CN112239393B - Nano composite ion exchange resin catalyst and application thereof - Google Patents
Nano composite ion exchange resin catalyst and application thereof Download PDFInfo
- Publication number
- CN112239393B CN112239393B CN201910643209.2A CN201910643209A CN112239393B CN 112239393 B CN112239393 B CN 112239393B CN 201910643209 A CN201910643209 A CN 201910643209A CN 112239393 B CN112239393 B CN 112239393B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- exchange resin
- ion
- nanocomposite
- hydration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a catalytic hydration reaction of alkylene oxide and a nano composite ion exchange resin catalyst thereof. The preparation process of the nano composite ion exchange resin catalyst comprises the copolymerization of nano materials, monomers and cross-linking agents, the functionalization reaction of the copolymer and the ion exchange reaction. The nano composite ion exchange resin catalyst has the following structural general formula: P-N + R 1 R 2 R 3 M ‑ Wherein P is a nanocomposite resin matrix; r is R 1 、R 2 、R 3 Are all aliphatic or aromatic radicals C x H y X is any integer from 1 to 10, and y is any integer from 3 to 21; m is M ‑ Is an anion selected from bicarbonate ion, hydroxide ion, bisulfide ion, carboxylate ion, citrate ion, heteropolyacid ion, triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate; the catalyst can be applied to organic reactions such as catalytic hydration of alkylene oxide.
Description
Technical Field
The invention relates to a nano composite ion exchange resin catalyst and application thereof.
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 stronger solvent stability. The ion exchange resin matrix is prepared by copolymerizing styrene and divinylbenzene, and the anion exchange resin is prepared by chloromethylation and amination reaction.
The application of ion exchange resin in the aspect of catalytic hydration is studied by Shell, dow, SD company at the end of the 20 th century, lemanski et al, which takes strong base ion exchange resin as a main catalyst for catalyzing the hydration of ethylene oxide and takes acid ion exchange resin as an additive, and the water ratio is found to be 5.5 at the temperature of 100 ℃ and the pressure of 1.0 MPa: 1 for 6 hours, the conversion of ethylene oxide as a starting material was 100%, and the selectivity of ethylene glycol was up to 88.3% (M.F.Lemanski, V.Kruchten, R.Kunin, US patent6,156,942 (2000)). However, the strong alkaline ion exchange resin applied to catalytic hydration is not high-temperature resistant and has poor thermal stability, so that the long-term service performance of the resin is reduced, and the industrialized prospect is not optimistic. Shell developed a quaternary ammonium type anion exchange resin and used it for catalytic hydration of ethylene oxide, the conversion of ethylene oxide is nearly 100%, the selectivity of ethylene glycol can reach 95%, but even at lower temperatures (< 95 ℃), the catalyst swelling is still severe.
In the reaction of catalyzing the hydration of the alkylene oxide, the reaction temperature is basically between 80 and 110 ℃, the heat resistance of the anion exchange resin is poor, and the catalyst is unstable at the temperature and can be degraded gradually, so that the catalytic activity is reduced. In the degradation process, the hydrocarbon radical is fallen to become weak base radical, so that the exchange equivalent and catalytic activity of the ion exchange resin are reduced simultaneously. At the same time, the reaction of base stripping occurs. The ion exchange resin is modified to a certain extent structurally, so that the heat resistance of the resin can be improved.
Chen Qun A styrene type strong base anion exchange resin with benzene ring nitro substituted is researched, and excellent heat stability and ethylene oxide hydration catalysis performance are shown. The target ion exchange resin is obtained by directly nitrifying and transforming a styrene type strong-alkaline anion exchange resin serving as a raw material. At a temperature of 75 ℃, a pressure of 1.0MPa and a space velocity of 1.0 hour -1 Under the condition of water ratio of 6:1, the conversion rate of the ethylene oxide is improved to 99.9% from 89.7% by using the ion exchange resin with the nitro group as a catalyst, the selectivity of the ethylene glycol is improved to 95.6% from 94.2%, and the activity of the resin is greatly improved. Mitsubishi corporation develops a class of anion exchange resins with higher heat resistance through suspension polymerization of functionalized styrene monomers and cross-linking agents, and the resins are connected between benzene rings and quaternary ammonium nitrogen atomsWith hydrocarbon or alkoxymethylene chains (friend man, jiubao Tian Yujiu, polymer processing (day) [ J)]1999,48 (2): 57-63). The quaternary ammonium groups in the resin are stable when heated, and can be used for a long time at 90 ℃. However, the synthetic route of the monomer in the route is long, the operation condition is harsh, the yield is low, the separation and purification of the functional monomer are difficult, the purity is not high, and the performance of the final polymer is affected.
The ion exchange resin material has the non-negligible defect, so that how to improve the performance of the resin and the service life of the catalyst can become a research hot spot.
Disclosure of Invention
The invention provides a method for preparing glycol by hydration of alkylene oxide.
A process for the hydration of alkylene oxides to glycol comprising the step of contacting alkylene oxides and water with a nanocomposite ion exchange resin catalyst under hydration reaction conditions, said nanocomposite ion exchange resin having the general structural formula:
P-N + R 1 R 2 R 3 M -
wherein P is a nano composite resin matrix, R 1 、R 2 、R 3 Are all substituent groups, M - Is an anion; the nanocomposite resin matrix P contains-CH (Ph) -CH 2 Structural fragments and POSS structural fragments, POSS being a cage silsesquioxane of the general formula (-SiO) 1.5 ) m M is 6, 8, 10 or 12; cage silsesquioxane (Polyhedral oligomeric silsesquioxanes, abbreviated POSS).
In the above technical scheme, the nanocomposite resin matrix P contains-CH (POSS) -CH 2 -a structural fragment.
In the technical scheme, the nanocomposite ion exchange resin has-CH (Ph-CH) 2 -N + R 1 R 2 R 3 )-CH 2 -a structural fragment.
In the technical scheme, the mass content of the pos in the nano composite resin matrix P is 0.1-10%.
In the above technical solution, R is 1 、R 2 、R 3 Are all alkyl orAn aryl group; preferably said R 1 、R 2 、R 3 Are all C 1-10 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, more preferably C 3-4 Alkyl, more preferably straight chain alkyl C 4 H 9 。
In the above technical solution, the M - Selected from bicarbonate ion, hydroxide ion, bisulfide ion, carboxylate ion, citrate ion, heteropolyacid ion, triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate; preferably, the hydrogen carbonate ion, the hydroxide ion, the hydrogen sulfite ion, the carboxylate ion, and the citrate ion are used, and more preferably, the hydrogen carbonate ion is used.
In the above technical scheme, the nanocomposite resin matrix P is a nanocomposite copolymer obtained by in-situ copolymerization of a styrene monomer, a crosslinking agent and a nanomaterial. Preferably, the nanocomposite resin matrix P is a nanocomposite copolymer obtained by in-situ copolymerization of 85-95 parts of styrene monomer, 2-5 parts of cross-linking agent and 0.1-10 parts of nanomaterial.
In the technical scheme, the nano material is at least one selected from vinyl-containing silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane and epoxy-containing polysilsesquioxane; more preferably, the crosslinking agent is at least one selected from the group consisting of ethylene glycol dimethacrylate, divinylbenzene-based methane and divinylbenzene, preferably divinylbenzene.
In the above technical scheme, the styrene monomer is at least one selected from styrene, alpha-methyl styrene or 4-butyl styrene; styrene is preferred.
In the above technical solution, the vinyl-containing silsesquioxane is selected from octavinyl silsesquioxanes.
In the technical scheme, the alkylene oxide has the following general formula:
wherein G is 1 、G 2 、G 3 、G 4 Is a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. Such as methyl, ethyl, propyl, butyl.
In the above technical solution, the hydration conditions include: the reaction temperature is 40-180 ℃, the reaction pressure is 0.1-10.0 megapascals, and the liquid airspeed is 0.1-6.0 h -1 The molar ratio of water to alkylene oxide is (1-150): 1.
the invention also provides a nano composite ion exchange resin catalyst, which has the following structural general formula:
P-N + R 1 R 2 R 3 M -
wherein P is a nano composite resin matrix; r is R 1 、R 2 、R 3 Are all substituent groups, M - Is an anion; the nanocomposite resin matrix P has a matrix containing-CH (Ph) -CH 2 -structural fragments and POSS structural fragments.
In the above technical scheme, the nanocomposite resin matrix P contains-CH (POSS) -CH 2 -a structural fragment.
In the technical scheme, 1111cm of the infrared spectrum of the nano composite resin matrix P -1 The structure has characteristic absorption peaks, which are attributed to the telescopic vibration absorption peaks of Si-O-Si frameworks in the silsesquioxane.
In the technical scheme, the mass content of the pos in the nano composite resin matrix P is 0.1-10%.
In the above technical solution, R is 1 、R 2 、R 3 Are all alkyl or aryl; preferably said R 1 、R 2 、R 3 Are all C 1-10 Alkyl, more preferably C 3-4 Alkyl, more preferably straight chain alkyl C 4 H 9 。；
In the above technical solution, the M - Selected from the group consisting of bicarbonate ion, hydroxide ion, bisulfide ion, carboxylate ion, citrate ion, heteropolyacid ion, triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroboric acidRoot or hexafluorophosphate;
in the above technical scheme, the nanocomposite resin matrix P is a nanocomposite copolymer obtained by in-situ copolymerization of a styrene monomer, a crosslinking agent and a nanomaterial.
In the technical scheme, the nano material is at least one selected from vinyl-containing silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane and epoxy-containing polysilsesquioxane; more preferably, the crosslinking agent is at least one selected from the group consisting of ethylene glycol dimethacrylate, divinylbenzene-based methane and divinylbenzene, preferably divinylbenzene.
In the above technical scheme, the styrene monomer is at least one selected from styrene, alpha-methyl styrene or 4-butyl styrene, preferably styrene.
In the above technical solution, the vinyl-containing silsesquioxane is selected from octavinyl silsesquioxanes.
The invention also provides a preparation method of the nanocomposite ion exchange resin catalyst, which comprises the following steps: styrene monomer, cross-linking agent and vinyl-containing silsesquioxane are subjected to in-situ polymerization to obtain a resin matrix, and chloromethylation reaction, quaternization and ion exchange reaction are carried out to prepare the nano composite ion exchange resin catalyst.
In the technical scheme, the nano material is at least one selected from vinyl-containing silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane and epoxy-containing polysilsesquioxane; more preferably, the crosslinking agent is at least one selected from the group consisting of ethylene glycol dimethacrylate, divinylbenzene-based methane and divinylbenzene, preferably divinylbenzene.
In the above technical scheme, the styrene monomer is at least one selected from styrene, alpha-methyl styrene or 4-butyl styrene, preferably styrene.
In the above technical solution, the vinyl-containing silsesquioxane is selected from octavinyl silsesquioxanes. In the technical scheme, the specific steps are that a) an auxiliary agent is prepared into an aqueous solution A with the weight percentage concentration of 0.5-3%, and a styrene monomer, a cross-linking agent, a nano material and an initiator are prepared into a solution B; wherein the auxiliary agent is at least one selected from polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite or calcium carbonate; the styrene monomer is at least one selected from styrene, alpha-methyl styrene or 4-butyl styrene; the cross-linking agent is at least one selected from ethylene glycol dimethacrylate, dipropenyl benzene, divinyl phenyl methane or divinyl benzene; the nano material is at least one selected from vinyl-containing silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane and epoxy-containing polysilsesquioxane; the initiator is at least one selected from benzoyl peroxide, azodiisobutyronitrile, azodiisoheptonitrile, lauroyl peroxide and cumene hydroperoxide; the styrene monomer is used in an amount of 85-95 parts by weight, the cross-linking agent is used in an amount of 2-5 parts by weight, the nano material is used in an amount of 0.1-10 parts by weight, and the initiator is used in an amount of 0.1-5 parts by weight; the dosage of the auxiliary agent is 150-400% of the dosage of the monomer;
b) Mixing the solution B and the solution A, stirring for 1-3 hours at normal temperature, and uniformly mixing. Then, the mixture is polymerized for 0.5 to 5 hours at the temperature of 60 to 75 ℃, gradually heated to 70 to 90 ℃ for reaction for 5 to 15 hours, and then heated to 90 to 100 ℃ for reaction for 5 to 15 hours; after the reaction is finished, extracting, washing, filtering, drying and sieving to obtain the composite microsphere with the particle size range of 0.35-0.60 mm;
c) Adding chloromethylation reagent which is 200-500% of the weight of the composite microsphere and zinc chloride catalyst which is 20-70% of the weight of the composite microsphere into the composite microsphere, reacting for 8-30 hours at 30-60 ℃, filtering and washing to obtain the composite chlorine sphere; the chloromethylation reagent is at least one of chloromethyl ether, chloromethyl ether or 1, 4-dichloro methoxybutane;
d) The mixture of the composite chlorine ball, tributylamine and N, N-dimethylformamide is reacted for 10 to 48 hours at the temperature of 60 to 90 ℃, and the composite quaternary ammonium microsphere is obtained after the reaction is finished and filtered and washed; in the mixture, the mol ratio of the composite chlorine ball to the tributylamine to the N, N-dimethylformamide is 1 (1-5) (10-50);
f) The compound quaternary ammonium microsphere is washed by a salt solution, wherein the molar ratio of the compound quaternary ammonium microsphere to the salt solution is (1:1) - (1:10); the concentration of the salt solution is 0.1-1 mol/L; washing with deionized water to ph=7 after washing is completed, to obtain the ion exchange resin. The salt solution is at least one selected from bicarbonate, hydroxide, sulfite, carboxylate with 1-10 carbon atoms and citrate salt solution.
The nano composite ion exchange resin catalyst has the following structural general formula: P-N + R 1 R 2 R 3 M - The nanocomposite resin matrix P comprises-CH (Ph) -CH 2 -structural fragments and POSS structural fragments.
The nano composite ion exchange resin catalyst is used in the hydration reaction of alkylene oxide, has high catalyst activity and high alkali resistance, has high ethylene oxide conversion rate under the condition of low water ratio in a 2000-hour life test, is easy to separate after the glycol selectivity reaction, and can be continuously used for multiple times.
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 is specifically noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be arbitrarily combined with each other, and the resulting solutions are part of the original disclosure of the present specification, while also falling within the scope of the present invention.
Drawings
FIG. 1 is an infrared spectrum of a substrate.
Detailed Description
[ example 1 ] ion exchange resin catalyst preparation
65.0 g of styrene, 1.0 g of divinylbenzene, 3.0 g of octavinylsilsesquioxane and 1.0 g of benzoyl peroxide were put into a 500ml three-necked flask, and the mixture was stirred for 0.5 hours by starting a stirrer; 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol was added and stirred for 2 hours. Then gradually heating to 75 ℃, reacting for 5 hours, heating to 90 ℃, reacting for 10 hours, and finally heating to 100 ℃ and reacting for 10 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite microspheres A1 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: 50 g of composite microsphere A1 and 200ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand at room temperature for 6 hours, 30 g of zinc chloride is added as a catalyst, stirring is started, the temperature is raised to 50 ℃ for reaction for 30 hours, the mixture is cooled to the room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered, repeatedly washed by methanol, and the mixture is dried at 100 ℃ for 8 hours, so that the composite microsphere A1 is obtained.
50 g of composite chlorine ball A1 (chlorine content is 4.5mmol Cl/g), tributylamine (225.0 mmol) and 300ml of N, N-dimethylformamide are added into a 500ml three-port bottle, reacted for 16 hours at 80 ℃, cooled to room temperature, filtered, washed with ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain composite quaternary ammonium microsphere A1.
In a 1000ml three-neck flask, 40 g of composite quaternary ammonium microsphere A1 and 400ml of NaHCO with the concentration of 1.0mol/L are added 3 Stirring deionized water solution of (2) at room temperature for ion exchange reaction for 12 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst, which is marked as Cat-A1 and has the following structural formula:
example 2 preparation of ion exchange resin catalyst
50.0 g of styrene, 1.6 g of divinylbenzene, 4.5 g of octavinylsilsesquioxane and 1.0 g of benzoyl peroxide were put into a 500ml three-necked flask, and the mixture was stirred for 0.5 hours by starting a stirrer; 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol was added and stirred for 2 hours. Then gradually heating to 60 ℃, reacting for 5 hours, heating to 90 ℃, reacting for 12 hours, and finally heating to 100 ℃ and reacting for 12 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting composite microspheres A2 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: 50 g of composite microsphere A2 and 200ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand at room temperature for 6 hours, 30 g of zinc chloride is added as a catalyst, stirring is started, the temperature is raised to 50 ℃ for reaction for 30 hours, the mixture is cooled to the room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered, repeatedly washed by methanol, and the mixture is dried at 100 ℃ for 8 hours, so that composite chlorine microsphere A2 is obtained.
50 g of composite chlorine ball A2 (chlorine content is 4.0mmol Cl/g), tributylamine (200.0 mmol) and 300ml of N, N-dimethylformamide are added into a 500ml three-port bottle, reacted for 16 hours at 80 ℃, cooled to room temperature, filtered, washed with ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain composite quaternary ammonium microsphere A2.
In a 1000ml three-neck flask, 40 g of composite quaternary ammonium microsphere A2 and 400ml of NaHCO with the concentration of 1.0mol/L are added 3 Stirring deionized water solution of (2) at room temperature for ion exchange reaction for 12 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst, which is marked as Cat-A2 and has the following structural formula:
example 3 preparation of ion exchange resin catalyst
Into a 500ml three-neck flask, 50.0 g of styrene, 2.6 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator were added, then 0.6 g of octavinylsilsesquioxane was added, 260 ml of deionized water solution in which 2.0 g of gelatin had been dissolved was added, the temperature was gradually raised, and the reaction was stirred at 60℃for 2.0 hours. Simultaneously gradually heating to 80 ℃ and reacting for 5 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 6 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting composite microspheres A3 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: in a 500ml three-neck flask, 40 g of composite microsphere A3 and 250ml of chloromethyl ether are added, standing is carried out at room temperature for 3 hours, stirring is started, 10 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 10 hours, cooling to the room temperature is carried out after chloromethylation is finished, the chloridized mother liquor is filtered, repeatedly washed by methanol, and dried at 100 ℃ for 8 hours, thus obtaining the composite chlorine microsphere A3.
30 g of composite chlorine ball A3 (chlorine content is 3.5mmol Cl/g), tributylamine (105.0 mmol) and 200ml of N, N-dimethylformamide are added into a 500ml three-port bottle, reacted for 24 hours at 60 ℃, cooled to room temperature, filtered, washed with ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain composite quaternary ammonium microsphere A3.
In a 1000ml three-neck flask, 30 g of composite quaternary ammonium microsphere A3 and 500ml of NaHCO with concentration of 0.1mol/L are added 3 Stirring the deionized water solution at room temperature for ion exchange reaction for 24 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst, which is marked as Cat-A3 and has the following structural formula:
example 4 preparation of ion exchange resin catalyst
Into a 500ml three-neck flask, 50.0 g of styrene, 2.6 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator were added, then 0.6 g of octavinylsilsesquioxane was added, 260 ml of deionized water solution in which 2.0 g of gelatin had been dissolved was added, the temperature was gradually raised, and the reaction was stirred at 60℃for 2.0 hours. Simultaneously gradually heating to 80 ℃ and reacting for 5 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 6 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting composite microspheres A4 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: in a 500ml three-neck flask, 40 g of composite microsphere A4 and 250ml of chloromethyl ether are added, standing is carried out at room temperature for 3 hours, stirring is started, 10 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 10 hours, cooling to the room temperature is carried out after chloromethylation is finished, the chloridized mother liquor is filtered, repeatedly washed by methanol, and dried at 100 ℃ for 8 hours, thus obtaining the composite chlorine microsphere A4.
30 g of composite chlorine ball A4 (chlorine content is 3.5mmol Cl/g), trimethylamine (105.0 mmol) and 200ml of N, N-dimethylformamide are added into a 500ml three-port bottle to react for 24 hours at 60 ℃, cooled to room temperature, filtered, washed with ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried for 12 hours at 60 ℃ in vacuum to obtain composite quaternary ammonium microsphere A4.
In a 1000ml three-neck flask, 30 g of composite quaternary ammonium microsphere A4 and 500ml of NaHCO with concentration of 0.1mol/L are added 3 Stirring the deionized water solution at room temperature for ion exchange reaction for 24 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst, which is marked as Cat-A4 and has the following structural formula:
comparative example 1 preparation of ion exchange resin catalyst (without nanomaterial)
65.0 g of styrene, 1.0 g of divinylbenzene and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and a stirrer is started to stir for 0.5 hours; 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol was added and stirred for 2 hours. Then gradually heating to 75 ℃, reacting for 5 hours, heating to 90 ℃, reacting for 10 hours, and finally heating to 100 ℃ and reacting for 10 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting microspheres B1 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: 50 g of microsphere B1 and 200ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand at room temperature for 6 hours, 30 g of zinc chloride is added as a catalyst, stirring is started, the temperature is raised to 50 ℃ for reaction for 30 hours, the mixture is cooled to the room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered, repeatedly washed by methanol, and the mixture is dried at 100 ℃ for 8 hours, so that the chlorine microsphere B1 is obtained.
50 g of chlorine ball B1 (chlorine content: 4.5mmol Cl/g), tributylamine (225.0 mmol) and 300ml of N, N-dimethylformamide were added into a 500ml three-necked flask, reacted at 80℃for 16 hours, cooled to room temperature, filtered, washed successively with ethyl acetate, 0.1mol/L HCl, deionized water and methanol, and then dried at 60℃under vacuum for 12 hours to obtain quaternary ammonium microsphere B1.
In a 1000ml three-necked flask, 40 g of quaternary ammonium microsphere B1 and 400ml of NaHCO with the concentration of 1.0mol/L are added 3 Stirring deionized water solution of (2) at room temperature for ion exchange reaction for 12 hours; subsequently washed with deionized water until the wash liquor ph=7, and dried in vacuo to give an ion exchange resin catalyst, designated Cat-B1, having the following structural formula:
[ comparative example 2 ] ion exchange resin catalyst preparation (without nanomaterial)
50.0 g of styrene, 1.6 g of divinylbenzene and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, and a stirrer is started to stir for 0.5 hours; 200ml of a mixed solution of deionized water and 4 g of polyvinyl alcohol was added and stirred for 2 hours. Then gradually heating to 60 ℃, reacting for 5 hours, heating to 90 ℃, reacting for 12 hours, and finally heating to 100 ℃ and reacting for 12 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting microspheres B2 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: 50 g of microsphere B2 and 200ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand at room temperature for 6 hours, 30 g of zinc chloride is added as a catalyst, stirring is started, the temperature is raised to 50 ℃ for reaction for 30 hours, the mixture is cooled to the room temperature after chloromethylation is finished, the chloridized mother liquor is filtered, repeatedly washed by methanol, and the mixture is dried at 100 ℃ for 8 hours, so that the chloridized sphere B2 is obtained.
50 g of chlorine ball B2 (chlorine content: 4.0mmol Cl/g), tributylamine (200.0 mmol) and 300ml of N, N-dimethylformamide were added into a 500ml three-port bottle, reacted at 80 ℃ for 16 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1mol/L HCl, deionized water and methanol in sequence, and then dried at 60 ℃ in vacuum for 12 hours to obtain quaternary ammonium microsphere B2.
In a 1000ml three-necked flask, 40 g of quaternary ammonium microsphere B2 and 400ml of NaHCO with the concentration of 1.0mol/L are added 3 Stirring deionized water solution of (2) at room temperature for ion exchange reaction for 12 hours; subsequently washed with deionized water until the wash liquor ph=7, and dried in vacuo to give an ion exchange resin catalyst, designated Cat-B2, having the following structural formula:
[ comparative example 3 ] ion exchange resin catalyst preparation (without nanomaterial)
Into a 500ml three-neck flask, 50.0 g of styrene, 2.6 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator were added, then 0.6 g of octavinylsilsesquioxane was added, 260 ml of deionized water solution in which 2.0 g of gelatin had been dissolved was added, the temperature was gradually raised, and the reaction was stirred at 60℃for 2.0 hours. Simultaneously gradually heating to 80 ℃ and reacting for 5 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 6 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting microspheres B3 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: in a 500ml three-neck flask, 40 g of microsphere B3 and 250ml of chloromethyl ether are added, standing is carried out at room temperature for 3 hours, stirring is started, 10 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 10 hours, cooling to room temperature is carried out after chloromethylation is finished, the chloridized mother liquor is filtered, repeatedly washed by methanol, and dried at 100 ℃ for 8 hours, thus obtaining the chloridized microsphere B3.
30 g of chlorine ball B3 (chlorine content: 3.5mmol Cl/g), tributylamine (105.0 mmol) and 200ml of N, N-dimethylformamide were put into a 500ml three-necked flask, reacted at 60℃for 24 hours, cooled to room temperature, filtered, washed successively with ethyl acetate, 0.1mol/L HCl, deionized water and methanol, and then dried at 60℃under vacuum for 12 hours to obtain quaternary ammonium microspheres B3.
In a 1000ml three-necked flask, 30 g of quaternary ammonium microsphere B3 and 500ml of NaHCO with the concentration of 0.1mol/L are added 3 Stirring the deionized water solution at room temperature for ion exchange reaction for 24 hours; subsequently washed with deionized water until the wash liquor ph=7, and dried in vacuo to give an ion exchange resin catalyst, designated Cat-B3, having the following structural formula:
into a 500ml three-necked flask, 50.0 g of styrene, 2.6 g of divinylbenzene and 1.6 g of benzoyl peroxide initiator were charged, and a 260 ml deionized water solution in which 2.0 g of gelatin had been dissolved was added, and the temperature was gradually raised, and the reaction was stirred at 60℃for 2.0 hours. Simultaneously gradually heating to 80 ℃ and reacting for 5 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 6 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting microspheres B4 with the particle size within the range of 0.35-0.60 mm.
Chloromethylation: in a 500ml three-neck flask, 40 g of microsphere B4 and 250ml of chloromethyl ether are added, standing is carried out at room temperature for 3 hours, stirring is started, 10 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 10 hours, cooling to room temperature is carried out after chloromethylation is finished, the chlorinated mother liquor is filtered, repeatedly washed by methanol, and dried at 100 ℃ for 8 hours, thus obtaining the chlorine microsphere B4.
30 g of chlorine ball B4 (chlorine content: 3.5mmol Cl/g), trimethylamine (105.0 mmol) and 200ml of N, N-dimethylformamide were put into a 500ml three-necked flask, reacted at 60℃for 24 hours, cooled to room temperature, filtered, washed successively with ethyl acetate, 0.1mol/L HCl, deionized water and methanol, and then dried at 60℃under vacuum for 12 hours to obtain quaternary ammonium microspheres B4.
In a 1000ml three-necked flask, 30 g of quaternary ammonium microsphere B4 and 500ml of NaHCO with the concentration of 0.1mol/L are added 3 Stirring the deionized water solution at room temperature for ion exchange reaction for 24 hours; subsequently washed with deionized water until the wash liquor ph=7, and dried in vacuo to give an ion exchange resin catalyst, designated Cat-B4, having the following structural formula:
example 5 catalytic application
The ion exchange resin catalyst prepared [ example 1 ] was used for the catalytic hydration of deionized water with alkylene oxides: the catalyst Cat-A1 prepared was charged in a fixed bed reactor, and its catalytic performance was examined. The conditions were as follows: the protective gas is high-purity nitrogen, the pressure is 1.2MPa, and the molar ratio of water to ethylene oxide is 10:1, liquid space velocity of 3.0h -1 Samples were taken for conversion and selectivity determinations. Ethylene oxide conversion C at 90 degrees EO Maintain the selectivity S of glycol above 99.2% EC The content was kept at 97.5%.
Examples 6-8 catalytic applications
The temperature of the hydration reaction was changed, and the rest of the reaction conditions were the same as those of [ example 5 ], and the catalytic hydration reaction of ethylene oxide and deionized water was performed, and the obtained reaction results are shown in table 1.
TABLE 1
| Examples | Catalyst | Molar ratio of | Temperature/. Degree.C | Airspeed/h -1 | pressure/MPa | C EO ,％ | S EC ,％ |
| 6 | Cat-A1 | 10：1 | 80 | 3.0 | 1.2 | 81.1 | 97.9 |
| 7 | Cat-A1 | 10：1 | 75 | 3.0 | 1.2 | 76.5 | 98.3 |
| 8 | Cat-A1 | 10：1 | 70 | 3.0 | 1.2 | 68.7 | 98.4 |
Examples 9-15 catalytic applications
The ion exchange resin catalysts prepared [ examples 2-8 ] were used for the catalytic hydration of deionized water with alkylene oxides: the prepared catalyst was charged in a fixed bed reactor, and its catalytic performance was examined. The conditions were as follows: the protective gas is high-purity nitrogen, the pressure is 1.2MPa, and the molar ratio of water to ethylene oxide is 10:1, liquid space velocity of 3.0h -1 Samples were taken for conversion and selectivity determinations, and the reaction results obtained are shown in Table 2.
TABLE 2
| Examples | Catalyst | Molar ratio of | Temperature/. Degree.C | Airspeed/h-1 | pressure/MPa | CEO,％ | SEC,％ |
| 9 | Cat-A2 | 10：1 | 90 | 3.0 | 1.2 | 99.4 | 97.4 |
| 10 | Cat-A3 | 10：1 | 90 | 3.0 | 1.2 | 99.1 | 97.3 |
| 11 | Cat-A4 | 10：1 | 90 | 3.0 | 1.2 | 99.2 | 97.4 |
| 12 | Cat-B1 | 10：1 | 90 | 3.0 | 1.2 | 95.3 | 96.3 |
| 13 | Cat-B2 | 10：1 | 90 | 3.0 | 1.2 | 95.6 | 96.1 |
| 14 | Cat-B3 | 10：1 | 90 | 3.0 | 1.2 | 95.3 | 96.5 |
| 15 | Cat-B4 | 10：1 | 90 | 3.0 | 1.2 | 95.5 | 96.0 |
Wherein:
initial ethylene oxide conversion C when catalyst Cat-B1 catalyzes the hydration reaction of ethylene oxide EO 95.3% of ethylene glycol selectivity S EC 96.3%. After 200 hours, the system gradually increased in pressure due to swelling of the resin, and the reactor was blocked, stopping the reaction.
Initial ethylene oxide conversion C when catalyst Cat-B2 catalyzes the hydration reaction of ethylene oxide EO 95.6% of ethylene glycol selectivity S EC 96.1%. After 300 hours, the conversion of ethylene oxide C EO The drop is obvious and is 90.8 percent, and the selectivity S of glycol is high EC 94.1%. Simultaneously, the system gradually increases the pressure due to the swelling of the resin, the reactor is blocked, and the reaction is stopped.
Catalyst Cat-B3 catalyzes ethylene oxideInitial ethylene oxide conversion C during hydration reaction EO 95.3% of ethylene glycol selectivity S EC 96.5%. After 400 hours, the conversion of ethylene oxide C EO The drop is 89.8 percent, and the selectivity S of glycol is the same as that of the ethylene glycol EC 93.2%. Simultaneously, the system gradually increases the pressure due to the swelling of the resin, the reactor is blocked, and the reaction is stopped.
Initial ethylene oxide conversion C when catalyst Cat-B4 catalyzes the hydration reaction of ethylene oxide EO 95.5% of glycol selectivity S EC 96.0%. After 300 hours, the conversion of ethylene oxide C EO The selectivity S of glycol is reduced to 85.8 percent EC 95.2%. Simultaneously, the system gradually increases the pressure due to the swelling of the resin, the reactor is blocked, and the reaction is stopped.
Example 16 catalytic application
The ion exchange resin catalyst prepared [ example 3 ] was used for the catalytic hydration of deionized water with alkylene oxides: the prepared catalyst Cat-A3 was charged in a fixed bed reactor, and its long-term use performance was examined. The conditions were as follows: the protective gas is high-purity nitrogen, the reaction temperature is 90 ℃, the pressure is 1.2MPa, and the molar ratio of water to ethylene oxide is 10:1, liquid space velocity of 3.0h -1 The conversion and selectivity were measured by sampling every 4 hours. Ethylene oxide conversion C in the 2000 hour life test EO Maintain the selectivity S of glycol above 98.9% EC The content is kept above 97.0%.
Examples 17-19 catalytic applications
The molar ratio of the hydration reaction was changed, the rest of the reaction conditions were the same as those of [ example 5 ], and the catalytic hydration reaction of ethylene oxide and deionized water was performed, and the obtained reaction results are shown in Table 3.
TABLE 3 Table 3
| Examples | Catalyst | Molar ratio of | Temperature/. Degree.C | Airspeed/h-1 | pressure/MPa | CEO,％ | SEC,％ |
| 17 | Cat-A3 | 20：1 | 90 | 3.0 | 1.2 | 99.8 | 97.9 |
| 18 | Cat-A3 | 8：1 | 90 | 3.0 | 1.2 | 97.5 | 98.3 |
| 19 | Cat-A3 | 5：1 | 90 | 3.0 | 1.2 | 91.7 | 98.4 |
Claims (21)
1. A process for the hydration of alkylene oxides to glycol comprising the step of contacting alkylene oxides and water with a nanocomposite ion exchange resin catalyst under hydration reaction conditions, said nanocomposite ion exchange resin having the general structural formula:
P-N + R 1 R 2 R 3 M -
wherein P is a nano composite resin matrix, R 1 、R 2 、R 3 Are all substituent groups, R is 1 、R 2 、R 3 Are all alkyl or aryl, M - Is an anion; the nanocomposite resin matrix P contains-CH (Ph) -CH 2 -structural fragment and-CH (POSS) -CH 2 Structural fragment, POSS is cage silsesquioxane, of which the general formula is (-SiO) 1.5 ) m M is 6, 8, 10 or 12; the nanometer composite resin matrix P is a nanometer composite copolymer obtained by in-situ copolymerization of styrene monomers, a cross-linking agent and a nanometer material, wherein the nanometer material is at least one selected from vinyl silsesquioxane, hydrogen group-containing polysilsesquioxane, alkoxy polysilsesquioxane and epoxy group-containing polysilsesquioxane.
2. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein said nanocomposite ion exchange resin has-CH (Ph-CH) 2 -N + R 1 R 2 R 3 )-CH 2 -a structural fragment.
3. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein the mass content of pos in the nanocomposite resin matrix P is 0.1 to 10%.
4. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein,
the R is 1 、R 2 、R 3 Are all C 1-10 An alkyl group.
5. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein,
the R is 1 、R 2 、R 3 Are all C 3-4 An alkyl group.
6. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein,
the R is 1 、R 2 、R 3 All straight-chain alkyl radicals C 4 H 9 。
7. The method for producing glycol by hydration of alkylene oxide according to claim 1, wherein said M - Selected from bicarbonate ion, hydroxide ion, bisulfide ion, carboxylate ion, citrate ion, heteropolyacid ion, triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate.
8. The method for preparing glycol by hydration of alkylene oxide according to claim 1, wherein the nanocomposite resin matrix P is a nanocomposite copolymer obtained by in-situ copolymerization of 85 to 95 parts of styrene monomer, 2 to 5 parts of cross-linking agent and 0.1 to 10 parts of nanomaterial.
9. The method for producing glycol by hydration of an alkylene oxide according to claim 8, wherein said styrene-based monomer is at least one selected from styrene, α -methylstyrene and 4-butylstyrene.
10. The method for producing glycol by hydration of an alkylene oxide according to claim 8, wherein said crosslinking agent is at least one selected from the group consisting of ethylene glycol dimethacrylate, dipropenyl benzene, divinyl phenyl methane and divinyl benzene.
11. The method of claim 8 wherein the vinyl-containing silsesquioxane is selected from octavinyl silsesquioxanes.
12. A nanocomposite ion exchange resin catalyst having the following structural formula:
P-N + R 1 R 2 R 3 M-
wherein P is a nano composite resin matrix; r is R 1 、R 2 、R 3 Are all substituent groups, R is 1 、R 2 、R 3 Are all alkyl or aryl, M - Is an anion; the nanocomposite resin matrix P contains-CH (Ph) -CH 2 -structural fragment and-CH (POSS) -CH 2 -a structural fragment; POSS is cage-type silsesquioxane, and has a general formula (-SiO) 1.5 ) m M is 6, 8, 10 or 12; the nano composite resin matrix P is a nano composite copolymer obtained by in-situ copolymerization of styrene monomer, cross-linking agent and nano material; the nanomaterial is selected from at least one of vinyl-containing silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane and epoxy-containing polysilsesquioxane.
13. The nanocomposite ion exchange resin catalyst according to claim 12, wherein the mass content of pos in the nanocomposite resin matrix P is 0.1 to 10%.
14. The nanocomposite ion exchange resin catalyst of claim 12, wherein R 1 、R 2 、R 3 Are all C 1-10 An alkyl group.
15. According toThe nanocomposite ion exchange resin catalyst of claim 12, wherein R 1 、R 2 、R 3 Are all C 3-4 An alkyl group.
16. The nanocomposite ion exchange resin catalyst of claim 12, wherein R 1 、R 2 、R 3 All straight-chain alkyl radicals C 4 H 9 。
17. The nanocomposite ion exchange resin catalyst of claim 12, wherein M - Selected from bicarbonate ion, hydroxide ion, bisulfide ion, carboxylate ion, citrate ion, heteropolyacid ion, triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate.
18. The nanocomposite ion exchange resin catalyst of claim 12, wherein the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene, or 4-butylstyrene.
19. The nanocomposite ion exchange resin catalyst of claim 12, wherein the cross-linking agent is selected from at least one of ethylene glycol dimethacrylate, dipropenyl benzene, divinyl phenyl methane, or divinyl benzene.
20. The nanocomposite ion exchange resin catalyst according to claim 12, wherein the vinyl-containing silsesquioxane is selected from octavinylsilsesquioxanes.
21. A method of preparing the nanocomposite ion exchange resin catalyst of any one of claims 12-20, comprising the steps of: styrene monomer, cross-linking agent and vinyl-containing silsesquioxane are subjected to in-situ polymerization to obtain a resin matrix, and chloromethylation reaction, quaternization and ion exchange reaction are carried out to prepare the nano composite ion exchange resin catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643209.2A CN112239393B (en) | 2019-07-17 | 2019-07-17 | Nano composite ion exchange resin catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643209.2A CN112239393B (en) | 2019-07-17 | 2019-07-17 | Nano composite ion exchange resin catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112239393A CN112239393A (en) | 2021-01-19 |
| CN112239393B true CN112239393B (en) | 2023-06-06 |
Family
ID=74167014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910643209.2A Active CN112239393B (en) | 2019-07-17 | 2019-07-17 | Nano composite ion exchange resin catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112239393B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112206A (en) * | 1997-04-30 | 1999-01-19 | Mitsubishi Chem Corp | Production of alkylene glycols |
| CN109574807A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The method of epoxyalkane catalysis hydration preparing ethylene glycol |
| CN109569717A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ion exchange resin and purposes |
| CN109772451A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefin epoxidation process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8053609B2 (en) * | 2007-10-15 | 2011-11-08 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Solid catalyst useful for converting an alkylene oxide to an alkylene glycol |
-
2019
- 2019-07-17 CN CN201910643209.2A patent/CN112239393B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112206A (en) * | 1997-04-30 | 1999-01-19 | Mitsubishi Chem Corp | Production of alkylene glycols |
| CN109574807A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The method of epoxyalkane catalysis hydration preparing ethylene glycol |
| CN109569717A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ion exchange resin and purposes |
| CN109772451A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefin epoxidation process |
Non-Patent Citations (2)
| Title |
|---|
| The preparation and catalytic performance of grapheme-reinforced ion-exchange resins;Yanan Li等;《RSC Adv.》;20141208;第5卷;第2550页摘要，第2552页流程1 * |
| Water soluble octa-functionalized POSS: all-click chemistry synthesis and efficient host–guest encapsulation;Jin Han等;《ChemComm》;20140519;第50卷;8712-8714 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112239393A (en) | 2021-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109574807B (en) | Method for preparing ethylene glycol by catalytic hydration of alkylene oxide | |
| CN101773852B (en) | Supported ionic liquid catalyst and preparation method and application thereof | |
| CN105503811B (en) | The method for preparing ethylene carbonate | |
| CN109569717B (en) | Ion exchange resin and use | |
| CN112619705B (en) | Alkylene oxide addition reaction catalyst and application thereof | |
| CN109575295B (en) | Method for catalytic hydration of alkylene oxides | |
| CN112239393B (en) | Nano composite ion exchange resin catalyst and application thereof | |
| CN109574793B (en) | Method for preparing glycol by hydrating alkylene oxide | |
| CN109574794B (en) | Method for producing ethylene glycol by catalytic hydration of alkylene oxide | |
| CN112625192B (en) | Nano composite ion exchange resin catalyst and application thereof | |
| CN105439866A (en) | A dimethyl carbonate preparing method by transesterification | |
| CN116622067A (en) | Hydrophilic covalent triazine frame and preparation method and application thereof | |
| CN109590029B (en) | Ion exchange resins and uses thereof | |
| CN109675631B (en) | Catalyst for preparing glycol by hydrating epoxy compound and application thereof | |
| CN109575162B (en) | Ion exchange resin and use | |
| CN114433229B (en) | Catalyst for preparing alkylene carbonate, and preparation method and application thereof | |
| CN112705263B (en) | Alkylene oxide hydration catalyst and application thereof | |
| CN114433230B (en) | Catalyst for alkylene oxide catalytic hydration reaction, preparation method and application thereof | |
| CN109575292B (en) | Ion exchange resin and use thereof | |
| CN114433228A (en) | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid | |
| CN105272858A (en) | Dimethyl carbonate production method | |
| CN109776264A (en) | The method of olefine aldehyde condensation reaction | |
| CN105085187B (en) | The method of preparing ethyl glycol by hydrolysis of ethylene carbonate | |
| CN105503528B (en) | The method that ethylene carbonate ester hydrolysis produces ethylene glycol | |
| CN105503520B (en) | The method of preparing ethyl glycol by hydrolysis of ethylene carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |