Intrinsic amphiphilic ZSM-5 molecular sieve and application thereof as catalyst

Abstract

The invention discloses an intrinsic amphiphilic ZSM-5 zeolite molecular sieve and application thereof as a catalyst, the ZSM-5 zeolite molecular sieve does not contain alkali metal and alkaline earth metal ions, the silica-alumina ratio is 16-51, and the anisotropy value is greater than or equal to 4; the ZSM-5 zeolite molecular sieve has high morphological anisotropy, so that the ZSM-5 zeolite molecular sieve has intrinsic Pickering emulsifying performance, that is, the ZSM-5 zeolite molecular sieve has emulsifying performance without any surface modification, so that the ZSM-5 zeolite molecular sieve can be applied as an emulsifier. Furthermore, when the ZSM-5 zeolite molecular sieve is used as a catalyst to catalyze a cyclohexene hydration reaction, the highest conversion rate gt is 21.4%; the cyclohexanol selectivity is 99%. When the catalyst is used for the hydration reaction of cyclopentene, the conversion rate and gt of 13.9% are shown; the selectivity of cyclopentanol is 99%. The ZSM-5 zeolite molecular sieve catalyst has the excellent characteristic that the cyclohexene conversion rate / cyclohexanol yield is higher than that of other ZSM-5 zeolite molecular sieve catalysts.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials, and particularly relates to a ZSM-5 molecular sieve and application of the ZSM-5 molecular sieve as a cyclohexene hydration catalyst. BACKGROUND

[0002] At present, solid molecular sieves are basically used as catalysts in the process of producing cyclohexanol by hydrating cyclohexene. The solid molecular sieves are the most successful in industrial application due to their advantages of insolubility in water, easy separation and regeneration, high mechanical strength and good heat resistance. In 1983, Asahi Kasei (JP60104029A) applied for a patent for a process for hydrating cyclohexene using a solid acid molecular sieve catalyst. When the molar ratio of Si / Al of the catalyst was 24, the cyclohexene was catalytically hydrated in an autoclave at 120℃ for 2h, and the yield of cyclohexanol was 12.7%. In 1986, the company (JP61221141A) disclosed a patent for preparation of a high-efficiency hydration molecular sieve catalyst. The yield of cyclohexanol using the molecular sieve catalyst was 10.8% at 100-180℃, and the service life of the catalyst was 240h. In view of the regeneration of the catalyst, Asahi Kasei also provided a patent for liquid-phase regeneration of the molecular sieve, and in 1990, a 60kt / a production device was built in Shuijia and put into operation. China Shenma Group Company introduced the technology and production device from Asahi Kasei and put it into operation. In the two-stage continuous stirred tank reactor, the single-pass conversion rate of cyclohexene was 9.5%. H. Zhang et al. (Chem. Eng. Sci., 2002, 57, 315-322) used ZSM-5 molecular sieves with a Si / Al ratio of 30-50 as catalysts in a cyclohexene hydration reaction system for preparing cyclohexanol, and the selectivity of cyclohexanol was greater than 99%. At the same time, the liquid-liquid distribution coefficient of cyclohexanol and the reaction kinetics based on the aqueous solution were obtained.

[0003] The cyclohexene / cyclopentene hydration reaction catalyzed by a zeolite molecular sieve is a liquid-liquid-solid three-phase catalytic reaction, in which the water phase and the cyclohexene phase are two immiscible liquid phases, and the contact area is limited, which greatly limits the occurrence of the reaction. Traditionally, the zeolite molecular sieve material exhibits hydrophilic material. Therefore, in the reaction, cyclohexene / cyclopentene is in the upper layer, the water phase is in the lower layer, and the zeolite molecular sieve is dispersed in the water phase. Only under mechanical stirring can it be temporarily dispersed in the oil phase. Therefore, the main improvement direction of the cyclohexene hydration catalyst is to increase the amphiphilicity (i.e. lipophilicity) of the zeolite molecular sieve. Make it more inclined to distribute at the oil-water interface rather than stay in the water phase. One method is to use silane reagents, such as using n-octyl trimethyl chlorosilane / trimethyl chlorosilane for surface modification (CN111450875A, CN111804347A, CN113559919B, Chem. J. Chin. U, 2005. 26, 731, RSC Adv., 2021, 11, 18299). Another idea is to use an alkali treatment / secondary crystallization method to realize the wrapping of a lipophilic pure silica silicalite-1 shell around a hydrophilic ZSM-5 core, thereby improving the amphiphilicity of the catalyst (CN116510768A). However, the surface modification of silane reagents is easy to block the pores of ZSM-5 molecular sieve, and the lipophilicity is easy to lose due to easy falling off during catalyst regeneration. The alkali treatment / secondary crystallization method increases the complexity of catalyst preparation and increases the preparation cost of the catalyst. Therefore, there is currently a lack of a ZSM-5 molecular sieve with intrinsic amphiphilicity, i.e. which has emulsifying performance without any surface modification, thereby improving the conversion rate of ZSM-5 molecular sieve catalyzed cyclohexene / cyclopentene hydration. SUMMARY

[0004] The purpose of the present application is to overcome the above-mentioned defects and deficiencies existing in the prior art, and to provide a ZSM-5 molecular sieve with intrinsic amphiphilicity.

[0005] The second purpose of the present application is to provide the application of the ZSM-5 molecular sieve as a catalyst.

[0006] The above-mentioned purpose of the present application is realized by the following technical scheme:

[0007] The present application first provides a ZSM-5 zeolite molecular sieve with intrinsic amphiphilicity, which does not contain alkali metal and alkaline earth metal ions, and the anisotropy value is greater than or equal to 4; the anisotropy value is calculated by formula (I): , wherein A is the anisotropy value, x is the average length of the c-axis of the zeolite molecular sieve crystal particles, y is the average width of the a-axis of the zeolite molecular sieve crystal particles, and z is the average thickness of the b-axis of the zeolite molecular sieve crystal particles, and x>y>z.

[0008] Specifically, x is the average length of n zeolite crystal particles in the c-axis direction, y is the average width of m zeolite crystal particles in the a-axis direction, and z is the average thickness of k zeolite crystal particles in the b-axis direction.

[0009] More specifically, the present application defines the size of the crystal particles in three directions, length (c), thickness (b), and width (a). The size of the three directions is measured by scanning electron microscope photos to measure the a-direction size of n particles a1…a n , the b-direction size of m particles b1…b m , and the c-direction size of k particles c1…c k We assume (where is the average of a1…a n , where is the average of c1…c k , and where is the average of b1…b m ), then let The anisotropy introduced by the present application is a measure of the difference in size of the zeolite crystal particles in each direction. The closer the zeolite crystal particles are to a spherical shape, the closer the anisotropy value is to 1. The greater the absolute value of the anisotropy, the more the surface of the crystal particles deviates from a spherical shape. According to the above definition, the absolute value of the anisotropy of platelet-shaped and fibrous particles will be greater than other shapes.

[0010] The ZSM-5 zeolite provided by the present application does not contain alkali metal and alkaline earth metal ions, and the anisotropy value is greater than or equal to 4, that is, the crystal particles of the ZSM-5 zeolite have high morphological anisotropy. The present application shows that the ZSM-5 zeolite with this crystal structure has intrinsic Pickering emulsification performance, that is, it has emulsification performance without any surface modification. Under certain silicon-aluminum ratio and high anisotropy value, the ZSM-5 zeolite has good emulsification performance. When the zeolite is used as a catalyst to catalyze the hydration reaction of cyclohexene, it shows a conversion rate of up to 21.4% and a cyclohexanol selectivity of >99%. As a cyclopentene hydration reaction, it shows a conversion rate of 13.9% and a cyclopentanol selectivity of >99%.

[0011] The application further provides a preparation method of the ZSM-5 zeolite molecular sieve, and the synthesis raw materials include a silicon source, an aluminum source, a template agent, a crystal face regulator, a structure assistant and water, the synthesis ratio of the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the crystal face regulator, the template agent, the structure assistant and water is 1:0.005-0.0125:0-0.035:0.3:0.8:20-35, the above raw materials are mixed according to the synthesis ratio, and then hydrothermal synthesis and calcination are carried out to obtain the ZSM-5 zeolite molecular sieve; and the raw materials do not contain alkali metals and alkaline earth metals.

[0012] Further, the aluminum source is selected from one or both of aluminum sulfate and aluminum isopropoxide; the silicon source is selected from tetraethyl orthosilicate, the crystal face regulator is selected from isopropyl alcohol, the template agent is selected from tetrapropylammonium hydroxide, and the structure assistant is selected from urea.

[0013] Further, when the aluminum source is aluminum sulfate, the synthesis ratio of the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the crystal face regulator, the template agent, the structure assistant and water is 1:0.005-0.01:0.035:0.3:0.8:20; when the aluminum source is aluminum isopropoxide, the synthesis ratio of the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the crystal face regulator, the template agent, the structure assistant and water is 1:0.00625-0.0125:0:0.3:0.8:35.

[0014] Further, the hydrothermal reaction is carried out at 150-200 ℃ for 24-96 hours.

[0015] Preferably, the hydrothermal reaction is carried out at 180 ℃ for 96 hours.

[0016] Further, the calcination is carried out at 500-600 ℃ for 5-10 hours in an ambient atmosphere.

[0017] Preferably, the calcination is carried out at 550 ℃ for 6 hours in an ambient atmosphere.

[0018] The application provides application of the ZSM-5 zeolite molecular sieve in preparation of a Pickering emulsifier.

[0019] The application provides application of the ZSM-5 zeolite molecular sieve in preparation of a catalyst for catalyzing hydration of cyclohexene or cyclopentene.

[0020] The ZSM-5 has intrinsic amphiphilicity, and in the hydration reaction of cyclohexene or cyclopentene, the water and oil phases form a stable emulsion system to improve the conversion rate of cyclohexene or cyclopentene, wherein the water and oil phase contact area in the emulsification process is related to the silicon aluminum ratio and the anisotropy value of the ZSM-5 zeolite molecular sieve crystal particles, and under the condition that the anisotropy values are close, the water and oil phase contact area is positively correlated with the silicon aluminum ratio, and the cyclohexene / cyclopentene conversion rate is positively correlated with the water and oil phase contact area.

[0021] The application provides a method for catalyzing the hydration of cyclohexene or cyclopentene, wherein the ZSM-5 zeolite molecular sieve is dispersed in water, an oil phase is added to form an emulsion, and the hydration reaction is carried out to obtain a product; and the oil phase is cyclohexene or cyclopentene.

[0022] Further, the ratio (g / mL) of the ZSM-5 zeolite molecular sieve to water is 0.01-0.04:1.

[0023] Preferably, the ratio (g / mL) of the ZSM-5 zeolite molecular sieve to water is 0.0288-0.0372:1, and further preferably 0.0372:1.

[0024] Further, the volume ratio of the water to the oil phase is 1.5-4.5:1.

[0025] Preferably, the volume ratio of the water to the oil phase is 2.5-4.5:1, and further preferably 3.5:1.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] The application first provides a ZSM-5 zeolite molecular sieve, wherein the ZSM-5 zeolite molecular sieve does not contain alkali metal and alkaline earth metal ions, the silicon aluminum ratio is 16-51, and the anisotropy value is greater than or equal to 4; the ZSM-5 zeolite molecular sieve has high morphological anisotropy, and therefore has intrinsic Pickering emulsification performance, that is, can have emulsification performance without any surface modification, and therefore can be applied as a Pickering emulsifier. Further, when the ZSM-5 zeolite molecular sieve is used as a catalyst to catalyze the hydration reaction of cyclohexene, a highest conversion rate of 21.4% and a cyclohexanol selectivity of >99% are exhibited, and when the ZSM-5 zeolite molecular sieve is used as a catalyst to catalyze the hydration reaction of cyclopentene, a conversion rate of 13.9% and a cyclopentanol selectivity of >99% are exhibited, and has the excellent characteristics that the cyclohexene conversion rate / cyclohexanol yield is higher than that of other ZSM-5 zeolite molecular sieve catalysts. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The XRD and electron microscope photos of the MFI-1 zeolite molecular sieve.

[0029] Figure 2 XRD and electron micrograph of MFI-2 zeolite molecular sieve.

[0030] Figure 3 XRD and electron micrograph of MFI-3 zeolite molecular sieve.

[0031] Figure 4 XRD and electron micrograph of MFI-4 zeolite molecular sieve.

[0032] Figure 5 Measurement of anisotropy values of MFI-1-4, IRZ-MFI-003 zeolite molecular sieves.

[0033] Figure 6 Emulsification test characterization results of MFI-1-4, IRZ-MFI-003 zeolite molecular sieves. DETAILED DESCRIPTION

[0034] The present application will be further described by the following description of the drawings and specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0035] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0036] Example 1

[0037] Preparation of an intrinsic amphiphilic ZSM-5 molecular sieve:

[0038] The synthesis conditions of MFI-1 are as follows, using tetraethyl orthosilicate (99%, TEOS, Aladdin), aluminum sulfate (99%, Al2(SO4)3·18H2O, Aladdin), isopropyl alcohol (99.9%, IPA, Aladdin), tetrapropylammonium hydroxide TPAOH (40% TPAOH, Bidepharm), urea (99.9%, CH4N2O, Macklin), deionized water. The synthesis ratio (molar ratio) is: 0.005 Al2O3 (aluminum sulfate) / SiO2 / 0.035 IPA / 0.3 TPAOH / 0.8 urea / 20 H2O.

[0039] and reacted at 180°C for 96 hours, the sample was collected by filtration, washed with water, and dried at 60°C overnight. The organic matter was removed by calcination at 550°C for 6 hours under ambient atmosphere. The MFI-1 sample was obtained.

[0040] The XRD and SEM analysis of the MFI-1 sample is shown in Figure 1As shown, XRD shows that the sample is a typical ZSM-5 molecular sieve diffraction pattern, no other impurity peaks appear, and the crystallinity is good. The electron micrograph shows that its morphology is regular nanosheet, and the size is uniform.

[0041] Example 2

[0042] The synthesis conditions of MFI-2 are as follows, using tetraethyl orthosilicate (99%, TEOS, Aladdin), aluminum sulfate (99%, Al2(SO4)3·18H2O, Aladdin), isopropyl alcohol (99.9%, IPA, Aladdin), tetrapropylammonium hydroxide TPAOH (40% TPAOH, Bidepharm), urea (99.9%, CH4N2O, Macklin), deionized water. The synthesis ratio (molar ratio) is: 0.01 Al2O3 (aluminum sulfate) / SiO2 / 0.035 IPA / 0.3 TPAOH / 0.8 urea / 20 H2O.

[0043] and reacted at 180°C for 96 hours, the sample was collected by filtration, washed with water, and dried at 60°C overnight. The organic matter was removed by calcination at 550°C for 6 hours under ambient atmosphere. The MFI-2 sample was obtained.

[0044] The XRD and SEM analysis of the MFI-2 sample are shown in Figure 2 As shown, XRD shows that the sample is a typical ZSM-5 molecular sieve diffraction pattern, no other impurity peaks appear, and the crystallinity is good. The electron micrograph shows that its morphology is regular nanosheet, and the size is uniform.

[0045] Example 3

[0046] The synthesis conditions of MFI-3 are as follows, using tetraethyl orthosilicate (99%, TEOS, Aladdin), isopropyl alcohol (99.9%, IPA, Aladdin), aluminum isopropoxide (99.9%, Al(OiPr)3, Aladdin), tetrapropylammonium hydroxide TPAOH (40% TPAOH, Bidepharm), urea (99.9%, CH4N2O, Macklin), deionized water. The synthesis ratio (molar ratio) is: 0.00625 Al2O3 (aluminum isopropoxide) / SiO2 / 0.3 TPAOH / 0.8 urea / 35 H2O.

[0047] and reacted at 180°C for 96 hours, the sample was collected by filtration, washed with water, and dried at 60°C overnight. The organic matter was removed by calcination at 550°C for 6 hours under ambient atmosphere. The MFI-3 sample was obtained.

[0048] The XRD and SEM analysis of the MFI-3 sample are shown in Figure 3As shown, XRD shows that the sample is a typical ZSM-5 molecular sieve diffraction pattern, no other impurity peaks appear, and the crystallinity is good. The electron micrograph shows that its morphology is regular nanosheet, and the size is uniform.

[0049] Example 4

[0050] The synthesis conditions of MFI-4 are as follows, using tetraethyl orthosilicate (99%, TEOS, Aladdin), isopropanol (99.9%, IPA, Aladdin), aluminum isopropoxide (99.9%, Al(OiPr)3, Aladdin), tetrapropylammonium hydroxide TPAOH (40% TPAOH, Bidepharm), urea (99.9%, CH4N2O, Macklin), deionized water. The synthesis ratio is 0.0125 Al2O3 (aluminum isopropoxide) / SiO2 / 0.3 TPAOH / 0.8 urea / 35 H2O.

[0051] And react at 180°C for 96 hours, filter the sample, wash with water, and dry at 60°C overnight. Remove organic matter by calcining at 550°C for 6 hours under ambient atmosphere. The MFI-4 sample can be obtained.

[0052] The XRD and SEM analysis of the MFI-4 sample are shown in Figure 4 As shown, XRD shows that the sample is a typical ZSM-5 molecular sieve diffraction pattern, no other impurity peaks appear, and the crystallinity is good. The electron micrograph shows that its morphology is regular nanosheet, and the size is uniform.

[0053] Comparative Example 1

[0054] The international standard sample IRZ-MFI-003 of the International Zeolite Molecular Sieve Association Catalysis Committee is an international standardized sample of ZSM-5 molecular sieve.

[0055] Test Example 1

[0056] As Figure 5 shown, in order to quantitatively express the anisotropy of the zeolite molecular sieve particles with a clear crystal axis orientation, the present application defines the size of the crystal particles in three directions, width (a), thickness (b), and length (c). The size in three directions is measured by scanning electron micrographs to measure the a direction size of n particles a1…a n , m b direction sizes b1…b m , and k c direction sizes c1…c k . It is assumed that (wherein is the average of a1…a n , wherein is the average of c1…c k , wherein b1…b m The anisotropy value of the sample can be expressed as:

[0057] Formula (I):

[0058] In the present application, the anisotropy values of the zeolite molecular sieves (MFI-1-4) prepared in Examples 1-4, and IRZ-MFI-003 of Comparative Example 1, measured in three directions and averaged, are shown in Table 1. Anisotropy is a measure of the difference in size of a crystal particle in different directions. Thus, the more a catalyst crystal particle approaches a spherical shape, the closer the anisotropy value is to 1. The greater the absolute value of anisotropy, the more the surface of the crystal particle deviates from a spherical shape. By definition, the absolute value of anisotropy is greater for platelet and fibrous particles than for other shapes.

[0059] Table 1. Anisotropy values of the samples of Examples 1-4 and IRZ-MFI-003 zeolite

[0060]

[0061] Test Example 2. Catalytic hydration of cyclohexene

[0062] The catalytic hydration of cyclohexene was tested using the International Zeolite Association Catalysis Commission standard sample IRZ-MFI-003 as a comparison, in combination with the four ZSM-5 type zeolite molecular sieves prepared in Examples 1-4 as catalysts.

[0063] The catalytic effect was evaluated as follows: 30 mg of calcined catalyst powder and 3 ml of water were placed in a 10 ml glass vial. The vial was shaken using an ultrasonic shaker for two minutes to disperse the powder uniformly, and then an equal volume of oil phase was added. The vial was shaken vigorously to mix, and then left to stand for a period of time to observe the morphology of the emulsion and any changes. Following the procedure described above for the preparation of Pickering emulsions, cyclohexene was used as the oil phase, and the oil to water ratio was adjusted to form an emulsion. Typically, the emulsion was transferred to a reactor and pressurized to 2.5 MPa with nitrogen to ensure the stability of the emulsion at high temperatures. The feed ratio, catalyst dosage, and reaction conditions are shown in Table 2, and the system was heated to the appropriate temperature and maintained for 6 hours of reaction. After the reaction was completed, the system temperature was allowed to decrease to room temperature, and then the pressure was released. The reaction mixture was washed and extracted with ethyl acetate, and the oil phase was collected and analyzed by gas chromatography-mass spectrometry (GC-MS) for the conversion of cyclohexene. The remaining solid zeolite could be easily recovered by filtration and could be calcined at 600°C under an oxygen atmosphere for reuse. The results are shown in Table 2.

[0064] Table 2. Catalytic effect evaluation of catalytic hydration of cyclohexene​

[0065]

[0066] In the above five ZSM-5 type zeolite catalysts, emulsion test characterization was also conducted, and the contact area of water-oil two phases was calculated according to the emulsion condition. The results are shown in Table 3. Figure 6 , Table 3. The emulsion water-oil two phase contact area of the catalyst is related to the silicon aluminum ratio and the anisotropy value of the catalyst crystal particles. The optimal conversion rate of cyclohexene is positively correlated with the water-oil two phase contact area (and both the anisotropy value and Si / Al).

[0067] Table 3 Sample emulsion test and catalytic performance characterization results

[0068]

[0069]

[0070] Test Example 3 Catalytic hydration of cyclopentene

[0071] The catalytic evaluation of using the zeolite molecular sieves of Examples 1-2, Comparative Example 1 as catalysts to catalyze the hydration of cyclopentene is as follows: 30 milligrams of calcined catalyst powder and 3 milliliters of water were placed in a 10 milliliter glass bottle. An ultrasonic shaker was used to shake for two minutes to evenly disperse the powder, and then an equal volume of oil phase was added. The bottle was shaken vigorously to mix, and then it was allowed to stand for a period of time to observe the morphology of the emulsion and any changes. According to the preparation procedure of Pickering emulsion described above, cyclopentene was used as the oil phase, and the oil-water ratio was adjusted to form an emulsion. Usually, the emulsion was transferred to a reactor and pressurized to 2.5 megapascals with nitrogen to ensure the stability of the emulsion at high temperature. The system was heated to 130°C and kept for 6 hours. After the reaction was completed, the system temperature was allowed to drop to room temperature, and then the pressure was released. The reaction mixture was washed and extracted with ethyl acetate, the oil phase was collected, and the conversion rate of cyclopentene was analyzed by gas chromatography-mass spectrometry (GC-MS). The remaining solid zeolite can be easily recovered by filtration, and can be calcined at 600°C under an oxygen atmosphere for reuse. The reaction results are shown in Table 4, and the cyclopentanol selectivity is all >99%.

[0072] Table 4 MFI-1~IRZ-MFI-003 catalytic hydration of cyclopentene results

[0073]

Claims

1. An intrinsically amphiphilic ZSM-5 zeolite molecular sieve, characterized in that, The ZSM-5 zeolite molecular sieve contains no alkali metal or alkaline earth metal ions and has an anisotropy value greater than or equal to 4; the anisotropy value is expressed by formula (I): The calculations show that A is the anisotropy value, x is the average length of the c-axis of the zeolite molecular sieve crystal particles, y is the average width of the a-axis of the zeolite molecular sieve crystal particles, and z is the average thickness of the b-axis of the zeolite molecular sieve crystal particles, with x > y > z.

2. The ZSM-5 zeolite molecular sieve according to claim 1, characterized in that, The silicon-to-aluminum ratio of the ZSM-5 zeolite molecular sieve is 16–51.

3. The method for preparing the ZSM-5 zeolite molecular sieve according to claim 1 or 2, characterized in that, The synthetic raw materials include a silicon source, an aluminum source, a template agent, a crystal facet modifier, a structural aid, and water. The silicon source is calculated as SiO2, the aluminum source as Al2O3, and the molar ratio of the crystal facet modifier, template agent, structural aid, and water is 1:0.005~0.0125:0~0.035:0.3:0.8:20~35. The above raw materials are mixed according to the synthetic ratio, and then subjected to hydrothermal synthesis and calcination to obtain the final product. The raw materials do not contain alkali metals or alkaline earth metals.

4. The preparation method according to claim 3, characterized in that, The aluminum source is selected from one or both of aluminum sulfate and aluminum isopropoxide; the silicon source is selected from tetraethyl orthosilicate; the crystal plane modifier is selected from isopropanol; the template agent is selected from tetrapropylammonium hydroxide; and the structural aid is selected from urea.

5. The preparation method according to claim 4, characterized in that, When the aluminum source is aluminum sulfate, the synthesis ratio of silicon source (SiO2), aluminum source (Al2O3), crystal facet modifier, template agent, structural aid, and water is 1:0.005-0.01:0.035:0.3:0.8:20; when the aluminum source is aluminum isopropoxide, the synthesis ratio of silicon source (SiO2), aluminum source (Al2O3), crystal facet modifier, template agent, structural aid, and water is 1:0.00625-0.0125:0:0.3:0.8:

35.

6. The use of the ZSM-5 zeolite molecular sieve according to claim 1 or 2 in the preparation of Pickering emulsifier.

7. The use of the ZSM-5 zeolite molecular sieve according to claim 1 or 2 in the preparation of catalysts for the hydration of cyclohexene or cyclopentene.

8. A method for catalytic hydration of cyclohexene or cyclopentene, characterized in that, The ZSM-5 zeolite molecular sieve of claim 1 or 2 is dispersed in water, an oil phase is added to form an emulsion, and a hydration reaction is carried out to obtain the product; the oil phase is cyclohexene or cyclopentene.

9. According to the method of claim 8, the ratio (g / mL) of the ZSM-5 zeolite molecular sieve to water is 0.01 to 0.04:

1.

10. The method according to claim 8, characterized in that, The volume ratio of water to oil phase is 1.5 to 4.5:1.

Images