CN109574807B - Method for preparing ethylene glycol by catalytic hydration of alkylene oxide - Google Patents

Method for preparing ethylene glycol by catalytic hydration of alkylene oxide Download PDF

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CN109574807B
CN109574807B CN201710904353.8A CN201710904353A CN109574807B CN 109574807 B CN109574807 B CN 109574807B CN 201710904353 A CN201710904353 A CN 201710904353A CN 109574807 B CN109574807 B CN 109574807B
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alkylene oxide
ethylene glycol
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ion exchange
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俞峰萍
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for preparing ethylene glycol by catalyzing and hydrating alkylene oxide, which comprises the steps of contacting the alkylene oxide and water with an ion exchange resin catalyst under the hydration reaction condition; the ion exchange resin catalyst has the following structural general formula:
Figure DDA0001423708470000011
wherein the content of the first and second substances,
Figure DDA0001423708470000012
is a macroporous nano composite resin matrix; m‑Is an anion selected from bicarbonate ion, hydroxide ion, bisulfite ion, carboxylate ion, citrate ion; POSS is a cage-type silsesquioxane unit;

Description

Method for preparing ethylene glycol by catalytic hydration of alkylene oxide
Technical Field
The invention relates to a method for preparing ethylene glycol by catalytic hydration of alkylene oxide.
Background
The ion exchange resin is a functional polymer material, contains rich ion exchange groups, is resistant to acid and alkali solution and a plurality of organic solvents, and has strong solvent stability. In industry, styrene and divinylbenzene are copolymerized to prepare a matrix of the ion exchange resin, and the anion exchange resin is prepared through chloromethylation and amination reaction. High molecular polymers typified by ion exchange resins are becoming a third material other than metal materials and inorganic nonmetallic materials. And has wide application in the fields of biomedicine, aerospace, information technology, multifunctional catalysis and the like.
The use of ion exchange resins in catalytic hydration was studied by Shell, Dow, SD companies at the end of the 20 th century, Lemanski et al, which use strong base ion exchange resins as the main catalyst for catalyzing the hydration of ethylene oxide and acidic ion exchange resins as additives, and found that the hydration of ethylene oxide at 100 ℃ under a pressure of 1.0MPa and a water ratio of 5.5: the reaction was carried out for 6 hours at 1 c, the conversion of the starting material ethylene oxide was 100%, and the selectivity to ethylene glycol was up to 88.3% (m.f. lemanski, v.kruchten, r.kunin, US patent6,156,942 (2000)). However, the strong-base ion exchange resin applied to catalytic hydration is not high-temperature resistant, has poor thermal stability, is easy to age and swell, so that the long-term service performance of the strong-base ion exchange resin is reduced, and the industrial prospect is not optimistic. Shell company developed a quaternary ammonium type anion exchange resin and used it for ethylene oxide catalytic hydration, the ethylene oxide conversion rate was close to 100%, the ethylene glycol selectivity was 95%, but even at lower temperatures (<95 ℃), the swelling of the catalyst was severe.
The quaternary ammonium type anion exchange resin is used as a catalyst, the reaction temperature is basically 80-110 ℃ in the reaction of catalyzing the hydration of the alkylene oxide, the anion exchange resin has poor heat resistance, and quaternary ammonium groups are unstable at the temperature and can be degraded. In the degradation process, the alkyl is dropped and changed into weak base group, so that the exchange equivalent and the catalytic activity of the ion exchange resin are simultaneously reduced. Also, a base-off reaction occurs. The ion exchange resin is modified to a certain extent from the structure, so that the heat resistance of the resin can be improved.
Chen group researches a styrene type strongly basic anion exchange resin substituted by benzene ring nitro group, and the resin shows excellent thermal stability and ethylene oxide hydration catalytic performance. Directly nitrifying styrene type strongly basic anion exchange resin serving as a raw material, and then transforming to obtain the target ion exchange resin. At 75 deg.C, 1.0MPa and 1.0 hr of space velocity-1And the water ratio is 6: 1, with water under the condition ofThe ion exchange resin is used as catalyst, the conversion rate of epoxy ethane is raised to 99.9% from 89.7%, the selectivity of glycol is raised to 95.6% from 94.2%, and the activity of resin is greatly raised. Mitsubishi corporation developed a class of anion exchange resins with higher heat resistance by suspension polymerization of functionalized styrene monomers and cross-linking agents, which resins had an alkyl or alkoxy methylene chain connected between the benzene ring and the quaternary ammonium nitrogen atom (Youjing Zheng Man, Long Bao Tianyu, Polymer processing (daily) [ J],1999,48(2): 57 to 63). The quaternary ammonium group in the resin is stable when heated and can be used for a long time at 90 ℃. However, the monomer synthesis route of the route is long, the operation conditions are harsh, the yield is low, the functional monomer is difficult to separate and purify, the purity is not high, and the performance of the final polymer is influenced.
The above ion exchange resin material has considerable disadvantages, so that how to improve the heat resistance and the swelling resistance of the resin becomes a research hotspot.
Disclosure of Invention
The invention provides a method for preparing ethylene glycol by catalytic hydration of alkylene oxide. The method comprises the steps of contacting an alkylene oxide and water with an ion exchange resin catalyst under hydration reaction conditions; the ion exchange resin catalyst has the following structural general formula:
Figure BDA0001423708460000021
wherein the content of the first and second substances,
Figure BDA0001423708460000022
is a macroporous nano composite resin matrix;
M-is an anion selected from bicarbonate ion, hydroxide ion, bisulfite ion, carboxylate ion, citrate ion;
POSS is a cage-type silsesquioxane unit with the general formula of (-SiO)1.5)m(ii) a m is 6, 8, 10 or 12;
Figure BDA0001423708460000023
is an imidazolium cationic unit;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene or arylene;
the macroporous nano composite resin matrix is a nano macroporous copolymer obtained by in-situ copolymerization of a styrene monomer, a comonomer, a nano material and a pore-foaming agent; the nano material is selected from at least one of single-layer graphene, multi-layer graphene, graphene oxide and graphite alkyne.
According to one aspect of the invention, the POSS units are present in the ion exchange resin in an amount of 5 to 15 wt.%.
According to one aspect of the invention, M-Is a bicarbonate ion.
According to one aspect of the invention, the alkylene group is selected from methylene, ethylene or propylene; the arylene group is selected from phenylene, naphthylene or phenylmethyl.
According to one aspect of the invention, the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene or 4-butylstyrene, preferably styrene; the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene, preferably divinylbenzene; the pore-foaming agent is selected from at least one of aliphatic hydrocarbon, polystyrene, gasoline, poly (propylene glycol), poly (ethylene glycol), polydimethylsiloxane, fatty acid or paraffin, and is preferably polystyrene.
According to one aspect of the invention, the styrene monomer is 85-95 parts, the comonomer is 2-5 parts, the nanomaterial is 0.1-3 parts, and the pore-forming agent is 10-100 parts.
According to one aspect of the invention, the nanomaterial is preferably multi-layer graphene.
According to one aspect of the invention, the hydration reaction conditions include: the reaction temperature is 60-180 ℃, the reaction pressure is 0.1-10.0 MPa, and the liquid airspeed is 0.5-5 h-1The molar ratio of water to alkylene oxide is (1-25): 1.
according to one aspect of the invention, the alkylene oxide has the general formula:
Figure BDA0001423708460000031
wherein R is1、R2、R3、R4Is a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. Preferably, R1、R2、R3、R4Is an alkyl group having 1 to 3 carbon atoms. More preferably R1、R2、R3Is a hydrogen atom and R4Is C1-C3An alkyl group. Most preferred is R1、R2、R3And R4All are hydrogen atoms.
The preparation method of the ion exchange resin catalyst comprises the following steps:
a) preparing an auxiliary agent into a water solution A with the weight percentage concentration of 0.5-2%, and preparing a styrene monomer, a comonomer, a nano material, an initiator and a pore-forming agent into a solution B; wherein, the styrene monomer is selected from at least one of styrene, alpha-methyl styrene or 4-butyl styrene; the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinyl phenyl methane or divinyl benzene; the nano material is selected from at least one of single-layer graphene, multi-layer graphene, graphene oxide and graphite alkyne; the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide or cumene hydroperoxide; the pore-foaming agent is selected from at least one of aliphatic hydrocarbon, polystyrene, gasoline, poly (propylene glycol), poly (ethylene glycol), polydimethylsiloxane, fatty acid or paraffin; the auxiliary agent is selected from at least one of polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite or calcium carbonate; the weight portion of the styrene monomer is 85-95 parts, the comonomer is 2-5 parts, the nano material is 0.1-3 parts, and the initiator is 0.1-10 parts; the dosage of the pore-foaming agent is 10-100 parts; the dosage of the auxiliary agent is 150-400% of the dosage of the monomer;
b) pre-polymerizing the solution B at 60-75 ℃ for 0.5-2.5 hours, then mixing the solution B with the solution A, heating to 70-90 ℃ for reaction for 5-15 hours, and heating to 90-100 ℃ for reaction for 5-15 hours; after the reaction is finished, extracting, washing, filtering, drying and sieving to obtain the composite macroporous microspheres with the particle size range of 0.35-0.60 mm;
c) chloromethylating the composite macroporous microspheres: adding a chloromethylation reagent which is 200-500% of the weight of the composite macroporous microspheres and a zinc chloride catalyst which is 20-70% of the weight of the composite macroporous microspheres into the composite macroporous microspheres, reacting for 8-30 hours at 30-60 ℃, filtering and washing to obtain composite macroporous chlorine spheres; the chloromethylation reagent is selected from at least one of chloromethyl ether, chloroethyl ether or 1, 4-dichloromethoxybutane;
d) reacting the mixture of the composite macroporous chlorine spheres, imidazole and acetonitrile at 60-90 ℃ to obtain composite imidazole microspheres; in the mixture, the mol ratio of the composite macroporous chlorine spheres to the imidazole to the acetonitrile is 1: (1-2): (30-150);
e) mixing the composite imidazole microspheres and alkyl halogenated POSS compounds according to the equimolar ratio of imidazole functional groups and halogenated functional groups, dissolving the mixture in tetrahydrofuran, filtering the mixture after the reaction is finished at 100 ℃ for 24-72 hours, and washing the mixture to obtain the composite imidazole/POSS microspheres; the alkyl halogenated POSS compound is selected from at least one of octachloromethyl POSS, octachloroethyl POSS and octachloropropyl POSS;
f) and washing the composite imidazole/POSS microspheres by using a salt solution, wherein the molar ratio of the composite imidazole/POSS microspheres to the salt solution is (1: 1) to (1: 10) (ii) a The concentration of the salt solution is 0.1-1 mol/L; and after washing, washing the product by deionized water until the pH value is 7 to obtain the ion exchange resin. The salt solution is selected from at least one of bicarbonate radical, hydroxide radical, bisulfite radical, carboxylate radical with 1-10 carbon atoms and citrate radical salt solution.
The invention has the beneficial effects that: the ion exchange resin catalyst of the invention contains two different nano materials: nanocarbon materials and Polyhedral oligomeric silsesquioxanes (abbreviated as polysilsesquioxanes)POSS). Under the action of an initiator, the nano carbon material, the monomer and the comonomer are introduced into the resin matrix through in-situ polymerization, so that the glass transition temperature of the resin matrix is increased; meanwhile, due to the introduction of the nano carbon material, the swelling resistance of the resin matrix is improved. And the POSS comprises an inorganic support structure consisting of Si and O, so that the ion exchange resin is endowed with good heat resistance, and the thermal stability is obviously improved. The preferred scheme of the invention is that the in-situ macroporous copolymer resin matrix of chloromethylated styrene, divinyl benzene and multilayer graphene reacts with imidazole to obtain composite imidazole microspheres, then the imidazole groups react with alkyl halogenated POSS compounds, and finally the composite imidazole microspheres undergo ion exchange reaction with a salt solution to prepare the macroporous ion exchange resin containing two different nano materials. Covalent bonding of graphene and a polymer matrix is realized through in-situ copolymerization reaction between graphene and monomers and comonomers, and bonding between POSS and a resin matrix is realized through chemical reaction of halogenated alkylated POSS compounds and imidazole groups. The macroporous ion exchange resin catalyst containing two different nano materials is used in the hydration reaction of water and alkylene oxide, the catalyst has high heat resistance, swelling resistance and activity, the product after the reaction is easy to separate, and the catalyst can be continuously used for a plurality of times. Ethylene oxide conversion C in a 2500 hour life testEOKeeping the selectivity S of the ethylene glycol above 99.2 percentECThe concentration was maintained at 98.0%.
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto, but is defined by the appended claims.
It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be combined with each other at will, and thus form part of the original disclosure of the specification, and also fall within the scope of the present invention.
Detailed Description
[ example 1 ] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene, 30 g of polystyrene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 1.5 hours at the temperature of 60 ℃; then 0.6 g of multi-layer graphene was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 8 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres A1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite macroporous microspheres: adding 40 g of composite macroporous microspheres A1 and 200ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 15 g of zinc chloride as a catalyst, heating to 50 ℃ for reaction for 12 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite macroporous chlorine microspheres A1.
30 g of composite macroporous chlorine ball A1 (the chlorine content is 3.3mmol Cl/g), imidazole (99.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 80 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A1.
30 g of composite imidazole microsphere A2 (imidazole group content is 3.0mmol/g), 9.4 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A1.
In a 1000ml three-neck flask, 30 g of composite imidazole/POSS microspheres A1, 500ml of NaHCO with the concentration of 0.1mol/L are added3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 24 hours; then washing the solution by deionized water until the pH value of the washing solution is 7, and drying the solution in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A1 and has the POSS unit content of11.2%, structural formula as follows:
Figure BDA0001423708460000061
[ example 2 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinylbenzene, 60 g of polystyrene, 1.6 g of multi-layer graphene and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 0.5 hour at 70 ℃), a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is raised to 85 ℃, the reaction is carried out for 3 hours, the temperature is raised to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is raised to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres B1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B1 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 24 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite macroporous chlorine sphere B1.
50 g of composite macroporous chlorine ball B (the chlorine content is 4.3mmol Cl/g), imidazole (215.0mmol) and 300ml of acetonitrile are added into a 500ml three-necked bottle, the mixture reacts for 16 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B1.
50 g of composite imidazole microsphere B1 (the imidazole group content is 3.8mmol/g), 19.3 g of octachloromethyl silsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 72 hours to obtain the composite imidazole/POSS microsphere B1.
In 1In a 000ml three-neck flask, 40 g of composite imidazole/POSS microspheres B1, 400ml of NaHCO with the concentration of 1.0mol/L are added3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 12 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-B1, wherein the POSS unit content is 13.3 percent, and the structural formula is as follows:
Figure BDA0001423708460000071
[ example 3 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 10 g of polystyrene, 0.1 g of multi-layer graphene and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 1.5 hours at 70 ℃, 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is performed for 3 hours, the temperature is increased to 90 ℃, the reaction is performed for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is performed for 10 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres C1 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C1 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorinated mother solution, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite macroporous chlorine sphere C1.
20 g of composite macroporous chlorine sphere C1 (the chlorine content is 1.4mmol Cl/g), imidazole (28.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C1.
20 g of composite imidazole microsphere C1 (the content of imidazole groups is 1.3mmol/g), 3.0 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C1.
In a 500ml three-neck flask, 20 g of composite imidazole/POSS microspheres C1, 300ml of NaHCO with the concentration of 0.5mol/L are added3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 12 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-C1, wherein the POSS unit content is 5.9%, and the structural formula is as follows:
Figure BDA0001423708460000081
[ example 4 ] preparation of ion exchange resin catalyst
47.0 g of styrene, 2.3 g of divinylbenzene, 40 g of polystyrene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 2.0 hours at the temperature of 60 ℃; then 0.6 g of monolayer graphene was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres A2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite macroporous microspheres: adding 40 g of composite macroporous microspheres A2 and 200ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 20 g of zinc chloride as a catalyst, heating to 60 ℃ for reaction for 10 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite macroporous chlorine microspheres A2.
30 g of composite macroporous chlorine ball A2 (the chlorine content is 3.4mmol Cl/g), imidazole (102.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 70 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere A2.
30 g of composite imidazole microsphere A2 (imidazole group content is 3.1mmol/g), 9.4 g of octachloromethyl silsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 24 hours to obtain the composite imidazole/POSS microsphere A2.
In a 1000ml three-neck flask, 30 g of composite imidazole/POSS microspheres A2, 500ml of NaHCO with the concentration of 0.1mol/L are added3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 24 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-A2, wherein the POSS unit content is 11.5 percent, and the structural formula is as follows:
Figure BDA0001423708460000091
[ example 5 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinylbenzene, 60 g of polystyrene, 1.6 g of single-layer graphene and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 0.5 hour at 70 ℃), a stirrer is started, a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is raised to 85 ℃, the reaction is carried out for 3 hours, the temperature is raised to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is raised to 100 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres B2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B2 and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 6 hours, adding 30 g of zinc chloride serving as a catalyst, starting stirring, heating to 50 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite macroporous chlorine sphere B2.
50 g of composite macroporous chlorine ball B2 (the chlorine content is 4.5mmol Cl/g), imidazole (225.0mmol) and 300ml of acetonitrile are added into a 500ml three-necked bottle, the mixture reacts for 16 hours at 80 ℃, the temperature is cooled to room temperature, the mixture is filtered, the ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere B2.
50 g of composite imidazole microsphere B2 (the imidazole group content is 3.9mmol/g), 19.8 g of octachloromethyl silsesquioxane and 500ml of tetrahydrofuran are added into a 1000ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence at 100 ℃ for 72 hours to obtain the composite imidazole/POSS microsphere B2.
In a 1000ml three-neck flask, 40 g of composite imidazole/POSS microspheres B2, 400ml of NaHCO with the concentration of 1.0mol/L are added3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 12 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-B2, wherein the POSS unit content is 13.6 percent, and the structural formula is as follows:
Figure BDA0001423708460000101
[ example 6 ] preparation of ion exchange resin catalyst
A monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 10 g of polystyrene, 0.1 g of single-layer graphene and 2.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and the solution is stirred and reacted for 1.5 hours at the temperature of 70 ℃), a mixed solution of 200ml of deionized water and 4 g of polyvinyl alcohol is added, the temperature is increased to 85 ℃, the reaction is performed for 3 hours, the temperature is increased to 90 ℃, the reaction is performed for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is performed for 10 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres C2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 20 g of composite microsphere C2 and 100 ml of 1, 4-dichloromethoxybutane into a 250ml three-neck flask, standing for 6 hours at room temperature, adding 8 g of zinc chloride as a catalyst, starting stirring, heating to 30 ℃ for reaction for 12 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorinated mother solution, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite macroporous chlorine sphere C2.
20 g of composite macroporous chlorine sphere C2 (the chlorine content is 1.6mmol Cl/g), imidazole (32.0mmol) and 150ml of acetonitrile are added into a 250ml three-neck flask, the mixture reacts for 16 hours at 90 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere C2.
20 g of composite imidazole microsphere C2 (the content of imidazole groups is 1.5mmol/g), 3.6 g of octachloroethyl silsesquioxane and 150ml of tetrahydrofuran are added into a 250ml three-neck flask, and after the reaction is finished, filtration is carried out for 72 hours at 100 ℃, and then the mixture is washed by tetrahydrofuran and deionized water in sequence to obtain the composite imidazole/POSS microsphere C2.
20 g of composite imidazole/POSS microspheres C2 and 300ml of deionized water solution of NaHCO3 with the concentration of 0.5mol/L are added into a 500ml three-neck flask, and the mixture is stirred at room temperature to carry out ion exchange reaction for 12 hours; then washing the catalyst by deionized water until the pH value of washing liquor is 7, and drying the catalyst in vacuum to obtain the ion exchange resin catalyst of two different nano materials, which is marked as Cat-C2, wherein the POSS unit content is 6.5 percent, and the structural formula is as follows:
Figure BDA0001423708460000111
comparative example 1 preparation of comparative catalyst
Preparing the macroporous microspheres without adding nano materials: in a 500ml three-necked flask, 47.0 g of styrene, 2.3 g of divinylbenzene, 30 g of polystyrene and 1.6 g of benzoyl peroxide initiator were charged, and 260 ml of a deionized water solution in which 2.0 g of gelatin had been dissolved was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 8 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the macroporous microspheres DZ-1 with the particle size of 0.35-0.60 mm.
Macroporous microsphere chloromethylation: adding 40 g of macroporous microspheres DZ-1 and 200ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 15 g of zinc chloride as a catalyst, heating to 50 ℃ for reaction for 12 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the macroporous chlorine microspheres DZ-1.
Without the use of haloalkylated POSS compounds: 30 g of macroporous chlorine ball DZ-1 (the chlorine content is 3.4mmol Cl/g), N-methylimidazole (102.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 80 ℃, the mixture is cooled to room temperature and filtered, and the mixture is washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence and then dried for 12 hours at 60 ℃ in vacuum to obtain the imidazole microsphere DZ-1.
30 g of imidazole microsphere DZ-1 are added into a 1000ml three-neck flask, and 500ml of NaHCO with the concentration of 0.1mol/L3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 24 hours; then washing the solution by deionized water until the pH value of washing liquor is 7, and drying the solution in vacuum to obtain the ion exchange resin catalyst which is marked as Cat-DZ-1 and has the following structural formula:
Figure BDA0001423708460000112
comparative example 2 preparation of comparative catalyst
47.0 g of styrene, 2.3 g of divinylbenzene, 30 g of polystyrene and 1.6 g of benzoyl peroxide initiator are added into a 500ml three-neck flask, and stirred and reacted for 1.5 hours at the temperature of 60 ℃; then 0.6 g of multi-layer graphene was added and stirring was continued for 1 hour for prepolymerization. A solution of 2.0 g of gelatin dissolved in 260 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 8 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite macroporous microspheres DZ-2 with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite macroporous microspheres: adding 40 g of composite macroporous microspheres DZ-2 and 200ml of chloromethyl ether into a 500ml three-neck flask, standing for 3 hours at room temperature, starting stirring, adding 15 g of zinc chloride as a catalyst, heating to 50 ℃ for reaction for 12 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying for 8 hours at 100 ℃ to obtain the composite macroporous chlorine microspheres DZ-2.
Without the use of haloalkylated POSS compounds: 30 g of composite macroporous chlorine ball DZ-2 (the chlorine content is 3.3mmol Cl/g), N-methylimidazole (99.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 80 ℃, the mixture is cooled to room temperature and filtered, ethyl acetate, 0.1mol/L HCl, deionized water and methanol are sequentially used for washing, and then the mixture is dried for 12 hours at 60 ℃ in vacuum to obtain the composite imidazole microsphere DZ-2.
30 g of compound imidazole microsphere DZ-2 are added into a 1000ml three-neck flask, 500ml of NaHCO with the concentration of 0.1mol/L3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 24 hours; then washing the solution by deionized water until the pH value of washing liquor is 7, and drying the solution in vacuum to obtain the ion exchange resin catalyst which is marked as Cat-DZ-2 and has the following structural formula:
Figure BDA0001423708460000121
comparative example 3 preparation of comparative catalyst
Preparing the macroporous microspheres without adding nano materials: in a 500ml three-necked flask, 47.0 g of styrene, 2.3 g of divinylbenzene, 30 g of polystyrene and 1.6 g of benzoyl peroxide initiator were charged, and 260 ml of a deionized water solution in which 2.0 g of gelatin had been dissolved was added. The stirring speed was adjusted and the mixture was stirred for 2 hours. Stirring and reacting for 2.0 hours at 60 ℃, then gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 8 hours. After the reaction is finished, pouring out the upper liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the macroporous microspheres DZ-3 with the particle size of 0.35-0.60 mm.
Macroporous microsphere chloromethylation: adding 40 g of macroporous microspheres DZ-3 and 200ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 3 hours, starting stirring, adding 15 g of zinc chloride as a catalyst, heating to 50 ℃ for reaction for 12 hours, cooling to room temperature after chloromethylation is finished, filtering out a chlorination mother solution, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the macroporous chlorine microspheres DZ-3.
30 g of macroporous chlorine ball DZ-3 (the chlorine content is 3.4mmol Cl/g), imidazole (102.0mmol) and 200ml of acetonitrile are added into a 500ml three-neck flask, the mixture reacts for 24 hours at 80 ℃, the mixture is cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain the imidazole microsphere DZ-3.
30 g of imidazole microsphere DZ-3 (the imidazole group content is 3.0mmol/g), 9.4 g of octachloromethylsilsesquioxane and 300ml of tetrahydrofuran are added into a 500ml three-neck flask, and after the reaction is finished, the mixture is filtered and washed by tetrahydrofuran and deionized water in sequence to obtain the imidazole/POSS microsphere DZ-3, wherein the temperature of the mixture is 24 hours at 100 ℃.
30 g of imidazole/POSS microspheres DZ-3 and 500ml of NaHCO with the concentration of 0.1mol/L are added into a 1000ml three-neck flask3Stirring the deionized water solution at room temperature to perform ion exchange reaction for 24 hours; then washing the solution by deionized water until the pH value of washing liquor is 7, and drying the solution in vacuum to obtain the ion exchange resin catalyst which is marked as Cat-DZ-1 and has the following structural formula:
Figure BDA0001423708460000131
[ example 7 ] catalytic application
The ion exchange resin catalyst prepared [ example 1 ] was used for the catalytic hydration reaction of water with alkylene oxide: the prepared catalyst Cat-A1 was charged into a fixed bed reactor, and its long-term service performance was examined. The conditions were as follows: the protective gas is high-purity nitrogen, the reaction temperature is 100 ℃, the pressure is 1.2MPa, and the molar ratio of water to ethylene oxide is 8: 1, the liquid space velocity is 3.0h-1Samples were taken every 4 hours for conversion and selectivity determinations. Ethylene oxide conversion C in a 2500 hour life testEOKeeping the selectivity S of the ethylene glycol above 99.2 percentECThe concentration was maintained at 98.0%.
[ examples 8 to 14 ] catalytic application
The resin catalyst used, and the temperature and pressure of the reaction were varied, and the remaining reaction conditions were the same as [ example 7 ] except that the test life of 2500 th test of catalytic hydration reaction of ethylene oxide and water was carried out, and the reaction results obtained are shown in Table 1.
TABLE 1
Figure BDA0001423708460000141
Comparative examples 4 to 6 catalytic applications
The ion exchange resin catalysts prepared in comparative examples 1 to 3 were used for catalytic hydration reaction of water and alkylene oxide. The prepared catalyst is loaded into a fixed bed reactor, and the long-term service performance of the catalyst is inspected. The conditions were as follows: the protective gas is high-purity nitrogen, the reaction temperature is 100 ℃, the pressure is 1.2MPa, and the molar ratio of water to ethylene oxide is 8: 1, the liquid space velocity is 3.0h-1Samples were taken every 4 hours for conversion and selectivity determinations. The results of the sampling analysis data are shown in Table 2.
TABLE 2
Figure BDA0001423708460000142
Wherein:
initial ethylene oxide conversion rate C when catalyst Cat-DZ-1 catalyzes ethylene oxide hydration reactionEO95.9%, selectivity S for ethylene glycolECThe content was 97.2%. After 100 hours, the system was clogged due to swelling of the resin, and the reaction was stopped.
Catalyst Cat-DZ-2 catalyzes the initial ethylene oxide conversion rate C during the hydration reaction of ethylene oxideEO98.9%, selectivity S for ethylene glycolECThe content was 97.7%. After 240 hours, the ethylene oxide conversion CEOThe reduction is obvious and is 91.6 percent, and the selectivity S of the ethylene glycol isECThe content was 95.8%.
Catalyst Cat-DZ-3 catalyzes the initial ethylene oxide conversion rate C during the hydration reaction of ethylene oxideEO97.9%, selectivity S for ethylene glycolECThe content was 97.4%. After 240 hours, the ethylene oxide conversion CEOReduced to 94.5 percent, and selectivity S of ethylene glycolECThe content was 95.5%.

Claims (8)

1. A method for preparing ethylene glycol by catalyzing and hydrating alkylene oxide comprises the steps of contacting alkylene oxide and water with an ion exchange resin catalyst under hydration reaction conditions; the ion exchange resin catalyst has the following structural general formula:
Figure FDA0002965007550000011
wherein the content of the first and second substances,
Figure FDA0002965007550000012
is a macroporous nano composite resin matrix;
M-is an anion selected from bicarbonate ions;
POSS is a chlorinated cage-type silsesquioxane unit, wherein the general formula of the cage-type silsesquioxane unit is (-SiO)1.5)m(ii) a m is 6, 8, 10 or 12;
Figure FDA0002965007550000013
is an imidazolium cationic unit;
r is a connecting group between the POSS unit and the imidazole cation unit, and R is alkylene or arylene;
the macroporous nano composite resin matrix is a nano macroporous copolymer obtained by in-situ copolymerization of a styrene monomer, a comonomer, a nano material and a pore-foaming agent; the nano material is selected from at least one of single-layer graphene, multi-layer graphene, graphene oxide and graphite alkyne; the comonomer is divinylbenzene; wherein the styrene monomer is 85-95 parts, the comonomer is 2-5 parts, the nano material is 0.1-3 parts, and the pore-forming agent is 10-100 parts.
2. The method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 1, wherein the content of POSS units in the ion exchange resin catalyst is 5-15 wt%.
3. The process for preparing ethylene glycol by catalytic hydration of alkylene oxide according to claim 1, wherein the alkylene group is selected from methylene, ethylene or propylene; the arylene group is selected from phenylene, naphthylene or phenylmethyl.
4. The method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 1, wherein the styrenic monomer is at least one selected from styrene, alpha-methylstyrene or 4-butylstyrene;
the pore-foaming agent is selected from at least one of aliphatic hydrocarbon, polystyrene, gasoline, poly (propylene glycol), poly (ethylene glycol), polydimethylsiloxane, fatty acid or paraffin.
5. The method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 4, wherein the styrenic monomer is selected from styrene; the pore-foaming agent is selected from polystyrene.
6. The method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 1, wherein the nano-material is selected from multi-layer graphene.
7. The method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 1, wherein the hydration reaction conditions comprise: the reaction temperature is 60-180 ℃, the reaction pressure is 0.1-10.0 MPa, and the liquid airspeed is 0.5-5 h-1The molar ratio of water to alkylene oxide is (1-25): 1.
8. the method for preparing ethylene glycol through catalytic hydration of alkylene oxide according to claim 1, wherein the alkylene oxide has the following general formula:
Figure FDA0002965007550000021
wherein R is1、R2、R3、R4Is a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms.
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