CN106391112A - Immobilized ionic liquid catalyst and application thereof - Google Patents

Immobilized ionic liquid catalyst and application thereof Download PDF

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CN106391112A
CN106391112A CN201510467792.8A CN201510467792A CN106391112A CN 106391112 A CN106391112 A CN 106391112A CN 201510467792 A CN201510467792 A CN 201510467792A CN 106391112 A CN106391112 A CN 106391112A
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ionic liquid
liquid catalyst
reaction
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俞峰萍
何文军
宗弘元
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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 an immobilized ionic liquid catalyst and application thereof. The immobilized ionic liquid catalyst has a general structural formula as defined in the specification. In the general structural formula, P is a nanogel resin matrix; n is an integer in a range of 2 to 12; and M<-> is a negative ion selected from a group consisting of a trifluoromethanesulfonate group, a p-toluenesulfonate group, a benzenesulfonate group, a methanesulfonate group, a tetrafluoroborate group and a hexafluorophosphate group. The immobilized ionic liquid catalyst can be applied to industrial olefine acid addition for preparation of corresponding esters.

Description

Immobilized ionic liquid catalyst and application thereof
Technical Field
The invention relates to an immobilized ionic liquid catalyst and application thereof.
Background
Butyl acrylate is an important high molecular monomer and an organic intermediate, is a colorless transparent liquid at normal temperature, and has good chemical and physical properties such as weather resistance, water resistance, oil resistance, chemical resistance and the like. The industrial production methods of acrylic ester mainly include a nitrile ethanol method, an acrylonitrile hydrolysis method, an acrylic acid esterification method and an ester exchange method. Foreign basf, Rohm and Haas, Mitsubishi, Japan Bright petrochemical company, Ehlev and Ato chemistry, and the like, carry out scientific research and development on the crystal, and mainly focus on the improvement of the production process, including the multiphase azeotropic process. The development of new catalytic system includes heteropoly acid and its salt, solid super acid, gel zeolite system and ionic resin system.
The preparation of esters of olefins and lower carboxylic acids can be catalyzed by cation exchange resins containing sulfonic acid groups, as reported in U.S. Pat. Nos. 3678099, 2678332, 3031495, 3172905 and 3173943. One drawback of this process is the phenomenon of olefin polymerization that occurs during esterification, which results in a decrease in yield and the formation of by-products such as dimers that interfere with subsequent product separation, e.g., isobutylene dimer forms an azeotrope with butyl acetate, making product separation difficult.
Document US3644497 describes the use of an improved catalyst for the reaction of olefins containing unsaturation with carboxylic acids, the catalyst being a molybdenum or tungsten heteropoly acid catalyst. The temperature of the catalytic reaction is preferably 20-140 ℃ under the anhydrous condition, and the pressure is preferably 0-3000 PSIG; and the temperature and pressure under the water condition are slightly harsh, the temperature is preferably 50-175 ℃, and the pressure is preferably 0-4000 PSIG. The amount of water in the reaction system is varied according to the difference in the desired product. The molar ratio of water to olefin is 1 to 75, depending on the equilibrium of the alcohol and the corresponding ester.
The document US5384426 describes a process for preparing isopropyl acetate by esterification of propylene and acetic acid using an acidic resin as a catalyst. Propylene is derived from the by-product of isobutene production by petroleum cracking or isobutane dehydration. Reacting at the molar ratio of 0.5-1, the pressure of 15-50 kg/cm2 and the temperature of 70-120 ℃, and distilling to obtain the isobutyl acetate with the purity of 99.9%.
Document US6849759B1 describes a process for the production of organic esters, primarily a process for the production of ethyl acetate catalyzed by supported heteropolyacids or salts.
In recent years, the ionic liquid provides a wide space for people to search an environment-friendly catalytic system, has excellent chemical and thermodynamic stability, almost does not have vapor pressure at room temperature, and has the characteristics of convenient product separation and catalyst recovery when being applied to catalytic reaction. Gu et al (J.mol.Catal.A: chem., 2004, 212: 71-75) examined their catalytic activity in various olefin esterification reactions using sulfonic acid functionalized ionic liquids. The result shows that the catalyst can obtain good catalytic activity in most of olefins, and simultaneously, due to the characteristics of the ionic liquid, after the reaction is finished, the catalyst and the product can be separated only by pouring, and the ionic liquid can be reused after vacuum drying. Document CN1600773A describes a method for synthesizing ester by catalyzing olefin and organic acid with sulfonic acid functionalized ionic liquid as a catalyst, which uses an ionic liquid composed of alkyl pyridine or 1, 3-dialkyl imidazole cation with sulfonic acid group at the end and anion as a catalyst to catalyze the reaction of acetic acid and propylene at 50-150 ℃ under 0.1-2.0 MPa, wherein the acetic acid conversion rate is above 66%, and the selectivity reaches 100%. Although the catalytic efficiency of the catalyst is not reduced after 4 times of repeated use. However, the ionic liquid catalyst can be continuously used after being extracted and dried in vacuum.
Therefore, it is very important to research and develop an olefinic acid addition catalytic system with high activity, high selectivity and easy separation.
Disclosure of Invention
One of the purposes of the invention is to provide a novel immobilized ionic liquid catalyst. The second purpose of the invention is to provide the application of the immobilized ionic liquid catalyst. When the immobilized ionic liquid catalyst is used for olefine acid addition, the catalyst has the characteristics of high catalytic activity, difficult inactivation and easy separation of reaction products.
In order to achieve one of the above purposes, the invention adopts the following technical scheme: an immobilized ionic liquid catalyst has the following structural general formula:
wherein,is a nano gel resin matrix; n is an integer from 2 to 12; m-Is an anion selected from triflate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate.
In the above technical solution, preferably, n is an integer of 2 to 4.
In the above technical solution, preferably, M-Is trifluoromethanesulfonate.
In the above technical solution, preferably, the nanogel resin matrix is a nanogel copolymer obtained by in-situ copolymerization of a styrene monomer, a comonomer, and a nanomaterial. 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, divinylphenylmethane or divinylbenzene. The nano material is at least one of multi-wall carbon nano tube, single-wall carbon nano tube, C60 or C70 fullerene.
In order to achieve the second purpose of the invention, the invention adopts the following technical scheme: the immobilized ionic liquid catalyst is used for catalyzing esterification reaction of olefin and organic acid.
In the above technical solution, preferably, the esterification reaction conditions are: the weight ratio of the immobilized ionic liquid catalyst to the reaction mixture is 0.001-0.1; the molar ratio of olefin to organic acid is 1: 5-5: 1; the reaction temperature is 60-150 ℃, and the reaction pressure is 0.5-3.0 MPa.
In the above technical solution, preferably, the olefin is carbon chain length C2To C18Linear, branched or cyclic olefins.
In the above technical solution, preferably, the organic acid is C1To C18Fatty acids or aromatic acids.
The preparation method of the immobilized ionic liquid catalyst comprises the following steps:
a) preparing an auxiliary agent into an aqueous solution A with the weight percentage concentration of 0.5-2%, and preparing a styrene monomer, a comonomer, a nano material and an initiator 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 multi-wall carbon nano tubes, single-wall carbon nano tubes, C60 or C70 fullerene;
the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide or cumene hydroperoxide;
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 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 composite gel microspheres with the particle size range of 0.35-0.60 mm;
c) chloromethylating composite gel microspheres: adding a chloromethylation reagent which is 200-500% of the weight of the composite gel microsphere and a zinc chloride catalyst which is 20-70% of the weight of the composite gel microsphere into the composite gel microsphere, reacting for 8-30 hours at 30-60 ℃, filtering, washing to obtain a composite gel chlorine ball, and drying to constant weight; the chloromethylation reagent is selected from at least one of chloromethyl ether, chloroethyl ether or 1, 4-dichloromethoxybutane;
d) reacting a mixture of composite gel chlorine spheres, imidazole and acetonitrile at 60-90 ℃ to obtain composite gel imidazole microspheres; in the mixture, the mol ratio of the composite gel chlorine ball to the imidazole to the acetonitrile is 1 (1-2) to (30-150);
e) mixing the composite gel imidazole microspheres with sultone reagents in an equimolar manner, and reacting at room temperature for 24-72 hours to obtain composite gel imidazole cationic microspheres; the sultone reagent is selected from at least one of 1, 4-butane sultone, 2, 4-butyl sultone and 1, 3-propane sultone;
f) mixing the composite gel imidazole cationic microspheres with organic sulfonic acid, and reacting at 25-60 ℃ for 1-5 hours to obtain the required nano gel resin loaded ionic liquid catalyst; wherein the molar ratio of the composite gel imidazole cationic microspheres to the organic sulfonic acid is (1:1) - (1: 2); the organic sulfonic acid is at least one selected from trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid.
The ionic liquid catalyst loaded by the nanogel resin is used in the addition reaction of olefine acid, the catalyst has high activity and selectivity, the product is easy to separate, and the catalyst can be continuously used for multiple times. The preferred scheme of the invention is that chloromethylated styrene, divinyl benzene and multi-walled carbon nano-tube in-situ gel copolymer resin matrix reacts with imidazole to form composite microspheres with imidazole groups, then the imidazole groups react with 1, 4-butyl sultone, and finally the composite microspheres react with trifluoromethanesulfonic acid to prepare the nano gel resin loaded ionic liquid catalyst. The ionic liquid catalyst loaded by the nano gel resin is used in the reaction of preparing sec-butyl acrylate by adding butene-1 and methacrylic acid, the catalyst activity is high, the conversion rate of the methacrylic acid can be up to 93.5%, the selectivity of the sec-butyl methacrylate can be up to 100%, the product is easy to separate, the catalyst is continuously used for 6 times, the activity is not obviously reduced, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
50.0 g of styrene, 2.0 g of divinylbenzene and 0.6 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 1.6 g of multi-walled carbon nanotubes were added and stirring was continued for 1 hour for prepolymerization. A solution of 2.5 g polyvinyl alcohol in 260ml of deionized water was added. Adjusting the stirring speed, 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 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing the upper layer liquid for several times by using hot water at 85 ℃, washing the upper layer liquid for several times by using cold water, then filtering the upper layer liquid, drying the upper layer liquid in a drying oven at 80 ℃, sieving the upper layer liquid, and collecting the composite gel microspheres A with the particle size of 0.35-0.60 mm.
Chloromethylation of composite gel microspheres: adding 50 g of composite gel microspheres A and 250ml of chloromethyl ether into a 500ml three-neck flask, standing at room temperature for 4 hours, starting stirring, adding 15 g of zinc chloride as a catalyst, 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 gel chlorine spheres A.
40 g of composite gel chlorine ball A (the chlorine content is 1.2mmol Cl/g), imidazole (48.0mmol) and 260ml of acetonitrile are added into a 500ml three-necked bottle, the mixture reacts for 28 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 A.
Adding 30 g of composite imidazole microsphere A, 1, 4-butyl sultone with equimolar amount and 200ml of acetonitrile into a 250ml three-neck flask, stirring and refluxing at room temperature for reaction for 60 hours, pouring out upper-layer liquid after the reaction is finished, washing the microsphere for a plurality of times by using toluene, and then drying in vacuum for later use to obtain the composite imidazole cationic microsphere A.
30 g of compound imidazole cation are added into a 250ml three-neck flaskReacting ionic microsphere A, trifluoromethanesulfonic acid and acetonitrile in equimolar amount at 50 ℃ for 3 hours, pouring out the upper liquid after the reaction is finished, washing the microspheres with toluene and diethyl ether for several times respectively, and drying in vacuum to obtain the ionic liquid catalyst loaded with the nanogel resin, which is marked as Cat-A and has a structural formula of
[ example 2 ]
A monomer mixture solution containing an initiator (60.0 g of styrene, 3.0 g of divinyl benzene, 0.1 g of multi-walled carbon nano tube and 1.0 g of benzoyl peroxide are added into a 500ml three-neck flask, the solution is stirred and reacted for 0.5 hour at 70 ℃, a stirrer is started, 200ml of mixed solution of deionized water and 5 g of gelatin is added, the temperature is increased to 85 ℃, the reaction is carried out for 3 hours, the temperature is increased to 90 ℃, the reaction is carried out for 9 hours, and finally the temperature is increased to 100 ℃, and the reaction is carried out for 10 hours. And after the reaction is finished, pouring out the upper layer liquid, washing with hot water at 85 ℃, washing with cold water, filtering, drying in an oven at 80 ℃, sieving, and collecting the composite gel microspheres B with the particle size of 0.35-0.60 mm.
Chloromethylation of the composite microspheres: adding 50 g of composite microsphere B and 200ml of chloroethyl ether into a 500ml three-neck flask, standing at room temperature for 7 hours, starting stirring, adding 10 g of zinc chloride serving as a catalyst, heating to 60 ℃ for reaction for 30 hours, cooling to room temperature after chloromethylation is finished, filtering out chlorinated mother liquor, repeatedly washing with methanol, and drying at 100 ℃ for 8 hours to obtain the composite gel chlorine sphere B.
50 g of composite gel chlorine ball B (the chlorine content is 1.0mmol Cl/g), imidazole (50.0mmol) and 260ml of acetonitrile are added into a 500ml three-necked bottle, the mixture reacts for 24 hours at the temperature of 60 ℃, the mixture is cooled to the 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 the temperature of 60 ℃ in vacuum to obtain the composite imidazole microsphere B.
Adding 30 g of composite imidazole microsphere B, 1, 3-propane sultone with equimolar amount and 200ml of acetonitrile into a 250ml three-neck flask, stirring and refluxing at room temperature for reaction for 72 hours, pouring out upper-layer liquid after the reaction is finished, washing the microsphere for multiple times by using toluene, and then drying in vacuum for later use to obtain the composite imidazole cationic microsphere B.
Adding 30 g of composite imidazole cationic microsphere B, equimolar trifluoromethanesulfonic acid and acetonitrile into a 250ml three-neck flask, reacting for 4 hours at 50 ℃, pouring out upper-layer liquid after the reaction is finished, washing the microspheres for several times by toluene and diethyl ether respectively, and drying in vacuum to obtain the nano gel resin supported ionic liquid catalyst, which is marked as Cat-B and has a structural formula of
[ example 3 ]
Changing the anion (adopting p-toluenesulfonic acid, the dosage is equal to the mol of the compound imidazole cation microspheres A) in the [ example 1 ], and the rest preparation conditions are the same as the [ example 1 ], and finally obtaining Cat-C, wherein the structural formula is shown in the specification
[ example 4 ]
Changing the anion (adopting benzenesulfonic acid, the dosage is equal to the mole of the compound imidazole cation microsphere B) in the (example 2), and the other preparation conditions are the same as the (example 1), and finally obtaining Cat-D, wherein the structural formula is shown in the specification
[ example 5 ]
The nanogel resin-supported ionic liquid catalyst prepared above was used for the reaction of C4 and methacrylic acid under the following conditions: 43.0 g of methacrylic acid and 10.0 g of nano gel resin loaded ionic liquid catalyst Cat-A are added into a high-pressure reaction kettle, 140.0 g of 1-butene is filled, high-purity nitrogen is filled, the reaction pressure is maintained at 1.5MPa, the reaction temperature is 80 ℃, the catalyst is removed by filtration after 3 hours of reaction, the conversion rate of the methacrylic acid is 94.0 percent, and the selectivity of the sec-butyl methacrylate is 100 percent.
[ examples 6 to 8 ]
The catalyst adopted in example 5 is changed, and Cat-B, Cat-C and Cat-D are used for replacing Cat-A to catalyze the addition esterification reaction of methacrylic acid and olefine acid of 1-butene. The reaction steps and conditions were the same as in [ example 5 ] except that the catalyst was changed, and analytical tests were performed after the reaction was completed, and the test results are shown in the following table.
Examples Catalyst and process for preparing same Conversion rate% Selectivity%
6 Cat-B 94.1 100
7 Cat-C 92.8 100
8 Cat-D 90.3 100
[ examples 9 to 13 ]
The catalyst Cat-a in example 5 was separated from the reactant after the reaction was completed, washed several times with toluene and ether, and then dried in vacuum. Then, according to the reaction steps and reaction conditions in [ example 5 ], the olefine acid addition esterification reaction of methacrylic acid and 1-butene is catalyzed, and the result that the catalyst Cat-A is recycled for 2 times is obtained, which is shown in the following table. By analogy, the catalytic reactions with the cycle times of 3-6 times are respectively carried out, and the reaction results are shown in the following table.
Examples Number of cycles Conversion rate% Selectivity%
9 2 93.5 100
10 3 93.6 100
11 4 93.7 100
12 5 93.3 100
13 6 93.3 100
[ example 14 ]
60.0 g of acetic acid and 15.0 g of ionic liquid catalyst Cat-A loaded by nano gel resin are added into a high-pressure reaction kettle, 126.0 g of propylene is filled, high-purity nitrogen is filled, the reaction pressure is maintained at 1.5MPa, the reaction temperature is 120 ℃, the catalyst is removed by filtration after 3 hours of reaction, the conversion rate of the acetic acid is 94.0 percent, and the selectivity of the isopropyl acetate is 100 percent.
[ COMPARATIVE EXAMPLE 1 ]
Comparative example 1 was defined as a comparative example to example 14. The catalyst adopts trifluoromethanesulfonic acid 1-hexyl-3- (4-sulfonic acid group) butyl imidazole ionic liquid (the preparation method is shown in document CN1600773A), the dosage is 21.5 g, the catalyst with the dosage, 4.5 g of acetic acid and 9.45 g of propylene are added into a high-pressure reaction kettle, high-purity nitrogen is filled, the reaction pressure is maintained at 3.0MPa, the reaction temperature is 120 ℃, and sampling analysis is carried out after 4 hours of reaction, so that the conversion rate of the acetic acid is 85.5 percent, and the selectivity of the isopropyl acetate is 100 percent.
[ examples 15 to 23 ]
The prepared nanogel resin loaded ionic liquid catalyst Cat-A is used for the esterification addition reaction of different olefins and organic acids, and the conditions are as follows: sequentially adding a catalyst, olefin and carboxylic acid into a high-pressure reaction kettle, wherein the catalyst accounts for 1.5% of the mass of the reaction mixture; the molar ratio of olefin to carboxylic acid is 3: 1, then charging high-purity nitrogen, maintaining the reaction system in a liquid phase condition, reacting for 4 hours at 120 ℃, then cooling to room temperature, and sampling and analyzing. The results of the reaction analysis are shown in the following table.
Examples Olefins Carboxylic acids Conversion rate% Selectivity%
15 2-methyl-2-butene Acetic acid 96.7 100
16 1-octene Acetic acid 95.9 100a
17 Cyclopentene Acetic acid 93.0 100
18 Dicyclopentadiene Acetic acid 93.1 100
19 Propylene (PA) Acetic acid 81.9 100
20 Propylene (PA) Propionic acid 91.1 100
21 Propylene (PA) Acrylic acid 91.2 100
22 Propylene (PA) Isooctanoic acid 83.8 100
23b 4-phenyl-1-butene Phenylacetic acid 92.6 100
Note a: the product has three isomers, and the ratio is 5: 4: 1.
b: the reaction temperature is 50 ℃, the reaction time is 20 hours, and the molar ratio of olefine acid is 4: the reaction system takes toluene as a solvent.

Claims (10)

1. An immobilized ionic liquid catalyst has the following structural general formula:
wherein,is a nano gel resin matrix; n is an integer from 2 to 12; m-Is an anion selected from the group consisting of trifluoromethylSulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, tetrafluoroborate or hexafluorophosphate.
2. The immobilized ionic liquid catalyst of claim 1, wherein n is an integer from 2 to 4; m-Is trifluoromethanesulfonate.
3. The immobilized ionic liquid catalyst of claim 1, wherein the nanogel resin matrix is a nanogel copolymer obtained by in-situ copolymerization of styrene monomers, comonomers and nanomaterials.
4. The supported ionic liquid catalyst as set forth in claim 3, wherein the styrenic monomer is at least one selected from the group consisting of styrene, α -methylstyrene and 4-butylstyrene.
5. The supported ionic liquid catalyst of claim 3 wherein the comonomer is selected from at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane or divinylbenzene.
6. The supported ionic liquid catalyst of claim 3, wherein the nanomaterial is selected from at least one of multi-walled carbon nanotubes, single-walled carbon nanotubes, C60, or C70 fullerenes.
7. The use of the supported ionic liquid catalyst of claim 1 for catalyzing the esterification of an olefin and an organic acid.
8. Use of the supported ionic liquid catalyst according to claim 7, characterized in that the esterification reaction conditions are: the weight ratio of the immobilized ionic liquid catalyst to the reaction mixture is 0.001-0.1; the molar ratio of the olefin to the organic acid is (1:5) to (5: 1); the reaction temperature is 60-150 ℃, and the reaction pressure is 0.5-3.0 MPa.
9. Use of the supported ionic liquid catalyst according to claim 7, characterized in that the olefin is of carbon chain length C2To C18Linear, branched or cyclic olefins.
10. Use of the immobilized ionic liquid catalyst according to claim 7, characterized in that the organic acid is C1To C18Fatty acids or aromatic acids.
CN201510467792.8A 2015-08-03 2015-08-03 Immobilized ionic liquid catalyst and application thereof Pending CN106391112A (en)

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CN107029784B (en) * 2017-04-25 2019-11-12 福州大学 A kind of Polymer-supported dual-core acidic ionic liquid catalyst and its preparation and application
CN109575292A (en) * 2017-09-29 2019-04-05 中国石油化工股份有限公司 Ion exchange resin and application thereof
CN109574794A (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 production 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
CN109569717B (en) * 2017-09-29 2021-11-30 中国石油化工股份有限公司 Ion exchange resin and use
CN109777626A (en) * 2017-11-13 2019-05-21 中国石油化工股份有限公司 The production method of biodiesel
CN109777628A (en) * 2017-11-13 2019-05-21 中国石油化工股份有限公司 The method for preparing biodiesel
CN109777626B (en) * 2017-11-13 2022-05-27 中国石油化工股份有限公司 Method for producing biodiesel
CN109777628B (en) * 2017-11-13 2022-05-27 中国石油化工股份有限公司 Method for preparing biodiesel
CN108579803A (en) * 2018-03-27 2018-09-28 北京理工大学 A kind of preparation method of supported ion liquid polyalcohol stephanoporate microballoons
CN108579803B (en) * 2018-03-27 2020-07-07 北京理工大学 Preparation method of ionic liquid loaded polymer porous microspheres

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