Synthetic method of high-crystallinity ETS-10 zeolite molecular sieve with adjustable morphology and pore structure
阅读说明：本技术 形貌和孔结构可调的高结晶度ets-10沸石分子筛的合成方法 (Synthetic method of high-crystallinity ETS-10 zeolite molecular sieve with adjustable morphology and pore structure ) 是由 向梅 张芬 张微 吴泽颖 张震威 朱文豪 仝林昌 于 2019-09-18 设计创作，主要内容包括：本发明公开了形貌和孔结构可调的高结晶度ETS-10沸石分子筛的合成方法,属于催化剂领域。该合成方法是以水玻璃为硅源,以P25(Degussa,气相二氧化钛)为钛源,以氯化1-乙基-3-甲基咪唑修饰的木质素磺酸钠为添加剂,水热合成制备得到多级孔ETS-10沸石。本发明合成方法简单、原料价格低廉且对设备要求不高,合成的多级孔ETS-10沸石具有较高的晶度,不仅促进孔结构、形貌和表面性质得到了有效调节,特别是作为催化剂使用时,对生物质加氢反应表现出了独特的分子识别特性,大大提升了相应催化过程的催化效率和目标产物的选择性。(The invention discloses a synthesis method of an ETS-10 zeolite molecular sieve with adjustable morphology and pore structure and high crystallinity, belonging to the field of catalysts. The synthetic method comprises the steps of taking water glass as a silicon source, taking P25(Degussa, gas-phase titanium dioxide) as a titanium source, taking sodium lignosulphonate modified by chlorinated 1-ethyl-3-methylimidazole as an additive, and carrying out hydrothermal synthesis to obtain the hierarchical-pore ETS-10 zeolite. The synthetic method is simple, the raw materials are low in price and have low requirements on equipment, the synthesized hierarchical pore ETS-10 zeolite has high crystallinity, the pore structure, the morphology and the surface property are effectively adjusted, and particularly when the hierarchical pore ETS-10 zeolite is used as a catalyst, the hierarchical pore ETS-10 zeolite shows unique molecular recognition characteristics for a biomass hydrogenation reaction, and the catalytic efficiency of a corresponding catalytic process and the selectivity of a target product are greatly improved.)
1. A synthetic method of an ETS-10 zeolite molecular sieve is characterized in that water glass is used as a silicon source, titanium dioxide P25 is used as a titanium source, sodium lignin sulfonate modified by chlorinated 1-ethyl-3-methylimidazole is used as an additive, and the hierarchical pore ETS-10 zeolite is prepared through hydrothermal synthesis.
2. The method for synthesizing the ETS-10 zeolite molecular sieve according to claim 1, wherein the sodium lignosulfonate modified by chlorinated 1-ethyl-3-methylimidazole is prepared by the following method: taking a certain amount of 1-ethyl-3-methylimidazolium chloride, fully mixing with a NaOH solution with the concentration of 1-2mol/L, stirring for 2-3h, then adding 1-2g of sodium lignosulfonate, continuously stirring, placing in a 50-80 ℃ oven for 12-24h, taking out, washing with water until the pH value is 6.5-7.5, and thus obtaining the 1-ethyl-3-methylimidazolium chloride modified sodium lignosulfonate IL-LnNa mixed solution.
3. The method for synthesizing ETS-10 zeolite molecular sieve according to claim 1 or 2, wherein SiO in the water glass2Na with the concentration of 5.0-6.0mol/L2The concentration of O is 1.5-2.0 mol/L.
4. The synthesis method of the ETS-10 zeolite molecular sieve as claimed in any one of claims 1 to 3, wherein the specific steps of the synthesis method are as follows:
(1) Measuring a certain volume of water glass, and mixing the water glass with water to obtain SiO2Is calculated as 30.0-35.0 wt.%, then adding certain amounts of sodium chloride, potassium fluoride and P25 in sequence, stirring and mixing, so that the concentration of sodium chloride in the mixed water solution is 15-20 wt.%, the concentration of potassium fluoride is 15.0-20.0 wt.%, and adding certain amounts of IL-LnNa mixed solution, wherein the feeding molar ratio of each raw material is Na2O：K2O：TiO2：SiO2：IL-LnNa：H2Calculated as O (3.0-4.0): (0.5-2): 1.0: (5.0-7.0): (0.040-0.11): (140-200), wherein Na2The mole number of O is the sum of sodium elements contained in the water glass and the sodium chloride;
(2) Crystallizing the mixture obtained in the step (1) in a hydrothermal reaction kettle to prepare the hierarchical pore ETS-10 zeolite, wherein the adding sequence of the IL-LnNa mixed solution is not limited.
5. The synthesis method of the ETS-10 zeolite molecular sieve as claimed in claim 4, wherein the specific steps of the synthesis method are as follows: the molar ratio of each raw material to be fed is Na2O：K2O：TiO2：SiO2：IL-LnNa：H2The O is preferably (3.4-4.0): (1.5-2): 1.0: (5.0-6.0): (0.040-0.11): (160-200); preferably, the molar ratio of each raw material is Na2O：K2O：TiO2：SiO2：IL-LnNa：H2The O is preferably (3.4-3.8): (1.5-1.9): 1.0: (5.0-5.5): (0.043-0.11): (180-200).
6. The method for synthesizing ETS-10 zeolite molecular sieve according to claim 4 or 5, wherein the feeding mole ratio of each raw material is Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181.
7. The method for synthesizing an ETS-10 zeolite molecular sieve according to any one of claims 4 to 6, wherein the crystallization conditions in the step (2) are as follows: the crystallization temperature is 200-230 ℃, and the crystallization time is 48-80 hours.
8. The hierarchical pore ETS-10 zeolite synthesized by the method for synthesizing the ETS-10 zeolite molecular sieve of any one of claims 1 to 7.
9. The multiwell ETS-10 zeolite of claim 8, wherein the multiwell ETS-10 zeolite has a specific surface area of 250-320 m2The mesoporous volume is 0.06-0.16 m3/g。
10. Use of the hierarchical pore ETS-10 zeolite of claim 8 in the field of biomass catalysis.
Technical Field
The invention relates to a synthesis method of an ETS-10 zeolite molecular sieve with adjustable morphology and pore structure and high crystallinity, belonging to the field of catalysts.
Background
The development and design of tailor-made zeolite catalysts has been challenged by their inherent microporous properties and stability in aqueous solution and the corresponding composition, morphology and acid/base conditioning treatments. Researches show that the introduction of the secondary pore channel can not only effectively solve the problems of contact and diffusion limitation of active sites, but also promote the transformation of the appearance and other physical and chemical properties of the zeolite molecular sieve. Therefore, a large number of bottom-up and bottom-up hierarchical pore zeolite molecular sieve synthesis methods emerge, but all focus on FAU and MFI series zeolites such as Y, USY, ZSM-5, Beta, and the like. In order to realize further application of zeolite molecular sieves in a wider range and meet the requirements of various catalytic reactions, thereby establishing a more stable and systematic synthesis-property-action relationship, all different zeolite molecular sieve catalysts, including molecular sieve catalysts such as silicon-aluminum, titanium-silicon, aluminum-phosphorus, aluminum-silicon-phosphorus, and the like, need to be deeply and widely associated.
ETS-10 is a novel titanium silicalite molecular sieve having a structure consisting of SiO4Tetrahedra and TiO6The octahedron is connected through an oxygen bridge to form a special three-dimensional channel crystal structure, and simultaneously contains twelve-membered rings, seven-membered rings, five-membered rings and three-membered rings, so that the octahedron is endowed with high thermal stability and acid resistance, shows unique shape-selective catalytic performance and ion exchange and adsorption capacity, and is widely applied to the fields of photocatalysis, organic synthesis, petrochemical industry and the like. However, it has long been the case that multi-stage hole ETSThe studies on the synthesis of zeolite-10 molecular sieves are very lacking and the results obtained are also very undesirable. The post-treatment (acid and alkali treatment) and the microwave radiation treatment method successfully introduce the hierarchical pores to a certain extent, but damage the microporous structure of the zeolite molecular sieve to a different extent, reduce the crystallinity and have very limited final porosity. Recently, a soft template method and the use of different additives are reported to successfully prepare the hierarchical pore ETS-10 zeolite molecular sieve with complete structure and realize effective regulation and control on the pore structure and morphology. The sodium lignosulfonate (LnNa) is used as an additive to simultaneously play three functions of a pore-forming agent, a morphology regulator and a structure directing agent in the preparation process of the zeolite molecular sieve, so that the synthesized hierarchical pore ETS-10 zeolite molecular sieve not only shows a unique cauliflower morphology, but also shows a unique molecular recognition characteristic when being used as a catalyst to catalyze a hydrogenation reaction process of biomass in an aqueous phase, and the catalytic performance of the zeolite molecular sieve is greatly improved. But also causes certain damage to the crystallinity and structural integrity of the zeolite molecular sieve, further influences the stability and activity of the zeolite molecular sieve in a catalytic reaction system, and is not beneficial to realizing the general application of the zeolite molecular sieve in a wider range.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
drawings
FIG. 1 is a scanning electron micrograph of a synthesized hierarchical pore ETS-10 zeolite (Experimental example 9)
FIG. 2 is a high resolution TEM image of the synthesized hierarchical pore ETS-10 zeolite (Experimental example 9).
FIG. 3 is an XRD, adsorption isotherm and pore distribution curve of the synthesized hierarchical pore ETS-10 zeolite (Experimental example 9).
Detailed Description
The present invention is further illustrated below with reference to experimental subjects, but the scope of the present invention is not limited thereto.
The raw materials and solutions used in the examples of the present invention are as follows:
The composition of water glass is as follows: SiO 22:5.4729mol/L，Na2O:1.5435mol/L，H2O:49.749mol/L；
IL-LnNa mixed solution: 2g of 1-ethyl-3-methylimidazolium chloride is fully mixed with 50mL of NaOH solution with the concentration of 1mol/L, stirred for 2h at room temperature, then 2g of sodium lignosulfonate is added and stirred continuously, the mixture is placed in an oven at the temperature of 80 ℃ for 12h, and then taken out and washed with water until the pH value is neutral.
Conversion rate ═ amount of initial reaction substance (mol) -amount of unconverted substance (mol))/amount of initial reaction substance (mol) × 100%;
The yield is the amount of the target product (mol)/the amount of the initial reaction substance (mol) × 100%.
Experimental example 1
Stirring 16mL of water glass at room temperature for 10min, mixing with 2mL of IL-LnNa solution, stirring for 1H, and adding 20mL of H2O and stirring is continued for 20min, then 6.9g of NaCl and 2.8g of KF are added successively and stirred for 1h, finally 1.3g P25 is added, and after stirring for 2h, the mixture is put into a hydrothermal reaction kettle to be sealed and is kept standing and crystallized in an oven at 230 ℃ for 60 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.043: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 2
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And stirring the mixture O uniformly, adding 2mL of IL-LnNa solution after 20min, fully mixing, sequentially adding 6.9g of NaCl and 2.8g of KF after stirring for 1h, adding 1.3g of 1.3g P25 after stirring for 1h, continuously stirring for 2h, filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at the temperature of 230 ℃ for 60 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.043: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 3
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1h respectively, 2mL of IL-LnNa solution is added for full mixing, after the mixture is stirred for 2h, 1.3g of P25 is added, the mixture is continuously stirred for 2h, the mixture is put into a hydrothermal reaction kettle for sealing, and the mixture is kept standing and crystallized in an oven at the temperature of 230 ℃ for 60 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.043: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 4
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2and O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 2mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 60 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.043: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
experimental example 5
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 3mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 60 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 6
Stirring 16mL of water glass at room temperature for 10minAdding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 4mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 60 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.085: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 7
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 5mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 60 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.11: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 8
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 3mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 64 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2and O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 9
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added and stirred for 1h, then 1.3g P25 is added and stirred for 2h, 3mL of IL-LnNa solution is added and fully mixed, the mixture is stirred for 2h, then the mixture is put into a hydrothermal reaction kettle and sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 72 h. Each matter in the systemMolar ratio of materials Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
In addition, as shown in fig. 1 and fig. 2, which are a scanning electron micrograph and a high-resolution transmission electron micrograph of the hierarchical pore ETS-10 zeolite synthesized in this example, respectively, it can be seen that the morphology of the zeolite is restored to a lamellar stacking cubic shape, the size of each cubic shape is relatively uniform, and the surface has obvious stacking defects. In addition, as can be seen from the figure, these individual cubes have a tendency to continue to aggregate to form larger crystal grains. The existence of abundant mesopores in the synthesized zeolite material is powerfully proved by abundant bright and dark stripes and white bright spots in a transmission electron microscope image of a sample, and the sizes of the mesopores are relatively uniform and are compared with N2The pore size distribution obtained by the adsorption result is consistent. Meanwhile, as can be seen from the figure, the lattice stripes of the zeolite crystals are relatively complete, which indicates that the microporous structure of the zeolite is not seriously damaged and remains intact in the process of multi-stage pore formation.
Experimental example 10
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added, the mixture is stirred for 1 hour, then 1.3g P25 is added, the mixture is stirred for 2 hours, 3mL of IL-LnNa solution is added, the mixture is fully mixed, stirred for 2 hours, then the mixture is put into a hydrothermal reaction kettle to be sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 80 hours. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2and O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 11
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added and stirred for 1h, then 1.3g P25 is added and stirred for 2h, 3mL of IL-LnNa solution is added and fully mixed, the mixture is stirred for 2h, then the mixture is put into a hydrothermal reaction kettle and sealed, and the mixture is kept stand and crystallized in an oven at 215 ℃ for 72 h. Each matter in the systemMolar ratio of materials Na2O：K2O：TiO2：SiO2：IL-LnNa：H2and O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 12
Stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl and 2.8g of KF are sequentially added and stirred for 1h, then 1.3g P25 is added and stirred for 2h, 3mL of IL-LnNa solution is added and fully mixed, the mixture is stirred for 2h, then the mixture is put into a hydrothermal reaction kettle and sealed, and the mixture is kept stand and crystallized in an oven at the temperature of 200 ℃ for 72 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：IL-LnNa：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 13
The adjusting and synthesizing system is as follows: stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And (3) uniformly stirring O, adding 8.8g of KCl after 20min, stirring for 1h, then adding 1.3g P25, stirring for 2h, then adding 3mL of IL-LnNa solution, fully mixing, stirring for 2h, then filling into a hydrothermal reaction kettle, sealing, and standing and crystallizing for 72h in an oven at 230 ℃. The molar ratio K of each material in the system2O：TiO2：SiO2：IL-LnNa：H2And O is 3.6: 1.0: 5.5: 0.064: 181. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.
Experimental example 14
The adjusting and synthesizing system is as follows: stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl, 1.39g of KOH and 1.39g of KCl are sequentially added and stirred for 1h, then 1.3g P25 is added and stirred for 2h, then 3mL of IL-LnNa solution is added and fully mixed, after stirring for 2h, the mixture is put into a hydrothermal reaction kettle and sealed, and then the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 72 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：TPOAB：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the mesoporous ETS-10 zeolite thus prepared are shown in Table 1.
Experimental example 15
The adjusting and synthesizing system is as follows: stirring 16mL of water glass at room temperature for 10min, and adding 20mL of H2And O is uniformly stirred, after 20min, 6.9g of NaCl, 1.39g of KCl and 1.39g of KF are sequentially added and stirred for 1h, then 1.3g P25 is added and stirred for 2h, then 3mL of IL-LnNa solution is added and fully mixed, after stirring for 2h, the mixture is put into a hydrothermal reaction kettle and sealed, and then the mixture is kept stand and crystallized in an oven at the temperature of 230 ℃ for 72 h. Molar ratio of materials in system Na2O：K2O：TiO2：SiO2：TPOAB：H2And O is 3.5: 1.6: 1.0: 5.5: 0.064: 181. the texture properties of the mesoporous ETS-10 zeolite thus prepared are shown in Table 1.
TABLE 1 texture Properties of the mesoporous ETS-10 Zeolite
Comparative example 1: preparation of conventional microporous ETS-10 zeolite
Compared with the synthesis step of the hierarchical pore ETS-10 zeolite in the example 9, the preparation process of the traditional microporous ETS-10 zeolite is the same except that no additive is added, the microporous ETS-10 zeolite molecular sieve is prepared, the texture property of the prepared microporous ETS-10 zeolite is shown in the table 2, and the microporous ETS-10 zeolite has almost no hierarchical pore distribution (the mesoporous pore volume is only 0.01 cm)3/g), and the mesoporous volume of the hierarchical pore ETS-10 zeolite (example 9) was 0.12cm3(ii) in terms of/g. Some difference in their BET surface area and micropore volume indicates that the crystallinity and structural integrity are different.
TABLE 2 texture Properties of the hierarchical and microporous ETS-10 zeolites synthesized under the same conditions
Comparative example 2: preparation method and preference of additives
The soft template method is also mentioned in earlier reported related patents on multi-pore ETS-10 zeolite, using templates such as N, N-diethyl-N-hexadecyl-N- (3-methoxysilanopropane) ammonium iodide (DMMC) and N, N-diethyl-N-octadecyl-N- (3-methoxysilanopropane) ammonium bromide (TPOAB). There is also a recent report in the literature on the synthesis of multipore ETS-10 zeolite using lignosulfonic acid (LnNa) directly as an additive. Therefore, the hierarchical pore ETS-10 synthesized by using DMMC as a soft template is recorded as M-ETS-10, the hierarchical pore ETS-10 synthesized by using LnNa as an additive is recorded as M-ETS-10-L, and the hierarchical pore ETS-10 synthesized by using IL-LnNa as an additive is recorded as M-ETS-10-IL (embodiment 9 of the invention), all of which are prepared according to the preparation method of the embodiment 9, the texture properties are shown in Table 3, and the hierarchical pore ETS-10 zeolite molecular sieve can be prepared under the condition of three additives.
TABLE 3 texture Properties of hierarchical porous ETS-10 synthesized under the same conditions with different methods and additives