CN105503609A - Production method of dimethyl carbonate - Google Patents
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- CN105503609A CN105503609A CN201410498142.5A CN201410498142A CN105503609A CN 105503609 A CN105503609 A CN 105503609A CN 201410498142 A CN201410498142 A CN 201410498142A CN 105503609 A CN105503609 A CN 105503609A
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Abstract
The invention relates to a production method of dimethyl carbonate, and mainly solves the problems of easy swelling and rapid activity decline of resin in the prior art. According to a technical scheme, ethylene carbonate and methanol are adopted as the raw materials, under the conditions of a reaction temperature of 60-160DEG C, a weight ratio of a catalyst to ethylene carbonate of 2-10, and a weight ratio of the catalyst to ethylene carbonate of 0.005-1, the raw materials and the catalyst contact to react so as to produce dimethyl carbonate. The catalyst is strong alkali type compound hydroxy imidazole resin. The method well solves the problem, and can be used for the industrial production of dimethyl carbonate.
Description
Technical field
The present invention relates to a kind of method of producing methylcarbonate.
Background technology
Methylcarbonate (DMC) chemical property is active, physical properties is excellent, and nontoxic, readily biodegradable, a kind of new low stain, environmentally friendly green basic chemical industry raw material, can be used as solvent, gasoline dope, lithium-ion battery electrolytes and carbonylation, methylate and carbomethoxy reagent, be widely used in chemical field, current each state is all in the Green Chemistry process of active research based on this eco-friendly industrial chemicals of DMC.Wherein ester-interchange method is better than reaction conditions gentleness, the high and coproduction ethylene glycol of yield or propylene glycol and become the method having now industrial prospect.
In general, transesterification reaction is mainly with (F.Risseetal., US2011040117 such as alkali metal hydroxide, alkaline carbonate and alkali metal alcohols; C.P.Allaisetal., WO2010063780) as catalyzer, but be homogeneous catalyst because of it, not easily with product separation, reuse difficulty.Conventional heterogeneous catalyst comprises and is carried on basic metal on carrier or an alkali metal salt, metal oxide catalyst, the zeolite of alkali (soil) metal exchange or clay material and ion exchange resin etc.Be carried on the basic metal on carrier or an alkali metal salt, as KF/Al
2o
3, NaOH/ chitosan and Cs
2cO
3/ SiO
2-Al
2o
3deng (H.Zhang, CN101249452; Y.Zhao, CN101121147; C.D.Changetal., WO0156971A1), their shortcoming is easily by water in air and CO
2impact, make activity decrease; Metal oxide catalyst, as Al
2o
3, (B.M.Bhanage, etal.Appl.Catal.A219 (2001) 259-266 such as MgO; J.S.Buchananetal., US2005080287; Z.Z.Jiangetal., US6207850), and the zeolite of alkali (soil) metal exchange or clay material, as (C.D.Changetal., the WO0073256 such as Cs-ZSM-5, Mg-smectite; B.M.Bhanageetal.Catal.Lett.83 (2002) 137-141), the shortcoming of this two classes catalyzer is that activity or selectivity are usually lower; Ion exchange resin, as quaternary ammonium type or tertiary amine resin (J.F.Kniftonetal., J.Mol.Catal.A67 (1991) 389-399; M.Caoetal.React.Kinet.Catal.Lett.88 (2006) 251-259), the usual not swelling resistance of this kind of catalyzer, and long-time activity decrease is than very fast.
Summary of the invention
It is easily swelling that technical problem to be solved by this invention is that prior art exists resin, and the problem that activity decrease is fast, provides a kind of method of production methylcarbonate newly.The method has catalyzer swelling resistance, the feature that activity decrease is slow.
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 methylcarbonate, with NSC 11801 and methyl alcohol for reaction raw materials, it is 60 ~ 160 DEG C in temperature of reaction, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, and raw material and catalyst exposure react and obtain methylcarbonate in 1 ~ 8 hour; Described catalyzer is strong base 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) halogen-type compound hydroxy imidazole resin is obtained add hydroxyhalide reaction in described compound imidazoles resin after;
6) add in described halogen-type compound hydroxy imidazole resin after highly basic exchanges and obtain described strong base 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: 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 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, step 6) reaction process is: adds in described halogen-type compound hydroxy imidazole resin and is equivalent to the highly basic of halogen-type compound hydroxy imidazole weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described strong base compound hydroxy imidazole resin after oven dry; Wherein, described highly basic comprises NaOH, KOH, LiOH, Ca (OH)
2, Sr (OH)
2or Ba (OH)
2in 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 ~ 140 DEG C, and the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 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 strong base compound hydroxy imidazole 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.The transesterification reaction that catalyzer of the present invention is used for NSC 11801 and methyl alcohol is prepared in methylcarbonate, temperature of reaction 100 DEG C, the mol ratio of methyl alcohol and NSC 11801 is 4, and the weight ratio of catalyzer and NSC 11801 is under 0.1 condition, reacts 4 hours, the transformation efficiency of NSC 11801 is 73.5%, the selectivity of methylcarbonate is 98.7%, and the selectivity of ethylene glycol is 99.2%, 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 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.
The transition of halogen-type compound hydroxy imidazole resin: in 200 ml beakers, add 10 grams of halogen-type compound hydroxy imidazole Resin A, 1,3 grams of NaOH and 180 gram deionized waters, stirring at room temperature is after 2 hours, filter, after deionized water wash, repeat said process 2 times, filter, with deionized water wash, dry under vacuo and obtain strong base compound hydroxy imidazole Resin A 3.
[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 4 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 5 under vacuo.
The transition of halogen-type compound hydroxy imidazole resin: in 200 ml beakers, add 10 grams of halogen-type compound hydroxy imidazole Resin A, 5,20 grams of Ba (OH)
2with 40 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 strong base compound hydroxy imidazole Resin A 6.
[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 and made the transition, obtains halogen-type compound hydroxy imidazole resin B 2 and strong base compound hydroxy imidazole resin B 3.
[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 4 under vacuo.
The method of halogen-type compound hydroxy imidazole resin B 4 described in [embodiment 2] is made the transition, obtains strong base compound hydroxy imidazole resin B 5.
[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.
The method of halogen-type compound hydroxy imidazole resin C2 described in [embodiment 2] is made the transition, obtains strong base compound hydroxy imidazole resin C3.
[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 C4 and strong base compound hydroxy imidazole resin C5.
[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 and strong base compound hydroxy imidazole resin CA3 respectively.
[embodiment 7]
Strong base compound hydroxy imidazole Resin A 3 prepared by [embodiment 1] is prepared in the reaction of methylcarbonate for NSC 11801 and methyl alcohol transesterify.22.0 grams of NSC 11801,32.0 grams of methyl alcohol and 2.2 grams of A3 catalyzer are placed in 100 milliliters of autoclaves (mol ratio of methyl alcohol and NSC 11801 is 4, and the weight ratio of catalyzer and NSC 11801 is 0.1), and 100 DEG C are reacted 4 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 73.5%, and the selectivity of methylcarbonate is 98.7%, and the selectivity of ethylene glycol is 99.2%, and the swelling capacity of resin catalyst is S
sWELLbe 4.2%.
[comparative example 2]
Catalyst activity test condition is identical with [embodiment 7], just catalyzer used is strong base compound hydroxy imidazole resin CA3, the transformation efficiency obtaining NSC 11801 is 71.5%, the selectivity of methylcarbonate is 98.5%, the selectivity of ethylene glycol is 98.9%, and the swelling capacity of resin catalyst is S
sWELLbe 21.5%.
[embodiment 8-12]
Change the strong base 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]
With [embodiment 7], just temperature of reaction is 120 DEG C.The transformation efficiency obtaining NSC 11801 is 70.3%, and the selectivity of methylcarbonate is 96.9%, and the selectivity of ethylene glycol is 97.2%.
[embodiment 14]
With [embodiment 7], just temperature of reaction is 140 DEG C.The transformation efficiency obtaining NSC 11801 is 66.5%, and the selectivity of NSC 11801 is 97.5%, and the selectivity of ethylene glycol is 93.5%.
[embodiment 15]
With [embodiment 7], just temperature of reaction is 80 DEG C.The transformation efficiency obtaining NSC 11801 is 46.5%, and the selectivity of NSC 11801 is 99.1%, and the selectivity of ethylene glycol is 98.5%.
[embodiment 16]
With [embodiment 7], just the quality of methyl alcohol is 48 grams (mol ratio of methyl alcohol and NSC 11801 is 6:1).Obtaining ethylene carbonate ester conversion rate is 74.3%, and the selectivity of methylcarbonate is 99.1%, and the selectivity of ethylene glycol is 98.3%.
[embodiment 17]
With [embodiment 7], just the quality of methyl alcohol is 16.0 grams (mol ratio of methyl alcohol and NSC 11801 is 2:1).Obtaining ethylene carbonate ester conversion rate is 53.2%, and the selectivity of methylcarbonate is 96.4%, and the selectivity of ethylene glycol is 97.9%.
[embodiment 18]
With [embodiment 7], just the quality of catalyzer is 0.55 gram (mass ratio of catalyzer and NSC 11801 is 0.025:1).Obtaining ethylene carbonate ester conversion rate is 63.8%, and the selectivity of methylcarbonate is 98.2%, and the selectivity of ethylene glycol is 97.1%.
[embodiment 19]
With [embodiment 7], just the quality of catalyzer is 1.1 grams (part by weight of catalyzer and NSC 11801 is 0.05:1).Obtaining ethylene carbonate ester conversion rate is 68.9%, and the selectivity of methylcarbonate is 95.2%, and the selectivity of ethylene glycol is 95.3%.
[embodiment 20]
With [embodiment 7], just the quality of catalyzer is 8.8 grams (mass ratio of catalyzer and NSC 11801 is 0.4:1).Obtaining ethylene carbonate ester conversion rate is 75.5%, and the selectivity of methylcarbonate is 97.2%, and the selectivity of ethylene glycol is 95.3%.
[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. produce the method for methylcarbonate for one kind, with NSC 11801 and methyl alcohol for reaction raw materials, it is 60 ~ 160 DEG C in temperature of reaction, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 10, the weight ratio of catalyzer and NSC 11801 is under the condition of 0.005 ~ 1, and raw material and catalyst exposure react and obtain methylcarbonate in 1 ~ 8 hour; Described catalyzer is strong base 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) halogen-type compound hydroxy imidazole resin is obtained add hydroxyhalide reaction in described compound imidazoles resin after;
6) add in described halogen-type compound hydroxy imidazole resin after highly basic exchanges and obtain described strong base compound hydroxy imidazole resin.
2. produce the method for methylcarbonate according to claim 1, it is characterized in that the weight percent concentration of described water solution A is 0.5 ~ 2%.
3. produce the method for methylcarbonate 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. produce the method for methylcarbonate 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. produce the method for methylcarbonate 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. produce the method for methylcarbonate 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 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. produce the method for methylcarbonate according to claim 1, it is characterized in that step 6) reaction process is: adds in described halogen-type compound hydroxy imidazole resin and is equivalent to the highly basic of halogen-type compound hydroxy imidazole weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described strong base compound hydroxy imidazole resin after oven dry; Wherein, described highly basic comprises NaOH, KOH, LiOH, Ca (OH)
2, Sr (OH)
2or Ba (OH)
2in at least one.
8. produce the method for methylcarbonate 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. produce the method for methylcarbonate 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. produce the method for methylcarbonate according to claim 1, it is characterized in that temperature of reaction is 80 ~ 140 DEG C, the mol ratio of methyl alcohol and NSC 11801 is 2 ~ 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4691041A (en) * | 1986-01-03 | 1987-09-01 | Texaco Inc. | Process for production of ethylene glycol and dimethyl carbonate |
| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
| CN102126927A (en) * | 2011-01-06 | 2011-07-20 | 中国科学院过程工程研究所 | Method for preparing glycol and carbonic ester by heterogeneous catalysis |
| CN103495437A (en) * | 2013-09-18 | 2014-01-08 | 华东师范大学 | Supported ionic liquid catalyst, as well as preparation and application thereof |
-
2014
- 2014-09-25 CN CN201410498142.5A patent/CN105503609B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4691041A (en) * | 1986-01-03 | 1987-09-01 | Texaco Inc. | Process for production of ethylene glycol and dimethyl carbonate |
| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
| CN102126927A (en) * | 2011-01-06 | 2011-07-20 | 中国科学院过程工程研究所 | Method for preparing glycol and carbonic ester by heterogeneous catalysis |
| CN103495437A (en) * | 2013-09-18 | 2014-01-08 | 华东师范大学 | Supported ionic liquid catalyst, as well as preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 赵峰等: "酯交换合成碳酸二甲酯催化剂研究进展", 《工业催化》 * |
| 马程明等: "碱性离子液体催化碳酸乙烯酯甲醇酯交换合成碳酸二甲酯", 《精细石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
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