CN115784253A - Aluminum-rich ZSM-5 zeolite molecular sieve microsphere, and method for synthesizing same in one step in high-fluorine system and application thereof - Google Patents
Aluminum-rich ZSM-5 zeolite molecular sieve microsphere, and method for synthesizing same in one step in high-fluorine system and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 64
- 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 64
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 63
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000010457 zeolite Substances 0.000 title claims abstract description 63
- 239000004005 microsphere Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 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 8
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical group [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005624 silicic acid group Chemical group 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000006229 carbon black Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 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 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 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
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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Abstract
An aluminum-rich ZSM-5 zeolite molecular sieve microsphere, a method for synthesizing the same in a high-fluorine system by one step and application thereof. The present invention belongs to the field of zeolite molecular sieve material. The invention aims to solve the technical problems that the existing micron-sized ZSM-5 zeolite molecular sieve microspheres have high preparation cost, complicated process and low mechanical strength, and are not suitable for industrial production. Mixing a silicon source, an aluminum source, a fluorine source, a template agent and deionized water, stirring for a certain time at room temperature, adding a hydrofluoric acid aqueous solution to adjust the pH value to 5-12, then transferring into a closed reaction kettle to carry out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres. The obtained product has uniform appearance and size, low framework silicon-aluminum ratio, simple and quick synthesis method operation and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of zeolite molecular sieve materials, and particularly relates to an aluminum-rich ZSM-5 zeolite molecular sieve microsphere, a method for synthesizing the same in a high-fluorine system in one step and application of the zeolite molecular sieve microsphere.
Background
Zeolitic molecular sieve materials have a highly crystalline framework structure and a system of regular and ordered channels. The material also has adjustable acidity and excellent stability, so the material is widely applied to the fields of adsorption, separation, catalysis and the like. In industrial application, zeolite molecular sieves are usually prepared into shapes such as strips and spheres for convenient separation. However, during the forming process, due to the addition of the binder, part of the active sites of the zeolite molecular sieve are covered and cannot be effectively utilized in the application. In addition, the widely studied nano zeolite molecular sieves can accelerate the diffusion rate and shorten the diffusion path in the catalytic reaction, but the separation is difficult in the preparation process, and in practical application, a binder is required to be added to prepare micron-sized spherical particles. Thus, self-adhering and zeolitic molecular sieve microspheres, either synthesized directly or prepared by incorporating a template, are of particular interest. However, at present, the preparation of micron-sized ZSM-5 zeolite molecular sieve microspheres mostly needs to introduce a template with higher price. The prior methods all have the problems of low mechanical strength of the zeolite microspheres, complex and fussy preparation process and the like.
Disclosure of Invention
The invention aims to solve the technical problems that the existing micron-sized ZSM-5 zeolite molecular sieve microspheres are high in preparation cost, complex in process and not suitable for industrial production, and the mechanical strength of the obtained microspheres is not high, and provides the aluminum-rich ZSM-5 zeolite molecular sieve microspheres, and a method for synthesizing the same in a high-fluorine system in one step and application of the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
One purpose of the invention is to provide a method for synthesizing aluminum-rich ZSM-5 zeolite molecular sieve microspheres in a high fluorine system by one step, which comprises the following steps:
mixing a silicon source, an aluminum source, a fluorine source, a template agent and deionized water, stirring for a certain time at room temperature, adding a hydrofluoric acid aqueous solution to adjust the pH value to 5-12, then transferring into a closed reaction kettle to carry out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Further defined, the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 Meter, siO 2 、Al 2 O 3 The molar ratio of the fluorine source to the template to the deionized water to the hydrofluoric acid is 1: (0.05-0.5): (0.1-5): (0.1-0.5): (10-100): (0.05-0.5).
Further limiting, the silicon source is silicic acid, silica sol, white carbon black or tetraethyl orthosilicate.
Further defined, the aluminum source is alumina, aluminum isopropoxide, aluminum hydroxide, aluminum sulfate, or sodium metaaluminate.
Further defined, the fluorine source is ammonium fluoride, potassium fluoride, cesium fluoride, or sodium fluoride.
Further defined, the templating agent is tetrapropylammonium bromide, tetraethylammonium bromide, or tetrabutylammonium bromide.
Further defined, the concentration of the aqueous hydrofluoric acid solution is 30-50wt.%.
Further limiting, stirring for 1-1.5h at room temperature.
Further limiting, the temperature of the hydrothermal reaction is 100-200 ℃, and the time is 1-10 days.
The invention also aims to provide the aluminum-rich ZSM-5 zeolite molecular sieve microsphere prepared by the method, wherein the microsphere is spherical, the crystal size is 5-8 mu m, and the framework Si/Al is less than or equal to 10.
The invention also aims to provide the application of the aluminum-rich ZSM-5 zeolite molecular sieve microspheres prepared by the method as a catalyst.
Compared with the prior art, the invention has the following remarkable effects:
1) The method can directly obtain the micron-sized ZSM-5 zeolite molecular sieve microspheres with uniform shapes and sizes by a simple one-step method, has simple and quick operation and low cost, and is suitable for industrial production.
2) According to the invention, a fluorine source is used for constructing a high fluorine-silicon ratio system, the uniformity of the morphology and the size of the obtained ZSM-5 zeolite molecular sieve microspheres is obviously improved, hydrofluoric acid is introduced to further improve the fluorine-silicon ratio of a reaction system, and the structural defects of the ZSM-5 zeolite molecular sieve microspheres are effectively reduced, so that the carbon deposition resistance when the microspheres are used as a catalyst is obviously improved, and the service life of the catalyst is further prolonged.
3) The ZSM-5 zeolite molecular sieve microsphere obtained by the invention consists of a plurality of nano small crystal grains, improves the surface area of the zeolite molecular sieve microsphere and is beneficial to the diffusion of reactants and products in the catalysis process.
4) The invention is carried out in the range that the framework silica-alumina ratio (Si/Al is less than or equal to 10) is not more than 10, and the obtained ZSM-5 zeolite molecular sieve microspheres have lower framework silica-alumina ratio so as to obtain more ZSM-5 zeolite molecular sieve microspheres
Catalytic material for acid sites.
Drawings
FIG. 1 is an X-ray diffraction pattern of ZSM-5 zeolite molecular sieve microspheres prepared in example 1-2;
FIG. 2 is a scanning electron micrograph of ZSM-5 zeolite molecular sieve microspheres prepared according to example 1-2; wherein figures (a) and (b) represent the ZSM-5 zeolite molecular sieve of example 1 and figures (c) and (d) represent the ZSM-5 zeolite molecular sieve of example 2;
FIG. 3 is a thermogravimetric plot of ZSM-5 zeolite molecular sieve microspheres prepared in examples 1-2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Example 1: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in the high fluorine system by one step comprises the following steps:
taking 2.6676g of potassium fluoride in a clean plastic beaker, then sequentially adding 1.8206g of white carbon black, 0.6316g of aluminum isopropoxide, 1.0291g of tetrapropylammonium bromide and 18g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, then dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH to 10.95, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging for 10min at 10000rpm, washing the product with deionized water for 3 times until the product is neutral, and drying in a 60 ℃ oven overnight to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Example 2: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in the high fluorine system by one step comprises the following steps:
taking 1.9476g of sodium fluoride in a clean plastic beaker, sequentially adding 1.8206g of white carbon black, 0.6316g of aluminum isopropoxide, 1.0291g of tetrapropylammonium bromide and 18g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH to 10.5, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging for 10min at 10000rpm, washing a product with deionized water for 3 times until the product is neutral, and drying in a 60 ℃ oven overnight to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Example 3: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in the high fluorine system by one step comprises the following steps:
taking 1.6006g of potassium fluoride in a clean plastic beaker, sequentially adding 1.8206g of white carbon black, 0.6316g of aluminum isopropoxide, 1.0291g of tetrapropylammonium bromide and 18g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, then dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH value to 9.85, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging for 10min at 10000rpm, washing a product with deionized water for 3 times until the product is neutral, and drying overnight in a 60 ℃ oven to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Example 4: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in one step in the high-fluorine system comprises the following steps of:
taking 1.3205g of potassium fluoride in a clean plastic beaker, sequentially adding 1.502g of white carbon black, 0.521g of aluminum isopropoxide, 2.0377g of tetrapropylammonium bromide and 18g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH to 9.58, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging for 10min at 10000rpm, washing the product with deionized water for 3 times until the product is neutral, and drying in an oven at 60 ℃ overnight to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Example 5: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in one step in the high-fluorine system comprises the following steps of:
taking 2.2008g of potassium fluoride in a clean plastic beaker, sequentially adding 1.502g of white carbon black, 0.521g of aluminum isopropoxide, 2.0377g of tetrapropylammonium bromide and 18g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, then dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH value to 10.02, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging at 10000rpm for 10min, washing a product with deionized water for 3 times until the product is neutral, and drying in a 60 ℃ oven overnight to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Example 6: the method for synthesizing the aluminum-rich ZSM-5 zeolite molecular sieve microspheres in one step in the high-fluorine system comprises the following steps of:
taking 2.2008g of potassium fluoride in a clean plastic beaker, sequentially adding 1.502g of white carbon black, 0.521g of aluminum isopropoxide, 2.0377g of tetrapropylammonium bromide and 14.63g of deionized water, stirring for 1.5 hours at room temperature to obtain a uniform aqueous solution, dropwise adding 0.1490g of 40wt.% hydrofluoric acid aqueous solution to adjust the pH to 10.29, transferring the obtained white concentrated solution into a closed reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 7 days, taking out the reaction kettle, naturally cooling, centrifuging for 10min at 10000rpm, washing the product with deionized water for 3 times until the product is neutral, and drying in a 60 ℃ oven overnight to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
Detection test
FIG. 1 is an X-ray diffraction pattern of the ZSM-5 zeolite molecular sieves prepared in examples 1-2. It can be seen from FIG. 1 that the ZSM-5 zeolite molecular sieves obtained in examples 1-2 all have a framework structure with high crystallinity.
FIG. 2 is a scanning electron micrograph of the ZSM-5 zeolite molecular sieve prepared in examples 1-2, wherein FIGS. (a) and (b) are the ZSM-5 zeolite molecular sieve of example 1, and FIGS. (c) and (d) are the ZSM-5 zeolite molecular sieve of example 2. As can be seen from FIG. 2, the ZSM-5 zeolite molecular sieves prepared in examples 1-2 all have high crystallinity and uniform crystal morphology, the crystal size distribution range is between 5 and 8 μm, and each zeolite molecular sieve microsphere consists of a nanocrystal, which shows that the high fluorine system of the invention significantly improves the morphology regularity and the size uniformity of the obtained product.
FIG. 3 is a thermogravimetric analysis curve of the ZSM-5 zeolite molecular sieve prepared in example 1-2, and it can be seen that the materials obtained by the preparation method for synthesizing the zeolite molecular sieve microspheres in one step in a high fluorine system have better thermal stability.
Tables 1-2 show XRF data for ZSM-5 zeolite molecular sieve microspheres prepared in examples 1-2, respectively. According to the data obtained, the silica-alumina molar ratio of the ZSM-5 zeolite molecular sieve microsphere material obtained in example 1 is 8, and the silica-alumina molar ratio of the ZSM-5 zeolite molecular sieve microsphere material obtained in example 2 is 5.6.
Table 1 XRF data for ZSM-5 zeolite molecular sieve microspheres from example 1
| Components | As a result, the | Unit |
| SiO 2 | 71.0 | mass％ |
| Al 2 O 3 | 7.57 | mass％ |
| F | 13.4 | mass％ |
Table 2 XRF data for ZSM-5 zeolite molecular sieve microspheres from example 2
| Components | Results | Unit of |
| SiO 2 | 55.5 | mass％ |
| Al 2 O 3 | 8.39 | mass％ |
| F | 24.4 | mass％ |
While the invention has been described with reference to specific preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and alternative embodiments, which may be apparent to those skilled in the art, within the spirit and scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for synthesizing aluminum-rich ZSM-5 zeolite molecular sieve microspheres in a high fluorine system by one step is characterized by comprising the following steps:
mixing a silicon source, an aluminum source, a fluorine source, a template agent and deionized water, stirring for a certain time at room temperature, then adding a hydrofluoric acid aqueous solution to adjust the pH value to 5-12, then transferring into a closed reaction kettle to carry out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain the aluminum-rich ZSM-5 zeolite molecular sieve microspheres.
2. The method of claim 1, wherein the silicon source is SiO 2 Calculated by Al as the aluminum source 2 O 3 Meter, siO 2 、Al 2 O 3 The molar ratio of the fluorine source to the template to the deionized water to the hydrofluoric acid is 1: (0.05-0.5): (0.1-5): (0.1-0.5): (10-100): (0.05-0.5).
3. The method of claim 1, wherein the silicon source is silicic acid, silica sol, silica white, or tetraethyl orthosilicate.
4. The method of claim 1, wherein the aluminum source is alumina, aluminum isopropoxide, aluminum hydroxide, aluminum sulfate, or sodium metaaluminate.
5. The method of claim 1, wherein the fluorine source is ammonium fluoride, potassium fluoride, cesium fluoride, or sodium fluoride.
6. The method of claim 1, wherein the templating agent is tetrapropylammonium bromide, tetraethylammonium bromide, or tetrabutylammonium bromide.
7. The method of claim 1, wherein the concentration of the aqueous hydrofluoric acid solution is 30-50wt.%.
8. The method according to claim 1, wherein the stirring is carried out at room temperature for 1-1.5h, and the hydrothermal reaction is carried out at 100-200 ℃ for 1-10 days.
9. The aluminum-rich ZSM-5 zeolite molecular sieve microspheres of any of claims 1-8 having a spherical morphology, a crystal size of 5-8 μm, and a framework Si/Al of 10 or less.
10. Use of an aluminum-rich ZSM-5 zeolite molecular sieve microsphere prepared by the process of any of claims 1 to 8 as a catalyst.
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| CN1421390A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | ZSM-s molecular sieve synthesizing process |
| CN106430236A (en) * | 2016-09-26 | 2017-02-22 | 中国科学院武汉物理与数学研究所 | Preparation method for mesoporous ZSM-5 molecular sieve |
| CN108751222A (en) * | 2018-06-25 | 2018-11-06 | 天津理工大学 | A kind of preparation method and its acoustic applications of the MFI molecular sieves with interaction twin pattern |
| CN112520754A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof |
| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN113070098A (en) * | 2021-03-05 | 2021-07-06 | 南昌大学 | Element modified BEA/MOR eutectic molecular sieve composite catalyst and preparation and application thereof |
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| CN1421390A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | ZSM-s molecular sieve synthesizing process |
| CN106430236A (en) * | 2016-09-26 | 2017-02-22 | 中国科学院武汉物理与数学研究所 | Preparation method for mesoporous ZSM-5 molecular sieve |
| CN108751222A (en) * | 2018-06-25 | 2018-11-06 | 天津理工大学 | A kind of preparation method and its acoustic applications of the MFI molecular sieves with interaction twin pattern |
| CN112520754A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof |
| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN113070098A (en) * | 2021-03-05 | 2021-07-06 | 南昌大学 | Element modified BEA/MOR eutectic molecular sieve composite catalyst and preparation and application thereof |
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