阅读说明：本技术 具有特定分子识别功能的多级孔ets-10沸石分子筛及合成方法 (Hierarchical pore ETS-10 zeolite molecular sieve with specific molecular recognition function and synthesis method ) 是由 向梅 张芬 张微 吴泽颖 张震威 仝林昌 朱文豪 于 2019-09-18 设计创作，主要内容包括：本发明公开了本具有特定分子识别功能的多级孔ETS-10沸石分子筛及合成方法,属于催化剂领域。本发明合成方法是以水玻璃为硅源,以三氯化钛盐酸溶液(15-20wt.％)为钛源,以羧甲基纤维素钠为添加剂,最后装入水热反应釜中密封晶化制备得到多级孔ETS-10沸石分子筛。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和分子识别特性,作为催化剂使用时,尤其是作用于纤维素类生物质化合物加氢反应,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 hierarchical pore ETS-10 zeolite molecular sieve with a specific molecular recognition function and a synthesis method thereof, belonging to the field of catalysts. The synthesis method of the invention uses water glass as a silicon source, titanium trichloride hydrochloric acid solution (15-20 wt.%) as a titanium source, sodium carboxymethyl cellulose as an additive, and finally the mixture is put into a hydrothermal reaction kettle to be sealed and crystallized to prepare the hierarchical pore ETS-10 zeolite molecular sieve. The synthetic method is simple, the raw materials are low in price and the requirement on equipment is not high, the synthesized hierarchical pore ETS-10 zeolite has high crystallinity and molecular recognition characteristics, and when the hierarchical pore ETS-10 zeolite is used as a catalyst, the hierarchical pore ETS-10 zeolite is particularly used for a cellulose biomass compound hydrogenation reaction, so that the catalytic efficiency of a corresponding catalytic process and the selectivity of a target product are greatly improved.)

1. A synthetic method of a hierarchical pore ETS-10 zeolite molecular sieve is characterized in that water glass is used as a silicon source, titanium trichloride is used as a titanium source, sodium carboxymethyl cellulose is used as an additive, and the hierarchical pore ETS-10 zeolite molecular sieve is prepared by hydrothermal synthesis.

2. The method for synthesizing a hierarchical pore ETS-10 zeolite molecular sieve according to claim 1, 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.

3. The method for synthesizing a hierarchical pore ETS-10 zeolite molecular sieve according to claim 1 or 2, characterized in that the method specifically comprises the following steps:

(1) Measuring a certain volume of water glass, mixing with water, and stirring for 10-20min to obtain SiO₂Is calculated to be 30.0-35.0 wt.%, followed by addition of a NaOH solution and stirring, the TiCl being added₃Adding a certain amount of sodium carboxymethylcellulose into the system, stirring, adding potassium fluoride solution, and adding Na in the molar ratio of the raw materials₂O：K₂O：TiO₂：SiO₂：CMC：H₂Calculated as O (3.0-5.0): (1.5-3): 1.0: (6.0-8.0): (0.04-0.3): (140-200), wherein Na₂The mole number of O is the sum of sodium elements contained in the water glass and NaOH;

(2) Crystallizing the mixture obtained in the step (1) in a hydrothermal reaction kettle to obtain the hierarchical porous ETS-10 zeolite molecular sieve.

4. The method of claim 3, wherein the concentration of the NaOH solution is 15-20 wt.%; the concentration of the potassium fluoride solution is 15.0-20.0 wt.%.

5. The method for synthesizing a hierarchical pore ETS-10 zeolite molecular sieve according to claim 3 or 4, wherein the feeding molar ratio of each raw material is Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂Calculated as O (4.0-5.0): (1.5-2.5): 1.0: (7.0-8.0): (0.04-0.25): (150- > 180); the molar ratio of each raw material to be fed is Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂The O is preferably (4.0-4.5): (1.5-2.0): 1.0: (7.0-7.5): (0.04-0.21): (160-180).

6. The method for synthesizing a hierarchical pore ETS-10 zeolite molecular sieve according to claim 5, wherein the molar ratio of each raw material is Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is 4.4: 1.9:1.0：7.1：0.13：163。

7. The method for synthesizing a hierarchical pore ETS-10 zeolite molecular sieve according to any one of claims 3 to 6, wherein the crystallization conditions in step (2) are as follows: the crystallization temperature is 190 ℃ and 245 ℃, and the crystallization time is 48-80 hours.

8. the hierarchical pore ETS-10 zeolite synthesized by the method for synthesizing the hierarchical pore ETS-10 zeolite molecular sieve of any one of claims 1 to 6.

9. The hierarchical pore ETS-10 zeolite molecular sieve of claim 8, wherein the hierarchical pore ETS-10 zeolite has a specific surface area of 240-320 m²The mesoporous volume is 0.05-0.16 m³/g。

10. Use of the multigraded-pore ETS-10 zeolite molecular sieve of claim 8 or 9 in the field of biomass catalysis.

Technical Field

The invention relates to a hierarchical pore ETS-10 zeolite molecular sieve with a specific molecular recognition function and a synthesis method thereof, belonging to the field of catalysts.

Background

The hierarchical pore zeolite has excellent acidity and hydrothermal stability of the microporous zeolite and a rich hierarchical pore structure, and the adsorption and diffusion performance of macromolecules is greatly improved on the basis of the microporous zeolite, so that the hierarchical pore zeolite is popular in the fields of catalysis and adsorption as a novel hierarchical pore material and has an industrial application prospect. In view of the excellent performance of the hierarchical pore zeolite in the fields of catalysis, adsorption and separation, the design and synthesis of the hierarchical pore zeolite has become a research focus, and various methods and routes have been tried by scientists to synthesize zeolite crystals with hierarchical pore structures, but the existing hierarchical pore zeolite molecular sieve synthesis methods from bottom to top and from bottom to top are all focused on FAU and MFI series zeolites such as Y, USY, ZSM-5 and Beta. 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 silicon-aluminum, titanium-silicon, phosphorus-aluminum-silicon, and the like, need to be deeply and widely associated.

ETS-10 is a novel titanium silicalite molecular sieve, and the special three-dimensional pore channel crystal structure of the novel titanium silicalite molecular sieve endows the novel titanium silicalite molecular sieve with high thermal stability, acid resistance, shape-selective catalytic performance, ion exchange and adsorption capacity, and the novel titanium silicalite molecular sieve has wide application in the fields of photocatalysis, organic synthesis, petrochemical industry and the like. In the early days, the introduction of multi-stage pores on the ETS-10 zeolite molecular sieve was only possible by post-treatment (acid, alkali treatment) and microwave radiation treatment, not only limited multi-stage pores were introduced to some extent, but also the destruction of the microporous structure and the reduction of crystallinity of the zeolite molecular sieve were caused. Recently, the soft template method and the use of different additives realize the successful synthesis of the hierarchical pore ETS-10 zeolite molecular sieve with complete structure, and can effectively regulate and control the pore structure and the morphology of the zeolite molecular sieve, particularly sodium lignosulfonate (LnNa) as an additive plays three functions of an excellent pore-forming agent, a morphology regulator and a structure directing agent simultaneously in the preparation process of the zeolite molecular sieve, but also causes certain damage to the crystallinity and the structural integrity of the zeolite molecular sieve, further influences the stability and the activity of the zeolite molecular sieve in a catalytic reaction system, and is not beneficial to realizing the universal 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).

Figure 3 is an XRD pattern of the synthesized hierarchical pore ETS-10 zeolite (experimental example 9).

Detailed Description

The composition of water glass is as follows: SiO 2₂:5.4729mol/L，Na₂O:1.5435mol/L，H₂O:49.749mol/L。

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

10mL of water glass is stirred at room temperature for 15min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And continuously stirring for 2 hours, then slowly adding 0.1g of CMC, stirring for 2 hours, then adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling into a hydrothermal reaction kettle, sealing, and standing and crystallizing in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂o is recorded as 4.4: 1.9: 1.0: 7.1: 0.042: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 2

Stirring 10mL of water glass at room temperature for 10min, fully mixing with 6mL of 6.3mol/L NaOH solution, stirring for 40min, and adding7mL TiCl₃And stirring the mixed solution with 0.1g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.042: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 3

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.2g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.083: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 4

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 5

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.4g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O noteIs 4.4: 1.9: 1.0: 7.1: 0.17: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 6

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.5g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 60 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.21: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 7

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃and stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 64 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 8

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 68 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 9

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 72 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

In addition, FIGS. 1 and 2 are a scanning electron micrograph and a high-resolution transmission electron micrograph of the hierarchical pore ETS-10 zeolite synthesized in this example, respectively. In the SEM image, although the zeolite surface had some floc accumulation, the original morphology of the zeolite was not affected, the sample was still layered, and the size of the accumulated cubes was relatively uniform, and there was no tendency to continue aggregation. And obvious white bright spots appear in a transmission electron microscope, which proves that a large number of hierarchical pores exist in the synthesized zeolite material, and the pore sizes are relatively consistent.

experimental example 10

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 76 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 11

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 230 ℃ for 80 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the prepared hierarchical pore ETS-1The texture properties of the 0 zeolite are shown in table 1.

Experimental example 12

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 215 ℃ for 72 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 13

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 200 ℃ for 72 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite are shown in table 1.

Experimental example 14

10mL of water glass is stirred at room temperature for 10min and then fully mixed with 6mL of 6.3mol/L NaOH solution, after stirring for 40min, 7mL of TiCl is added₃And stirring the mixed solution with 0.3g of CMC for 2 hours, adding 7.6mL of KF solution, continuously stirring for 1 hour, finally filling the mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, and standing and crystallizing the mixture in an oven at 245 ℃ for 72 hours. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂O is recorded as 4.4: 1.9: 1.0: 7.1: 0.13: 163. the texture properties of the prepared hierarchical pore ETS-10 zeolite 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 33mL of H₂O is stirred evenly, after 20min, 6.8g NaCl, 1.39g KCl, 1.39g KOH and 1.39g KF are added in turn, and the mixture is stirred for 1h respectivelyThen adding 1.3g P25, stirring for 2h, adding 0.3g CMC, stirring for 2h, sealing in a hydrothermal reaction kettle, and standing and crystallizing for 72h in an oven at 230 ℃. Molar ratio of materials in system Na₂O：K₂O：TiO₂：SiO₂：CMC：H₂And O is 3.5: 1.5: 1.0: 5.5: 0.13: 163. 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

The procedure for preparing the conventional microporous ETS-10 zeolite was the same as that for the synthesis of the multi-pore ETS-10 zeolite of example 9, except that no additives were added. The texture properties of the prepared microporous ETS-10 zeolite are shown in Table 2, and Table 2 shows BET surface area, mesoporous pore volume and microporous pore volume of the synthesized hierarchical pore ETS-10 zeolite (prepared in example 9) and the microporous ETS-10 zeolite. Obviously, there is almost no hierarchical pore distribution in microporous ETS-10 zeolite (mesoporous pore volume is only 0.02 cm)³/g), and the mesoporous volume of the hierarchical pore ETS-10 zeolite is 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, the hierarchical pore ETS-10 synthesized by using CMC as an additive is recorded as M-ETS-10-CMC (embodiment 9 of the invention), the three are prepared according to the embodiment 9 (the additives are respectively replaced by DMMC and LnNa), and the texture properties are shown in Table 3.

TABLE 3 texture Properties of hierarchical porous ETS-10 synthesized under the same conditions with different methods and additives