CN105503528A - Method for production of ethylene glycol by hydrolysis of ethylene carbonate - Google Patents
Method for production of ethylene glycol by hydrolysis of ethylene carbonate Download PDFInfo
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Abstract
The invention relates to a method for production of ethylene glycol by hydrolysis of ethylene carbonate, and mainly solves the problems of easy swelling and rapid activity decline of resin in the prior art. According to an adopted technical scheme, under the conditions of a reaction temperature of 60-180DEG C, a water-to-ethylene carbonate molar ratio of 1-10, and a catalyst-to-ethylene carbonate weight ratio of 0.005-1, the reaction raw materials and the catalyst contact for 1-8h to produce ethylene glycol; and the catalyst is exchange type composite carboxyl imidazole resin. The method well solves the problems, and can be used for the industrial production of ethylene glycol by hydrolysis of ethylene carbonate.
Description
Technical field
The present invention relates to a kind of method that ethylene carbonate Ester hydrolysis produces ethylene glycol.
Background technology
The hydrolysis of ester class is a kind of important chemical reaction, is widely used in the every field of petrochemical iy produced, wherein cyclic carbonate, and the hydrolysis as NSC 11801 (EC), propylene carbonate etc. has very important fundamental position especially.
The hydrolysis of EC is the important step of being produced ethylene glycol (EG) by oxyethane (EO) catalytic hydration two-step approach.EG is a kind of important Organic Chemicals, is mainly used to produce trevira, frostproofer, unsaturated polyester resin, nonionogenic tenside, thanomin and explosive etc.The production technology of EG is mainly divided into petrochemical industry route and non-petrochemical industry route.In petrochemical industry route, have EO direct hydration method and EO catalytic hydration, direct hydration method needs higher water ratio (being greater than 20) guarantee to have higher EG yield, and it is higher to consume energy in the process of the EG that purifies.EO catalytic hydration comprises again direct catalytic hydration and EC route.Direct catalytic hydration water than relatively low (about about 5), but still needs to evaporate a large amount of water of removing, and first EC route then utilizes the CO discharged during oxidation of ethylene EO
2for raw material and EO generate EC under the effect of catalyzer, be then that intermediate product catalytic hydrolysis generates EG with EC, this process water, than close to stoichiometric ratio 1, is the industrialization direction of EO EG from now on.
Mainly contain for the catalyzer of annular carbonic acid esters hydrolysis at present: compound (JP822106631,1982 of alkali (soil) metal carbonate (hydrogen) salt (US4524224,1985), Mo and W; WO2009071651,2009), quaternary ammonium salt, quaternary ammonium salt and ion exchange resin (EP0133763,1989; US6080897,2000; US20090156867,2009) etc.But more or less there is the problems such as catalyst separating difficulty, activity is low, stability is not high in these catalyst system.
Strong base ion exchange resin is all better for activity and selectivity during annular carbonic acid esters hydrolysis, but because its resistance to gentle swell-resistant can be poor, very fast (the YuFP of activity decrease in catalytic reaction process, CaiH, HeWJ, etal.J.Appl.Polym.Sci., 2010,115:2946 ~ 2954), this causes this catalyzer to fail industrialized major cause.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists resin catalyst not heatproof, problem that easily swelling, activity decrease is fast, provides a kind of new ethylene carbonate Ester hydrolysis to produce the method for ethylene glycol.The method has the slow feature of catalyzer heatproof, swelling resistance, activity decrease.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ethylene carbonate Ester hydrolysis produces the method for ethylene glycol, with NSC 11801 and water for raw material, it is 60 ~ 180 DEG C in temperature of reaction, water and NSC 11801 mole be 1 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, reaction raw materials and catalyst exposure 1 ~ 8 hour, generating glycol; Described catalyzer is crossover compound carboxyl imidazoles 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) carboxyl imidazoles is obtained after Halogen carboxylic acid and imidazoles being reacted;
5) in described compound chlorine ball, add described carboxyl imidazoles, after reaction, obtain described compound carboxyl imidazoles resin;
6) in described compound carboxyl imidazoles resin, add exchanger, after reaction, obtain described crossover compound hydroxy imidazole resin.
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: in imidazoles, add the Halogen carboxylic acid X-R-COOH being equivalent to imidazoles mol ratio 1:1 and the organic solvent being equivalent to imidazoles mass ratio 200 ~ 1000%, react 4 ~ 30 hours under reflux state, reaction terminates rear underpressure distillation and obtains carboxyl imidazoles except after desolventizing; In described Halogen carboxylic acid, X is Cl, Br or I, and R is methylene radical, ethyl, propyl group, sec.-propyl, normal-butyl or n-pentyl; 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: add in compound chlorine ball be equivalent to complex microsphere weight 200 ~ 700% organic solvent, 30 ~ 300% carboxyl imidazoles, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain compound carboxyl 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 6) reaction process is: adds in compound carboxyl imidazoles resin and is equivalent to the exchanger of compound carboxyl imidazoles weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described crossover compound hydroxy imidazole resin after oven dry; Wherein, described exchanger comprises NaHCO
3or KHCO
3in at least one.
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 the mol ratio of water and NSC 11801 is 1 ~ 8, and the weight ratio of catalyzer and NSC 11801 is 0.01 ~ 0.5, and the reaction times is 1 ~ 6 hour.
The inventive method adopts crossover compound carboxyl imidazolyl resin to be catalyzer, owing to being mixed with the nano material of high strength in resin base material, thus enhance the swelling resistance performance of resin, in addition, because hydroxyl can provide hydrogen bond with priming reaction substrate, thus improve catalytic activity.Catalyzer of the present invention is used in the reaction of preparing ethyl glycol by hydrolysis of ethylene carbonate, temperature of reaction 100 DEG C, the mol ratio of water and NSC 11801 is 1.5, the weight ratio of catalyzer and NSC 11801 is under 0.05 condition, the transformation efficiency of NSC 11801 is 98.3%, and the selectivity of ethylene glycol is 99.4%, after catalyzer reuses 5 times, activity decrease 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 synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 28.2 grams of Mono Chloro Acetic Acids and 120 milliliters of tetrahydrofuran (THF)s, reacts 8 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S1.
The synthesis of compound carboxyl imidazoles resin: add 20 grams of complex microspheres in 500 milliliters of there-necked flasks, 8 grams of carboxyl imidazoles S1 and 150 milliliter tetrahydrofuran (THF)s, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, use methylene dichloride, acetone and water washing successively respectively, dry under vacuo and obtain compound carboxyl imidazoles Resin A 1.
The exchange of compound carboxyl imidazoles resin: in 200 ml beakers, adds 10 grams of compound carboxyl imidazoles Resin A, 1,20 grams of NaHCO
3with 100 grams of deionized waters, stirring at room temperature, after 18 hours, is filtered, and after deionized water wash, repeats said process 2 times, filters, and with deionized water wash, dries under vacuo and obtains crossover compound carboxyl imidazoles Resin A 2.
[embodiment 2]
Complex microsphere is identical with [embodiment 1] with the building-up process of compound chlorine ball.
The synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 41.5 grams of bromoacetic acids and 120 milliliters of acetonitriles, reacts 30 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S2.
The synthesis of compound carboxyl imidazoles resin: add 20 grams of complex microspheres in 500 there-necked flasks, 38 grams of carboxyl imidazoles S2 and 120 milliliter toluene, stirring reaction 30 hours at reflux, reaction terminates rear mistake and filters mother liquor, use methylene dichloride, acetone and water washing successively respectively, dry under vacuo and obtain compound carboxyl imidazoles Resin A 3.
The exchange of compound carboxyl imidazoles resin: in 200 ml beakers, adds 10 grams of compound carboxyl imidazoles Resin A, 1,10 grams of KHCO
3with 120 grams of deionized waters, stirring at room temperature, after 18 hours, is filtered, and after deionized water wash, repeats said process 2 times, filters, and with deionized water wash, dries under vacuo and obtains crossover compound carboxyl imidazoles Resin A 4.
[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 synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 45.7 grams of 3-bromo-propionic acids and 120 milliliters of acetonitriles, reacts 30 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S3.
The synthesis of compound carboxyl imidazoles resin and exchange, with [embodiment 2], are that used compound chlorine ball and hydroxy imidazole are respectively compound chlorine ball B and carboxyl imidazoles S3, obtain compound carboxyl imidazoles resin B 1 and crossover compound carboxyl imidazoles resin B 2.
[embodiment 4]
The synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 45.7 grams of 3-bromo-propionic acids and 120 milliliters of acetonitriles, reacts 30 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S4.
The synthesis of compound carboxyl imidazoles resin and exchange, with [embodiment 2], are that used compound chlorine ball and hydroxy imidazole are respectively compound chlorine ball B and carboxyl imidazoles S4, obtain compound carboxyl imidazoles resin B 3 and crossover compound carboxyl imidazoles resin B 4.
[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 synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 54.0 grams of 5-bromine valeric acids and 120 milliliters of acetonitriles, reacts 30 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S5.
The synthesis of compound carboxyl imidazoles resin and exchange, with [embodiment 2], are that used compound chlorine ball and hydroxy imidazole are respectively compound chlorine ball C and carboxyl imidazoles S5, obtain compound carboxyl imidazoles resin C1 and crossover compound carboxyl imidazoles resin C2.
[embodiment 6]
The synthesis of carboxyl imidazoles: in 500 milliliters of there-necked flasks, adds 20 grams of imidazoles, 50.0 grams of 4-bromo-butyric acids and 100 milliliters of toluene, reacts 8 hours at reflux, after reaction terminates, boils off solvent, obtains carboxyl imidazoles S6.
The synthesis of compound carboxyl imidazoles resin and exchange, with [embodiment 2], are that used compound chlorine ball and hydroxy imidazole are respectively compound chlorine ball C and carboxyl imidazoles S6, obtain compound carboxyl imidazoles resin C3 and crossover compound carboxyl imidazoles resin C4.
[comparative example 1]
The preparation process of catalyzer is identical with [embodiment 1], does not just add multi-walled carbon nano-tubes, obtains compound carboxyl imidazoles resin CA1 and crossover compound carboxyl imidazoles resin CA2.
[embodiment 7]
Crossover compound carboxyl imidazoles Resin A 2 prepared by [embodiment 1] is prepared in the reaction of NSC 11801 for ethylene carbonate Ester hydrolysis.44.0 grams of NSC 11801,13.5 grams of deionized waters and 2.2 grams of catalyzer are placed in 100 milliliters of autoclaves (mol ratio of water and NSC 11801 is 1.5, and the mass ratio of catalyzer and NSC 11801 is 0.05), and 100 DEG C are reacted 2 hours.After reaction terminates, autoclave is cooled to room temperature, emptying.Get liquid product and carry out gas chromatographic analysis, the transformation efficiency recording NSC 11801 is 98.3%, and the selectivity of ethylene glycol is 99.4%, and the swelling capacity of resin catalyst is SSWELL is 5.2%.
[comparative example 2]
Catalyst activity test condition is identical with [embodiment 7], just catalyzer used is strong base hydroxy imidazole resin CA2, the transformation efficiency obtaining NSC 11801 is 98.5%, the selectivity of ethylene glycol is 99.6%, the selectivity of many ethylene glycol is 0.4%, and the swelling capacity of resin catalyst is SSWELL is 18.5%.
[embodiment 8-12]
Change the crossover compound carboxyl imidazoles 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]
With [embodiment 7], just temperature of reaction is 120 DEG C.The transformation efficiency obtaining NSC 11801 is 99.0%, and the selectivity of ethylene glycol is 99.1%, and the selectivity of many ethylene glycol is 0.9%.
[embodiment 14]
With [embodiment 7], just temperature of reaction is 140 DEG C.The transformation efficiency obtaining NSC 11801 is 99.5%, and the selectivity of ethylene glycol is 99.1%, and the selectivity of many ethylene glycol is 0.9%.
[embodiment 15]
With [embodiment 7], just temperature of reaction is 80 DEG C.The transformation efficiency obtaining NSC 11801 is 80.2%, and the selectivity of ethylene glycol is 99.2%, and the selectivity of many ethylene glycol is 0.8%.
[embodiment 16]
With [embodiment 7], just the quality of deionized water is 27.0 grams (mol ratio of water and NSC 11801 is 3:1).Obtaining ethylene carbonate ester conversion rate is 99.1%, and the selectivity of ethylene glycol is 99.2%, and the selectivity of many ethylene glycol is 0.8%.
[embodiment 17]
With [embodiment 7], just the quality of deionized water is 72.0 grams (mol ratio of water and NSC 11801 is 8:1).Obtaining ethylene carbonate ester conversion rate is 99.3%, and the selectivity of ethylene glycol is 99.2%, and the selectivity of many ethylene glycol is 0.8%.
[embodiment 18]
With [embodiment 7], just the consumption of catalyzer is 1.1 grams (ratio of catalyzer and NSC 11801 is 0.025:1).Obtaining ethylene carbonate ester conversion rate is 81.5%, and the selectivity of ethylene glycol is 99.3%, and the selectivity of many ethylene glycol is 0.7%.
[embodiment 19]
With [embodiment 7], just catalyst levels is 8.8 grams (ratio of catalyzer and NSC 11801 is 0.2:1).Obtaining ethylene carbonate ester conversion rate is 99.2%, and the selectivity of ethylene glycol is 98.1%, and the selectivity of many ethylene glycol is 1.9%.
[embodiment 20]
With [embodiment 7], just the quality of catalyzer is 17.6 grams (mass ratio of catalyzer and NSC 11801 is 0.4:1).Obtaining ethylene carbonate ester conversion rate is 99.7%, and the selectivity of ethylene glycol is 95.0%, and the selectivity of many ethylene glycol is 5.0%.
[embodiment 21]
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 2.
Table 2
[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 3.
Table 3
Claims (10)
1. the method for an ethylene carbonate Ester hydrolysis production ethylene glycol, with NSC 11801 and water for raw material, it is 60 ~ 180 DEG C in temperature of reaction, water and NSC 11801 mole be 1 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, reaction raw materials and catalyst exposure 1 ~ 8 hour, generating glycol; Described catalyzer is crossover compound carboxyl imidazoles 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) carboxyl imidazoles is obtained after Halogen carboxylic acid and imidazoles being reacted;
5) in described compound chlorine ball, add described carboxyl imidazoles, after reaction, obtain described compound carboxyl imidazoles resin;
6) in described compound carboxyl imidazoles resin, add exchanger, after reaction, obtain described crossover compound hydroxy imidazole resin.
2. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that the weight percent concentration of described water solution A is 0.5 ~ 2%.
3. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol 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. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol 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. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that step 4) reaction process is: in imidazoles, add the Halogen carboxylic acid X-R-COOH being equivalent to imidazoles mol ratio 1:1 and the organic solvent being equivalent to imidazoles mass ratio 200 ~ 1000%, react 4 ~ 30 hours under reflux state, reaction terminates rear underpressure distillation and obtains carboxyl imidazoles except after desolventizing; In described Halogen carboxylic acid, X is Cl, Br or I, and R is methylene radical, ethyl, propyl group, sec.-propyl, normal-butyl or n-pentyl; Described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
6. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that step 5) reaction process is: add in compound chlorine ball be equivalent to complex microsphere weight 200 ~ 700% organic solvent, 30 ~ 300% carboxyl imidazoles, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain compound carboxyl imidazoles resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
7. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that step 6) reaction process is: adds in compound carboxyl imidazoles resin and is equivalent to the exchanger of compound carboxyl imidazoles weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described crossover compound hydroxy imidazole resin after oven dry; Wherein, described exchanger comprises NaHCO
3or KHCO
3in at least one.
8. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it 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.
9. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that described auxiliary agent one is selected from polyvinyl alcohol; Described auxiliary agent two is selected from polystyrene.
10. ethylene carbonate Ester hydrolysis produces the method for ethylene glycol according to claim 1, it is characterized in that temperature of reaction is 80 ~ 160 DEG C, the mol ratio of water and NSC 11801 is 1 ~ 8, and the weight ratio of catalyzer and NSC 11801 is 0.01 ~ 0.5, and the reaction times is 1 ~ 6 hour.
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| CN107915578A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method that ethylene carbonate ester hydrolysis produces ethylene glycol |
| CN107915578B (en) * | 2016-10-08 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by ethylene carbonate hydrolysis |
| CN107999130A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of dicyclopentadiene/N- Nvinylimidazole copolymers type ester hydrolysis catalyst and preparation method thereof |
| CN107999130B (en) * | 2016-10-28 | 2022-02-08 | 中国石油化工股份有限公司 | Dicyclopentadiene/N-vinyl imidazole copolymer type ester hydrolysis catalyst and preparation method thereof |
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| CN105503528B (en) | 2017-09-15 |
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