selective catalytic performance is maintained, so that the carbon deposition of high-temperature reaction is reduced, and the stability of the catalyst is improved. The synthesis of the traditional hierarchical pore ZSM-5 molecular sieve generally takes more than tens of hours, and a mesoporous pore-forming agent with a special structure is generally required to be used, so that the production period is long, the cost is high, and the large-scale use of the hierarchical pore ZSM-5 molecular sieve in the actual industrial process is not facilitated. The synthesis of multi-stage pore ZSM-5 zeolite molecular sieves using TPAOH and CTAB double templates has been reported by Barakov et al (Microporous and Mesoporous Materials,2017,237,90-107), but crystallization times are as long as 6 days. Choi et al (Nature, 2009,4619,246-249) developed a novel bifunctional quaternary ammonium salt template for preparing a multi-stage pore ZSM-5 nanosheet molecular sieve with a crystallization time of up to 11 days. Chen et al (Industrial and Engineering Chemistry Research,2018,57,32) reported that ZSM-5 zeolite molecular sieves with a multi-stage pore structure were synthesized by using a commercial organosilane surfactant TPOAC as a mesoporous pore former, but crystallization times were also as long as 4 days. Therefore, developing a new simple and efficient synthetic way of porous ZSM-5 zeolite molecular sieve has important significance for industrial application.
CN108128786a discloses a method for preparing a hierarchical pore SAPO-11 molecular sieve with the assistance of ultrasound. The method comprises the following steps: mixing an aluminum source, a phosphorus source, a silicon source, deionized water, a microporous template agent and a mesoporous template agent in proportion, performing ultrasonic treatment, stirring at room temperature until the mixture becomes sol, drying, grinding, performing hydrothermal crystallization, separating and drying a product, and then roasting to remove the microporous template agent to obtain the multistage pore SAPO-11 molecular sieve. The technology has the defects that a microporous template agent and a mesoporous pore-forming agent are required to be added into a synthesis system in the synthesis process, the synthesis process is complex, and the synthesis cost is high.
CN113275034a discloses a hierarchical pore molecular sieve catalyst for eliminating VOCs and a preparation method thereof. The preparation of the catalyst comprises the following steps: (1) Mixing a silicon source, an aluminum source, an alkali source and water together, uniformly stirring, and removing alcohol organic matters generated by decomposition to obtain gel; (2) Transferring the gel into a reaction kettle for sealing and crystallizing to obtain white powdery solid, namely a ZSM-5 molecular sieve carrier; (3) Dipping ZSM-5 molecular sieve carrier in water solution containing noble metal soluble salt, and obtaining noble metal loaded multistage pore molecular sieve catalyst through ultrasonic treatment, stirring, standing, drying and roasting. The multistage pore molecular sieve catalyst prepared by the invention has low cost and simple application, can be directly used for purifying VOCs in the environment without reduction treatment, has stable performance, and has higher catalytic performance and lower catalytic elimination temperature for the catalytic elimination of the VOCs under different conditions. The disadvantages of this technique or the shortcomings with respect to the present invention: the patent adopts the steps of drying aged sol gel to prepare dry gel, grinding the dry gel into powdery dry gel powder, and then putting the powder into a reaction kettle for crystallization reaction, so that the synthesis process is complex and is not suitable for industrialized synthesis.
CN201611234074.7 provides a method for synthesizing an integral hierarchical pore ZSM-5 molecular sieve, which comprises the following steps: (1) Adding an aluminum source, sodium hydroxide, an organic template agent and deionized water into a beaker (1), uniformly stirring, gradually adding a silicon source into the beaker, vigorously stirring to form uniform gel, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 100-220 ℃ for 1-7 days; (2) Repeatedly washing the product obtained in the step (1) with deionized water until the pH value is close to neutral, and drying at 90-110 ℃ to obtain a ZSM-5 type molecular sieve; (3) And roasting the ZSM-5 molecular sieve, and removing the organic template agent to obtain the integral multi-level pore ZSM-5 molecular sieve. The disadvantages of this technique or the shortcomings with respect to the present invention: the monolithic catalyst prepared by the invention needs step treatment in the synthesis process, has complex operation procedures, and has higher synthesis cost.
Disclosure of Invention
Based on the above, the invention aims to provide a synthesis method of a ZSM-5 zeolite molecular sieve with a multistage pore canal, which is quickly synthesized by ultrasonic assistance without adding an additional mesoporous pore-forming agent and has extremely short crystallization time, and the obtained ZSM-5 zeolite molecular sieve has regular morphology and micropores and abundant mesopores, so that the synthesis method has important application prospects in the fields of shape selective catalysis and the like.
In order to achieve the above purpose, the invention provides a synthesis method of ZSM-5 molecular sieve, the mole ratio of raw materials of the adopted synthesis solution is SiO 2 ：Al 2 O 3 ：Na 2 O: template agent: h 2 O=1: (0.01-0.04): (0.01-0.04): (0.1-0.4): (30-80), and crystallizing the synthetic solution for 15-60min under the ultrasonic condition.
The synthesis method of the ZSM-5 molecular sieve provided by the invention is preferable, and comprises the following steps:
(1) Dissolving a template agent in part of water to obtain solution A, taking a silicon source as solution B, and dissolving an aluminum source in the rest of water to obtain solution C;
(2) The solution A is kept to be stirred rapidly, the solution B is dripped into the solution A, and after the solution D is obtained, stirring is kept continuously to enable the silicon source to be hydrolyzed fully;
(3) The solution D is kept to be stirred rapidly, the solution C is added into the solution D in a dropwise manner for a plurality of times, and the solution D is kept to be stirred for a period of time to obtain a synthetic solution;
(4) And (3) carrying out crystallization reaction on the synthetic liquid obtained in the step (3) under the ultrasonic condition, centrifuging, washing, drying and roasting after crystallization is finished, and finally obtaining the multi-stage pore canal ZSM-5 molecular sieve.
The synthesis method of the ZSM-5 molecular sieve provided by the invention is characterized in that the template agent is tetrapropylammonium hydroxide.
The synthesis method of the ZSM-5 molecular sieve provided by the invention is characterized in that the aluminum source is preferably sodium metaaluminate or aluminum isopropoxide.
The synthesis method of ZSM-5 molecular sieve of the invention is characterized in that preferably, part of water is H 2 60-80wt% of the total amount of O.
The synthesis method of the ZSM-5 molecular sieve provided by the invention is characterized in that preferably, after the solution B is added into the solution A, the stirring time is 12-20h; and after the solution C is added into the solution D, stirring for 1-3h.
The synthesis method of the ZSM-5 molecular sieve according to the invention is characterized in that the reactor adopted in the step (4) is preferably a tubular reactor, the length is 10-30cm, preferably 20cm, the inner diameter is 2-8mm, preferably 6mm, and the outer diameter is 5-10mm, preferably 8mm.
The synthesis method of ZSM-5 molecular sieve of the invention is characterized in that the crystallization conditions are as follows: the temperature is 180-250deg.C, and the time is 15-60min.
The synthesis method of ZSM-5 molecular sieve of the invention, wherein in the step (4), the roasting condition is preferably as follows: the temperature is 500-600 ℃ and the time is 4-6 hours.
Therefore, the invention also provides a ZSM-5 molecular sieve synthesized by the synthesis method, wherein the ZSM-5 molecular sieve is a multi-stage pore canal ZSM-5 zeolite molecular sieve and has an inter-crystal mesoporous and intra-crystal microporous structure, the particle size of primary nano crystal particles is 20-100nm, and the particle size of secondary stacked particles is 0.5-2 mu m.
The beneficial effects of the invention are as follows:
the method for simply and rapidly synthesizing the hierarchical pore ZSM-5 molecular sieve provided by the invention can shorten the reaction time and avoid using expensive mesoporous pore formers, namely, under the condition of not adding mesoporous pore formers, the hierarchical pore ZSM-5 molecular sieve is synthesized by adopting an ultrasonic treatment technology, and the high-quality hierarchical pore ZSM-5 molecular sieve can be rapidly synthesized within 1 hour (only 15 minutes is needed at maximum). The mass transfer rate between interfaces can be improved by applying ultrasonic waves to a chemical reaction medium, the dissolution of substances and the growth rate of crystals are accelerated, and the crystallization time is greatly shortened. The synthesis process provided by the invention is simple, raw materials are easy to obtain, the synthesis time is extremely short, and the method has important significance for further promoting the actual industrial application of the multi-stage pore canal ZSM-5 molecular sieve.
Drawings
Figure 1 is an XRD pattern of the sample obtained in example 1.
Fig. 2 is an SEM image of the sample obtained in example 1.
FIG. 3 is N of the sample obtained in example 1 2 Adsorption and desorption isotherm plot.
FIG. 4 is a sample obtained in example 1 based on N 2 Adsorbed NLDFT pore size distribution plot.
Figure 5 is an XRD pattern of the sample obtained in example 2.
Fig. 6 is an SEM image of the sample obtained in example 2.
FIG. 7 is a sample N obtained in example 2 2 Adsorption and desorption isotherm plot.
FIG. 8 is a sample obtained in example 2 based on N 2 Adsorbed NLDFT pore size distribution plot.
Fig. 9 is an XRD pattern of the sample obtained in example 3.
Fig. 10 is an SEM image of the sample obtained in example 3.
Fig. 11 is an XRD pattern of the sample obtained in example 4.
Fig. 12 is an SEM image of the sample obtained in example 4.
Fig. 13 is an SEM image of the sample obtained in comparative example 5.
Fig. 14 is an XRD pattern of the sample obtained in comparative example 5.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and the experimental methods of specific conditions are not noted in the following examples, and generally, the% is weight% according to conventional conditions.
Example 1
(1) Adding 4.6g of 25wt% tetrapropylammonium hydroxide solution into 10g of water, stirring and mixing uniformly, adding 4.5g of tetraethoxysilane, and hydrolyzing for 12 hours at normal temperature to obtain a silicon source solution;
(2) Adding 0.117g of sodium metaaluminate into 7.5g of water, and stirring until the sodium metaaluminate is completely dissolved to obtain an aluminum source solution;
(3) Maintaining the silicon source solution obtained in the step (1) in a stirring state, and slowly dripping the aluminum source solution obtained in the step (2) into the silicon source solution for three times at intervals of 10 minutes each time; stirring for 3h after dripping is completed, and the proportion of the obtained final synthetic solution is SiO 2 ：Al 2 O 3 ：Na 2 O：M：H 2 O=1: 0.033:0.033:0.26:50, wherein M is a templating agent.
(4) Transferring 5g of the synthetic sol obtained in the step (3) into a stainless steel tube reactor, performing hydrothermal reaction at 250 ℃ for 20min, and cooling to room temperature after the reaction is finished;
(5) Centrifuging and washing the product obtained in the step (4), drying overnight at 60 ℃, and roasting for 6 hours at 550 ℃ to obtain the hierarchical pore ZSM-5 zeolite molecular sieve;
referring to fig. 1, fig. 1 is an XRD pattern of the obtained sample, with distinct characteristic peaks at 7.9 °, 8.8 °, 23.1 °, 23.9 ° and 24.4 °, and it is known that the product prepared is a ZSM-5 zeolite molecular sieve. Referring to FIG. 2, FIG. 2 is an SEM image of the obtained sample, which shows that the sample is formed by stacking nano-sized grains, the primary grain size is 20-50nm, and the secondary stacking particle size is 1-2. Mu.m. Referring to FIG. 3, FIG. 3 shows N of the obtained sample 2 Adsorption/desorption isotherms, which have obvious hysteresis loop structures, are IV-type isotherms, indicate that the obtained molecular sieve sample has obvious mesoporous characteristics. Referring to FIG. 4, FIG. 4 shows that the resulting sample is N-based 2 The adsorbed NLDFT pore diameter distribution diagram has mesoporous pore diameter distribution of 10-40nm and average pore diameter of 20nm.
Example 2
(1) Adding 4.6g of 25wt% tetrapropylammonium hydroxide solution into 10g of water, stirring and mixing uniformly, adding 4.5g of 98wt% tetraethoxysilane, and hydrolyzing at normal temperature for 12 hours to obtain a silicon source solution;
(2) Adding 0.117g of sodium metaaluminate into 7.5g of water, and stirring until the sodium metaaluminate is completely dissolved to obtain an aluminum source solution;
(3) Maintaining the silicon source solution obtained in the step (1) in a stirring state, and slowly dripping the aluminum source solution obtained in the step (2) into the silicon source solution for three times at intervals of 10 minutes each time; stirring is continued for 3 hours after the completion of the dripping, and the synthetic liquid sol is obtained. The proportion of the synthetic solution is SiO2: al2O3: na2O: m: h2o=1: 0.033:0.033:0.26:50, wherein M is a templating agent.
(4) Transferring 5g of the synthetic sol obtained in the step (3) into a stainless steel tube reactor, performing hydrothermal reaction at 250 ℃ for 15min, and cooling to room temperature after the reaction is finished;
(5) Centrifuging and washing the product obtained in the step (4), drying overnight at 60 ℃, and roasting for 6 hours at 550 ℃ to obtain the ZSM-5 zeolite molecular sieve with the hierarchical pore structure;
referring to fig. 5, fig. 5 is an XRD pattern of the obtained sample, with distinct characteristic peaks at 7.9 °, 8.8 °, 23.1 °, 23.9 ° and 24.4 °, and it is known that the product prepared is a ZSM-5 zeolite molecular sieve. Referring to FIG. 6, FIG. 6 is an SEM image of the obtained sample, which shows that the sample is formed by stacking nano-sized grains, the primary grain size is 20-50nm, and the secondary stacking particle size is 1-2. Mu.m. Referring to FIG. 7, FIG. 7 shows N of the obtained sample 2 Adsorption/desorption isotherms, which have obvious hysteresis loop structures, are IV-type isotherms, indicate that the obtained molecular sieve sample has obvious mesoporous characteristics. Referring to FIG. 8, FIG. 8 shows that the resulting sample is based on N 2 The adsorbed NLDFT pore diameter distribution diagram has mesoporous pore diameter of 4-30nm and average pore diameter of 15nm.
Example 3
(1) Adding 18.4g of 25wt% tetrapropylammonium hydroxide solution into 50g of water, stirring and mixing uniformly, adding 18g of tetraethoxysilane, and hydrolyzing at normal temperature for 20h to obtain a silicon source solution;
(2) Adding 0.458g of sodium metaaluminate into 20g of water, and stirring until the sodium metaaluminate is completely dissolved to obtain an aluminum source solution;
(3) Maintaining the silicon source solution obtained in the step (1) in a stirring state, and slowly dripping the aluminum source solution obtained in the step (2) into the silicon source solution for three times at intervals of 10 minutes each time; continuously stirring for 3 hours after the dripping is completed to obtain the final synthetic sol with the following proportion of SiO2: al2O3: na2O: m: h2o=1: 0.033:0.033:0.26:50, wherein M is a templating agent.
(4) Transferring 5g of the synthetic sol obtained in the step (3) into a stainless steel tube reactor, performing hydrothermal reaction at 200 ℃ for 60min, and cooling to room temperature after the reaction is finished;
(5) And (3) centrifuging and washing the product obtained in the step (4), drying overnight at 60 ℃, and roasting for 6 hours at 550 ℃ to obtain the hierarchical pore ZSM-5 zeolite molecular sieve.
Referring to fig. 9, fig. 9 is an XRD pattern of the obtained sample, with distinct characteristic peaks at 7.9 °, 8.8 °, 23.1 °, 23.9 ° and 24.4 °, and it is known that the product prepared is a ZSM-5 zeolite molecular sieve. Referring to FIG. 10, FIG. 10 is an SEM image of the obtained sample, which shows that the sample is formed by stacking nano-sized grains, the primary grain size is 10-30nm, and the secondary stacked grain size is 300-600nm.
Example 4
(1) 13.8g of 25wt% tetrapropylammonium hydroxide solution is taken and added into 20g of water, and the mixture is stirred and mixed uniformly, and then 9g of tetraethoxysilane is added, and the mixture is hydrolyzed for 18 hours at normal temperature to obtain a silicon source solution;
(2) Adding 0.25g of sodium metaaluminate into 10g of water, and stirring until the sodium metaaluminate is completely dissolved to obtain an aluminum source solution;
(3) Maintaining the silicon source solution obtained in the step (1) in a stirring state, and slowly dripping the aluminum source solution obtained in the step (2) into the silicon source solution for three times at intervals of 10 minutes each time; continuously stirring for 3 hours after the dripping is completed to obtain the final synthetic liquid sol with the proportion of SiO2: al2O3: na2O: m: h2o=1: 0.033:0.033:0.39:50, wherein M is a templating agent.
(4) Transferring 5g of the synthetic sol obtained in the step (3) into a stainless steel tube reactor, performing hydrothermal reaction at 200 ℃ for 40min, and cooling to room temperature after the reaction is finished;
(5) Centrifuging and washing the product obtained in the step (4), drying overnight at 60 ℃, and roasting for 6 hours at 550 ℃ to obtain the ZSM-5 zeolite molecular sieve with the hierarchical pore structure;
referring to fig. 11, fig. 11 is an XRD pattern of the obtained sample, with distinct characteristic peaks at 7.9 °, 8.8 °, 23.1 °, 23.9 ° and 24.4 °, and it is known that the product prepared is a ZSM-5 zeolite molecular sieve. Referring to FIG. 12, FIG. 12 is an SEM image of the obtained sample, which shows that the sample is formed by stacking nano-sized grains, the primary grain size is 10-30nm, and the secondary stacked particle size is 200-300nm.
Comparative example 1
(1) Adding 4.6g of 25wt% tetrapropylammonium hydroxide solution into 10g of water, stirring and mixing uniformly, adding 3.2g of silica sol (AS-40, 40 wt%) and aging for 12h at normal temperature to obtain a silicon source solution;
(2) Adding 0.117g of sodium metaaluminate into 7.5g of water, and stirring until the sodium metaaluminate is completely dissolved to obtain an aluminum source solution;
(3) Maintaining the silicon source solution obtained in the step (1) in a stirring state, and slowly dripping the aluminum source solution obtained in the step (2) into the silicon source solution for three times at intervals of 10 minutes each time; stirring for 3h after the dripping is completed to obtain the final synthetic liquid sol with the proportion of SiO 2 ：Al 2 O 3 ：Na 2 O：M：H 2 O=1: 0.033:0.033:0.26:50, wherein M is a templating agent.
(4) Transferring 5g of the synthetic sol obtained in the step (3) into a stainless steel tube reactor, performing hydrothermal reaction at 250 ℃ for 60min, and cooling to room temperature after the reaction is finished;
(5) Centrifuging and washing the product obtained in the step (4), drying overnight at 60 ℃, and roasting for 6 hours at 550 ℃ to obtain the hierarchical pore ZSM-5 zeolite molecular sieve;
referring to fig. 13, fig. 13 is an SEM image of the resulting sample, which is predominantly amorphous; referring to fig. 14, fig. 14 is an XRD pattern of the obtained sample, and characteristic peaks at 7.9 °, 8.8 °, 23.1 °, 23.9 ° and 24.4 ° were not present, further confirming that the prepared product was an amorphous substance.
Comparison of examples and comparative examples shows that even if the synthesis ratio is within the scope of the present invention, rapid synthesis of multi-pore ZSM-5 cannot be achieved when a silicon-aluminum source outside the scope of the present invention is used.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A synthesis method of ZSM-5 molecular sieve is characterized in that the molar ratio of raw materials of the adopted synthetic solution is SiO 2 ：Al 2 O 3 ：Na 2 O: template agent: h 2 O=1: (0.01-0.04): (0.01-0.04): (0.1-0.4): (30-80), and crystallizing the synthetic solution for 15-60min under the ultrasonic condition.
2. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein the method for synthesizing comprises the following steps:
(1) Dissolving a template agent in part of water to obtain solution A, taking a silicon source as solution B, and dissolving an aluminum source in the rest of water to obtain solution C;
(2) The solution A is kept to be stirred rapidly, the solution B is dripped into the solution A, and after the solution D is obtained, stirring is kept continuously to enable the silicon source to be hydrolyzed fully;
(3) The solution D is kept to be stirred rapidly, the solution C is added into the solution D in a dropwise manner for a plurality of times, and the solution D is kept to be stirred for a period of time to obtain a synthetic solution;
(4) And (3) carrying out crystallization reaction on the synthetic liquid obtained in the step (3) under the ultrasonic condition, centrifuging, washing, drying and roasting after crystallization is finished, and finally obtaining the multi-stage pore canal ZSM-5 molecular sieve.
3. The method for synthesizing a ZSM-5 molecular sieve according to claim 1, wherein the template agent is tetrapropylammonium hydroxide.
4. The method for synthesizing a ZSM-5 molecular sieve according to claim 1, wherein the aluminum source is sodium metaaluminate or aluminum isopropoxide.
5. The method for synthesizing a ZSM-5 molecular sieve according to claim 1, wherein the part of the water is H 2 60-80wt% of the total amount of O.
6. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein the stirring time is 12-20h after the solution B is added to the solution A; and after the solution C is added into the solution D, stirring for 1-3h.
7. The method for synthesizing a ZSM-5 molecular sieve according to claim 1, wherein the reactor used in the step (4) is a tubular reactor having a length of 10 to 30cm, preferably 20cm, an inner diameter of 2 to 8mm, preferably 6mm, and an outer diameter of 5 to 10mm, preferably 8mm.
8. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein the crystallization conditions are as follows: the temperature is 180-250deg.C, and the time is 15-60min.
9. The method for synthesizing a ZSM-5 molecular sieve according to claim 1, wherein in the step (4), the roasting condition is: the temperature is 500-600 ℃ and the time is 4-6 hours.
10. A ZSM-5 molecular sieve synthesized by the synthesis method as claimed in any one of claims 1 to 9, wherein the ZSM-5 molecular sieve is a multi-stage pore ZSM-5 zeolite molecular sieve, and has an inter-crystalline mesoporous and intra-crystalline microporous structure, the primary nano-crystalline particle size is 20 to 100nm, and the secondary stacked particle size is 0.5 to 2 μm.
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