CN108046287B - Preparation method of nano Y zeolite self-assembly - Google Patents
Preparation method of nano Y zeolite self-assembly Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 74
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 72
- 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 69
- 238000001338 self-assembly Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 11
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- 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 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000003863 metallic catalyst Substances 0.000 abstract description 2
- 238000005504 petroleum refining Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 3
- 239000002149 hierarchical pore Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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Abstract
A preparation method of a nano Y zeolite self-assembly body belongs to the field of inorganic non-metallic material and catalyst preparation, can solve the problems that the existing preparation method of nano zeolite is difficult to separate from a reaction system and the performance of the prepared zeolite is difficult to meet the requirements of petroleum refining industry, and adopts 9-11 Na2O:0.6~2.0Al2O3:10SiO20.19 to 0.34 surfactant: 160-300H2The material molar ratio of O, long-chain alkyl trimethyl ammonium bromide surfactant is added into a zeolite synthesis system, and the zeolite is synthesized in a relatively concentrated batching system and at a low temperature of gelatinization, aging and crystallization. The method has the advantages that the prepared nano Y zeolite self-assembly has large external specific surface, the intercrystalline mesopore porosity and the pore size distribution are adjustable, and the synthesis method is simple, green and energy-saving.
Description
Technical Field
The invention relates to a preparation method of a nano Y zeolite self-assembly. Belonging to the field of preparation of inorganic non-metallic materials and catalysts. In particular to a preparation method of a Y zeolite self-assembly body which is formed by self-polymerization of nano zeolite grains and has a hierarchical pore structure.
Background
Y-zeolite is a zeolite molecular sieve material with FAU framework structure and three-dimensional cage-like pore structure, has been a major catalyst in catalytic cracking (FCC) and hydrocracking oil refining technologies, and has been playing an important role in the petroleum refining industry since its first use in the last 60 th century. However, as the crude oil is increasingly heavy, the content of macromolecular hydrocarbons such as polycyclic aromatic hydrocarbons in the oil raw material is significantly increased, and the application of the zeolite catalyst is limited. The reason is that due to the limitation of zeolite microporous channels (the diameter of the pore opening is 0.74 nm), accessibility of Y zeolite active sites to macromolecules in crude oil and diffusibility of the Y zeolite active sites in the zeolite channels are greatly restricted, so that the utilization rate of the catalyst is greatly reduced, and the catalyst is easily inactivated by carbon deposition in a catalytic reaction. To overcome the limitations of conventional micron-sized microporous zeolites, zeolite crystallite sizes are reducedTo prepare nano Y zeolites has proven to be an effective method. The preparation of the nano zeolite can effectively improve the accessibility of zeolite active sites to macromolecules and promote the diffusion capability of molecules in zeolite channels by increasing the external surface area of the zeolite and shortening the diffusion distance, thereby improving the catalytic performance of the traditional microporous zeolite. However, the dispersible nano zeolite has a problem of difficulty in separation from a reaction system during preparation and use due to the nanocrystallization of its particles, and thus practical application thereof is hindered. How to keep the superiority of the nano zeolite and overcome the defects of difficult sedimentation and difficult separation of the nano zeolite, and the preparation of the nano zeolite self-assembly becomes a new research direction. Sh. Xu et al investigated the addition of TMOAC ([ (CH)3O)3SiC3H6N(C2H5)2C16H33]Cl) in 1.0Al2O3/4.4Na2O/9.8SiO2/0.8TMOAC/153H2Preparing nano Y zeolite assembly under the molar ratio of O ingredient, wherein the external surface area of the obtained material reaches 158 m2(ii)/g, and rich intercrystalline mesopores and macropores due to aggregation of nanoparticles, but with a broad pore size distribution (RSC adv., 2016, 6, 69822-; t, Tang et Al report Al as a molar charge ratio2O3/14.4Na2O/9.8SiO2/590H2O, the crystallization condition of 75 ℃ synthesizes the product with the external surface area of 111 m2A nano Y zeolite assembly (RSC adv., 2017, 7, 7711-7717) with the particle size of 400-900 nm. In addition, CN 107055567A discloses a preparation method of nano Y zeolite aggregates with the feeding molar ratio of Al2O3：(9.0~10.8)SiO2：(14.5~15.5)Na2O：(580~680)H2O, the crystallization temperature is 70-80 ℃, the particle size of the prepared nano Y zeolite aggregate containing the intercrystalline mesopores is 400-900 nm, and the specific surface area is 650-780 m2Per g, the pore volume of the micropores is 0.23-0.27 cm3The mesoporous volume is 0.16-0.25 cm3The mesoporous aperture is 4-9 nm.
Disclosure of Invention
The invention relates to a method for preparing a nano Y zeolite self-assembly, which aims to provide a method for preparing a Y zeolite self-assembly with a hierarchical pore structure formed by self-polymerization of nano zeolite grains.
The invention adopts the following technical scheme:
a process for preparing the self-assembled nano Y-zeolite includes such steps as adding long-chain alkyl trimethyl ammonium bromide surfactant to the zeolite synthesizing system, and synthesizing zeolite in concentrated mixture system at low temp for gelatinizing, ageing and crystallizing, and includes such steps as:
according to Na2O： Al2O3：SiO2: surfactant (b): h2The molar ratio of the O to the material is 9-11: 0.6-2.0: 10: 0.19 to 0.34: 160-300, first, Al is added2O3Adding 41 mass percent of sodium metaaluminate and sodium hydroxide into deionized water to obtain a mixture, placing the mixture in a water bath at 20-30 ℃ for stirring, adding a long-chain alkyl trimethyl ammonium bromide surfactant after the sodium metaaluminate and the sodium hydroxide are fully dissolved and the solution is clarified, and continuing stirring until the surfactant is fully dissolved to obtain a solution A; then slowly adding the solution A into SiO-containing solution at the temperature of 0-5 DEG C26.228mol/L of water glass or SiO-containing28.533mol/L silica sol, fully stirring at a constant temperature to ensure uniform mixing to form a mixed solution B, and aging the mixed solution B in a water bath at 20-30 ℃ for 18-24 h; and finally, filling the aged mixed solution B into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, crystallizing for 15-20 days at the crystallization temperature of 40-60 ℃, filtering the obtained product, washing the product to be neutral by using deionized water, drying the product at 100-120 ℃, and roasting the product in air at 450-500 ℃ for 5-6 hours to obtain the powdery nano Y zeolite self-assembly.
The long-chain alkyl trimethyl ammonium bromide surfactant is C12~ C16One of alkyl trimethyl ammonium bromides of (1).
The invention has the following beneficial effects:
1. the self-assembly body of the nano Y zeolite reserves the advantages of the nano zeolite, overcomes the defect of difficult separation of the nano zeolite, enables the practical application of the nano zeolite to be possible, and simultaneously has the characteristics of hierarchical pore zeolite due to the existence of rich intercrystalline mesopores; and because the prepared nano zeolite has regular crystal grain shape and small and uniform particle size, the prepared nano Y zeolite has large external specific surface of a self-assembly body and narrow mesopore size distribution, and the porosity and the pore size of the mesopores can be adjusted by changing the adding amount of the long-chain alkyl trimethyl ammonium bromide surfactant and the length of an alkyl chain.
2. According to the preparation method of the nano Y zeolite self-assembly, long-chain alkyl trimethyl ammonium bromide added in a synthesis system belongs to a cheap and nontoxic green surfactant; meanwhile, zeolite is synthesized by adopting high-concentration ingredients and low-temperature crystallization, so that the problems of huge equipment and water waste caused by the use of a large amount of water are solved, and energy is saved.
Drawings
FIG. 1 is an XRD spectrum of the product of example 1 of the present invention;
FIG. 2 shows the present invention N2Adsorption/desorption isotherms and DFT pore size distribution;
FIG. 3 is a 20K magnification scanning electron micrograph of a product of example 1 according to the present invention;
FIG. 4 is a scanning electron micrograph at 80K magnification of the product of example 1 of the present invention.
Detailed Description
In the case of the example 1, the following examples are given,
according to 9Na2O: 0.7Al2O3: 10SiO2: 0.19CTAB: 160H2Adding 1.09g of sodium metaaluminate and 2.7g of sodium hydroxide into 13mL of deionized water, stirring the mixture in a water bath at 30 ℃, adding 0.455g of hexadecyl trimethyl ammonium bromide (CTAB) after the sodium metaaluminate and the sodium hydroxide are fully dissolved and the solution is clarified, and continuously stirring until the CTAB is completely dissolved to obtain a solution A; then the solution A is slowly added to water glass with the temperature of 0 ℃ and the volume of 10mL, and the solution is fully stirred at the constant temperature to ensure thatUniformly mixing to form a mixed solution B, and putting the mixed solution B in a water bath at the temperature of 30 ℃ for aging for 24 hours; and finally, filling the aged mixed solution into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, crystallizing at 55 ℃ for 17d, filtering the obtained product, washing the product to be neutral by deionized water, drying at 100 ℃, and roasting in air at 450 ℃ for 5h to obtain the powdery nano Y-zeolite self-assembly Y-1.
The XRD spectrogram of figure 1 shows that the product is FAU zeolite with high crystallinity, the diffraction line is widened, the average grain diameter is 45nm calculated by a Scherrer formula, the framework Si/Al is 2.0 calculated by unit cell parameters, and the synthesis of Y zeolite is proved; n of FIG. 22The adsorption/desorption isotherm shows the coexistence of micropores and mesopores in the product, and DFT pore size distribution analysis shows that the mesopore size is 2-6 nm; BET surface area, external surface area and mesoporous pore volume are respectively 830m2/g、233m2G and 0.259cm3(ii)/g; the scanning electron microscope shows that the product is formed by stacking nano crystal grains with uniform grain size and appearance, and rich mesopore pores exist among the crystal grains.
In the case of the example 2, the following examples are given,
the feeding molar ratio is changed to 9Na2O: 0.6Al2O3: 10SiO2: 0.19CTAB:160H2O, the addition of sodium metaaluminate is 0.855g, the aging time is changed to 22h, crystallization is carried out at 50 ℃ for 18d, the roasting time is 6h, other conditions are the same as in example 1, and the obtained powdery nano Y zeolite self-assembly is Y-2, and the structural properties are shown in Table 1.
In the case of the example 3, the following examples are given,
the feeding molar ratio is changed to 9Na2O:0.6Al2O3:10SiO2:0.32CTAB:160H2O, the addition of sodium metaaluminate is 0.855g, the addition of CTAB is 0.65g, crystallization is carried out at 40 ℃ for 20d, roasting is carried out at 500 ℃ for 6h, other conditions are the same as in example 1, and the obtained powdery nano Y zeolite self-assembly is Y-3, and the structural properties are shown in Table 1.
In the case of the example 4, the following examples are given,
the feeding molar ratio is changed to 9Na2O: 0.7Al2O3: 10SiO20.19 tetradecyltrimethylammonium bromide (TTAB): 200H2Adding 17.5mL of deionized water and 0.34g of TTAB into the mixture, stirring the mixture in a water bath at 20 ℃, adding the solution A into water glass at 3 ℃, aging the mixture for 24 hours at 20 ℃, crystallizing the mixture for 18d at 55 ℃, drying the mixture at 105 ℃, and obtaining the powdery nano Y zeolite self-assembly body which is Y-4 under the same conditions as the example 1, wherein the structural properties of the powdery nano Y zeolite self-assembly body are shown in Table 1.
In the case of the example 5, the following examples were conducted,
the feeding molar ratio is changed to 9Na2O: 0.9Al2O3: 10SiO2: 0.19CTAB: 250H2O, adding 1.40g of sodium metaaluminate and 23.13mL of deionized water, adding the solution A into water glass at the temperature of 5 ℃, aging for 18h, crystallizing at 60 ℃ for 15d, drying at 120 ℃, and obtaining the powdery nano Y zeolite self-assembly Y-5 under the same conditions as the example 1, wherein the structural properties of the powdery nano Y zeolite self-assembly are shown in Table 1.
In the case of the example 6, it is shown,
the feeding molar ratio is changed to 9Na2O: 0.7Al2O3: 10SiO2: 0.27CTAB: 300H2Adding 3.96g of sodium hydroxide, 28.75mL of deionized water and 0.6g of CTAB into 7.3mL of silica sol at the temperature of 5 ℃, aging for 22h, crystallizing for 17d at the temperature of 45 ℃, roasting for 5h in air at the temperature of 470 ℃, and obtaining the powdery nano Y zeolite self-assembly Y-6 under the same conditions as in example 1, wherein the structural properties of the powdery nano Y zeolite self-assembly Y-6 are shown in Table 1.
In the case of the example 7, the following examples are given,
the feeding molar ratio is changed to 9Na2O: 0.9Al2O3: 10SiO2: 0.20CTAB: 160H2Adding 0.479g of O and CTAB, stirring in a water bath at 25 ℃, aging for 20h at 25 ℃, crystallizing for 16d at 60 ℃, drying at 110 ℃, roasting in air at 475 ℃ for 2.5h, and obtaining the powdery nano Y zeolite self-assembly Y-7 under the same conditions as in example 1, wherein the structural properties of the powdery nano Y zeolite self-assembly Y-7 are shown in Table 1.
In the case of the example 8, the following examples are given,
the feeding molar ratio is changed to 9Na2O: 1.5Al2O3: 10SiO2: 0.25CTAB: 160H2O, sodium metaaluminate sodium is added in 1.81g, CTAB is added in 0.600g, stirring is carried out in water bath at 25 ℃, aging is carried out for 20h at 25 ℃, crystallization is carried out for 16d at 60 ℃, drying is carried out at 110 ℃, and air at 475 DEG is carried outAnd (3) roasting for 5.5h under the other conditions same as in example 1 to obtain powdery nano Y zeolite self-assembly Y-8, wherein the structural properties of the powdery nano Y zeolite self-assembly Y-8 are shown in Table 1.
In the case of the example 9, the following examples are given,
the feeding molar ratio is changed to 11Na2O: 0.7Al2O3: 10SiO2: 0.34DTAB: 160H2O and sodium hydroxide are added in an amount of 3.5g, DTAB is added in an amount of 0.58g, the mixture is stirred in a water bath at 25 ℃, aged at 25 ℃ for 20h, crystallized at 60 ℃ for 16d, dried at 115 ℃ and roasted at 475 ℃ in the air for 6h, and the other conditions are the same as those of example 1, so that powdery nano Y zeolite self-assembly Y-9 is obtained, and the structural properties of the powdery nano Y zeolite self-assembly Y-9 are shown in Table 1.
In the light of the above example 10,
the feeding molar ratio is changed to 10Na2O: 2.0Al2O3: 10SiO20.19 Dodecyl Trimethyl Ammonium Bromide (DTAB): 160H2O, 3.11g of sodium metaaluminate, 3.1g of sodium hydroxide and 0.385g of DTAB, drying at 115 ℃, and obtaining the powdery nano Y zeolite self-assembly body of Y-10 under the same conditions as the example 1, wherein the structural properties are shown in Table 1.
In the case of the embodiment 11, the following examples are given,
the feeding molar ratio is changed to 9Na2O: 1.1Al2O3: 10SiO2: 0.27DTAB: 160H2O, changing the adding amount of sodium metaaluminate to be 1.71g, the adding amount of sodium hydroxide to be 3.96g, the adding amount of DTAB to be 0.75g, adding the solution A to silica sol with the temperature of 5 ℃ and the volume of 7.3mL, and obtaining the powdery nano Y zeolite self-assembly body Y-11 by the same conditions as the example 1, wherein the structural properties are shown in the table 1.
Table 1 structural properties of Y zeolite prepared in each example
Claims (2)
1. A method for preparing a nano Y zeolite self-assembly body is characterized by comprising the following steps: the long-chain alkyl trimethyl ammonium bromide surfactant is added into a zeolite synthesis system, and the zeolite is synthesized in a concentrated ingredient system at low gelling, aging and crystallization temperatures, and the specific preparation process is as follows:
according to Na2O： Al2O3：SiO2: surfactant (b): h2The molar ratio of the O to the material is 9-11: 0.6-2.0: 10: 0.19 to 0.34: 160-300, first, Al is added2O3Adding 41 mass percent of sodium metaaluminate and sodium hydroxide into deionized water to obtain a mixture, placing the mixture in a water bath at 20-30 ℃ for stirring, adding a long-chain alkyl trimethyl ammonium bromide surfactant after the sodium metaaluminate and the sodium hydroxide are fully dissolved and the solution is clarified, and continuing stirring until the surfactant is fully dissolved to obtain a solution A; then slowly adding the solution A into SiO-containing solution at the temperature of 0-5 DEG C26.228mol/L of water glass or SiO-containing28.533mol/L silica sol, fully stirring at a constant temperature to ensure uniform mixing to form a mixed solution B, and aging the mixed solution B in a water bath at 20-30 ℃ for 18-24 h; and finally, filling the aged mixed solution B into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, crystallizing for 15-20 days at the crystallization temperature of 40-60 ℃, filtering the obtained product, washing the product to be neutral by using deionized water, drying the product at 100-120 ℃, and roasting the product in air at 450-500 ℃ for 5-6 hours to obtain the powdery nano Y zeolite self-assembly.
2. The method of claim 1, wherein the method comprises the steps of: the long-chain alkyl trimethyl ammonium bromide surfactant is C12~ C16One of alkyl trimethyl ammonium bromides of (1).
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| CN105692644A (en) * | 2016-02-17 | 2016-06-22 | 苏州大学 | Hierarchical-porous zeolite preparation method |
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| CN101691228A (en) * | 2009-10-12 | 2010-04-07 | 定州市荣鼎水环境生化技术有限公司 | Microporous and mesoporous composite molecular sieve and method of producing same |
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| Y沸石纳米晶在碱性环境中的模板组装;石冈等;《化学反应工程与工艺》;20131031;第29卷(第5期);第470-480页 * |
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