Hydration catalysts, their preparation methods and applications, and methods for catalytic hydration of epoxides.

Abstract

This invention relates to the field of resin catalysts, and discloses a hydration catalyst, its preparation method and application, and a method for catalytic hydration of epoxy compounds. The catalyst comprises a molded molecular sieve support and an ion exchange resin supported on the support. The structure of the catalyst is shown in formula (I), where is a molded molecular sieve, is a styrene copolymer matrix, R1, R2, and R3 are each independently an alkyl group, and M... ‑ It is an anionic compound. This hydrated catalyst exhibits excellent resistance to swelling and good temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of resin catalyst technology, specifically to a hydration catalyst and its preparation method and application, and a method for catalytic hydration of epoxy compounds. Background Technology

[0002] Ethylene glycol is an important basic organic raw material in petrochemicals. It is mainly used in the production of polyester fibers, antifreeze, lubricants, surfactants, etc. In addition, it can also be used to produce special solvents such as ethylene glycol ethers. Its applications are very wide.

[0003] Currently, there are three main methods for the industrial production of ethylene glycol: direct hydration of ethylene oxide, coal / syngas to ethylene glycol, and biomass to ethylene glycol. The most important method worldwide remains the ethylene oxide hydration method, which is primarily monopolized by Shell, SD, and Dow, and its basic process flow is identical. It typically involves reacting hydrated ethylene oxide at a molar ratio of 22-25:1, a temperature of 190-200℃, and a pressure of 2.2 MPa. Due to the use of excess water, the concentration of ethylene glycol in the crude product is very low, and subsequent concentration of ethylene glycol consumes a large amount of energy. From the perspective of energy conservation and emission reduction requirements in the chemical industry, this process urgently needs improvement. The EO catalytic hydration process for producing MEG, with its advantages of low water ratio and high selectivity, is replacing the traditional non-catalytic hydration method and represents the development trend of ethylene glycol production technology.

[0004] The catalytic hydration of ethylene oxide to ethylene glycol typically uses strongly basic anion exchange resins. However, due to the resin's low strength, it undergoes severe swelling during the reaction, significantly limiting its application. CN112041292A describes a method to mitigate resin swelling through a process-specific approach, employing an adiabatic reactor for the catalytic hydration of ethylene oxide while maintaining low resin swelling and high selectivity. However, this method does not fundamentally alter the resin's inherent swelling properties. In extreme cases, the resin can eventually break down, leading to reactor blockage and increased pressure.

[0005] Therefore, the preparation of resins with a reasonable framework and low expansion rate has always been a goal pursued. Currently, two methods are generally used: one is to improve the stability of the material itself. For example, DuPont's Nafion R, Nafion XR, and Nafion 511 use perfluorosulfonic acid resins, which have good thermal and chemical stability, and the highest operating temperature of this series is 180–190℃, but anion exchange resins cannot be prepared. The other method is to improve the stability of ion exchange resins by introducing nanomaterials into the raw materials. For example, CN102372830A and CN102372812A introduce a method of introducing carbon nanotubes, graphene, or modified graphene into the resin, which can significantly improve the swelling resistance of the catalyst and has good catalytic performance.

[0006] CN101333265B discloses a method for preparing a strong base anion exchange resin with long spacer arms, which is obtained by amine alkylation, tertiary amination, and quaternization reactions. Direct amine alkylation of white beads to introduce primary amine groups simplifies the operation, but the amine alkylation reagent is expensive, which is not conducive to large-scale production. Keiko K et al. (Power Plant Chemistry, 2002, 4(6): 349-353) reported a method for preparing anion exchange resin with long-chain spacer arms between the benzene ring and nitrogen atom using functionalized styrene monomers via suspension polymerization and quaternization. This route involves complex and long functionalized monomer synthesis, and the purity of the product also affects the performance of the final catalyst. Furthermore, the swelling problem of the resin remains unresolved.

[0007] Therefore, the research and development of catalysts with good anti-swelling properties for ion exchange resin catalysts used in the catalytic hydration reaction of epoxy compounds remains a research hotspot, while maintaining the catalytic performance of ion exchange resins. Summary of the Invention

[0008] The purpose of this invention is to overcome the problem of poor swelling resistance of existing hydration catalysts, and to provide a hydration catalyst, its preparation method and application, and a method for catalytic hydration of epoxy compounds. This hydration catalyst has excellent swelling resistance. When used in hydration reactions, such as the reaction of alkyl epoxides with deionized water to prepare diols, the catalyst exhibits good catalytic activity and excellent selectivity for the target product under high hydration ratio conditions.

[0009] A first aspect of the present invention provides a hydration catalyst, wherein the catalyst comprises a shaped molecular sieve support and an ion exchange resin supported on the support.

[0010] The structure of the catalyst is shown in formula (I).

[0011]

[0012] In formula (I), For forming molecular sieves, It is a styrene-based copolymer matrix, where R1, R2, and R3 are each independently an alkyl group, and M... - It is an anion.

[0013] The second aspect of the present invention provides a method for preparing the hydrated catalyst described in the first aspect of the present invention, wherein the preparation method includes: S1 polymerizing a molded molecular sieve support adsorbed with an oil phase; S2 subjecting the solid intermediate obtained from the polymerization reaction to halomethylation, quaternization, and ion exchange to obtain the catalyst; wherein the oil phase contains styrene monomers, crosslinking agents, and initiators.

[0014] The third aspect of this invention provides the application of the catalyst described in the first aspect of this invention in the reaction of hydration of epoxides to prepare diols.

[0015] A fourth aspect of the present invention provides a method for catalytic hydration of an epoxy compound, wherein the method comprises: catalytically hydrating the epoxy compound with water in the presence of the catalyst described in the first aspect of the present invention.

[0016] The present invention has at least the following beneficial effects:

[0017] The hydrated catalyst of the present invention has a good interaction between the molecular sieve support and the ion exchange resin supported on the support, the catalyst has good catalytic activity, and it also has good thermal stability, which can effectively solve the swelling problem of resin catalysts and enable hydrated catalytic reactions to be carried out for a long time. Attached Figure Description

[0018] Figure 1 This is the BET diagram of the hydrated catalyst in Example 1. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] A first aspect of the present invention provides a hydration catalyst, wherein the catalyst comprises a shaped molecular sieve support and an ion exchange resin supported on the support.

[0021] The structure of the catalyst is shown in formula (I).

[0022]

[0023] In formula (I), For forming molecular sieves, It is a styrene-based copolymer matrix, where R1, R2, and R3 are each independently an alkyl group, and M... - It is an anion.

[0024] In this invention, the hydrated catalyst comprising a molded molecular sieve support and an ion exchange resin supported on the support exhibits superior swelling resistance. At a high hydration ratio, the catalyst demonstrates excellent activity and high selectivity for the target product. Furthermore, the catalyst can be used continuously multiple times. The inventors hypothesize that the molded molecular sieve in this invention has a porous structure, and the ion exchange resin is located between the inner and outer surfaces of the molded molecular sieve, possessing a stable organic-inorganic interpenetrating network structure, which enables the hydrated catalyst to exhibit good stability and catalytic performance.

[0025] In this invention, it is understood that in formula (I), This indicates the structure of an ion exchange resin.

[0026] According to the present invention, the mass ratio of the ion exchange resin to the support is not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the loading of the ion exchange resin is 15-55 wt%, for example, 15 wt%, 25 wt%, 29 wt%, 35 wt%, 35 wt%, 40 wt%, or 55 wt%, or any combination of two of the above values, preferably 30-45 wt%. Using the foregoing embodiments, the hydrated catalyst exhibits excellent catalytic properties and stability.

[0027] In this invention, the loading of ion exchange resin refers to the percentage of the mass of ion exchange resin to the total mass of the hydrated catalyst.

[0028] According to the present invention, in some embodiments, the specific surface area of ​​the catalyst is 30-500 m². 2 / g, for example, 30m 2 / g、40m 2 / g, 50m 2 / g, 100m 2 / g, 150m 2 / g or 200m 2 / g, and the range of any two of the above values, preferably 50-200m. 2 / g. Using the aforementioned embodiments, the hydrated catalyst exhibits better swelling resistance, a more uniform distribution of active sites, and good activity and selectivity for the target product during use.

[0029] In this invention, "shaped molecular sieve" refers to a shaped molecular sieve with a certain shape obtained by preparing molecular sieve powder raw materials according to conventional molding methods in the art. As long as the purpose of this invention can be achieved, the shape of the shaped molecular sieve is not particularly limited. In some embodiments, the shape of the shaped molecular sieve is selected from one or more of strip-shaped, spherical, columnar, honeycomb-shaped, and corrugated shapes. Using the aforementioned embodiments, there is a strong interaction between the ion exchange resin and the shaped molecular sieve, and the hydrated catalyst exhibits better catalytic activity, stability, and swelling resistance.

[0030] According to the present invention, as long as the purpose of the present invention can be achieved, there is no special limitation on the particle size of the shaped molecular sieve. In some embodiments, the particle size of the shaped molecular sieve is 0.4-5 mm, preferably 1.3-2.4 mm.

[0031] In this invention, when the molecular sieve is strip-shaped or columnar, the particle size of the molecular sieve refers to its height; when the molecular sieve is spherical, the particle size of the molecular sieve refers to its diameter.

[0032] According to the present invention, in some embodiments, the specific surface area of ​​the shaped molecular sieve is 300-1000 m². 2 / g, for example, 300m 2 / g、400m 2 / g、600m 2 / g、700m 2 / g, 1000m 2 / g or 300m 2 / g, and the range of any two of the above values, preferably 400-700m. 2 / g. Using the aforementioned embodiments, the hydrated catalyst has more functional active sites and its catalytic performance is better.

[0033] According to the present invention, in some embodiments, the bulk density of the shaped molecular sieve is 0.4-1.1 g / mL, preferably 0.6-0.9 g / mL. Using the aforementioned embodiments, the hydrated catalyst exhibits good stability, swelling resistance, and catalytic activity.

[0034] According to the present invention, in some embodiments, the compressive strength of the shaped molecular sieve is not less than 30 N, preferably 60-100 N. Using the aforementioned embodiments, the hydrated catalyst exhibits good stability, swelling resistance, and catalytic activity.

[0035] According to the present invention, in some embodiments, the pore size of the shaped molecular sieve is 0.1-10 nm, for example, 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, or 10 nm, or any combination of two of the above values, preferably 0.3-3 nm. Using the aforementioned embodiments, the hydrated catalyst exhibits good catalytic activity, excellent swelling resistance, and can be used continuously multiple times.

[0036] According to the present invention, the type of the shaped molecular sieve is not particularly limited as long as the purpose of the present invention can be achieved. The shaped molecular sieve is selected from one or more of the following: shaped A-type molecular sieve, shaped zeolite molecular sieve, shaped X-type molecular sieve, shaped ZSM-type molecular sieve, and shaped Y-type molecular sieve. Using the foregoing embodiments, the hydrated catalyst exhibits good stability and swelling resistance.

[0037] According to the present invention, in some preferred embodiments, the shaped molecular sieve is a shaped type A molecular sieve. Using the aforementioned embodiments, the hydrated catalyst provides more active sites, and the catalyst not only exhibits good catalytic activity but also superior swelling resistance and stability.

[0038] According to some preferred embodiments of the present invention, the shaped A-type molecular sieve is selected from one or more of shaped 3A molecular sieves, shaped 4A molecular sieves, and shaped 5A molecular sieves. Using the aforementioned embodiments, the hydrated catalyst exhibits good catalytic activity, swelling resistance, and stability.

[0039] According to some preferred embodiments of the present invention, the shaped A-type molecular sieve is a shaped 4A molecular sieve and / or a shaped 5A molecular sieve. Using the aforementioned embodiments, the hydrated catalyst exhibits good catalytic activity, swelling resistance, and stability.

[0040] According to the present invention, the specific structure of the styrene-based copolymer matrix is ​​not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the styrene-based copolymer matrix contains structural unit A from a monovinyl aromatic monomer and structural unit B from a crosslinking agent. Using the aforementioned embodiments, the hydrated catalyst exhibits good catalytic activity and stability.

[0041] According to the present invention, those skilled in the art can select the content of structural unit A and structural unit B as needed. In some embodiments, based on the total mass of structural unit A and structural unit B, the content of structural unit A is 80-98% by mass, and the content of structural unit B is 2-20% by mass. Using the foregoing embodiments, the hydrated catalyst has good catalytic activity, stability, and swelling resistance.

[0042] According to the present invention, the type of monovinyl aromatic monomer providing structural unit A is not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the monovinyl aromatic monomer is selected from one or more of styrene, α-methylstyrene, ortho-, meta-, and para-alkylstyrene.

[0043] According to the present invention, the type of crosslinking agent for providing structural unit B is not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the crosslinking agent is selected from one or more of diethylene glycol dimethacrylate, diallylbenzene, 1,2-bis(4-vinylphenyl)ethane and divinylbenzene.

[0044] In this invention, "alkyl" includes branched alkyl and branched alkyl groups, and there are no special limitations on this.

[0045] According to the present invention, the number of carbon atoms in the alkyl groups R1, R2, and R3 in formula (I) is not particularly limited, as long as the purpose of the present invention can be achieved. In some embodiments, R1, R2, and R3 are each independently C1-C10 alkyl groups, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, preferably C1-C5 alkyl groups. Using the aforementioned embodiments, the hydrated catalyst exhibits good stability and catalytic activity.

[0046] According to the present invention, as long as the objective of the present invention can be achieved, the anion M - There are no special restrictions on the specific type; in some implementations, M - It is selected from bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, or citrate ions.

[0047] The second aspect of the present invention provides a method for preparing the hydrated catalyst described in the first aspect of the present invention, wherein the preparation method includes: S1 polymerizing a molded molecular sieve support adsorbed with an oil phase; S2 subjecting the solid intermediate obtained from the polymerization reaction to halomethylation, quaternization, and ion exchange to obtain the catalyst; wherein the oil phase contains styrene monomers, crosslinking agents, and initiators.

[0048] In this invention, the molded molecular sieve has a porous structure. During the preparation of the hydrated catalyst, small molecule styrene monomers and crosslinking agents can form styrene copolymer molecular chains loaded on the inner and outer surfaces of the molded molecular sieve in the presence of an initiator, thereby forming a stable organic-inorganic interpenetrating network structure. Finally, the functionalization reactions of halomethylation, quaternization, and ion exchange are carried out, so that the prepared catalyst not only has excellent stability and swelling resistance, but also has better catalytic activity.

[0049] According to the present invention, it is understood that the "molded molecular sieve carrier adsorbed with oil phase" refers to the molded molecular sieve having an oil phase containing styrene monomers, crosslinking agents and initiators adsorbed on its inner and outer surfaces. As long as the purpose of the present invention can be achieved, the method for obtaining the molded molecular sieve carrier adsorbed with oil phase is not particularly limited. In some embodiments, the method for obtaining the molded molecular sieve carrier adsorbed with oil phase includes: immersing the oil phase in contact with the molded molecular sieve carrier and then filtering to obtain the molded molecular sieve carrier adsorbed with oil phase.

[0050] According to the present invention, the conditions for immersion contact are not particularly limited as long as the purpose of the present invention can be achieved. For example, the conditions for immersion contact include: room temperature (15-25°C); and / or immersion time of 12-36 hours. By adopting the aforementioned embodiments, it can be ensured that the molded molecular sieve fully absorbs the oil phase.

[0051] According to the present invention, as long as the objective of the present invention can be achieved, there are no special restrictions on the amount of each raw material used in the preparation of the hydrated catalyst. In some embodiments, based on the total mass of the oil phase and the molded molecular sieve, the amount of the styrene monomer is 35-60% by mass, the amount of the crosslinking agent is 2-10% by mass, the amount of the initiator is 0.1-3% by mass, and the amount of the molded molecular sieve is 30-60% by mass. Using the aforementioned embodiments, the hydrated catalyst prepared has excellent catalytic activity and stability.

[0052] According to the present invention, those skilled in the art can select the type of initiator as needed. In some embodiments, the initiator is an azo initiator and / or a peroxide initiator.

[0053] In this invention, azo initiators that can be listed include azobisisobutyronitrile, azobisisoheptanenitrile, etc.; peroxide initiators that can be listed include benzoyl peroxide, lauroyl peroxide, and cumene hydroperoxide, etc.

[0054] According to the present invention, the conditions for the polymerization reaction are not particularly limited as long as the purpose of the present invention can be achieved. In some embodiments, the conditions for the polymerization reaction include a reaction temperature of 80-100°C. According to the present invention, in some embodiments, the conditions for the polymerization reaction include a reaction time of 4-12 hours.

[0055] According to the present invention, it is understood that styrene monomers, crosslinking agents and initiators will polymerize and crosslink within the pores of the molded molecular sieve and / or on its surface to obtain a resin polymer, ultimately forming a solid intermediate molecular sieve / resin. Some raw materials may still remain on its surface. The mixture obtained after the polymerization reaction can be washed and dried to obtain the solid intermediate; for example, methanol washing can be used; drying is a conventional drying method in the art and will not be described in detail in the present invention.

[0056] According to the present invention, those skilled in the art can select a halomethylation method as needed. In some embodiments, the halomethylation method includes: mixing a solid intermediate (molecular sieve / resin) with a halomethylation reagent, then adding a Lewis acid catalyst to carry out the halomethylation reaction, then cooling to room temperature, filtering out the halogenation mother liquor, washing repeatedly with methanol several times, and finally drying to obtain the halomethylation product; wherein there are no special restrictions on the mixing method, but it is preferred to let it stand for 1-5 hours after mixing before adding the Lewis acid catalyst.

[0057] According to the present invention, as long as the purpose of the present invention can be achieved, there is no special limitation on the amount of solid intermediate (molecular sieve / resin) and halomethylating agent. In some embodiments, the ratio of molecular sieve / resin balls to halomethylating agent is (1-10) g to (10-30) mL.

[0058] According to some embodiments of the present invention, the halomethylating agent is selected from one or more of chloromethyl methyl ether (chloromethyl ether), bromomethyl methyl ether, chloromethyl ethyl ether, and bromomethyl ethyl ether.

[0059] According to the present invention, in order to ensure that the halomethylation reaction can proceed smoothly, those skilled in the art can select the amount and type of Lewis acid catalyst as needed. In some embodiments, the mass of the Lewis acid catalyst is 2-10 wt% of the molecular sieve / resin ball mass.

[0060] According to the present invention, Lewis acid catalysts can be selected from zinc chloride, zinc bromide, ferric chloride, ferric bromide, and tin tetrachloride, etc.

[0061] According to the present invention, in some embodiments, the conditions for the halomethylation reaction include a reaction temperature of 50-60°C.

[0062] According to the present invention, in some embodiments, the conditions for the halomethylation reaction include a reaction time of 5-15 hours.

[0063] According to the present invention, those skilled in the art will understand that after halomethylation, there may still be impurities and halogenation mother liquor. After halomethylation is completed, the halogenation mother liquor can be filtered out, and the solid product can be repeatedly washed with methanol and dried to obtain the halomethylated product. The halomethylated product is then subjected to quaternization.

[0064] According to the present invention, those skilled in the art can select the quaternization method as needed. In some embodiments, the quaternization method includes: in the presence of a solvent, the halomethylation product is subjected to a quaternization reaction with a quaternizing agent, then cooled to room temperature, followed by filtration to remove the reaction solution, and then washing with ethyl acetate, 0.05-0.15 mol / L HCl aqueous solution, and water in sequence, and then drying (e.g., vacuum drying at 50-70°C for 8-15 hours) to obtain molecular sieve / ammonium resin.

[0065] According to the present invention, as long as the quaternization reaction can proceed smoothly, there is no special limitation on the amount of solvent used. In some embodiments, the solvent: halomethylation product = 10 mL: (1-8) g.

[0066] According to the present invention, in some embodiments, the solvent is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide and dimethyl sulfoxide.

[0067] According to the present invention, in some embodiments, the ratio of halomethylated product to quaternizing agent is (1-5) g to 5 mL.

[0068] According to the present invention, in some embodiments, the conditions for the quaternization reaction include a reaction temperature of 50-70°C.

[0069] According to the present invention, in some embodiments, the conditions for the quaternization reaction include a reaction time of 12-36 hours.

[0070] According to the present invention, those skilled in the art can select the quaternization ion exchange method as needed. In some embodiments, the ion exchange method includes: reacting a molecular sieve / ammonium resin with an M-containing... - The catalyst is obtained by ion exchange reaction with an aqueous solution of a salt or base of the group, followed by washing with deionized water until the washing solution pH=7, and finally drying.

[0071] According to the present invention, during quaternization, an ingredient containing M can be added as needed. - Aqueous solutions of salts or bases containing M groups, such as molecular sieves / ammonium resins: containing M - An aqueous solution of a salt or base containing a group = 1 g : (10-50) mL, preferably containing M - The concentration of the aqueous solution of the salt or base of the group is 0.1-0.5 mol / L.

[0072] According to the present invention, the conditions for the ion exchange reaction are not particularly limited, but the ion exchange reaction is preferably carried out with stirring at room temperature, and the ion exchange reaction time is preferably 12-48 hours.

[0073] The third aspect of the present invention provides the application of the catalyst described in the first aspect of the present invention in the reaction of hydration of epoxides to prepare diols.

[0074] In this invention, the catalyst is used in the hydration reaction of epoxides. The catalyst not only has good catalytic activity and diol selectivity, but also has excellent swelling resistance and can be used continuously multiple times.

[0075] A fourth aspect of the present invention provides a method for catalytic hydration of an epoxy compound, wherein the method comprises: catalytically hydrating the epoxy compound with water in the presence of the catalyst described in the first aspect of the present invention.

[0076] In this invention, in the presence of the catalyst of this invention, an epoxy compound undergoes a catalytic hydration reaction with water. The epoxy compound has a high conversion rate, the diol has a high yield, and the catalyst has excellent swelling resistance and can maintain good catalytic activity during continuous use.

[0077] According to the present invention, the specific type of epoxy compound can be selected as needed. In some embodiments, the epoxy compound is selected from ethylene oxide, propylene oxide, or styrene oxide.

[0078] According to the present invention, the conditions for the hydration reaction can be selected as needed. In some embodiments, the conditions for the hydration reaction include a molar ratio of water to epoxide of (1-50):1, preferably (6-20):1.

[0079] According to the present invention, in some embodiments, the conditions for the hydration reaction include: a reaction temperature of 40-180°C, preferably 80-110°C.

[0080] According to the present invention, in some embodiments, the conditions for the hydration reaction include: a reaction pressure of 0.1-10.0 MPa, preferably 1.0-2.5 MPa.

[0081] According to the present invention, in some embodiments, the liquid space velocity is 0.5-3 h⁻¹. -1 .

[0082] The present invention will be described in detail below through embodiments. In the following embodiments and comparative examples:

[0083] The prepared hydrated catalyst was loaded into a fixed-bed reactor to conduct experiments on the catalytic hydration reaction of ethylene oxide to produce ethylene glycol. The conditions were as follows: reaction temperature 90℃; molar ratio of water to ethylene oxide 9:1; liquid hourly space velocity 1.5 h⁻¹. -1 The reaction pressure is 1.2 MPa.

[0084] Example 1

[0085] In a 500ml flask, add 150g styrene, 12g divinylbenzene, and 3g benzoyl peroxide. After stirring for 1 hour, add 100g spherical 5A molecular sieve (particle size 2.2mm; specific surface area 390m²). 2 / g; bulk density of 0.69g / ml; compressive strength of 65N; pore size of 0.5nm), soaked at room temperature for 24 hours, then filtered to obtain a molecular sieve with adsorbed oil phase, placed at 90℃ for 10 hours, then washed with methanol and dried to obtain molecular sieve / resin;

[0086] In a 500 mL three-necked flask, add 60 g of molecular sieve / resin and 200 mL of chloromethyl ether, let stand at room temperature for 2 hours, then add 5 g of zinc chloride as a catalyst and start stirring. Gradually raise the temperature to 60 °C and react for 10 hours. After the reaction is complete, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol 3 times, and dry at 100 °C for 8 hours to obtain molecular sieve / chlorination resin.

[0087] Add 60 g of molecular sieve / chlorinated resin balls, 100 ml of tributylamine, and 200 ml of N,N-dimethylformamide to a 500 mL three-necked flask. After reacting at 60 °C for 24 hours, cool to room temperature, filter to remove the reaction solution, and then wash with ethyl acetate, 0.1 mol / L HCl, and deionized water in sequence. Finally, dry under vacuum at 60 °C for 12 hours to obtain molecular sieve / ammonium resin balls.

[0088] In a 1000 mL three-necked flask, 20 g of molecular sieve / ammonium resin and 800 mL of 0.1 mol / L deionized water of NaHCO3 were added to carry out an ion exchange reaction at room temperature for 24 hours with stirring. The solution was then washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the hydrated catalyst was obtained and denoted as Cat-A1.

[0089] The structure of the obtained hydrated catalyst is as follows:

[0090] It is a spherical 5A molecular sieve. It is a styrene-based copolymer matrix;

[0091] In the hydrated catalyst, the loading of ion exchange resin was 36 wt%; the specific surface area of ​​the catalyst was 60 m². 2 / g.

[0092] The BET diagram of the hydrated catalyst is shown below. Figure 1 As shown.

[0093] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A1 showed that the conversion rate of ethylene oxide was 99.8% and the selectivity of ethylene glycol was 98.9%.

[0094] Example 2

[0095] In a 500ml flask, add 150g α-methylstyrene, 18g ethylene glycol dimethacrylate, and 4g benzoyl peroxide. After stirring for 1 hour, add 100g columnar 3A molecular sieve (particle size 1.5mm; specific surface area 500m²). 2 / g; bulk density is 0.68g / ml; compressive strength is 80N; pore size is 0.3nm), soaked at room temperature for 15 hours, then filtered to obtain a molecular sieve with adsorbed oil phase, placed at 90℃ for 10 hours, then washed with methanol and dried to obtain molecular sieve / resin;

[0096] In a 500 mL three-necked flask, add 100 g of molecular sieve / resin and 300 mL of chloromethyl ether, let stand at room temperature for 2 hours, then add 8 g of zinc chloride as a catalyst and start stirring. Gradually raise the temperature to 60 °C and react for 12 hours. After the reaction is complete, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol 3 times, and dry at 100 °C for 8 hours to obtain molecular sieve / chlorination resin.

[0097] Add 90 g of molecular sieve / chlorinated resin balls, 150 ml of tributylamine, and 200 ml of N,N-dimethylformamide to a 500 mL three-necked flask. After reacting at 60 °C for 24 hours, cool to room temperature, filter to remove the reaction solution, and then wash with ethyl acetate, 0.1 mol / L HCl, and deionized water in sequence. Then dry under vacuum at 60 °C for 12 hours to obtain molecular sieve / ammonium resin balls.

[0098] In a 1000 mL three-necked flask, 20 g of molecular sieve / ammonium resin and 400 mL of 0.25 mol / L deionized water of NaHCO3 were added to carry out an ion exchange reaction at room temperature for 24 hours. The solution was then washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the hydrated catalyst was obtained and denoted as Cat-A2.

[0099] The structure of the obtained hydrated catalyst is as follows:

[0100] It is a spherical 3A molecular sieve. It is a styrene-based copolymer matrix;

[0101] In the hydrated catalyst, the loading of ion exchange resin was 41 wt%; the specific surface area of ​​the catalyst was 190 m². 2 / g.

[0102] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A2 showed that the conversion rate of ethylene oxide was 97.5% and the selectivity of ethylene glycol was 98.6%.

[0103] Example 3

[0104] In a 500ml flask, add 150g styrene, 20g divinylphenylmethane, and 5g benzoyl peroxide. After stirring for 1 hour, add 100g spherical 4A molecular sieve (particle size 3.2mm; specific surface area 900m²). 2 / g; bulk density is 0.64g / ml; compressive strength is 85N; pore size is 0.4nm), soaked at room temperature for 12 hours, then filtered to obtain a molecular sieve with adsorbed oil phase, placed at 90℃ for 10 hours, then washed with methanol and dried to obtain molecular sieve / resin;

[0105] In a 500 mL three-necked flask, add 100 g of molecular sieve / resin and 300 mL of chloromethyl ethyl ether, let stand at room temperature for 2 hours, then add 3 g of zinc chloride as a catalyst and start stirring. Gradually raise the temperature to 50 °C and react for 12 hours. After the reaction is complete, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol 3 times, and dry at 100 °C for 8 hours to obtain molecular sieve / chlorination resin.

[0106] Add 60 g of molecular sieve / chlorinated resin balls, 150 ml of tributylamine, and 200 ml of N,N-dimethylformamide to a 500 mL three-necked flask. After reacting at 50 °C for 36 hours, cool to room temperature, filter to remove the reaction solution, and then wash with ethyl acetate, 0.15 mol / L HCl, and deionized water in sequence. Finally, dry under vacuum at 60 °C for 12 hours to obtain molecular sieve / ammonium resin balls.

[0107] In a 1000 mL three-necked flask, 20 g of molecular sieve / ammonium resin and 500 mL of 0.2 mol / L deionized water of NaHCO3 were added to carry out an ion exchange reaction at room temperature for 24 hours with stirring. The solution was then washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the hydrated catalyst was obtained and denoted as Cat-A3.

[0108] The structure of the obtained hydrated catalyst is as follows:

[0109] It is a spherical 4A molecular sieve. It is a styrene-based copolymer matrix;

[0110] In the hydrated catalyst, the loading of ion exchange resin was 38 wt%; the specific surface area of ​​the catalyst was 300 m². 2 / g.

[0111] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A3 showed that the conversion rate of ethylene oxide was 99.7% and the selectivity of ethylene glycol was 98.5%.

[0112] Example 4

[0113] The method is the same as in Example 1, except that spherical ZSM-5 molecular sieves (particle size 2-3 mm; specific surface area 360 m²) are used. 2 / g; bulk density is 0.7g / mL; compressive strength is 70; pore size is 0.58nm) to replace spherical 5A molecular sieve;

[0114] The structure of the obtained hydrated catalyst is as follows:

[0115] It is a ZSM-5 molecular sieve. It is a styrene-based copolymer matrix;

[0116] In the hydrated catalyst, the loading of ion exchange resin is 35 wt%; the specific surface area of ​​the catalyst is 80 m². 2 / g;

[0117] The final hydrated catalyst was designated as Cat-A4.

[0118] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A4 showed that the conversion rate of ethylene oxide was 98.6% and the selectivity of ethylene glycol was 93.7%.

[0119] Example 5

[0120] The method is the same as in Example 1, except that spherical 13X molecular sieves (particle size 5 mm, specific surface area 950 m²) are used. 2 / g; bulk density is 0.6g / mL; compressive strength is 30N; pore size is 1.0nm) to replace spherical 5A molecular sieve;

[0121] The structure of the obtained hydrated catalyst is as follows:

[0122] It is a spherical 13X molecular sieve. It is a styrene-based copolymer matrix;

[0123] In the hydrated catalyst, the loading of ion exchange resin is 40 wt%; the specific surface area of ​​the catalyst is 100 m². 2 / g;

[0124] The final hydrated catalyst was designated as Cat-A5.

[0125] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A5 showed that the conversion rate of ethylene oxide was 96.6% and the selectivity of ethylene glycol was 97.3%.

[0126] Example 6

[0127] The method of Example 1 was followed, except that triheptylamine was used instead of tributylamine as the reaction reagent. The structure of the resulting hydrated catalyst is as follows:

[0128] It is a spherical 5A molecular sieve. It is a styrene-based copolymer matrix;

[0129] In the hydrated catalyst, the loading of ion exchange resin was 16 wt%; the specific surface area of ​​the catalyst was 100 m². 2 / g;

[0130] The final hydrated catalyst was designated Cat-A6.

[0131] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-A6 showed that the conversion rate of ethylene oxide was 95.6% and the selectivity of ethylene glycol was 98.5%.

[0132] Comparative Example 1

[0133] In a 500ml flask, add 150g styrene, 12g divinylbenzene, and 1g benzoyl peroxide. Stir for 30 minutes, then add 100g of unformed powdered 5A molecular sieve (particle size 2-4 micrometers; specific surface area 900m²). 2 / g; bulk density of 0.43g / mL; pore size of 0.5nm), soaked at room temperature for 24 hours, then filtered to obtain the adsorbed molecular sieve, placed at 90℃ for 10 hours, then washed with methanol and dried to obtain molecular sieve / resin ball B1.

[0134] In a 500 mL three-necked flask, add 60 g of molecular sieve / resin ball B1 and 200 mL of chloromethyl ether, let stand at room temperature for 2 hours, then add 15 g of zinc chloride as a catalyst and start stirring. Gradually raise the temperature to 60 °C and react for 10 hours. After the reaction is completed, cool to room temperature, filter out the chlorination mother liquor, wash repeatedly with methanol 3 times, and dry at 100 °C for 8 hours to obtain molecular sieve / resin chlorination ball B1.

[0135] Add 60 g of molecular sieve / resin ammonium spheres A1, 100 ml of tributylamine, and 200 ml of N,N-dimethylformamide to a 500 mL three-necked flask. After reacting at 60 °C for 24 hours, cool to room temperature, filter to remove the reaction solution, and then wash with ethyl acetate, 0.1 mol / L HCl, and deionized water in sequence. Then dry under vacuum at 60 °C for 12 hours to obtain molecular sieve / resin ammonium spheres B1.

[0136] In a 1000 mL three-necked flask, 50 g of molecular sieve / ammonium resin balls B1 and 2000 mL of 0.1 mol / L deionized water of NaHCO3 were added to carry out an ion exchange reaction at room temperature for 24 hours. The solution was then washed with deionized water until the pH of the washing solution was 7. After vacuum drying, the solution was finally rolled into 2 mm diameter hydrated catalysts, denoted as Cat-B1.

[0137] The hydrated catalyst contains 25 wt% ion exchange resin; the specific surface area of ​​the catalyst is 39 m². 2 / g;

[0138] The experiment of preparing ethylene glycol by catalytic hydration of ethylene oxide using Cat-B1 showed that the conversion rate of ethylene oxide was 85.3% and the selectivity of ethylene glycol was 93.1%.

[0139] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrated catalyst, characterized in that, The catalyst comprises a shaped molecular sieve support and an ion exchange resin supported on the support. The structure of the catalyst is shown in formula (I). Formula (I), In formula (I), To form molecular sieves, It is a styrene-based copolymer matrix, where R1, R2, and R3 are each independently an alkyl group, and M... - It is an anion; The loading of the ion exchange resin is 15-55 wt%; The specific surface area of ​​the shaped molecular sieve is 300-1000 m². 2 / g, The compressive strength of the shaped molecular sieve is not less than 30N.

2. The catalyst according to claim 1, wherein, The loading of the ion exchange resin is 30-45 wt%; and / or The catalyst has a specific surface area of ​​30-500 m². 2 / g.

3. The catalyst according to claim 2, wherein, The catalyst has a specific surface area of ​​50-200 m². 2 / g.

4. The catalyst according to claim 1, wherein, The shape of the shaped molecular sieve is selected from one or more of the following: strip-shaped, spherical, columnar, honeycomb-shaped, and corrugated; and / or The particle size of the shaped molecular sieve is 0.4-5 mm; and / or The specific surface area of ​​the shaped molecular sieve is 400-700 m². 2 / g; and / or The bulk density of the shaped molecular sieve is 0.4-1.1 g / mL; and / or The compressive strength of the shaped molecular sieve is 60-100N; and / or The pore size of the shaped molecular sieve is 0.1-10 nm.

5. The catalyst according to claim 4, wherein, The particle size of the shaped molecular sieve is 1.3-2.4 mm; and / or The bulk density of the shaped molecular sieve is 0.6-0.9 g / mL; and / or The pore size of the shaped molecular sieve is 0.3-3 nm.

6. The catalyst according to claim 1, wherein, The shaped molecular sieve is selected from one or more of the following: shaped A-type molecular sieve, shaped zeolite molecular sieve, shaped X-type molecular sieve, shaped ZSM-type molecular sieve, and shaped Y-type molecular sieve.

7. The catalyst according to claim 6, wherein, The shaped molecular sieve is a shaped type A molecular sieve.

8. The catalyst according to claim 7, wherein, The molded type A molecular sieve is selected from one or more of the molded 3A molecular sieve, molded 4A molecular sieve, and molded 5A molecular sieve.

9. The catalyst according to claim 8, wherein, The molded type A molecular sieve is a molded 4A molecular sieve and / or a molded 5A molecular sieve.

10. The catalyst according to claim 1, wherein, The styrene copolymer matrix contains structural unit A from a monovinyl aromatic monomer and structural unit B from a crosslinking agent.

11. The catalyst according to claim 10, wherein, Based on the total mass of structural unit A and structural unit B, the content of structural unit A is 80-98% by mass, and the content of structural unit B is 2-20% by mass; and / or The monovinyl aromatic monomer is selected from one or more of styrene, α-methylstyrene, and ortho-, meta-, and para-alkylstyrene; and / or The crosslinking agent is selected from one or more of ethylene glycol dimethacrylate, diallylbenzene, 1,2-bis(4-vinylphenyl)ethane, and divinylbenzene.

12. The catalyst according to claim 1, wherein, R1, R2, and R3 are each independently a C1-C10 alkyl group; and / or M - It is selected from bicarbonate ions, hydroxide ions, bisulfite ions, formate ions, acetate ions, or citrate ions.

13. The catalyst according to claim 12, wherein, R1, R2 and R3 are each independently C1-C5 alkyl groups.

14. A method for preparing the catalyst according to any one of claims 1-13, characterized in that, The preparation method includes: S1 is a molded molecular sieve support with an oil phase adsorbed for polymerization reaction; The solid intermediate obtained from the S2 polymerization reaction is subjected to halomethylation, quaternization, and ion exchange to obtain the catalyst. The oil phase contains styrene monomers, crosslinking agents, and initiators.

15. The preparation method according to claim 14, wherein, A method for obtaining a molded molecular sieve carrier adsorbed with an oil phase includes: immersing and contacting the oil phase with the molded molecular sieve carrier, followed by filtration to obtain the molded molecular sieve carrier adsorbed with the oil phase; and / or The conditions for the polymerization reaction include: a reaction temperature of 80-100℃ and / or a reaction time of 4-12 hours.

16. The preparation method according to claim 15, wherein, In the method for obtaining a molded molecular sieve carrier adsorbed with an oil phase, based on the total mass of the oil phase and the molded molecular sieve, the amount of styrene monomer is 35-60% by mass, the amount of crosslinking agent is 2-10% by mass, the amount of initiator is 0.1-3% by mass, and the amount of molded molecular sieve is 30-60% by mass.

17. The use of the catalyst according to any one of claims 1-13 in the reaction of hydration of epoxides to prepare diols.

18. A method for catalytic hydration of an epoxy compound, characterized in that, The method includes: catalytically hydrating an epoxy compound with water in the presence of a catalyst comprising any one of claims 1-13.

19. The method according to claim 18, The epoxy compound is selected from ethylene oxide, propylene oxide, or styrene oxide; and / or The conditions for the hydration reaction include: The molar ratio of water to epoxy compound is (1-50):1; and / or The reaction temperature is 40-180℃; and / or The reaction pressure is 0.1-10.0 MPa; and / or Liquid space velocity is 0.5-3 h⁻¹ -1 .

20. The method according to claim 19, The conditions for the hydration reaction include: The molar ratio of water to epoxy compound is (6-20):1; and / or The reaction temperature is 80-110℃; and / or The reaction pressure is 1.0-2.5 MPa.

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