CN116409799A - Preparation method of ZSM-5 molecular sieve with low template dosage - Google Patents
Preparation method of ZSM-5 molecular sieve with low template dosage Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 51
- 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 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 24
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 44
- 238000001354 calcination Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- OJHHSNMXLORHKW-UHFFFAOYSA-L [OH-].C(CC)[N+](CCC)(CCC)CCC.[Br-].C(CC)[N+](CCC)(CCC)CCC Chemical compound [OH-].C(CC)[N+](CCC)(CCC)CCC.[Br-].C(CC)[N+](CCC)(CCC)CCC OJHHSNMXLORHKW-UHFFFAOYSA-L 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000010335 hydrothermal treatment Methods 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 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
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000001291 vacuum drying 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/14—Pore volume
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a preparation method of a ZSM-5 molecular sieve with low template dosage, which belongs to the field of catalytic materials, and comprises the following steps: tetraethyl orthosilicate is used as a silicon source, sodium metaaluminate is used as an aluminum source, tetrapropylammonium hydroxide is used as a template agent, and water is used according to the molar ratio: silicon source: aluminum source: alkali source: template = 3250:100:0.625:14: (0.83-2.5) for preparation. The addition time of the alkali source sodium hydroxide is adjusted, so that the consumption of the template agent is effectively reduced. The method of the invention can synthesize Si/TPA + ZSM-5 molecular sieve=120 and surface area between 300 and 400m 2 And/g, the prepared ZSM-5 molecular sieve also has a mesoporous structure, and the process is simple to operate, high in production efficiency and wide in application in the petrochemical field.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a preparation method of a ZSM-5 molecular sieve with low template dosage.
Background
ZSM-5 is a porous aluminosilicate molecular sieve having a typical MFI-type structure. The porous material has the characteristics of large specific surface area, uniform and adjustable pore structure, high adsorption capacity, adjustable acidity, excellent hydrothermal stability, shape selectivity and the like, so that the porous material is widely applied to petroleum refining, petrochemical and related industrial processes.
In the synthesis process of the ZSM-5 molecular sieve, organic amine is usually used as a template agent, however, the use of the template agent not only increases the synthesis cost, but also generates a large amount of harmful gas in the process of removing the organic template, and increases air pollution. So much work has been done at present around how to reduce the amount of templating agent used, specifically as follows, (1) Si/TPA without introducing other additives + Is 17, [ Karimi R,Bayati B,Charchi Aghdam N,Powder Techology,2012,229,229-236]If the content of the template agent is further reduced, triethylene tetramine needs to be added, and Si/TPA can be realized + =34, and synthesis conditions are severe, requiring hydrothermal 5 days at 175 ℃. (2) Preparation of high-silicon ZSM-5 molecular sieve aggregate [ Li H, wang Y, meng F, RSC Advances,2016,6,99129-99138 ] by steam assisted method]，Si/TPA + =20, and has an adjustable mesoporous structure, which provides guidance for reducing the content of templating agent. (3) The continuous freezing and vacuum drying technology is adopted to reduce the dosage of the template agent and Si/TPA + About 22[Chen Z,Li Z,Zhang Y,Chemical Engineering Journal,2020,338,124322-124331]. (4) Without adding other additives, the steam auxiliary method is used for preparing Si/TPA + The values of 34, [ Zang Y, wang J, gu J, journal of Solid State Chemistry,2020,291,121643-121649 ] were further increased]But the specific surface area of the synthesized ZSM-5 molecular sieve is only 186m 2 ·g -1 The pore volume is also lower than 0.14cm 3 ·g -1 . In summary, the problems of large consumption of template agent and relatively complex experimental procedures exist in the preparation of the ZSM-5 molecular sieve, which is unfavorable for realizing the low-cost production of the molecular sieve on the premise of not influencing the quality of the molecular sieve.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a ZSM-5 molecular sieve with low template dosage. The process is that tetraethyl orthosilicate is used as a silicon source, sodium metaaluminate is used as an aluminum source, tetrapropylammonium hydroxide is used as a template agent, and the preparation of the ZSM-5 molecular sieve with high crystallinity is realized when the dosage of the template agent is extremely low by adjusting the adding time of sodium hydroxide as an alkali source. The ZSM-5 molecular sieve prepared by the invention has the advantages of uniform particle diameter, mesoporous structure, low cost and the like, and has higher application value in petroleum refining, petrochemical and related industrial processes.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
(1) Dissolving a template agent and an aluminum source in water, stirring in a water bath at room temperature to obtain a uniform mixture, then adding a silicon source into the mixture, continuously stirring, and finally adding an alkali source, continuously stirring until the solution is uniformly mixed to obtain a precursor;
(2) Transferring the obtained precursor into an autoclave with a polytetrafluoroethylene lining, and performing hydrothermal crystallization; taking out the autoclave, cooling to room temperature, washing the obtained product to be neutral by distilled water, separating by a centrifuge, drying, and calcining to obtain the ZSM-5 molecular sieve.
In the step (1), water is added according to the molar ratio: silicon source: aluminum source: alkali source: template = 3250:100:0.625:14: (0.83-2.5);
the template agent in the step (1) is one or more of tetrapropylammonium hydroxide, tetrapropylammonium hydroxide bromine, tetramethylammonium hydroxide and tetraethylammonium hydroxide; preferably, the template is tetrapropylammonium hydroxide (TPAOH);
the aluminum source in the step (1) is sodium metaaluminate (NaAlO) 2 )；
The silicon source in the step (1) is silica sol, fumed silica, tetraethyl orthosilicate or tetramethyl orthosilicate, and preferably the silicon source is tetraethyl orthosilicate (TEOS);
the alkali source in the step (1) is sodium hydroxide (NaOH);
the stirring time in the step (1) is 20-40min;
the room temperature in the step (1) is 25-30 ℃;
the stirring time after the silicon source is added in the step (1) is 3-6h;
the stirring time after the alkali source is added in the step (1) is 1-5h;
the hydrothermal crystallization in the step (2) is carried out for 1-2 days at 140-170 ℃;
the separation of the centrifugal machine in the step (2) is specifically carried out for 2-3 times, 3-5 min/time; the centrifugal speed is 4000r/min;
the drying in the step (2) is carried out at 100 ℃ for 4-8 hours;
the calcining temperature in the step (2) is 450-600 ℃, the calcining time is 3-5h, and the heating rate is 1-2 ℃ min -1 ；
The specific surface area of the ZSM-5 molecular sieve in the step (2) is 300-400m 2 ·g -1 ；
The ZSM-5 molecular sieve in the step (2) has the particle size of 15-20 mu m, contains mesopores and has the pore diameter of 2-3nm;
the method can prepare ZSM-5 molecular sieve with uniform size and high crystallinity under the condition of low template dosage.
The uniform ZSM-5 molecular sieve with low template dosage takes tetraethyl orthosilicate (TEOS) as a silicon source, and sodium metaaluminate (NaAlO) 2 ) The preparation method is characterized in that tetrapropylammonium hydroxide (TPAOH) is used as a template agent, and the preparation method is synthesized under hydrothermal conditions by adjusting the adding time of alkali source sodium hydroxide (NaOH). The method can change the hydrolysis process of tetraethyl orthosilicate, thereby changing the polymerization degree of silicate ions, accelerating the synthesis rate in the hydrothermal process, and effectively reducing the consumption of template agent and Si/TPA under the same hydrothermal time + The molar ratio of (2) is between 40 and 120.
The invention has the beneficial effects that:
1. the ZSM-5 molecular sieve disclosed by the invention has the advantages of uniform particle size, mesoporous structure, high stability and the like.
2. The preparation method disclosed by the invention is a process for changing the hydrolysis process of tetraethyl orthosilicate by adjusting the adding time of NaOH for the first time so as to influence the crystallinity of the molecular sieve, and has the technical advantages of simple preparation process, low cost, obvious effect, wide application range, good reproducibility and the like.
3. The preparation method disclosed by the invention can control the particle size of the molecular sieve by changing the adding time of sodium hydroxide in the preparation process, and can adjust the pore structure of the molecular sieve by changing parameters such as alkalinity, silicon-aluminum ratio and the like.
4. The ZSM-5 molecular sieve disclosed by the invention has the advantages of mesoporous structure, low production cost and the like, and has a good application prospect in the petrochemical field.
Drawings
FIG. 1 is an XRD image, an SEM image, a nitrogen adsorption and desorption curve and a pore size distribution curve of a ZSM-5 molecular sieve prepared in example 1 of the present invention; fig. 1 (a) is an XRD pattern, fig. 1 (b) is an SEM pattern, and fig. 1 (c) is a nitrogen adsorption-desorption curve and a pore size distribution curve;
FIG. 2 is an XRD image, SEM image, nitrogen adsorption and desorption curve and pore size distribution curve of ZSM-5 molecular sieve prepared in example 2 according to the present invention; fig. 2 (a) is an XRD pattern, fig. 2 (b) is an SEM pattern, and fig. 2 (c) is a nitrogen adsorption-desorption curve and a pore size distribution curve.
Detailed Description
The present invention will be described in further detail with reference to examples.
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention without departing from the spirit of the invention are intended to be within the scope of the invention.
Template tetrapropylammonium hydroxide (TPAOH), analytically pure;
tetraethyl orthosilicate (TEOS) relative density 0.93g cm -3 Analytically pure;
sodium metaaluminate (NaAlO) 2 ) Analytically pure;
sodium hydroxide (NaOH), analytically pure;
a preparation method of ZSM-5 molecular sieve with low template dosage comprises the following steps:
(1) The preparation method comprises the following steps of: silicon source: aluminum source: alkali source: template molar ratio = 3250:100:0.625:14: (0.83-2.5) for preparation. The template agent and the aluminum source are dissolved in water, the mixture is stirred in a water bath for a certain time at room temperature to obtain a uniform mixture, then a certain amount of silicon source is added into the mixture to continue stirring for a certain time, and finally an alkali source is added to continue stirring until the solution is uniform. Wherein the silicon source is TEOS, silica sol and fumed silica; the template agent is TPAOH, tetrapropyl bromide and tetramethyl ammonium hydroxide; the aluminum source is NaAlO 2 The method comprises the steps of carrying out a first treatment on the surface of the The alkali source is NaOH.
(2) Transferring the obtained precursor into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal crystallization at 140-170 ℃ for 1-2 days, taking out the autoclave, cooling to room temperature, washing the obtained product to be neutral by distilled water, and separating, drying and calcining to obtain the target product.
Example 1
24.83g deionized water, 0.045g NaAlO 2 0.92g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles followed by stirring for 3 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. As shown in FIG. 1, the particles were uniform in size and particle diameter, about 15 μm, and had a crystallinity of about 103.4% (as compared with commercial powder at Tianjin university, the same applies below) and a mesoporous structure with pore diameters of 2.2nm and 32.8nm and pore volumes of 0.21cm 3 ·g -1 Specific surface area 339m 2 ·g -1 。
Example 2
24.83g deionized water, 0.045g NaAlO 2 0.31g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles followed by stirring for 3 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. As shown in FIG. 2, the particles were uniform in size, had a particle diameter of about 13 μm, a crystallinity of about 98.7%, a pore diameter of 2.5nm and a pore volume of 0.17cm 3 ·g -1 Specific surface area 317m 2 ·g -1 。
Example 3
24.83g deionized water, 0.045g NaAlO 2 0.92g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 1 hour after the completion of the addition, followed by addition of 0.235g of NaOH solid particles followed by stirring for 5 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. Heating rateThe rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle diameter of about 5.2 μm, high crystallinity of about 104.5%, pore diameter of 2.1nm, and pore volume of 0.25cm 3 ·g -1 Specific surface area 379m 2 ·g -1 。
Example 4
24.83g deionized water, 0.045g NaAlO 2 0.92g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 5 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles and stirring was performed for 1 hour, thereby obtaining a precursor solution before hydrothermal reaction. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle diameter of about 10.6 μm, high crystallinity of about 97.0%, pore diameter of 2.3nm, and pore volume of 0.22cm 3 ·g -1 Specific surface area 358m 2 ·g -1 。
Example 5
24.83g deionized water, 0.045g NaAlO 2 0.46g of TPAOH and 0.235g of NaOH solid particles are stirred in a water bath at 30 ℃ for 30min, so that the solutions are uniformly mixed. Then, 9.15g of TEOS was slowly added with stirring, and after the completion of the addition, stirring was performed for 6 hours, thereby obtaining a precursor solution before hydrothermal reaction. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. The particle size is lath-shaped and contains a small amount of mordenite impurity phase, and the crystallinity is about 86.7%.
Example 6
24.83g deionized water, 0.023g NaAlO 2 0.92g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles followed by stirring for 3 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into autoclave, hydrothermal at 140 ℃ for 2 days, and finally, usingCentrifugal washing with ionized water, drying and calcining. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle diameter of about 12.2 μm, high crystallinity of about 96.3%, mesoporous structure, pore diameter of 3.2nm and 20.5nm, and pore volume of 0.21cm 3 ·g -1 Specific surface area 323m 2 ·g -1 。
Example 7
24.83g deionized water, 0.045g NaAlO 2 0.41g of tetrapropyl bromide was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles followed by stirring for 3 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle diameter of about 11.2 μm, high crystallinity of about 95.5%, pore diameter of 3.5nm, and pore volume of 0.21cm 3 ·g -1 Specific surface area 333m 2 ·g -1 。
Example 8
24.83g deionized water, 0.045g NaAlO 2 0.14g of tetramethylammonium hydroxide was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 9.15g of TEOS was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles followed by stirring for 3 hours, and then a precursor solution before hydrothermal reaction was obtained. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle size of about 6.3 μm, high crystallinity of about 96.0% and pore volume of 0.17cm 3 ·g -1 Specific surface area 311m 2 ·g -1 。
Example 9
24.83g deionized water, 0.045g NaAlO 2 Stirring 0.31g of TPAOH in a water bath kettle at 30 DEG CAnd (3) uniformly mixing the solution for 30 min. Then 2.63g of fumed silica was slowly added with stirring, stirring was performed for 3 hours after the addition was completed, followed by adding 0.235g of NaOH solid particles and stirring was performed for 3 hours, thereby obtaining a precursor solution before hydrothermal reaction. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle size of about 5.5 μm, high crystallinity of about 95.0% and pore volume of 0.18cm 3 ·g -1 Specific surface area 325m 2 ·g -1 。
Example 10
24.83g deionized water, 0.045g NaAlO 2 0.31g of TPAOH was stirred in a water bath at 30℃for 30min to allow the solution to mix homogeneously. Then 8.76g of silica sol was slowly added with stirring, stirring was performed for 3 hours after the completion of the addition, followed by adding 0.235g of NaOH solid particles and stirring was performed for 3 hours, thereby obtaining a precursor solution before hydrothermal reaction. Transferring the solution into an autoclave, carrying out hydrothermal treatment at 140 ℃ for 2 days, and finally, centrifugally washing, drying and calcining with deionized water. Calcination conditions: 550 ℃ for 4 hours. The temperature rising rate is 1.5 ℃ min -1 Obtaining ZSM-5 molecular sieve. Uniform size, uniform particle size of about 7.6 μm, high crystallinity of about 98.2% and pore volume of 0.19cm 3 ·g -1 Specific surface area 322m 2 ·g -1 。
Claims (9)
1. The preparation method of the ZSM-5 molecular sieve with low template dosage is characterized by comprising the following steps:
(1) Dissolving a template agent and an aluminum source in water, stirring in a water bath at room temperature to obtain a uniform mixture, then adding a silicon source into the mixture, continuously stirring, finally adding an alkali source, and continuously stirring until the solution is uniformly mixed to obtain a precursor;
(2) Transferring the obtained precursor into an autoclave with a polytetrafluoroethylene lining, and performing hydrothermal crystallization; taking out the autoclave, cooling to room temperature, washing the obtained product to be neutral by distilled water, separating by a centrifuge, drying, and calcining to obtain the ZSM-5 molecular sieve.
2. The method for preparing ZSM-5 molecular sieve with low template according to claim 1, wherein the template in the step (1) includes one or more of tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium hydroxide bromide, tetramethylammonium hydroxide and tetraethylammonium hydroxide; the aluminum source is sodium metaaluminate (NaAlO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Silicon sources include tetraethyl orthosilicate (TEOS), silica sol, fumed silica, and tetramethyl orthosilicate; the alkali source is sodium hydroxide (NaOH).
3. The method for preparing ZSM-5 molecular sieve with low template according to claim 1, wherein the template in the step (1) is preferably tetrapropylammonium hydroxide (TPAOH); the silicon source is preferably tetraethyl orthosilicate (TEOS).
4. The method for preparing the ZSM-5 molecular sieve according to claim 1 with low template dosage, wherein in the step (1), water is used according to the molar ratio: silicon source: aluminum source: alkali source: template = 3250:100:0.625:14: (0.83-2.5).
5. The method for preparing ZSM-5 molecular sieve with low template dosage according to claim 1, wherein the water bath stirring time in the step (1) is 20-40min, and the room temperature is 25-30 ℃.
6. The method for preparing ZSM-5 molecular sieve with low template agent dosage according to claim 1, wherein the stirring time after adding the silicon source in the step (1) is 3-6 hours; the stirring time after the alkali source is added is 1-5h.
7. The method for preparing ZSM-5 molecular sieve with low template agent consumption according to claim 1, wherein the hydrothermal crystallization performed in the step (2) is specifically hydrothermal crystallization at 140-170 ℃ for 1-2 days; the separation of the centrifugal machine is specifically carried out for 2-3 times and 3-5 min/time; the centrifugation rate was 4000r/min.
8. The method for preparing ZSM-5 molecular sieve with low template dosage according to claim 1, wherein the drying in the step (2) is drying at 100 ℃ for 4-8 hours; the calcining temperature of the calcining is 450-600 ℃, the calcining time is 3-5h, and the heating rate is 1-2 ℃ min -1 。
9. The method for preparing ZSM-5 molecular sieve according to claim 1, wherein the specific surface area of the ZSM-5 molecular sieve in step (3) is 300 to 400m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The ZSM-5 molecular sieve has the particle size of 15-20 mu m and a mesoporous structure.
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| WO2016086362A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing multilevel pore zsm-5 zeolite |
| CN109721078A (en) * | 2019-02-26 | 2019-05-07 | 吉林大学 | A method of mesopore molecular sieve is prepared without mesoporous template Direct Hydrothermal method in the system that mesoporous silicon oxide is silicon source presoma |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016086362A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing multilevel pore zsm-5 zeolite |
| CN109721078A (en) * | 2019-02-26 | 2019-05-07 | 吉林大学 | A method of mesopore molecular sieve is prepared without mesoporous template Direct Hydrothermal method in the system that mesoporous silicon oxide is silicon source presoma |
Non-Patent Citations (1)
| Title |
|---|
| 张克立，袁良杰，冯传启编著: "《无机合成化学 第2版》", 31 January 2012, 武汉大学出版社, pages: 295 * |
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