Nanocatalytic material, preparation method thereof and olefin hydration method
By preparing nanocatalytic materials, the problem of insufficient conversion rate and selectivity of existing carbon nanocatalytic materials in olefin hydration reactions has been solved, and high conversion rate and target product selectivity of olefins, especially C6+ macromolecules, have been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2022-09-30
- Publication Date
- 2026-06-16
AI Technical Summary
Existing carbon nanocatalytic materials exhibit low conversion rates and selectivity in the selective hydration of hydrocarbons, especially in the conversion of olefins to alcohols, and further improvements are needed.
Nanocatalysts were prepared by electrolyzing a first and a second conductive material in an electrolyte containing an inorganic base, mixing an aluminum source, a silicon source, and a cationic surfactant, followed by hydrothermal treatment and calcination. These nanocatalysts are then used for olefin hydration reactions.
High conversion rates of olefins and high selectivity of target products were achieved under mild conditions, especially the hydration reaction of C6+ macromolecules such as cyclooctene, which showed excellent reactivity.
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Abstract
Description
Technical Field
[0001] This disclosure relates to a nanocatalytic material, its preparation method, and a method for olefin hydration. Background Technology
[0002] In fields such as selective hydration catalysis of hydrocarbons, carbon nanoparticles and other carbon materials show promising application prospects. However, existing carbon nanoparticle catalytic materials still require improvement and optimization in terms of material properties, necessitating further research and development by scientists and engineers to promote the industrial upgrading and transformation of the petrochemical industry. In the selective hydration reaction of hydrocarbons, the hydration of olefins into alcohols, such as the hydration of cyclohexene into cyclohexanol and cyclooctene into cyclooctanol, plays a crucial role in national production. Existing hydration preparation technologies still have room for improvement in many aspects, and some even urgently require refinement. Summary of the Invention
[0003] The purpose of this disclosure is to provide a nanocatalytic material, its preparation method, and a method for olefin hydration. The nanocatalytic material can achieve high feed conversion and target product selectivity in olefin hydration reactions.
[0004] To achieve the above objectives, this disclosure provides a method for preparing nanocatalytic materials, the method comprising:
[0005] S1. Connect the first conductive material and the second conductive material to the positive and negative terminals of a DC power supply, respectively, and place them in an electrolyte containing inorganic alkali. Electrolyze them at a voltage of 5-50V for 1-5 days to obtain an electrolyzed solution; wherein, the first conductive material is a graphite molded body.
[0006] S2. The electrolyzed solution, aluminum source, silicon source and cationic surfactant are mixed to obtain a first mixture;
[0007] S3. The mixture is subjected to hydrothermal treatment, and the resulting solid product is calcined.
[0008] Optionally, in step S1, the concentration of inorganic base in the solution after electrolysis is 10-5000 mmol / L; the concentration of inorganic base in the electrolyte containing inorganic base is 5-5000 mmol / L.
[0009] Optionally, step S2 includes:
[0010] (1) Divide the electrolyzed solution into a first part of the electrolyzed solution and a second part of the electrolyzed solution;
[0011] (2) The silicon source, the aluminum source and the solution after the first part of electrolysis are mixed to obtain a second mixture;
[0012] The cationic surfactant is mixed with the solution after the second part of electrolysis treatment to obtain a third mixture;
[0013] (3) Mix the second mixture and the third mixture to obtain the first mixture;
[0014] Optionally, the volume ratio of the solution after the first part of electrolysis to the solution after the second part of electrolysis is 1:(0.1-2).
[0015] Optionally, in step S2, the weight ratio of the electrolyzed solution, the silicon source, the aluminum source and the cationic surfactant is 100:(1-200):(0.1-20):(1-100).
[0016] Optionally, in step S3, the conditions for the hydrothermal treatment include: a time of 2-24 hours and a temperature of 100-300℃.
[0017] The roasting conditions include: a time of 1-12 hours and a temperature of 350-700℃.
[0018] Optionally, the method further includes: contacting the solid obtained in step S3 with the solution after electrolysis to perform a modification treatment;
[0019] The modification treatment conditions include: time of 1-48h, temperature of 20-200℃, pressure of 0-1MPa, and the weight ratio of the solid to the solution after electrolysis is 1:(1-20).
[0020] Optionally, the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, and hydrazine hydrate;
[0021] The silicon source is an inorganic silicon source and / or an organic silicon source;
[0022] Optionally, the organosilicon source is an organosilicon ester;
[0023] The cationic surfactant is selected from one or more of alkylammonium bromide with 15-20 carbon atoms, alkylammonium chloride with 15-20 carbon atoms, and alkylammonium fluoride with 15-20 carbon atoms.
[0024] The aluminum source is aluminum isopropoxide and / or aluminum sulfate.
[0025] The second aspect of this disclosure provides nanocatalytic materials prepared using the method described in the first aspect of this disclosure.
[0026] A third aspect of this disclosure provides a method for hydrating olefins, the method comprising: contacting an olefin and a hydrating agent in the presence of a catalyst to carry out a hydration reaction, said catalyst comprising the nanocatalytic material described in the second aspect of this disclosure.
[0027] Optionally, the conditions for the hydration reaction include: a temperature of 100-300℃, a pressure of 0.1-5MPa, and a time of 0.1-24h;
[0028] The olefin is a cyclic olefin;
[0029] Optionally, the cyclic olefin is a monocyclic olefin with 5-12 cyclic carbon atoms (substituted or unsubstituted) and / or a bicyclic olefin with 8-16 cyclic carbon atoms (substituted or unsubstituted); the hydrating agent is water.
[0030] The weight ratio of the olefin to the catalyst is 100:(0.1-20);
[0031] The molar ratio of the hydrating agent to the olefin is greater than 1.
[0032] The nanocatalytic materials prepared by the method disclosed herein using the above technical solution can be used in olefins, especially C464 nanocatalysts. 6+ When hydrating macromolecular olefins such as cyclooctene, the conversion rate of reactants is high and the selectivity of the target product is good.
[0033] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation
[0034] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of this disclosure.
[0035] The first aspect of this disclosure provides a method for preparing nanocatalytic materials, the method comprising:
[0036] S1. Connect the first conductive material and the second conductive material to the positive and negative terminals of a DC power supply, respectively, and place them in an electrolyte containing inorganic alkali. Electrolyze them at a voltage of 5-50V for 1-5 days to obtain an electrolyzed solution; wherein, the first conductive material is a graphite molded body.
[0037] S2. The electrolyzed solution, aluminum source, silicon source and cationic surfactant are mixed to obtain a first mixture;
[0038] S3. The mixture is subjected to hydrothermal treatment, and the resulting solid product is calcined.
[0039] The nanocatalytic materials prepared by the method disclosed herein can achieve hydration of olefins under mild conditions, with high olefin conversion and selectivity for target products.
[0040] In this disclosure, the first mixture in step S2 does not include any other metal sources, except for those introduced from inorganic bases, aluminum sources, silicon sources, and cationic surfactants.
[0041] In this disclosure, the amount of electrolyte used is not specifically limited and can be selected according to actual needs. In a preferred embodiment, the size of the first conductive graphite molded body matches the size of the second conductive body. The size of the first conductive body can vary within a wide range; for example, the diameter of the rod-shaped graphite can be 3-20 mm, and the length can be 5-50 cm, where the length refers to the axial length of the graphite rod. The type and shape of the second conductive body are not specifically limited; it can be any conductive material, such as iron, copper, graphite, etc., preferably graphite, and its shape can be rod-shaped, plate-shaped, etc., preferably rod-shaped. During electrolysis, a certain distance can be maintained between the first and second conductive bodies, for example, 5-40 cm.
[0042] According to one embodiment of this disclosure, in step S1, the concentration of inorganic base in the solution after electrolysis is 10-5000 mmol / L, preferably 50-2500 mmol / L; the concentration of inorganic base in the electrolyte containing inorganic base is 5-5000 mmol / L, preferably 20-2000 mmol / L.
[0043] According to one embodiment of this disclosure, step S2 includes:
[0044] (1) Divide the electrolyzed solution into a first part of the electrolyzed solution and a second part of the electrolyzed solution;
[0045] (2) The silicon source, the aluminum source and the solution after the first part of electrolysis are mixed to obtain a second mixture;
[0046] The cationic surfactant is mixed with the solution after the second part of electrolysis treatment to obtain a third mixture;
[0047] (3) The second mixture and the third mixture are mixed to obtain the first mixture; preferably, under stirring conditions, the silicon source and aluminum source are mixed with the solution after the first part of electrolysis treatment, and the cationic surfactant is mixed with the solution after the second part of electrolysis treatment; stirring is well known to those skilled in the art, for example, mechanical stirring can be used. Using the above method, nanocatalytic materials with superior catalytic performance can be prepared.
[0048] According to one embodiment of this disclosure, the volume ratio of the solution after the first part of electrolysis treatment and the solution after the second part of electrolysis treatment is 1:(0.1-2), preferably 1:(0.2-1).
[0049] According to one embodiment of this disclosure, in step S2, the weight ratio of the electrolyzed solution, silicon source, aluminum source and cationic surfactant can vary within a wide range, for example, it can be 100:(1-200):(0.1-20):(1-100); preferably, the weight ratio of the electrolyzed solution, silicon source, aluminum source and cationic surfactant is 100:(1-50):(1-20):(1-50), more preferably 100:(5-30):(2-10):(2-30).
[0050] In this disclosure, the inorganic base is well known to those skilled in the art, and is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia and hydrazine hydrate, preferably one or more of sodium hydroxide, potassium hydroxide and hydrazine hydrate, and more preferably hydrazine hydrate.
[0051] In this disclosure, the silicon source is well known to those skilled in the art, such as an inorganic silicon source and / or an organosilicon source, and the organosilicon source can be an organosilicon ester; the silicon source can be selected from one or more of silica gel, silica sol and organosilicon ester, wherein the organosilicon ester can be tetraethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, butyl orthosilicate, etc., with tetraethyl orthosilicate being the most commonly used.
[0052] In this disclosure, the aluminum source is well known to those skilled in the art, and may include aluminum-containing organic and / or inorganic aluminum salts, preferably aluminum-containing substances such as aluminum isopropoxide and / or aluminum sulfate.
[0053] In this disclosure, cationic surfactant refers to a surfactant in which the cation is a macromolecular hydrophobic group, such as one or more selected from alkylammonium bromide, alkylammonium chloride and alkylammonium fluoride with 15-20 carbon atoms, preferably selected from one or more selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide and tetradecyltrimethylammonium chloride.
[0054] According to one embodiment of this disclosure, step S3 further includes: performing solid-liquid separation on the solid-liquid mixture obtained by hydrothermal treatment to obtain a solid product. The method of solid-liquid separation is not specifically limited. For example, the solid can be collected by centrifugation or filtration. Preferably, the collected solid is first washed and dried, and then calcined. The solution used for washing is not specifically limited. For example, deionized water can be used for washing. Drying can be carried out in a vacuum drying oven. Preferably, vacuum drying is carried out at a temperature of 40-160°C and a pressure of 0-0.1 MPa for 1-24 hours.
[0055] According to one embodiment of this disclosure, in step S3, the hydrothermal reaction can be carried out in a heat-resistant sealed container, which is conventional in the art, such as a reaction vessel. The hydrothermal treatment conditions include: a time of 2-24 hours and a temperature of 100-300°C, preferably, a time of 6-12 hours and a temperature of 120-200°C; the calcination conditions include: a time of 1-12 hours and a temperature of 350-700°C, preferably, a time of 2-6 hours.
[0056] According to one embodiment of this disclosure, the method further includes: contacting the solid obtained in step S3 with the electrolyzed solution for modification treatment; the modification treatment conditions include: time of 1-48h, temperature of 20-200℃, pressure of 0-1MPa, and the weight ratio of solid to electrolyzed solution of 1:(1-20), preferably, the temperature of 40-100℃, pressure of 0-0.1MPa, time of 2-12h, and the mass ratio of solid to electrolyzed solution of 1:(5-10).
[0057] According to one embodiment of this disclosure, a solid-liquid mixture obtained after modification is subjected to solid-liquid separation, and the solid product is washed, dried, and calcined to obtain a nanocatalytic material. The method of solid-liquid separation is not specifically limited; for example, the solid can be collected by centrifugation or filtration. The washing liquid used for washing is not specifically limited; for example, deionized water can be used. Drying can be vacuum drying, and specific conditions may include: temperature 20-200℃, pressure 0-1MPa, and time 1-48h; preferably, temperature 40-100℃, pressure 0-0.1MPa, and time 2-12h. Vacuum drying can be performed in apparatus conventionally used by those skilled in the art, such as in a vacuum drying oven. Calcination conditions include: time 2-6h and temperature 350-700℃.
[0058] The second aspect of the present invention provides nanocatalytic materials prepared using the method provided in the first aspect of the present invention.
[0059] A third aspect of this disclosure provides a method for hydrating olefins, the method comprising: contacting an olefin and a hydrating agent in the presence of a catalyst to carry out a hydration reaction, said catalyst comprising the nanocatalytic material described in the second aspect of this disclosure.
[0060] According to one embodiment of this disclosure, the olefin can be a cyclic olefin. Specifically, the cyclic olefin can be a monocyclic olefin with 5-12 cyclic carbon atoms (substituted or unsubstituted) and / or a bicyclic olefin with 8-16 cyclic carbon atoms (substituted or unsubstituted). Further, when the cyclic olefin is selected from a monocyclic olefin with 5-12 cyclic carbon atoms (substituted) and / or a bicyclic olefin with 8-16 cyclic carbon atoms (substituted), the substituent can be a halogen or a methyl group. In a preferred embodiment, the olefin can be cyclooctene, cyclohexene, cyclopentene, dicyclohexene, methylcyclohexene, methylcyclopentene, halocyclohexene (such as bromocyclohexene), and halocyclopentene (such as chlorocyclopentene), preferably cyclooctene or cyclohexene, and more preferably cyclooctene.
[0061] According to one embodiment of this disclosure, the catalyst is the nanocatalytic material of this invention, and the weight ratio of olefin to catalyst can be 100:(0.1-20), preferably 100:(0.5-5).
[0062] According to one embodiment of this disclosure, the hydrating agent is water, and the molar amount of water can be 1-200 times the theoretical value of the amount of water required to hydrate the olefin into the desired product. In one specific embodiment, the molar ratio of water to olefin is greater than 1, preferably (5-100):1.
[0063] According to one embodiment of this disclosure, the hydration reaction can be carried out in a catalytic reactor well known to those skilled in the art, such as a batch reactor, fixed-bed reactor, moving-bed reactor, suspended-bed reactor, or slurry-bed reactor. The amount of catalyst used can be appropriately selected based on the amounts of olefins and hydrating agents, as well as the type of reactor.
[0064] According to one embodiment of the present disclosure, the hydration reaction is carried out in a slurry bed reactor. Based on 100 mL of cyclic olefins, the amount of catalyst used can be 0.1-20 g, preferably 0.5-5 g, calculated based on the nanocatalytic material of the present disclosure contained in the catalyst.
[0065] According to one embodiment of this disclosure, the hydration reaction is carried out in a fixed-bed reactor, and the weight hourly space velocity (WHSV) of the olefins can be 0.01-10 h⁻¹. -1 Preferably 0.05-5h -1 .
[0066] According to one embodiment of this disclosure, the conditions for the hydration reaction may include: a temperature of 100-300°C, a pressure of 0.1-5 MPa, and a time of 0.1-24 h; preferably, the temperature is 120-280°C, the pressure is 0.5-3 MPa, and the time is 1-12 h.
[0067] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.
[0068] All reagents used in this invention are commercially available analytical grade reagents.
[0069] The concentration of inorganic base in the solution after electrolysis is calculated as follows: Since water evaporates during electrolysis, the volume of the electrolyte decreases, which in turn increases the concentration of inorganic base in the electrolyte. The specific calculation method is: (molar amount of inorganic base added / volume after electrolysis) * 100%.
[0070] Example 1
[0071] S1. Add 5000 mL of sodium hydroxide aqueous solution (sodium hydroxide concentration of 1000 mmol / L) to a beaker as electrolyte. Place two identical graphite rods (8 mm in diameter and 50 cm in length) in the beaker, keeping the distance between the rods 10 cm. Connect the graphite rods to the positive and negative terminals of a DC power supply respectively, apply a voltage of 15 V and electrolyze for 5 days to obtain the electrolyzed solution. The inorganic base concentration of the electrolyzed solution is 1160 mmol / L.
[0072] S2. Divide the electrolyzed solution into two equal volumes. Mix tetraethyl orthosilicate, aluminum sulfate, and the first electrolyzed solution with stirring to obtain a second mixture. Mix hexadecyltrimethylammonium bromide with the second electrolyzed solution with stirring to obtain a third mixture. Slowly mix the second and third mixtures until homogeneous to obtain a first mixture. The weight ratio of the electrolyzed solution, tetraethyl orthosilicate, aluminum sulfate, and hexadecyltrimethylammonium bromide is 100:20:1:5.
[0073] S3. The first mixture is sealed in a reactor and hydrothermally treated at 150°C for 24 hours. The solid product is obtained by filtration. The obtained solid product is washed with deionized water, dried and calcined. The drying is carried out in a vacuum drying oven at 120°C for 24 hours and at a pressure of 0.02 MPa. The calcination time is 4 hours and the temperature is 600°C.
[0074] S4. The calcined solid is mixed with twice the mass of the electrolyzed solution and stirred at 75℃ and 0.1MPa for 6 hours for modification. The resulting solid-liquid mixture is filtered, and the resulting solid product is washed with deionized water, dried, and calcined to obtain nanocatalytic material A1. The drying is carried out in a vacuum drying oven at 120℃ for 12 hours, and the calcination time is 6 hours at 500℃.
[0075] Example 2
[0076] Nanocatalyst material A2 was prepared using the same method as in Example 1, except that in step S2, the weight ratio of the electrolyzed solution, tetraethyl orthosilicate, aluminum sulfate and hexadecyltrimethylammonium bromide was 100:50:5:45.
[0077] Example 3
[0078] Nanocatalyst material A3 was prepared using the same method as in Example 1, except that in step S3, the hydrothermal treatment temperature was 180°C and the time was 2 hours.
[0079] Example 4
[0080] Nanocatalyst material A4 was prepared using the same method as in Example 1, except that step S4 was omitted.
[0081] Example 5
[0082] Nanocatalyst material A5 was prepared using the same method as in Example 1, except that in step S2, the electrolyzed solution was not divided into two equal volumes. Instead, the electrolyzed solution, tetraethyl orthosilicate, aluminum sulfate, and hexadecyltrimethylammonium bromide were mixed to obtain the first mixture.
[0083] Example 6
[0084] Nanocatalyst material A6 was prepared using the same method as in Example 1, except that in step S2, the weight ratio of the electrolyzed solution, tetraethyl orthosilicate, aluminum sulfate and hexadecyltrimethylammonium bromide was 100:25:4:20.
[0085] Example 7
[0086] Nanocatalyst material A7 was prepared using the same method as in Example 1, except that sodium hydroxide was replaced with an equal mass of ammonia, tetraethyl orthosilicate was replaced with solid silica gel with an equal silicon content, aluminum sulfate was replaced with an equal mass of aluminum isopropoxide, and hexadecyltrimethylammonium bromide was replaced with an equal mass of tetradecyltrimethylammonium chloride.
[0087] Example 8
[0088] Nanocatalyst material A8 was prepared using the same method as in Example 1, except that in step S1, sodium hydroxide was replaced with an equimolar amount of hydrazine hydrate.
[0089] Example 9
[0090] Nanocatalyst material A9 was prepared using the same method as in Example 1, except that the voltage was 45V, the electrolysis time was 2 days, and the alkali concentration of the solution after electrolysis was 1085mmol / L.
[0091] Comparative Example 1
[0092] A sodium hydroxide aqueous solution (sodium hydroxide concentration of 1000 mmol / L), tetraethyl orthosilicate, aluminum sulfate, and hexadecyltrimethylammonium bromide were directly mixed in a weight ratio of 100:20:1:5, then sealed in a reactor and kept at 120°C for 24 h. The mixture was filtered to obtain a solid product, which was then washed with deionized water, dried, and calcined. The drying was carried out in a vacuum drying oven at 120°C for 24 h; the calcination time was 4 h at 600°C to obtain catalyst D1.
[0093] Comparative Example 2
[0094] A sodium hydroxide aqueous solution (sodium hydroxide concentration of 1160 mmol / L), tetraethyl orthosilicate, aluminum sulfate, and hexadecyltrimethylammonium bromide were directly mixed in a weight ratio of 100:20:1:5, then sealed in a reactor and kept at 120°C for 24 h. The mixture was filtered to obtain a solid product, which was then washed with deionized water, dried, and calcined. The drying was carried out in a vacuum drying oven at 120°C for 24 h; the calcination time was 4 h at 600°C to obtain catalyst D2.
[0095] In the following test examples, gas chromatography (GC: Agilent, 7890A) and gas chromatography-mass spectrometry (GC-MS: Thermo Fisher Trace ISQ) were used to analyze the hydration products. The following formulas were used to calculate the feed conversion and target product selectivity:
[0096] Olefin conversion % = (molar amount of olefin added before reaction - molar amount of olefin remaining after reaction) / molar amount of olefin added before reaction × 100%;
[0097] Target product selectivity % = (molar amount of target product generated after reaction) / molar amount of olefin added before reaction × 100%.
[0098] Test case
[0099] 250 mg of the nanocatalytic material prepared in the examples and comparative examples was added as a catalyst, along with an appropriate amount of water and cyclooctene, into a 250 mL high-pressure reactor. After sealing, the reactor was pressurized to 2.0 MPa with nitrogen. The molar ratio of water to cyclooctene was 8:1, and the weight ratio of cyclooctene to catalyst was 100:7. The reactor was stirred and reacted at 150 °C and 2.0 MPa for 3 h. The results are listed in Table 1.
[0100] Table 1
[0101]
[0102]
[0103] As shown in Table 1, the nanocatalytic materials prepared by the method disclosed herein are suitable for use with olefins, especially C464 nanoparticles. 6+ In the hydration reaction of macromolecular olefins, the conversion rate of reactants is high and the selectivity of target products is good.
[0104] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.
[0105] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.
[0106] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.
Claims
1. A method for hydrating an olefin, the method comprising: A hydration reaction is carried out by contacting an olefin and a hydrating agent in the presence of a catalyst, wherein the catalyst contains a nanocatalytic material, characterized in that the method for preparing the nanocatalytic material includes: S1. Connect the first and second conductive materials to the positive and negative terminals of a DC power supply, respectively, and place them in an electrolyte containing inorganic alkali. Electrolyze them for 1-5 days at a voltage of 5-50V to obtain the electrolyzed solution. The first conductive material is a graphite molded body; S2. The electrolyzed solution, aluminum source, silicon source and cationic surfactant are mixed to obtain a first mixture; S3. The mixture is subjected to hydrothermal treatment, and the resulting solid product is calcined. In step S3, the hydrothermal treatment conditions include: a time of 2-24 hours and a temperature of 100-300℃; the calcination conditions include: a time of 1-12 hours and a temperature of 350-700℃. The method for preparing the nanocatalytic material further includes: contacting the solid obtained in step S3 with the solution after electrolysis for modification treatment; performing solid-liquid separation on the solid-liquid mixture obtained after modification treatment; washing, drying, and calcining the solid product to obtain the nanocatalytic material; the calcination conditions include: a time of 2... 6 hours, temperature 350 700℃; The conditions for the modification treatment include: time of 1-48h, temperature of 20-200℃, and pressure of 0-1MPa.
2. The method according to claim 1, wherein, In step S1, the concentration of inorganic base in the solution after electrolysis is 10-5000 mmol / L; the concentration of inorganic base in the electrolyte containing inorganic base is 5-5000 mmol / L.
3. The method according to claim 1, wherein, Step S2 includes: (1) Divide the electrolyzed solution into a first part of the electrolyzed solution and a second part of the electrolyzed solution; (2) The silicon source, the aluminum source and the solution after the first part of the electrolytic treatment are mixed to obtain a second mixture; The cationic surfactant is mixed with the solution after the second part of electrolysis treatment to obtain a third mixture; (3) Mix the second mixture and the third mixture to obtain the first mixture.
4. The method according to claim 3, wherein, The volume ratio of the solution after the first part of electrolysis to the solution after the second part of electrolysis is 1:(0.1-2).
5. The method according to claim 1, wherein, In step S2, the weight ratio of the electrolyzed solution, the silicon source, the aluminum source and the cationic surfactant is 100:(1-200):(0.1-20):(1-100).
6. The method according to claim 1, wherein the weight ratio of the solid to the electrolyzed solution is 1:(1-20).
7. The method according to claim 1, wherein, The inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, and hydrazine hydrate; The silicon source is an inorganic silicon source and / or an organic silicon source; The cationic surfactant is selected from one or more of alkylammonium bromide with 15-20 carbon atoms, alkylammonium chloride with 15-20 carbon atoms, and alkylammonium fluoride with 15-20 carbon atoms. The aluminum source is aluminum isopropoxide and / or aluminum sulfate.
8. The method according to claim 7, wherein, The organosilicon source is an organosilicon ester.
9. The method according to claim 1, wherein, The conditions for the hydration reaction include: temperature of 100-300℃, pressure of 0.1-5MPa, and time of 0.1-24h; The olefin is a cyclic olefin; The hydrating agent is water; The weight ratio of the olefin to the catalyst is 100:(0.1-20). The molar ratio of the hydrating agent to the olefin is greater than 1.
10. The method according to claim 9, wherein, The cyclic olefins are monocyclic olefins with 5-12 cyclic carbon atoms (substituted or unsubstituted) and / or bicyclic olefins with 8-16 cyclic carbon atoms (substituted or unsubstituted).