CN105503608B

CN105503608B - The method for producing ethylene carbonate

Info

Publication number: CN105503608B
Application number: CN201410498073.8A
Authority: CN
Inventors: 陈梁锋; 何文军
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2014-09-25
Filing date: 2014-09-25
Publication date: 2017-10-27
Anticipated expiration: 2034-09-25
Also published as: CN105503608A

Abstract

The present invention relates to a kind of method for producing ethylene carbonate, the problem of prior art has low catalyst activity, easy in inactivation is mainly solved.The present invention is by using using oxirane and carbon dioxide as raw material, it it is 60~200 DEG C in reaction temperature, reaction pressure is 0.1~10.0 MPa, and the weight ratio of catalyst and oxirane is that under conditions of 0.001~1, reaction raw materials are contacted with catalyst generates ethylene carbonate；The catalyst is that the technical scheme of the compound hydroxy imidazole resin of halogen-type preferably solves the problem, in the industrial production that ethylene carbonate is prepared available for oxirane and carbon dioxide.

Description

The method for producing ethylene carbonate

Technical field

The present invention relates to a kind of method for producing ethylene carbonate.

Background technology

Ethylene carbonate is the solvent and fine-chemical intermediate of a kind of function admirable, is that the potential basis of organic chemical industry is former Material.While CO₂It is a kind of greenhouse gases, how effectively fixation has become one of problem of this century most challenge, and Pass through oxirane and CO₂It is exactly the good fixing means of one of which to react synthesizing ethylene carbonate.With recently with carbonic acid Vinyl acetate is that raw material co-producing dimethyl carbonate and glycol reaction are of increasing concern, and CO is fixed by cyclic carbonate₂Way Footpath also receives increasing attention.

The method majority for the production cyclic carbonate reported at present is to use Lewis acid metal compounds and Lewis alkali The binary homogeneous catalyst of composition, wherein the Lewis acid metal compounds used include alkali (soil) metal halide, transition metal Salt, transition metal or Main group metal complexes, used Lewis alkali have organic base (such as DMF, DMAP etc.), quaternary ammonium salt, quaternary phosphines Salt, imidazole salts, crown ether etc..Perhaps activity, selectivity be not high for these catalyst system and catalyzings, or has used toxicity very strong organic molten Agent, and homogeneous catalysis system have the shortcomings that catalyst be difficult to separation.And more heterogeneous catalysis system bag is used at present Include metal oxide system (such as CeO₂-ZrO₂, Green Chem.2004,6,206-214), basic zeolite system (such as Cs/KX, J.Catal.2001,199,85-91) etc., these active catalyst systems are low, and the required reaction time is longer.Xia Chungu etc. By ZnCl₂It is immobilized on chitin carrier, although achieving higher catalytic activity, catalyst applies mechanically activity drop after 5 times It is low by about 8%, thus it is speculated that to be the loss (Appl.Catal.A 2005,279,125- of catalyst activity component the reason for possible 129).Therefore, developing a kind of easily separated, active high, reaction condition, gently, the catalyst system and catalyzing of easy in inactivation does not seem particularly significant.

The content of the invention

The technical problems to be solved by the invention are the problem of prior art have that catalyst activity is low, easily inactivated, and are carried For a kind of method of new production ethylene carbonate.The characteristics of this method has catalyst activity height, not easy in inactivation.

In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method for producing ethylene carbonate, It it is 60~200 DEG C in reaction temperature, reaction pressure is 0.1~10.0 MPa, catalysis using oxirane and carbon dioxide as raw material The weight ratio of agent and oxirane be 0.001~1 under conditions of, reaction raw materials contacted with catalyst generates ethylene carbonate；Institute State catalyst and be combined hydroxy imidazole resin for halogen-type, its preparation method comprises the following steps：

1) auxiliary agent one is made into water solution A；Monomer, comonomer, nano material, initiator and auxiliary agent two are made into molten Liquid B；

The monomer is selected from methyl methacrylate, butyl acrylate, styrene, α-methylstyrene, 4- butyl benzene second At least one of alkene or acrylonitrile；The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl At least one of base phenylmethane or divinylbenzene；The nano material be selected from multi-walled carbon nanotube, single-walled carbon nanotube, At least one of C60 or C70 fullerenes；The initiator is selected from benzoyl peroxide, azodiisobutyronitrile, peroxidating bay At least one of acyl or isopropyl benzene hydroperoxide；The auxiliary agent one is selected from polyvinyl alcohol, gelatin, starch, methylcellulose, swollen At least one of profit soil or calcium carbonate；The auxiliary agent two is in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or paraffin It is at least one；

Wherein, by weight percentage, the consumption of monomer is 85~95%, and the consumption of comonomer is 2~5%, nanometer The consumption of material is 0.1~3%, and the consumption of initiator is 0.1~10%；The consumption of auxiliary agent one for monomer consumption 150~ 400%, the consumption of auxiliary agent two is the 50~100% of monomer consumption；

2) solution B is mixed with solution A, reaction obtains complex microsphere；

3) chloromethylation reagents and zinc chloride are added into the complex microsphere, compound chlorine ball is obtained；

4) added into the compound chlorine ball and compound imidazoles resin is obtained after imidazoles reaction；

5) added into the compound imidazoles resin and the compound hydroxy imidazole of the halogen-type is obtained after hydroxyhalide reaction Resin.

In above-mentioned technical proposal, it is preferable that the weight percent concentration of the water solution A is 0.5~2%.

In above-mentioned technical proposal, it is preferable that step 2) course of reaction is：Solution B is in 60~75 DEG C of prepolymerizations 0.5~2.5 Hour, then solution B is mixed with solution A, 70~90 DEG C is warming up to and reacts 5~15 hours, then be warming up to 90~100 DEG C of reactions 5~15 hours；After reaction terminates, through extracting, washing, filtering, dry, sieving, 0.35~0.60 millimeter of particle size range is obtained Complex microsphere.

In above-mentioned technical proposal, it is preferable that step 3) course of reaction is：Added into the complex microsphere equivalent to compound The chloromethylation reagents of microspheres weight 200~500%, and be catalyzed equivalent to the zinc chloride of complex microsphere weight 20~70% Agent, is reacted 8~30 hours at 30~60 DEG C, and compound chlorine ball, drying to constant weight are obtained through filtering, washing；The chloromethylation Reagent is selected from least one of chloromethyl ether or 1,4- dichloro methyl butyl ethers.

In above-mentioned technical proposal, it is preferable that step 4) course of reaction is：Added into the compound chlorine ball equivalent to compound Reacted 4~30 hours under the organic solvent of microspheres weight 200~700%, 30~300% imidazoles, reflux state, scrubbed, The compound imidazoles resin is obtained after drying；Wherein, the organic solvent is selected from acetonitrile, benzonitrile, toluene, tetrahydrofuran, two At least one of NMF, chloroform or dichloroethanes.

In above-mentioned technical proposal, it is preferable that step 5) course of reaction is：Added into the compound imidazoles resin equivalent to Under hydroxyhalide X-R-OH, 300~1000% organic solvent of compound imidazoles weight resin 30~300%, reflux state Reaction 4~30 hours, obtains the halogen-type after scrubbed, drying and is combined hydroxy imidazole resin；Wherein, the organic solvent choosing From at least one of acetonitrile, benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform or dichloroethanes, hydroxyhalide X is Cl, Br or I in thing X-R-OH, and R is ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl or n-hexyl.

In above-mentioned technical proposal, it is preferable that the monomer is selected from styrene.

In above-mentioned technical proposal, it is preferable that the comonomer is selected from divinylbenzene.

In above-mentioned technical proposal, it is preferable that the nano material is selected from multi-walled carbon nanotube.

In above-mentioned technical proposal, it is preferable that the initiator is selected from benzoyl peroxide.

In above-mentioned technical proposal, it is preferable that the auxiliary agent one is selected from polyvinyl alcohol.

In above-mentioned technical proposal, it is preferable that the auxiliary agent two is selected from polystyrene.

In above-mentioned technical proposal, it is preferable that reaction temperature is 80~160 DEG C, reaction pressure is 0.5~8.0 MPa, catalysis The weight ratio of agent and oxirane is 0.005~0.5.

The inventive method uses halogen-type to be combined hydroxy imidazole resin for catalyst, due to being mixed in resin base material The nano material of high intensity, so as to enhance the resistance to swelling energy of resin, prevents catalyst due to being lost caused by being swelled It is living.Further, since hydroxyl can provide hydrogen bond with priming reaction substrate, so as to improve catalytic activity.The catalyst of the present invention It is 120 DEG C in reaction temperature, reaction pressure is 2.0MPa, is reacted 3 hours when the mass ratio of catalyst and oxirane is 0.02, The conversion ratio of oxirane is 98.6%, and the selectivity of ethylene carbonate is 99.7%, and catalyst separates rear enclosure with 5 times, activity Reduction is less than 5%, achieves preferable technique effect.

Below by embodiment, the invention will be further elaborated.It is necessarily pointed out that following examples are only used Further illustrated in the present invention, it is impossible to be interpreted as limiting the scope of the invention.

Embodiment

【Embodiment 1】

58.0 grams of styrene, 0.6 gram of divinylbenzene, 30 grams of polystyrene and 0.6 are added in 500 milliliters of three-necked flasks Gram benzoyl peroxide initiator, in being stirred 2.0 hours at 60 DEG C；Then 2.8 grams of multi-walled carbon nanotubes are added, continue to stir 1 Hour carries out prepolymerization.Add the 260 ml deionized water solution for being dissolved with 2.5 grams of polyvinyl alcohol.Mixing speed is adjusted, together When be progressively warming up to 80 DEG C, react 5 hours；90 DEG C are warming up to again, is reacted 5 hours, 98 DEG C are finally warming up to, and are reacted 6 hours. After reaction terminates, supernatant liquid is poured out, is washed with 85 DEG C of hot washes, then with cold water, is then filtered, be put into baking oven 80 DEG C Drying, sieving, complex microsphere A of the collection cut size in the range of 0.35~0.60 millimeter.

The chloromethylation of complex microsphere：In 500 milliliters of three-necked flask, 50 grams of complex microsphere A and 250 milliliters of chlorine are added Methyl ether, is stored at room temperature 4 hours, starts stirring, and it is catalyst to add 15 grams of zinc chloride, is warming up to 50 DEG C and reacts 8 hours, chlorination knot Room temperature is cooled to after beam, chlorination mother solution is filtered out, methanol cyclic washing is used, dried 8 hours at 100 DEG C, compound chlorine ball A is obtained.

The imidazoles of compound chlorine ball：In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball A of addition, 100 milliliters of tetrahydrofurans, 8 grams of imidazoles, stirring reaction 12 hours at reflux, reaction is filtered to remove mother liquor after terminating, respectively successively with dichloromethane, Acetone and water washing, imidazoles Resin A 1 must be combined under vacuo by drying.

The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks A1,9.2 grams of ethylene bromohyrins and 200 milliliters of acetonitriles, react 20 hours at reflux, and reaction is filtered to remove mother liquor after terminating, Use dichloromethane, acetone and water washing successively respectively, the compound hydroxy imidazole Resin A 2 of halogen-type is dried to obtain under vacuo.

【Embodiment 2】

In 500 milliliters of there-necked flasks, 20 grams are added【Embodiment 1】The compound chlorine ball A of gained, 150 milliliters of toluene, 35.0 grams Imidazoles, stirring reaction 30 hours, react and mother liquor are filtered to remove after terminating, use dichloromethane, third successively respectively at reflux Ketone and water washing, imidazoles Resin A 3 must be combined under vacuo by drying.

The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks A1,30.2 grams of ethylene iodohydrins and 200 milliliters of benzonitriles, react 10 hours at reflux, and reaction is filtered to remove mother after terminating Liquid, uses dichloromethane, acetone and water washing successively respectively, and the compound hydroxy imidazole Resin A 4 of halogen-type is dried to obtain under vacuo.

【Embodiment 3】

Monomer mixture solution (60.0 grams of styrene, 1.7 grams containing initiator are added in 500 milliliters of three-necked flasks Divinylbenzene, 60 grams of polystyrene, 1.6 grams of multi-walled carbon nanotubes and 1.0 grams of benzoyl peroxides, the solution are stirred prior to 70 DEG C Mix reaction 0.5 hour), agitator is started, the mixed solution of 200 ml deionized waters and 5 grams of gelatin is added, is warming up to 85 DEG C, Reaction 3 hours, then it is warming up to 90 DEG C, react 9 hours, be finally warming up to 100 DEG C, react 10 hours.After reaction terminates, pour out Supernatant liquid, is washed with 85 DEG C of hot washes, then with cold water, then filters, and is put into 80 DEG C of drying in baking oven, and grain is collected in sieving Complex microsphere B of the footpath in the range of 0.35~0.60 millimeter.

The chloromethylation of complex microsphere：In 500 milliliters of three-necked flask, 50 grams of complex microsphere B and 150 milliliters of chlorine are added Methyl ether, is stored at room temperature 6 hours, starts stirring, and it is catalyst to add 30 grams of zinc chloride, is warming up to 50 DEG C and reacts 24 hours, chlorination Room temperature is cooled to after end, chlorination mother solution is filtered out, methanol cyclic washing is used, dried 8 hours at 100 DEG C, compound chlorine ball is obtained B。

The imidazoles of compound chlorine ball：In 500 milliliters of there-necked flasks, 20 grams of compound chlorine ball B of addition, 150 milliliters of tetrahydrofurans, 20.0 grams of imidazoles, stirring reaction 24 hours, react and are filtered to remove mother liquor after terminating, use dichloromethane successively respectively at reflux Alkane, acetone and water washing, imidazoles resin B 1 must be combined under vacuo by drying.

Compound imidazoles resin B 1 is used【Embodiment 2】Described method is reacted with hydroxyhalide, is obtained halogen-type and is combined Hydroxy imidazole resin B 2.

【Embodiment 4】

In 500 milliliters of there-necked flasks, 15 grams are added【Embodiment 3】1,150 milliliters of acetonitriles of compound imidazoles resin B of gained, 20.0 grams of 3- chloropropyl alcohols, stirring reaction 10 hours, react and mother liquor are filtered to remove after terminating, respectively successively with two at reflux Chloromethanes, acetone and water washing, dry to obtain the compound hydroxy imidazole resin B 3 of halogen-type under vacuo.

【Embodiment 5】

Change【Embodiment 3】In monomer mixture solution (76.0 grams of α-methylstyrenes, 3.5 grams of divinylbenzenes, 75 Gram gasoline, 2.4 grams of multi-walled carbon nanotubes and 1.4 grams of benzoyl peroxides), remaining preparation condition with【Embodiment 3】It is identical, obtain Complex microsphere C.

The chloromethylation of complex microsphere：In 500 milliliters of three-necked flask, 40 grams of complex microsphere C and 150 milliliter 1 are added, 4- dichloro methyl butyl ethers, are stored at room temperature 6 hours, start stirring, and it is catalyst to add 25 grams of zinc chloride, is warming up to 50 DEG C of reactions 24 hours, chlorination was cooled to room temperature after terminating, and filters out chlorination mother solution, used methanol cyclic washing, dries 8 hours, obtains at 100 DEG C To compound chlorine ball C.

The imidazoles of compound chlorine ball：With【Embodiment 1】Method is identical, obtains compound imidazoles resin C1.

The reaction of compound imidazoles resin and hydroxyhalide：20 grams of compound imidazoles resins are added in 500 milliliters of there-necked flasks C1,10.5 grams of 5- bromines amylalcohols and 200 milliliters of acetonitriles, react 20 hours at reflux, and reaction is filtered to remove mother liquor after terminating, Use dichloromethane, acetone and water washing successively respectively, the compound hydroxy imidazole resin C2 of halogen-type is dried to obtain under vacuo.

【Embodiment 6】

Catalyst preparation step with【Embodiment 5】The step of it is identical, simply hydroxyhalide used is 6- bromine hexanols, is obtained Hydroxy imidazole resin C3 is combined to halogen-type.

【Comparative example 1】

The preparation process of catalyst with【Embodiment 1】It is identical, multi-walled carbon nanotube is simply added without, compound miaow is respectively obtained Azoles resin CA1, halogen-type are combined hydroxy imidazole resin CA2.

【Embodiment 7】

Will【Embodiment 1】Obtained catalyst halogen-type is combined imidazole radicals Resin A 2 and is used as oxirane and carbon dioxide The catalyst of reaction generation ethylene carbonate, reaction condition is as follows：In 300mL autoclaves add 150.0g oxirane and 3.0g catalyst, is filled with 1.0MPa CO₂, 120 DEG C are warming up to, CO is re-filled with₂, maintenance reaction pressure is after 2.0MPa, reaction 3h Cooling, opens reactor, and liquid is analyzed with form and aspect chromatogram, measures oxirane conversion ratio (C_EO%) it is 98.6%, carbonic acid Vinyl acetate (S_EC%) selectivity is 99.7%, the swellbility S of resin catalyst_SWELLFor 5.1%.

【Comparative example 2】

Catalyst activity test condition with【Embodiment 7】Identical, simply catalyst used is combined hydroxyl miaow for halogen-type Azoles resin CA2, the conversion ratio for obtaining oxirane is 97.4%, and the selectivity of ethylene carbonate is 99.5%, resin catalyst Swellbility be S_SWELLFor 22.3%.

【Embodiment 8-12】

Halogen-type used in changing is combined hydroxy imidazole resin types, remaining condition with【Embodiment 7】Described is identical, Obtained result is as shown in table 1.

Table 1

【Embodiment 13-17】

Using A2 as catalyst, change the mass ratio of reaction temperature, reaction pressure catalyst and oxirane, other Part with【Embodiment 7】Identical, catalyst activity and selectivity is as shown in table 2.

Table 2

【Embodiment 18】

Will【Embodiment 7】Catalyst after reaction terminates is applied mechanically 5 times by same reaction conditions, and activity is not decreased obviously. 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】

Will【Comparative example 2】Catalyst after reaction terminates is applied mechanically 5 times by same reaction conditions, and activity is decreased obviously.Reaction It the results are shown in Table shown in 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

1. a kind of method for producing ethylene carbonate, is 60~200 in reaction temperature using oxirane and carbon dioxide as raw material DEG C, reaction pressure is 0.1~10.0 MPa, and the weight ratio of catalyst and oxirane is that under conditions of 0.001~1, reaction is former Material contacts generation ethylene carbonate with catalyst；The catalyst is that halogen-type is combined hydroxy imidazole resin, its preparation method bag Include following steps：

1) auxiliary agent one is made into water solution A；By monomer, comonomer, nano material, initiator and the wiring solution-forming B of auxiliary agent two；

The monomer be selected from methyl methacrylate, butyl acrylate, styrene, α-methylstyrene, 4- butylstyrenes or At least one of acrylonitrile；The comonomer is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinylbenzene At least one of methylmethane or divinylbenzene；The nano material is selected from multi-walled carbon nanotube, single-walled carbon nanotube, C60 At least one of or C70 fullerenes；The initiator is selected from benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide At least one of or isopropyl benzene hydroperoxide；The auxiliary agent one is selected from polyvinyl alcohol, gelatin, starch, methylcellulose, swelling At least one of soil or calcium carbonate；The auxiliary agent two in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or paraffin extremely Few one kind；

Wherein, by weight percentage, the consumption of monomer is 85~95% in solution B, and the consumption of comonomer is 2~5%, is received The consumption of rice material is 0.1~3%, and the consumption of initiator is 0.1~10%；The consumption of auxiliary agent one for monomer consumption 150~ 400%, the consumption of auxiliary agent two is the 50~100% of monomer consumption；

2) solution B is mixed with solution A, reaction obtains complex microsphere；

5) added into the compound imidazoles resin and the compound hydroxy imidazole resin of the halogen-type is obtained after hydroxyhalide reaction.

2. the method for ethylene carbonate is produced according to claim 1, it is characterised in that the percentage by weight of the water solution A Concentration is 0.5~2%.

3. the method for ethylene carbonate is produced according to claim 1, it is characterised in that step 2) course of reaction is：Solution B In 60~75 DEG C of prepolymerizations 0.5~2.5 hour, then solution B is mixed with solution A, 70~90 DEG C of reactions 5~15 are warming up to small When, then be warming up to 90~100 DEG C react 5~15 hours；After reaction terminates, through extracting, washing, filtering, dry, sieving, obtain The complex microsphere that 0.35~0.60 millimeter of particle size range.

4. the method for ethylene carbonate is produced according to claim 1, it is characterised in that step 3) course of reaction is：To described The chloromethylation reagents equivalent to complex microsphere weight 200~500% are added in complex microsphere, and equivalent to complex microsphere weight The zinc chloride catalyst of amount 20~70%, reacts 8~30 hours at 30~60 DEG C, obtains compound chlorine ball through filtering, washing, dries Do to constant weight；The chloromethylation reagents are selected from least one of chloromethyl ether or 1,4- dichloro methyl butyl ethers.

5. the method for ethylene carbonate is produced according to claim 1, it is characterised in that step 4) course of reaction is：To described Organic solvent, 30~300% imidazoles, reflux state equivalent to complex microsphere weight 200~700% are added in compound chlorine ball Lower reaction 4~30 hours, the compound imidazoles resin is obtained after scrubbed, drying；Wherein, the organic solvent be selected from acetonitrile, At least one of benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform or dichloroethanes.

6. the method for ethylene carbonate is produced according to claim 1, it is characterised in that step 5) course of reaction is：To described Added in compound imidazoles resin hydroxyhalide X-R-OH equivalent to compound imidazoles weight resin 30~300%, 300~ Reacted 4~30 hours under 1000% organic solvent, reflux state, obtaining the halogen-type after scrubbed, drying is combined hydroxyl Imidazoles resin；Wherein, the organic solvent is selected from acetonitrile, benzonitrile, toluene, tetrahydrofuran, dimethylformamide, chloroform or two In at least one of chloroethanes, hydroxyhalide X-R-OH X be Cl, Br or I, R be ethyl, propyl group, isopropyl, normal-butyl, Isobutyl group, n-pentyl or n-hexyl.

7. the method for ethylene carbonate is produced according to claim 1, it is characterised in that the monomer is selected from styrene；It is described Comonomer is selected from divinylbenzene；The nano material is selected from multi-walled carbon nanotube；The initiator is selected from benzoyl peroxide first Acyl.

8. the method for ethylene carbonate is produced according to claim 1, it is characterised in that the auxiliary agent one is selected from polyvinyl alcohol； The auxiliary agent two is selected from polystyrene.

9. the method for ethylene carbonate is produced according to claim 1, it is characterised in that reaction temperature is 80~160 DEG C, instead It is 0.5~8.0 MPa to answer pressure, and the weight ratio of catalyst and oxirane is 0.005~0.5.