Macroporous composite ion exchange resin, preparation method, method for preparing diol by hydrating epoxyalkane and application of macroporous composite ion exchange resin

Abstract

The invention discloses macroporous composite ion exchange resin, a preparation method, a method for preparing diol by hydrating epoxyalkane and application of the macroporous composite ion exchange resin. The macroporous composite ion exchange resin is provided with a spherical or sphere-like pore channel; the macroporous composite ion exchange resin comprises a macroporous composite resin matrix and a functional group connected to the macroporous composite resin matrix, the general formula of the functional group is-N + R1R2R3X-, R1, R2 and R3 are respectively and independently at least one of C1-10 alkyl or aromatic groups, and X-is an anion or an anion group. The unique pore structure of the macroporous composite ion exchange resin disclosed by the invention is very beneficial to substance diffusion and reaction heat transfer, and shows high activity and stability in a reaction for preparing ethylene glycol by hydration of ethylene oxide at a low water ratio.

Description

Technical Field

[0001] The present invention relates to the technical field of ion exchange resins, and particularly to a macroporous composite ion exchange resin, a preparation method thereof, a method for hydrating epoxy alkane to produce diol, and an application thereof. Background Art

[0002] As an important organic chemical raw material and intermediate, ethylene glycol can be used to produce polyester fibers, engineering plastics, bottle resins, films, antifreeze agents, coolants, etc. (Chem Soc Rev, 2012, 41, 4218). Currently, ethylene glycol is mainly produced by the direct hydration method of ethylene oxide in industry. In order to reduce the content of by-products such as diethylene glycol and triethylene glycol, this technology needs to be carried out under the condition that the molar ratio of water to ethylene oxide in the feed (abbreviated as water ratio) is 20 - 25:1, which results in a very high water content in the product. Removing such a large amount of water requires the use of a multi-effect evaporation system and consumes a large amount of steam (for example, when the water ratio is 20:1, 5.5 tons of steam are consumed to produce 1 ton of ethylene glycol), ultimately making the entire production process of ethylene glycol energy-consuming, with complex equipment, a long process, and high production costs (Petrochemical Technology, 2010, 39: 562). Therefore, developing a catalytic hydration technology for epoxy alkane with a low water ratio is expected to achieve energy conservation and consumption reduction, and the core is the development of catalysts.

[0003] So far, a variety of catalysts have been developed, such as supported metal oxides (Journal of Catalysis, 2006, 241: 173; CN100413579A), Sn zeolites (ACS Catalysis, 2016, 6: 2955; CN104437607A), anion / cation exchange resins (RSC Advances, 2015, 5: 2550; CN102372815A; Journal of Applied Polymer Science, 2010, 115: 2946), etc. Among them, anion exchange resins are used in the hydration reaction of ethylene oxide, which can effectively reduce the reaction water ratio and improve the selectivity of ethylene glycol, reducing the energy consumption of ethylene glycol production by 10 - 14%. In particular, ion exchange resins added with carbon nanomaterials have shown good performance in the catalytic hydration reaction of ethylene oxide with a low water ratio due to the great improvement in their heat resistance and swelling resistance. However, since the hydration of ethylene oxide is an exothermic reaction and the product ethylene glycol may undergo self-polymerization, the stability of the ion exchange resin composite with carbon nanomaterials still needs to be further improved. Summary of the Invention

[0004] To solve the problems existing in the prior art, the present invention provides a macroporous composite ion exchange resin, a preparation method thereof, a method for preparing diols by hydration of epoxyalkanes, and an application thereof. The pore channels of the macroporous composite ion exchange resin of the present invention are spherical or quasi-spherical, with uniform and adjustable pore sizes, and its unique pore channel structure is very conducive to mass diffusion and reaction heat transfer; the ion exchange resin exhibits high activity and stability in the reaction of hydration of ethylene oxide with a low water ratio to produce ethylene glycol. The preparation method provided by the present invention is simple and feasible, and can provide reference for the preparation of other catalysts with higher performance.

[0005] One of the objectives of the present invention is to provide a macroporous composite ion exchange resin having spherical or quasi-spherical pore channels; the macroporous composite ion exchange resin includes a macroporous composite resin matrix and a functional group with the general formula -N + R 1 R 2 R 3 X - connected thereto, where R 1 , R 2 , R 3 are each independently at least one of C 1-10 alkyl groups or aromatic groups, and X - is an anion or an anion group.

[0006] In a preferred embodiment of the present invention,

[0007] the most probable pore size of the macroporous composite ion exchange resin is 20 - 500 nm, preferably 70 - 200 nm, more preferably 70 - 120 nm; and / or,

[0008] the R 1 , R 2 , R 3 are each independently at least one of C 1-8 alkyl groups or aromatic groups, preferably at least one of C 1-4 alkyl groups, more preferably methyl; and / or,

[0009] the X - is at least one of bicarbonate ion, hydroxide ion, bisulfite ion, carboxylate ion, citrate ion; and / or,

[0010] the macroporous composite ion exchange resin is spherical or quasi-spherical particles, preferably, its particle size is 350 - 600 μm; and / or,

[0011] The macroporous composite resin matrix is ​​prepared by using modified silica nanoparticles as pore-forming agents; the present invention uses modified silica nanoparticles as pore-forming agents (template agents or pore-forming agents) to successfully synthesize macroporous composite resin matrices with spherical or quasi-spherical pores and uniform and adjustable pore sizes; preferably,

[0012] The macroporous composite resin matrix is ​​prepared by a preparation method including polymerizing components including styrene monomers, comonomers, modified silica nanoparticles, and carbon nanomaterials and then treating them with an acid or alkaline solution.

[0013] In a preferred embodiment of the present invention,

[0014] The styrene monomer is selected from at least one of styrene and its derivatives, preferably at least one of styrene, α-methylstyrene and 4-butylstyrene; and / or,

[0015] The comonomer is selected from at least one of divinylbenzenes, preferably at least one of diisopropenylbenzene and divinylbenzene; and / or,

[0016] The most possible particle size of the modified silica nanoparticles is 20 to 500 nm, preferably 70 to 200 nm, more preferably 70 to 120 nm; and / or,

[0017] The modified silica nanoparticles are obtained by modifying silica nanoparticles with a double-bond silane coupling agent; the size change of the silica nanoparticles before and after the modification is very small and can be ignored; and / or,

[0018] The carbon nanomaterial is a conventional carbon nanomaterial in the prior art, and its size is also a conventional size. Those skilled in the art can select it according to the actual situation. The carbon nanomaterial in the present invention is preferably at least one of graphene and carbon nanotubes; and / or,

[0019] The acid solution is an HF aqueous solution; and / or the alkaline solution is at least one of an aqueous ammonia solution, an alkali metal carbonate aqueous solution, and an alkali metal hydroxide aqueous solution, preferably an aqueous ammonia solution, a carbonate solution, or a hydroxide solution.

[0020] At least one of sodium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution; and / or, the concentration of the acid or alkali solution is 0.005-1.0 mol / L, preferably 0.05-1.0 mol / L; the amount of the acid or alkali solution is at least enough to completely disperse the resin beads before the acid or alkali treatment in the acid or alkali solution, preferably, the amount of the acid or alkali solution is 1g of the resin beads before the acid or alkali treatment corresponds to 5-40mL of the acid or alkali solution; and / or,

[0021] ​The mass ratio of the styrene monomer, comonomer, carbon nanomaterial, and modified silica nanoparticles is 1:(0.01 - 0.05):(0.001 - 0.1):(0.001 - 0.2), preferably 1:(0.01 - 0.03):(0.001 - 0.05):(0.01 - 0.1).

[0022] In a preferred embodiment of the present invention,

[0023] The silane coupling agent containing double bonds is selected from at least one of allyl triethoxysilane, allyl trimethoxysilane, 3 - butene triethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, diethoxymethylvinylsilane, and methylvinyldimethoxysilane; and / or,

[0024] The most probable particle size of the silica nanoparticles before modification is 20 - 500 nm, preferably 70 - 200 nm, more preferably 70 - 120 nm; and / or,

[0025] The silica nanoparticles before modification can be obtained commercially or prepared by any method of the prior art. In the present invention, it is preferred that the silica nanoparticles before modification are obtained by hydrolysis and polycondensation of silicate compounds; preferably,

[0026] The preparation process of the silica nanoparticles before modification may specifically include the following steps: Mix alcohol, water, and a catalyst evenly, and then add a silicate compound to react to obtain the silica nanoparticles before modification; wherein, the alcohol is preferably at least one of absolute ethanol and absolute methanol, and / or, the catalyst is preferably at least one of ammonia water and sodium carbonate, and / or, the volume ratio of alcohol to water is (1 - 15):1, and / or, the mass ratio of the catalyst to water is (0.01 - 1):1, and / or, the volume ratio of the silicate compound to water is (0.1 - 0.8):1, and / or, the reaction temperature is preferably 10 - 60°C, and the reaction time is preferably 0.1 - 5 h; preferably, the reaction is carried out under stirring, and the stirring rate is preferably 300 - 800 rpm.

[0027] The silicate compound is selected from at least one of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate; and / or, the volume ratio of the silane coupling agent containing double bonds to the silicate compound is 0.1 - 0.8, preferably 0.2 - 0.4; and / or,

[0028] The modification temperature is 10 - 60°C, preferably 20 - 40°C; and / or, the modification time is 0.1 - 12 h, preferably 0.5 - 5 h.

[0029] In a preferred embodiment of the present invention,

[0030] The components including styrene monomers, comonomers, modified silica nanoparticles, and carbon nanomaterials are polymerized in the presence of a dispersant and an initiator; preferably,

[0031] The dispersant is selected from at least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite, and calcium carbonate, preferably at least one of polyvinyl alcohol and gelatin; and / or,

[0032] The initiator is selected from at least one of peroxide initiators and azo initiators, preferably at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide, and cumene hydroperoxide, more preferably at least one of benzoyl peroxide and azobisisobutyronitrile; and / or,

[0033] The mass ratio of the styrene monomer, dispersant, and initiator is 1:(0.04 - 0.15):(0.001 - 0.1), preferably 1:(0.04 - 0.1):(0.001 - 0.02).

[0034] In a preferred embodiment of the present invention,

[0035] The temperature of the polymerization is 40 - 120°C, and / or the time of the polymerization is 10 - 72 hours; preferably, the polymerization is carried out in a stepwise temperature-rising manner, preferably stirring at 40 - 50°C for 0.5 - 2 h for pre-polymerization, then raising the temperature to 60 - 85°C for reaction for 1 - 24 h, then raising the temperature to 85 - 95°C for reaction for 1 - 24 h, and finally raising the temperature to 95 - 120°C for reaction for 1 - 24 h; and / or,

[0036] The temperature of the treatment is 10 - 100°C, preferably 60 - 100°C; and / or the time of the treatment is 0.5 - 12 h, preferably 0.5 - 3 h; preferably, the treatment includes a stirring reaction step, and the stirring rate is preferably 300 - 800 rpm.

[0037] In a preferred embodiment of the present invention,

[0038] After the macroporous composite resin matrix is prepared, chloromethylation, amination, and transformation are carried out in sequence to obtain the macroporous composite ion exchange resin.

[0039] The second object of the present invention is to provide a preparation method of the macroporous composite ion exchange resin of one of the objects of the present invention, which includes polymerizing components including styrene monomers, comonomers, modified silica nanoparticles, and carbon nanomaterials, and then treating with an acid or alkali solution to prepare a macroporous composite resin matrix, and then successively performing chloromethylation, amination, and transformation on the macroporous composite resin matrix to obtain the macroporous composite ion exchange resin.

[0040] In a preferred embodiment of the present invention,

[0041] The chloromethylation reagent used for the chloromethylation is a conventional chloromethylation reagent in the art, preferably at least one selected from chloromethyl methyl ether, chloromethyl ethyl ether, and chloromethyl isopropyl ether, more preferably at least one selected from chloromethyl methyl ether and chloromethyl isopropyl ether; and / or,

[0042] The temperature of the chloromethylation is 30-60°C, preferably 30-50°C, and / or the time of the chloromethylation is 8-30 h, preferably 8-15 h; and / or,

[0043] The amination reagent used for the amination is selected from at least one of ammonium salts containing NR 4 R 5 R 6 , where R 4 , R 5 , and R 6 are each independently at least one of C 1-10 alkyl groups or aromatic groups, preferably at least one of C 1-8 alkyl groups or aromatic groups, more preferably at least one of C 1-4 alkyl groups; preferably, the amination reagent used for the amination is selected from at least one of trimethylamine salts, triethylamine salts, diethylamine salts, and tributylamine salts, preferably at least one of trimethylamine salts and tributylamine salts, more preferably at least one of trimethylamine hydrochloride and tributylamine hydrochloride; and / or,

[0044] The temperature of the amination is 20-60°C, preferably 20-40°C, and / or the time of the amination is 4-24 h, preferably 4-10 h; and / or,

[0045] The transformation agent used for the transformation is a conventional transformation agent in the art, preferably at least one selected from sodium hydroxide, sodium bicarbonate, sodium bisulfite, carboxylate, and sodium citrate, more preferably at least one of sodium hydroxide and sodium bicarbonate; and / or,

[0046] The temperature of the transformation is 20-60°C, preferably 20-35°C, and / or the time of the transformation is 4-72 h, preferably 12-36 h.

[0047] The present invention may adopt the following specific technical solutions:

[0048] The synthesis method of the macroporous composite ion exchange resin includes the following steps:

[0049] (1) First, synthesize silica nanoparticles, and then modify them with a silane coupling agent containing a double bond to obtain silica nanoparticles modified with a double bond-containing group;

[0050] (2) Polymerize the silica nanoparticles modified with a double bond-containing group prepared in step (1) together with a styrene monomer, a comonomer, a carbon nanomaterial, and a dispersant under the action of an initiator, and then disperse the obtained resin beads into an acid or base solution for treatment for 0.5 - 12 h to obtain a macroporous composite resin matrix; in the present invention, dispersing the resin beads into an acid or base solution for treatment is to remove the silica nanoparticles in the resin, thereby generating spherical or quasi-spherical macroporous channels with uniform and adjustable pore sizes in the resin; the pore channels of the macroporous composite resin matrix prepared by this method are basically not deformed or only slightly deformed relative to the shape of the modified silica nanoparticles (pore-forming agent), and the pore channel size of the macroporous composite resin matrix can be conveniently regulated by regulating the size of the modified silica nanoparticles;

[0051] (3) Chloromethylate and aminate the macroporous composite resin matrix prepared in step (2) in sequence, and transform it to obtain a macroporous composite ion exchange resin. The change in the pore channel size during the chloromethylation, amination, and transformation of the macroporous composite resin matrix can be ignored.

[0052] In the above technical solution, preferably, in step (3), a chloromethylation reagent and a zinc chloride catalyst are added to the macroporous composite resin matrix for a functionalization reaction. After the reaction is completed, it is washed with methanol and water and dried to obtain a macroporous chlorinated resin bead.

[0053] In the above technical solution, preferably, the weight of the chloromethylation reagent is 200% - 500% of the weight of the macroporous composite resin matrix, and the weight of the zinc chloride catalyst is 20% - 70% of the weight of the macroporous composite resin matrix.

[0054] In the above technical solution, preferably, a swelling agent, an amination reagent, and a base are added to the macroporous chlorinated resin bead for a functionalization reaction; after the reaction is completed, it is washed with water and optionally dried, then a transformation agent is added for transformation, and then washed with water until the eluate is neutral to obtain a macroporous composite ion exchange resin.

[0055] In the above technical solution, preferably, the swelling agent is selected from at least one of dichloromethane, 1,2-dichloroethane, chloroform, or tetrahydrofuran, and more preferably, it is one of dichloromethane or tetrahydrofuran.

[0056] In the above technical solution, preferably, the weight of the swelling agent is 110% - 250% of the weight of the macroporous chlorinated resin beads, and more preferably, it is 150% - 200%.

[0057] In the above technical solution, preferably, the weight of the amination reagent in step (3) is 70% - 200% of the weight of the macroporous chlorinated resin beads, and more preferably, it is 100% - 180%.

[0058] In the above technical solution, preferably, the base is selected from at least one of sodium hydroxide or potassium hydroxide;

[0059] In the above technical solution, preferably, the weight of the base is 120% - 360% of the weight of the macroporous chlorinated resin beads, and more preferably, it is 160% - 300%.

[0060] In the above technical solution, preferably, the transformation agent is used in the form of a solution, and its concentration is preferably 0.01 - 2 mol / L.

[0061] In the present invention, the conditions for chloromethylation, amination, and transformation can all adopt the conventional conditions in the art, and those skilled in the art can adjust according to the actual situation.

[0062] The third object of the present invention is to provide a method for preparing diol by the hydration of epoxyalkane, which includes the step of reacting epoxyalkane and water under the condition that the macroporous composite ion exchange resin of the first object of the present invention or the macroporous composite ion exchange resin obtained by the preparation method of the second object of the present invention exists.

[0063] In a preferred embodiment of the present invention,

[0064] The epoxyalkane has the following general formula:

[0065]

[0066] wherein, R 1 , R 2 , R 3 , R 4 are independently a hydrogen atom or an alkyl group having 1 - 6 carbon atoms; and / or,

[0067] The molar ratio of water to epoxyalkane is (1 - 25):1, preferably (5 - 15):1; and / or,

[0068] The reaction conditions include: the reaction temperature is 60 - 180 °C, preferably 80 - 120 °C, the reaction pressure is 0.1 - 10.0 MPa, preferably 1.0 - 5.0 MPa, and the liquid hourly space velocity is 0.5 - 5 h -1 , preferably 2 - 5 h -1 .

[0069] A fourth object of the present invention is to provide a macroporous composite ion exchange resin according to one of the objects of the present invention, or a macroporous composite ion exchange resin obtained by the preparation method according to the second object of the present invention, or an application of the method according to the third object of the present invention in the reaction of epoxide hydration to produce diol.

[0070] Advantages of the present invention:

[0071] The pore channels of the catalyst (macroporous composite ion exchange resin) of the present invention are spherical or quasi-spherical, with uniform and adjustable pore sizes, which are very conducive to mass diffusion and reaction heat transfer, thereby improving the activity and stability of the catalyst. Using the catalyst of the present invention, in the 1800-hour epoxide hydration life test, at a low water ratio, the conversion rate of ethylene oxide remains above 98.5%, and the selectivity of ethylene glycol remains above 98.5%. In addition, the method for preparing the catalyst provided by the present invention is simple and feasible, which is conducive to industrial production. Description of the drawings

[0072] Figure 1 is the SEM photograph of the macroporous composite ion exchange resin prepared in Example 1.

[0073] Figure 2 is the SEM photograph of the ion exchange resin prepared in Comparative Example 2. Detailed implementation manners

[0074] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only used for further illustration of the present invention, and cannot be understood as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the content of the present invention still fall within the protection scope of the present invention.

[0075] The raw materials used in the examples and comparative examples, if not specifically limited, are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0076] The morphology of the resins prepared in the examples and comparative examples was measured by scanning electron microscopy (SEM); SiO 2 The size of the nanoparticles was measured by a nanoparticle size and zeta potential analyzer (NanoZS90); the pore size of the resin pore channels was measured by a mercury porosimeter Pascal140 / 240.

[0077]

Example 1

[0078] 71.4 mL of absolute ethanol, 10 mL of deionized water, and 1.57 mL of ammonia water (ammonia water concentration 14.84 mol / L) were uniformly mixed and placed in a water bath at 30 °C for magnetic stirring at a stirring speed of 400 rpm. After the temperature was balanced, 3 mL of tetraethyl orthosilicate was quickly added to the above reaction solution, and the reaction was carried out for 1 h to obtain solid SiO 2 nanoparticles, the most probable particle size of which was 100 nm. 1 mL of allyltriethoxysilane was added and the reaction was continued for 1 h. After centrifugation, it was washed thoroughly with ethanol and dried to obtain SiO 2 nanoparticles modified with double bond-containing groups.

[0079] 4 g of gelatin was dissolved in 260 mL of deionized water and ultrasonically dispersed evenly; 58 g of styrene, 1.2 g of divinylbenzene, 0.5 g of benzoyl peroxide, 5.0 g of modified SiO 2 nanoparticles, and 1.0 g of multi-walled carbon nanotubes (Macklin, product number C805976) were ultrasonically dispersed for 1 h, added to the previous aqueous gelatin solution, and stirred at 400 rpm at 40 °C for 2 h for prepolymerization. The temperature was gradually raised to 80 °C and the reaction was carried out for 5 h, then the temperature was raised to 90 °C and the reaction was carried out for 5 h, and finally the temperature was raised to 98 °C and the reaction was carried out for 6 h. After the reaction was completed, the upper liquid was poured out. After washing and filtering with hot water, it was dried at 80 °C and sieved to collect resin beads with a particle size in the range of 350 - 600 μm. Then the obtained resin beads were dispersed in 1000 mL of 0.6 mol / L Na 2 CO 3 aqueous solution, and stirred and reacted at 400 rpm at 80 °C for 1 h. The product was collected, washed thoroughly with water, and dried to obtain a macroporous composite resin matrix.

[0080] 40 g of the macroporous composite resin matrix was taken, 150 mL of chloromethyl ethyl ether was added, and after standing at room temperature for 2 h, 10 g of zinc chloride was added with stirring at 400 rpm. The temperature was raised to 40 °C and the reaction was carried out for 10 h. After the reaction was completed, it was cooled to room temperature and the reaction solution was poured out. After washing repeatedly with methanol and then washing with water and drying, macroporous chlorinated beads were obtained. 40 g of chlorinated beads were taken and swollen in 60 mL of dichloroethane at 30 °C for 2 h. 40 g of trimethylamine hydrochloride and 600 g of a 20% sodium hydroxide solution were added, and the reaction was carried out at 30 °C for 6 h. After the reaction was completed, it was washed with water and then 500 mL of saturated sodium bicarbonate solution was added and stirred and reacted at 400 rpm at 25 °C for 24 h. Subsequently, the resin was washed with deionized water until the washing liquid was neutral and dried at room temperature (25 °C) to obtain macroporous carbon nanotube composite ion exchange resin A (catalyst A). The obtained catalyst A was spherical or quasi-spherical, and its particle size was 350 - 600 μm; the SEM photograph of the obtained catalyst A was as Figure 1As shown, it can be seen that the pores of catalyst A are spherical or quasi-spherical, and their pore sizes are uniform. The most probable pore size is measured to be 99 nm. The general formula of the functional groups on the macroporous carbon nanotube composite ion exchange resin A is -N + (CH 3 ) 3 HCO 3 - 。

[0081]

Example 2

[0082] 71.4 mL of absolute ethanol, 10 mL of deionized water and 3 mL of ammonia water (ammonia water concentration 14.84 mol / L) were uniformly mixed and placed in a water bath at 30 °C for magnetic stirring, and the stirring speed was 400 rpm. After the temperature was balanced, 3 mL of tetraethyl orthosilicate was quickly added to the above reaction solution, and the reaction was carried out for 1 h to obtain solid SiO 2 nanoparticles with the most probable particle size of 80 nm. 1 mL of allyltriethoxysilane was added and the reaction was continued for 1 h. After centrifugation, it was washed thoroughly with ethanol and dried to obtain SiO 2 nanoparticles modified with double bond-containing groups.

[0083] 4 g of gelatin was dissolved in 260 mL of deionized water and ultrasonically dispersed evenly; 58 g of styrene, 1.2 g of divinylbenzene, 0.5 g of benzoyl peroxide, 3.0 g of modified SiO 2 nanoparticles and 1.1 g of graphene (Macklin, product number G835835) were ultrasonically dispersed for 1 h and added to the previous gelatin aqueous solution. Stirring was carried out at 400 rpm at 40 °C for 2 h for prepolymerization, and the temperature was gradually raised to 80 °C, and the reaction was carried out for 5 h. Then the temperature was raised to 90 °C and the reaction was carried out for 5 h. Finally, the temperature was raised to 98 °C and the reaction was carried out for 6 h. After the reaction was completed, the upper layer liquid was poured out, washed with hot water and filtered, and then dried at 80 °C and sieved to collect resin beads with particle sizes in the range of 350 - 600 μm. Then the obtained resin beads were dispersed in 1000 mL of 0.05 mol / L NaOH aqueous solution, and stirred and reacted at 400 rpm at 80 °C for 1 h. The product was collected, washed thoroughly with water, and dried to obtain the macroporous composite resin matrix.

[0084] Take 40 g of the macroporous composite resin matrix, add 150 mL of chloromethyl ethyl ether, let it stand at room temperature for 2 h, then stir at 400 rpm and add 10 g of zinc chloride. Heat up to 40 °C and react for 10 h. After the reaction is completed, cool to room temperature and pour out the reaction solution. Wash it repeatedly with methanol and then wash with water and dry to obtain macroporous chlorinated beads. Take 40 g of the chlorinated beads, add 60 mL of dichloroethane, swell at 30 °C for 2 h, add 40 g of trimethylamine hydrochloride and 600 g of a 20% sodium hydroxide solution, and react at 30 °C for 6 h. After the reaction is completed, wash with water, add 500 mL of saturated sodium bicarbonate solution, stir at 400 rpm at 25 °C and react for 24 h. Then wash the resin with deionized water until the washing solution is neutral, and dry it at room temperature (25 °C) to obtain macroporous graphene composite ion exchange resin B (catalyst B). The obtained catalyst B is spherical or quasi-spherical, and its particle size is 350 - 600 μm; the pore channels of the obtained catalyst B are spherical or quasi-spherical, and their pore sizes are uniform. The most probable pore size measured is 80 nm. The general formula of the functional groups on the macroporous carbon nanotube composite ion exchange resin B is -N + (CH 3 ) 3 HCO 3 - 。

[0085]

Example 3

[0086] 71.4 mL of absolute ethanol, 10 mL of deionized water and 3 mL of ammonia water (ammonia water concentration 14.84 mol / L) are uniformly mixed and placed in a water bath at 30 °C for magnetic stirring, and the stirring speed is 400 rpm. After the temperature is balanced, quickly add 4 mL of tetraethyl orthosilicate to the above reaction solution and react for 1 h to obtain solid SiO 2 nanoparticles, the most probable particle size of which is 90 nm. Add 1 mL of allyl triethoxysilane and continue to react for 1 h. After centrifugation, wash it thoroughly with ethanol and dry to obtain SiO 2 nanoparticles modified with double bond-containing groups.

[0087] Dissolve 4 g of gelatin in 260 mL of deionized water and disperse it evenly by ultrasonic wave; take 58 g of styrene, 1.2 g of divinylbenzene, 0.5 g of benzoyl peroxide, 4.0 g of modified SiO 2The nanoparticles and 0.9 g of single-walled carbon nanotubes (Macklin, catalog number C822928) were ultrasonically dispersed for 1 hour and added to the previous aqueous gelatin solution. Pre-polymerization was carried out by stirring at 400 rpm at 40 °C for 2 hours, gradually heating up to 80 °C, reacting for 5 hours, then heating up to 90 °C and reacting for 5 hours, and finally heating up to 98 °C and reacting for 6 hours. After the reaction ended, the upper liquid was poured out. After washing with hot water and filtering, it was dried at 80 °C and sieved to collect resin beads with a particle size in the range of 350 - 600 μm. Then the obtained resin beads were dispersed into 1000 mL of an aqueous solution of 0.01 mol / L KOH, and stirred and reacted at 400 rpm at 80 °C for 1 hour. The product was collected, washed thoroughly with water, and dried to obtain a macroporous composite resin matrix.

[0088] Take 40 g of the macroporous composite resin matrix, add 150 mL of chloromethyl ethyl ether, let it stand at room temperature for 2 h, then stir and add 10 g of zinc chloride at 400 rpm, heat up to 40 °C, and react for 10 h. After the reaction ended, it was cooled to room temperature and the reaction solution was poured out. After repeatedly washing with methanol and then washing with water and drying, macroporous chlorinated beads were obtained. Take 40 g of the chlorinated beads, add 60 mL of dichloroethane, swell at 30 °C for 2 h, add 40 g of tributylamine hydrochloride and 600 g of a 20% sodium hydroxide solution, and react at 30 °C for 6 h. After the reaction ended, after washing with water, 500 mL of saturated sodium bicarbonate solution was added and stirred and reacted at 400 rpm at 25 °C for 24 h. Subsequently, the resin was washed with deionized water until the washing liquid was neutral, and dried at room temperature (25 °C) to obtain macroporous carbon nanotube composite ion exchange resin C (catalyst C). The obtained catalyst C is spherical or quasi-spherical, with a particle size of 350 - 600 μm; the pore channels of the obtained catalyst C are spherical or quasi-spherical, and their pore sizes are uniform, and the most probable pore size measured is 89 nm. The general formula of the functional groups on the macroporous carbon nanotube composite ion exchange resin A is -N + (C 4 H 9 ) 3 HCO 3 - 。

[0089]

Comparative Example 1

Compared with Example 1, the difference is that 1 mL of allyltriethoxysilane-modified SiO 2 nanoparticles was not added

[0090] 71.4 mL of absolute ethanol, 10 mL of deionized water and 1.57 mL of ammonia water (ammonia water concentration 14.84 mol / L) were uniformly mixed and placed in a water bath at 30 °C for magnetic stirring, and the stirring speed was 400 rpm. After the temperature was balanced, 3 mL of tetraethyl orthosilicate was quickly added to the above reaction solution, and solid SiO 2 nanoparticles were obtained after reacting for 1 h, and after centrifugation, they were washed thoroughly with ethanol and dried.

[0091] Dissolve 4 g of gelatin in 260 mL of deionized water and disperse it evenly by ultrasonic treatment; take 58 g of styrene, 1.2 g of divinylbenzene, 0.5 g of benzoyl peroxide, 5.0 g of solid SiO 2 nanoparticles and 1.0 g of multi-walled carbon nanotubes (Macklin, catalog number C805976) and disperse them by ultrasonic treatment for 1 hour. It is found that the solid SiO 2 nanoparticles are difficult to disperse evenly. Add them to the previous gelatin aqueous solution, and carry out prepolymerization by stirring at 400 rpm at 40 °C for 2 hours. Gradually raise the temperature to 80 °C and react for 5 hours, then raise the temperature to 90 °C and react for 5 hours, and finally raise the temperature to 98 °C and react for 6 hours. During the whole reaction process, most of the solid SiO 2 nanoparticles are distributed outside the suspension-polymerized small balls. After the reaction is completed, pour out the upper liquid. After washing with hot water and filtering, dry at 80 °C and sieve to collect resin small balls with a particle size in the range of 350 - 600 μm. Then disperse the obtained resin small balls into 1000 mL of 0.6 mol / L Na 2 CO 3 aqueous solution, stir and react at 400 rpm at 80 °C for 1 hour, wash thoroughly with water and then dry to obtain resin matrix small balls.

[0092] Take 40 g of resin matrix small balls, add 150 mL of chloromethyl ether, let it stand at room temperature for 2 h, then stir and add 10 g of zinc chloride at 400 rpm, raise the temperature to 40 °C, and react for 10 h. After the reaction is completed, cool to room temperature and pour out the reaction solution. Wash repeatedly with methanol and then wash with water and dry to obtain chlorinated balls. Take 40 g of chlorinated balls and add 60 mL of dichloroethane, swell at 30 °C for 2 h, add 40 g of trimethylamine hydrochloride and 600 g of a 20% sodium hydroxide solution, and react at 30 °C for 6 h. After the reaction is completed, wash with water, then add 500 mL of saturated sodium bicarbonate solution and stir and react at 400 rpm at 25 °C for 24 h. Subsequently, wash the resin with deionized water until the washing liquid is neutral, and dry at room temperature (25 °C) to obtain carbon nanotube composite ion exchange resin D (catalyst D). The obtained catalyst D is basically pore-free.

[0093]

Comparative Example 2

Compared with Example 1, the difference is that the added pore-forming agent is toluene

[0094] Dissolve 4 g of gelatin in 260 mL of deionized water and disperse it evenly by ultrasonic treatment; take 58 g of styrene, 1.2 g of divinylbenzene, 0.5 g of benzoyl peroxide, 5 g of toluene and 1.0 g of multi-walled carbon nanotubes (Macklin, product number C805976) and disperse them by ultrasonic treatment for 1 hour. Add them to the previous gelatin aqueous solution, and carry out pre-polymerization by stirring at 400 rpm at 40 °C for 2 hours, gradually raise the temperature to 80 °C, react for 5 hours, then raise the temperature to 90 °C and react for 5 hours, and finally raise the temperature to 98 °C and react for 6 hours. After the reaction is completed, pour out the upper liquid, wash it with hot water, filter it, dry it at 80 °C, and sieve it to collect resin beads with a particle size in the range of 350 - 600 μm. Then disperse the obtained resin beads into 1000 mL of an aqueous solution of 0.6 mol / L Na 2 CO 3 , stir and react at 400 rpm at 80 °C for 1 hour, wash it thoroughly with water and then dry it to obtain resin matrix beads.

[0095] Take 40 g of resin matrix beads, add 150 mL of chloromethyl ethyl ether, let it stand at room temperature for 2 h, then stir and add 10 g of zinc chloride at 400 rpm, raise the temperature to 40 °C, react for 10 h, after the reaction is completed, cool it to room temperature, pour out the reaction solution, wash it repeatedly with methanol and then wash it with water and dry it to obtain chlorinated beads. Take 40 g of chlorinated beads, add 60 mL of dichloroethane, swell it at 30 °C for 2 h, add 40 g of trimethylamine hydrochloride and 600 g of a 20% sodium hydroxide solution, and react at 30 °C for 6 h. After the reaction is completed, wash it with water, add 500 mL of saturated sodium bicarbonate solution, stir and react at 400 rpm at 25 °C for 24 h, then wash the resin with deionized water until the washing liquid is neutral, and dry it at room temperature (25 °C) to obtain carbon nanotube composite ion exchange resin E (catalyst E). The SEM photograph of the obtained catalyst E is as Figure 2 shown, and it can be seen from Figure 2 that the pores generated by the traditional pore-forming agent have no fixed shape and are of uneven size.

[0096]

Test Examples 1 - 5

[0097] Use the prepared macroporous composite ion exchange resin as a catalyst for the catalytic hydration reaction of water and alkylene oxide: load the prepared catalyst (macroporous composite ion exchange resin) into a fixed-bed reactor, and carry out a 1800-hour life test for the catalytic hydration reaction of ethylene oxide. The conditions are as follows: the protective gas is high-purity nitrogen, the reaction temperature is 95 - 100 °C, the pressure is 1.2 - 3.0 MPa, the molar ratio of water to ethylene oxide is 10:1, and the liquid hourly space velocity is 3.5 h -1 , and samples are taken every 4 hours for the determination of conversion rate and selectivity. In the life test of catalysts A - C, the conversion rate of ethylene oxide is above 98.5%, and the selectivity of ethylene glycol remains above 98.5% (see Table 1).

[0098] Table 1 Activity evaluation results of catalysts A-C in ethylene oxide hydration

[0099]

[0100]

Comparative Examples 3-4

[0101] Under the same conditions, the performances of catalysts D and E were investigated. It was found that when catalysts D and E catalyzed the ethylene oxide hydration reaction, the initial ethylene oxide conversion was above 98%, and the ethylene glycol selectivity was above 98%; however, after the reaction proceeded for 1300 hours, the ethylene oxide conversions catalyzed by catalysts D and E began to decrease significantly: the ethylene oxide conversion of D decreased to 92.5%, and the ethylene glycol selectivity decreased to 97.0%; the ethylene oxide conversion of E decreased to 93.5%, and the selectivity of ethylene glycol decreased to 97.5% (see Table 2).

[0102] Table 2 Activity evaluation results of catalysts D and E in ethylene oxide hydration

[0103]

[0104] It can be seen from Example 1, Comparative Example 1 and Tables 1-2 that: in Comparative Example 1, since the SiO 2 nanoparticles without being modified by a silane coupling agent containing double bonds were directly used as pore formers, the resulting resin was basically poreless, thus its catalytic activity and stability were both inferior to those of the macroporous composite ion exchange resin of the present invention.

[0105] It can be seen from Example 1, Comparative Example 2 and Tables 1-2 that: compared with the ion exchange resin obtained by using traditional pore formers, the catalytic activity and stability of the macroporous composite ion exchange resin prepared by the present invention by using modified SiO 2 nanoparticles as pore formers have made remarkable progress.

[0106] The above are only the preferred examples of the present invention. It should be pointed out that for those of ordinary skill in the art, under the technical inspiration provided by the present invention, as common general knowledge in the art, other equivalent variations and improvements can also be made, which should also be regarded as the protection scope of the present invention.

Claims

1. A macroporous composite ion exchange resin having spherical or quasi-spherical pores; the macroporous composite ion exchange resin comprises a macroporous composite resin matrix and a macroporous composite resin matrix having a general formula of -N + R1R2R3X - The functional groups, wherein R1, R2, and R3 are each independently C 1-10 At least one of an alkyl group or an aromatic group, X - An anion or anionic group.

2. The macroporous composite ion exchange resin according to claim 1, characterized in that: The maximum pore size of the macroporous composite ion exchange resin is 20 to 500 nm, preferably 70 to 200 nm; and / or, The R1, R2, and R3 are independently C 1-8 At least one of an alkyl or aromatic group, preferably C 1-4 At least one of alkyl groups; and / or, The X - is at least one of bicarbonate ion, hydroxide ion, bisulfite ion, carboxylate ion, and citrate ion; and / or, The macroporous composite ion exchange resin is a spherical or quasi-spherical particle, preferably, the particle size is 350-600 μm; and / or, The macroporous composite resin matrix is ​​prepared using modified silica nanoparticles as pore-forming agents; preferably, The macroporous composite resin matrix is ​​prepared by a preparation method comprising polymerizing components including styrene monomers, comonomers, modified silicon dioxide nanoparticles and carbon nanomaterials and then treating them with an acid or alkaline solution.

3. The macroporous composite ion exchange resin according to claim 2, characterized in that: The styrene monomer is selected from at least one of styrene and its derivatives, preferably at least one of styrene, α-methylstyrene and 4-butylstyrene; and / or, The comonomer is selected from at least one of divinylbenzenes, preferably at least one of diisopropenylbenzene and divinylbenzene; and / or, The modified silica nanoparticles have a most possible particle size of 20 to 500 nm, preferably 70 to 200 nm; and / or, The modified silica nanoparticles are obtained by modifying silica nanoparticles with a silane coupling agent containing double bonds; and / or, The carbon nanomaterial is selected from at least one of graphene and carbon nanotubes; and / or, The acid solution is an HF aqueous solution; and / or, the alkaline solution is at least one of an aqueous ammonia solution, an alkali metal carbonate aqueous solution, and an alkali metal hydroxide aqueous solution, preferably at least one of an aqueous ammonia solution, an aqueous sodium carbonate solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution; and / or, the concentration of the acid or alkaline solution is 0.005 to 1.0 mol / L, preferably 0.05 to 1.0 mol / L; and / or, The mass ratio of the styrene monomer, comonomer, carbon nanomaterial and modified silica nanoparticles is 1: (0.01-0.05): (0.001-0.1): (0.001-0.2), preferably 1: (0.01-0.03): (0.001-0.05): (0.01-0.1).

4. The macroporous composite ion exchange resin according to claim 3, characterized in that: The double bond-containing silane coupling agent is selected from at least one of allyltriethoxysilane, allyltrimethoxysilane, 3-butenetriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, diethoxymethylvinylsilane and methylvinyldimethoxysilane; and / or, The most possible particle size of the silica nanoparticles before modification is 20 to 500 nm, preferably 70 to 200 nm; and / or, The silica nanoparticles before modification are obtained by hydrolysis and polycondensation of silicate compounds; preferably, the silicate compounds are selected from at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; and / or, the volume ratio of the double-bond silane coupling agent to the silicate compound is 0.1 to 0.8, preferably 0.2 to 0.4; and / or, The modification temperature is 10-60° C., preferably 20-40° C.; and / or the modification time is 0.1-12 h, preferably 0.5-5 h.

5. The macroporous composite ion exchange resin according to claim 2, characterized in that: The components including styrene monomers, comonomers, modified silica nanoparticles, and carbon nanomaterials are polymerized in the presence of a dispersant and an initiator; preferably, The dispersant is selected from at least one of polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite, and calcium carbonate, preferably at least one of polyvinyl alcohol and gelatin; and / or, The initiator is selected from at least one of a peroxide initiator and an azo initiator, preferably at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide, and cumene hydroperoxide; and / or, The mass ratio of the styrene monomer, the dispersant and the initiator is 1:(0.04-0.15):(0.001-0.1), preferably 1:(0.04-0.1):(0.001-0.02).

6. The macroporous composite ion exchange resin according to claim 2, characterized in that: The polymerization temperature is 40-120° C., and / or, the polymerization time is 10-72 hours; preferably, the polymerization is carried out in a step-by-step heating manner, preferably stirring at 40-50° C. for 0.5-2 hours for prepolymerization, then heating to 60-85° C. for reaction for 1-24 hours, then heating to 85-95° C. for reaction for 1-24 hours, and finally heating to 95-120° C. for reaction for 1-24 hours; and / or, The treatment temperature is 10 to 100° C., preferably 60 to 100° C.; and / or the treatment time is 0.5 to 12 hours, preferably 0.5 to 3 hours.

7. The macroporous composite ion exchange resin according to any one of claims 1 to 6, characterized in that: After the macroporous composite resin matrix is ​​prepared, chloromethylation, amination and transformation are sequentially performed to obtain the macroporous composite ion exchange resin.

8. A method for preparing a macroporous composite ion exchange resin as described in any one of claims 1 to 7, comprising the steps of polymerizing components including styrene monomers, comonomers, modified silica nanoparticles, and carbon nanomaterials, and then treating them with an acid or alkaline solution to prepare a macroporous composite resin matrix, and then sequentially chloromethylating, aminating, and transforming the macroporous composite resin matrix to obtain the macroporous composite ion exchange resin.

9. The preparation method according to claim 8, characterized in that: The chloromethylation agent used in the chloromethylation is selected from at least one of chloromethyl ether, chloroethyl ether and chloromethyl ethyl ether, preferably at least one of chloromethyl ether and chloromethyl ethyl ether; and / or, The temperature of the chloromethylation is 30 to 60° C., preferably 30 to 50° C., and / or the time of the chloromethylation is 8 to 30 hours, preferably 8 to 15 hours; and / or, The amination reagent used in the amination is selected from at least one of the ammonium salts comprising NR4R5R6, wherein R4, R5, and R6 are independently C 1-10 At least one of an alkyl group or an aromatic group; preferably, the aminating agent used in the amination is selected from at least one of trimethylamine salt, triethylamine salt, diethylamine salt and tributylamine salt, preferably at least one of trimethylamine salt and tributylamine salt; and / or, The amination temperature is 20 to 60° C., preferably 20 to 40° C., and / or the amination time is 4 to 24 hours, preferably 4 to 10 hours; and / or, The transformation agent used in the transformation is selected from at least one of sodium hydroxide, sodium bicarbonate, sodium bisulfite, sodium carboxylate, and sodium citrate, preferably at least one of sodium hydroxide and sodium bicarbonate; and / or, The temperature of the transformation is 20 to 60° C., preferably 20 to 35° C., and / or the time of the transformation is 4 to 72 hours, preferably 12 to 36 hours.

10. A method for preparing glycol by hydrating alkylene oxide, comprising the step of reacting alkylene oxide with water in the presence of the macroporous composite ion exchange resin according to any one of claims 1 to 7 or the macroporous composite ion exchange resin prepared by the method according to any one of claims 8 to 9.

11. The method according to claim 10, characterized in that: The alkylene oxide has the following general formula: Among them, R 1 , R 2 , R 3 , R 4 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and / or, The molar ratio of water to alkylene oxide is (1-25):1, preferably (5-15):1; and / or, The reaction conditions include: reaction temperature of 60-180°C, preferably 80-120°C, reaction pressure of 0.1-10.0 MPa, preferably 1.0-5.0 MPa, liquid space velocity of 0.5-5 h -1 , preferably 2 to 5 hours -1 .

12. Use of the macroporous composite ion exchange resin as claimed in any one of claims 1 to 7 or the macroporous composite ion exchange resin prepared by the method as claimed in any one of claims 8 to 9 or the method as claimed in any one of claims 10 to 11 in the reaction of hydration of alkylene oxide to prepare glycol.

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