CN105503608A - Production method of ethylene carbonate - Google Patents
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Abstract
The invention relates to a production method of ethylene carbonate, and mainly solves the problems of low catalyst activity and easy deactivation in the prior art. According to a technical scheme, ethylene oxide and carbon dioxide are adopted as the raw materials, under the conditions of a reaction temperature of 60-200DEG C, a reaction pressure of 0.1-10.0MPa, a weight ratio of a catalyst to ethylene oxide of 0.001-1, the reaction raw materials and the catalyst contact to generate ethylene carbonate; and the catalyst is halogen type compound hydroxy imidazole resin. The method well solves the problems, and can be used for the industrial production of ethylene carbonate from ethylene oxide and carbon dioxide.
Description
Technical field
The present invention relates to a kind of method of producing NSC 11801.
Background technology
NSC 11801 is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.CO simultaneously
2be a kind of greenhouse gases, how effectively fix and become one of challenging problem of most in this century, and by oxyethane and CO
2reactive Synthesis NSC 11801 is exactly wherein a kind of well fixing means.Along with being recently that raw material co-producing dimethyl carbonate and glycol reaction receive publicity, day by day by cyclic carbonate fixation of C O with NSC 11801
2approach also receive increasing attention.
The method majority of the production cyclic carbonate reported at present is the binary homogeneous catalyst using Lewis acid metal compound and Lewis alkali composition, the Lewis acid metal compound wherein used comprises alkali (soil) metal halide, transition metal salt, transition metal or Main group metal complexes, the Lewis alkali used has organic bases (as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.These catalyst system perhaps active, selectivity is not high, or employs the very strong organic solvent of toxicity, and there is the shortcoming that catalyzer is difficult to be separated in homogeneous catalysis system.And use more heterogeneous catalysis system to comprise metal oxide system (as CeO at present
2-ZrO
2, GreenChem.2004,6,206-214), basic zeolite system (as Cs/KX, J.Catal.2001,199,85-91) etc., these active catalyst system are low, and the required reaction times is longer.Xia Chungu etc. are by ZnCl
2immobilized on chitin carrier, although achieve higher catalytic activity, after catalyzer applies mechanically 5 times, activity reduces about 8%, infers that possible reason is the loss (Appl.Catal.A2005,279,125-129) of catalyst activity component.Therefore, develop a kind of easily separated, activity is high, reaction conditions is gentle, not the catalyst system of easy in inactivation seem very important.
Summary of the invention
Technical problem to be solved by this invention is the problem that prior art exists low, the easy inactivation of catalyst activity, provides a kind of method of new production NSC 11801.The method has catalyst activity feature that is high, not easy in inactivation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing NSC 11801, with oxyethane and carbonic acid gas for raw material, it is 60 ~ 200 DEG C in temperature of reaction, reaction pressure is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and oxyethane is under the condition of 0.001 ~ 1, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyzer is halogen-type compound hydroxy imidazole resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) compound imidazoles resin is obtained add imidazoles reaction in described compound chlorine ball after;
5) described halogen-type compound hydroxy imidazole resin is obtained add hydroxyhalide reaction in described compound imidazoles resin after.
In technique scheme, preferably, the weight percent concentration of described water solution A is 0.5 ~ 2%.
In technique scheme, preferably, step 2) reaction process is: solution B, 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then mixes with solution A by solution B, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
In technique scheme, preferably, step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
In technique scheme, preferably, step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imidazoles of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described compound imidazoles resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
In technique scheme, preferably, step 5) reaction process is: adds in described compound imidazoles resin and is equivalent to the hydroxyhalide X-R-OH of compound imidazoles weight resin 30 ~ 300%, the organic solvent of 300 ~ 1000%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described halogen-type compound hydroxy imidazole resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride, in hydroxyhalide X-R-OH, X is Cl, Br or I, and R is ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, n-pentyl or n-hexyl.
In technique scheme, preferably, described monomer is selected from vinylbenzene.
In technique scheme, preferably, described comonomer is selected from Vinylstyrene.
In technique scheme, preferably, described nano material is selected from multi-walled carbon nano-tubes.
In technique scheme, preferably, described initiator is selected from benzoyl peroxide.
In technique scheme, preferably, described auxiliary agent one is selected from polyvinyl alcohol.
In technique scheme, preferably, described auxiliary agent two is selected from polystyrene.
In technique scheme, preferably, temperature of reaction is 80 ~ 160 DEG C, and reaction pressure is 0.5 ~ 8.0 MPa, and the weight ratio of catalyzer and oxyethane is 0.005 ~ 0.5.
The inventive method adopts halogen-type compound hydroxy imidazole resin to be catalyzer, owing to being mixed with the nano material of high strength in resin base material, thus enhances the swelling resistance performance of resin, prevents catalyzer due to swelling and inactivation that is that cause.In addition, because hydroxyl can provide hydrogen bond with priming reaction substrate, thus improve catalytic activity.Catalyzer of the present invention is 120 DEG C in temperature of reaction, reaction pressure is 2.0MPa, the mass ratio of catalyzer and oxyethane reacts 3 hours when being 0.02, the transformation efficiency of oxyethane is 98.6%, the selectivity of NSC 11801 is 99.7%, apply mechanically 5 times after catalyst separating, active reduction is less than 5%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.Be necessary to herein means out be following examples only for further illustrating of the present invention, can not limiting the scope of the invention be interpreted as.
Embodiment
[embodiment 1]
In 500 milliliters of there-necked flasks, add 58.0 grams of vinylbenzene, 0.6 gram of Vinylstyrene, 30 grams of polystyrene and 0.6 gram of benzoyl peroxide initiator, stir 2.0 hours at 60 DEG C; Then add 2.8 grams of multi-walled carbon nano-tubes, continue stirring and carry out prepolymerization in 1 hour.Add the 260 ml deionized water solution being dissolved with 2.5 grams of polyvinyl alcohol.Regulate stirring velocity, be progressively warming up to 80 DEG C simultaneously, react 5 hours; Be warmed up to 90 DEG C again, react 5 hours, be finally warming up to 98 DEG C, react 6 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere A of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere A and 250 milliliter chloromethyl ethers, room temperature leaves standstill 4 hours, starts to stir, and adding 15 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 8 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball A.
The imidazoles of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball A, 100 milliliters of tetrahydrofuran (THF)s, 8 grams of imidazoles, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain compound imidazoles Resin A 1 under vacuo.
The reaction of compound imidazoles resin and hydroxyhalide: add 20 grams of compound imidazoles Resin A, 1,9.2 grams of ethylene bromohyrins and 200 milliliters of acetonitriles in 500 milliliters of there-necked flasks, react 20 hours at reflux, reaction terminates rear mistake and filters mother liquor, use methylene dichloride, acetone and water washing successively respectively, dry to obtain halogen-type compound hydroxy imidazole Resin A 2 under vacuo.
[embodiment 2]
In 500 milliliters of there-necked flasks, add the compound chlorine ball A of 20 grams of [embodiment 1] gained, 150 milliliters of toluene, 35.0 gram imidazoles, stirring reaction 30 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain compound imidazoles Resin A 3 under vacuo.
The reaction of compound imidazoles resin and hydroxyhalide: add 20 grams of compound imidazoles Resin A, 1,30.2 grams of ethylene iodohydrins and 200 milliliters of cyanobenzenes in 500 milliliters of there-necked flasks, react 10 hours at reflux, reaction terminates rear mistake and filters mother liquor, use methylene dichloride, acetone and water washing successively respectively, dry to obtain halogen-type compound hydroxy imidazole Resin A 4 under vacuo.
[embodiment 3]
Monomer mixture solution (60.0 grams of vinylbenzene, 1.7 grams of Vinylstyrenes, the 60 grams of polystyrene containing initiator are added in 500 milliliters of there-necked flasks, 1.6 grams of multi-walled carbon nano-tubes and 1.0 grams of benzoyl peroxides, this solution was prior to 70 DEG C of stirring reactions 0.5 hour), start agitator, add the mixing solutions of 200 ml deionized water and 5 grams of gelatin, be warming up to 85 DEG C, react 3 hours, then be warmed up to 90 DEG C, react 9 hours, finally be warming up to 100 DEG C, react 10 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere B of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere B and 150 milliliter chloromethyl ethers, room temperature leaves standstill 6 hours, starts to stir, and adding 30 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 24 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball B.
The imidazoles of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball B, 150 milliliters of tetrahydrofuran (THF)s, 20.0 gram imidazoles, stirring reaction 24 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain compound imidazoles resin B 1 under vacuo.
Compound imidazoles resin B 1 method described in [embodiment 2] and hydroxyhalide are reacted, obtains halogen-type compound hydroxy imidazole resin B 2.
[embodiment 4]
In 500 milliliters of there-necked flasks, add the compound imidazoles resin B 1 of 15 grams of [embodiment 3] gained, 150 milliliters of acetonitriles, 20.0 grams of 3-propylene chlorohydrins, stirring reaction 10 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain halogen-type compound hydroxy imidazole resin B 3 under vacuo.
[embodiment 5]
Change monomer mixture solution (the 76.0 grams of alpha-methyl styrenes in [embodiment 3], 3.5 grams of Vinylstyrenes, 75 grams of gasoline, 2.4 grams of multi-walled carbon nano-tubes and 1.4 grams of benzoyl peroxides), all the other preparation conditions are identical with [embodiment 3], obtain complex microsphere C.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 40 grams of complex microsphere C and 150 milliliter Isosorbide-5-Nitrae-dichloro methyl butyl ether, room temperature leaves standstill 6 hours, start to stir, adding 25 grams of zinc chloride is catalyzer, is warming up to 50 DEG C of reactions 24 hours, is cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball C.
The imidazoles of compound chlorine ball: identical with [embodiment 1] method, obtains compound imidazoles resin C1.
The reaction of compound imidazoles resin and hydroxyhalide: add 20 grams of compound imidazoles resin C1,10.5 grams of 5-bromine amylalcohols and 200 milliliters of acetonitriles in 500 milliliters of there-necked flasks, react 20 hours at reflux, reaction terminates rear mistake and filters mother liquor, use methylene dichloride, acetone and water washing successively respectively, dry to obtain halogen-type compound hydroxy imidazole resin C2 under vacuo.
[embodiment 6]
Catalyst preparation step is identical with the step of [embodiment 5], and just hydroxyhalide used is 6-bromine hexanol, obtains halogen-type compound hydroxy imidazole resin C3.
[comparative example 1]
The preparation process of catalyzer is identical with [embodiment 1], does not just add multi-walled carbon nano-tubes, obtains compound imidazoles resin CA1, halogen-type compound hydroxy imidazole resin CA2 respectively.
[embodiment 7]
Catalyzer halogen-type compound imidazolyl Resin A 2 obtained by [embodiment 1] is used as the catalyzer of oxyethane and carbon dioxide reaction Formed vinyl acetate, reaction conditions is as follows: in 300mL autoclave, add 150.0g oxyethane and 3.0g catalyzer, be filled with 1.0MPaCO
2, be warming up to 120 DEG C, then be filled with CO
2, maintain reaction pressure at 2.0MPa, cool after reaction 3h, open reactor, liquid form and aspect chromatogram is analyzed, and records oxyethane transformation efficiency (C
eo%) be 98.6%, NSC 11801 (S
eC%) selectivity is 99.7%, the swelling capacity S of resin catalyst
sWELLbe 5.1%.
[comparative example 2]
Catalyst activity test condition is identical with [embodiment 7], and just catalyzer used is halogen-type compound hydroxy imidazole resin CA2, and the transformation efficiency obtaining oxyethane is 97.4%, and the selectivity of NSC 11801 is 99.5%, and the swelling capacity of resin catalyst is S
sWELLbe 22.3%.
[embodiment 8-12]
Change the halogen-type compound hydroxy imidazole resin types that uses, identical with described in [embodiment 7] of all the other conditions, the result obtained is as shown in table 1.
Table 1
[embodiment 13-17]
Use A2 as catalyzer, change the mass ratio of temperature of reaction, reaction pressure catalyzer and oxyethane, other condition is all identical with [embodiment 7], and catalyst activity and selectivity is as shown in table 2.
Table 2
[embodiment 18]
Catalyzer after [embodiment 7] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity does not obviously decline.Reaction result is shown in Table 3.
Table 3
| Apply mechanically number of times | C EO％ | S EC％ |
| 1 | 97.9 | 99.5 |
| 2 | 97.4 | 99.6 |
| 3 | 96.5 | 99.5 |
| 4 | 97.0 | 99.3 |
| 5 | 96.0 | 99.4 |
[comparative example 3]
Catalyzer after [comparative example 2] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity obviously declines.Reaction result is shown in Table 4.
Table 4
| Apply mechanically number of times | C EO％ | S EC％ |
| 1 | 94.2 | 99.7 |
| 2 | 86.2 | 99.6 |
| 3 | 81.5 | 99.7 |
| 4 | 75.6 | 99.5 |
| 5 | 71.4 | 99.6 |
Claims (9)
1. produce the method for NSC 11801 for one kind, with oxyethane and carbonic acid gas for raw material, be 60 ~ 200 DEG C in temperature of reaction, reaction pressure is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and oxyethane is under the condition of 0.001 ~ 1, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyzer is halogen-type compound hydroxy imidazole resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) compound imidazoles resin is obtained add imidazoles reaction in described compound chlorine ball after;
5) described halogen-type compound hydroxy imidazole resin is obtained add hydroxyhalide reaction in described compound imidazoles resin after.
2. the method for production NSC 11801 according to claim 1, is characterized in that the weight percent concentration of described water solution A is 0.5 ~ 2%.
3. the method for production NSC 11801 according to claim 1, it is characterized in that step 2) reaction process is: solution B was 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then solution B is mixed with solution A, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
4. the method for production NSC 11801 according to claim 1, it is characterized in that step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
5. the method for production NSC 11801 according to claim 1, it is characterized in that step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imidazoles of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described compound imidazoles resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
6. the method for production NSC 11801 according to claim 1, it is characterized in that step 5) reaction process is: adds in described compound imidazoles resin and is equivalent to the hydroxyhalide X-R-OH of compound imidazoles weight resin 30 ~ 300%, the organic solvent of 300 ~ 1000%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described halogen-type compound hydroxy imidazole resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride, in hydroxyhalide X-R-OH, X is Cl, Br or I, and R is ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, n-pentyl or n-hexyl.
7. the method for production NSC 11801 according to claim 1, is characterized in that described monomer is selected from vinylbenzene; Described comonomer is selected from Vinylstyrene; Described nano material is selected from multi-walled carbon nano-tubes; Described initiator is selected from benzoyl peroxide.
8. the method for production NSC 11801 according to claim 1, is characterized in that described auxiliary agent one is selected from polyvinyl alcohol; Described auxiliary agent two is selected from polystyrene.
9. the method for production NSC 11801 according to claim 1, it is characterized in that temperature of reaction is 80 ~ 160 DEG C, reaction pressure is 0.5 ~ 8.0 MPa, and the weight ratio of catalyzer and oxyethane is 0.005 ~ 0.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109590029A (en) * | 2017-09-29 | 2019-04-09 | 中国石油化工股份有限公司 | Ion exchange resin and its purposes |
| TWI801462B (en) * | 2017-12-08 | 2023-05-11 | 荷蘭商蜆殼國際研究所 | Process for preparing ethylene carbonate and ethylene glycol using an alkyl iodide guard bed system |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109590029A (en) * | 2017-09-29 | 2019-04-09 | 中国石油化工股份有限公司 | Ion exchange resin and its purposes |
| CN109590029B (en) * | 2017-09-29 | 2021-11-30 | 中国石油化工股份有限公司 | Ion exchange resins and uses thereof |
| TWI801462B (en) * | 2017-12-08 | 2023-05-11 | 荷蘭商蜆殼國際研究所 | Process for preparing ethylene carbonate and ethylene glycol using an alkyl iodide guard bed system |
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