CN102513158A - Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst - Google Patents
Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst Download PDFInfo
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Abstract
The invention relates to a continuous heterogeneous catalyst and a process for synthesizing ethylene carbonate through continuous heterogeneous catalysis. The ethylene carbonate is prepared through carrying out a catalytic addition reaction on a packed bed reactor device by taking ethylene oxide and carbon dioxide as raw materials and taking a novel functional ionic liquid polymer adsorbed on an inorganic particle as a solid catalyst. The catalyst is prepared by stirring and coating a functional imidazolium ionic liquid polymer on an inorganic carrier. The ethylene carbonate is prepared by mixing ethylene oxide and the carbon dioxide by using nitrogen gas as carrier gas in the packed bed reactor device and carrying out a cyclic addition reaction under the action of the catalyst, wherein the reaction pressure is 1.0-6.0MPa, the reaction temperature is 80-150 DEG C, and the reaction time is 1-6h. The continuous heterogeneous catalyst and the process for synthesizing ethylene carbonate through continuous heterogeneous catalysis have the advantages that the method with a continuous process is simple in operation, low in cost, free of separation and distillation and suitable for large-scale industrial production; and the catalyst has high activity, low loss, high ethylene oxide conversion ratio up to 97% and high electivity up to 98%.
Description
Technical field
The present invention relates to the method that a kind of continual multi-phase prepares ethylene carbonate; Especially be after raw material mixes, on the fixed bed micro-reaction device, to prepare the ethylene carbonate product continuously with oxirane and carbon dioxide through the inorganic particle catalyst that scribbles functional imidazol ion liquid high polymer.
Background technology
Ethylene carbonate (EC) is a kind of organic solvent and surfactant raw material of of many uses, function admirable; It can be used as organic synthesis intermediate; The raw material, the waterglass that also can be used as synthetic furazolidone are (Zhang Yubao such as slurry, fibre finish agent and high-performance lithium battery electrolyte; The character of woods pine ethylene carbonate and application [J]. chemistry world, 1998, (1): 10-12; The Ministry of Chemical Industry's scientific information research institute world's fine chemistry industry handbook [M]. Beijing: Ministry of Chemical Industry's science and technology information that learns a skill grinds institute, 1982.356.).Synthetic method has phosgenation, ester-interchange method, halohydrin method, urea method, oxirane addition process, and its oxirane addition process is with oxirane and CO
2Be raw material, remove have that production cost is low, conversion ratio and selectivity advantages of higher, be fit to large-scale industrial production, the more important thing is to have great environmental effect, can alleviate global air temperature warming.
(Wei-Li Dai, Lang Chen, Shuang-Feng Yin, et.High-Efficiency Synthesis of Cyclic Carbonates from Epoxides and CO such as Wei-Li Dai, Lang Cheng, Shuang-Feng Yin
2Over Hydroxyl Ionic Liquid Catalyst Grafted onto Cross-Linked Polymer [J] Catal Lett (2010) 137:74-80) synthesized and a kind ofly contain the grafting of functional groups imidazol ion liquid and on high polymer and inorganic carrier silica, process catalyst; Catalysis carbon dioxide and epoxides cycloaddition prepare cyclic carbonate under autoclave; Reaction pressure 2MPa; Reaction temperature 120-140 ℃; Reaction time 2-4h, the very high and not loss of catalyst of catalytic activity.
CN1817877 (a kind of synthetic method of cyclic carbonate; Chinese Academy Of Sciences Process Engineering Research Institute; 2006-08-16) and CN1817878 (high-activity catalyst prepares the method for cyclic carbonate; Chinese Academy Of Sciences Process Engineering Research Institute, 2006-08-16) adopt transition metal salt respectively with the binary catalyst of bidentate ionic liquid with halogenation quaternary phosphonium salt ionic liquid composition, reaction pressure 0.1-5MPa; Reaction temperature 40-210 ℃, through the cleaner technology of cycloaddition reaction synthesizing annular carbonate.
US20080071096 (Process for the preparation of alkylene carbonate; Shell oil company; 2008-3-20.) a kind of process for preparing ethylene carbonate is disclosed, use the slaine solid-carried catalyst in reaction temperature as under 40-200 ℃, reaction pressure 0.1-5MPa condition, oxirane and carbon dioxide addition reaction; The slaine cation is period 3 the 2nd family; Period 4 the 2nd, 4,12 family, the period 5 the 2nd, 4,7,12,14 family, the period 6 the 2nd, 4,6 family; Anion is organic acid or inorganic acid, immobilized body be quaternary ammonium, quaternary phosphonium, season arsenic, season antimony and season sulphur.
CN101037431 (carbon dioxide and epoxide cycloaddition reaction method for cyclic carbonates; Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences; 2007-09-19) adopt slaine, ionic liquid and quaternary ammonium salt to form catalyst; Reaction pressure is 0.5-10MPa, reaction temperature 30-200 ℃, realizes the preparation cyclic carbonate through catalysis carbon dioxide and epoxides cycloaddition.In course of reaction, do not add any organic solvent, this catalyst can be reused and keep catalyst activity constant.CN1631886 (the synthetic method of cyclic carbonate; Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences; 2005-06-29) adopt zinc salt and imidazoles halogeno salt, pyridine halo class ionic liquid, a kind of in the quaternary ammonium salt as catalyst, reaction pressure is 0.5-5MPa; Reaction temperature 50-200 ℃, through catalysis carbon dioxide and preparation of epoxides cyclic carbonate.In course of reaction, do not add any organic solvent, promptly realize separating of catalyst and product through simple decompression distillation, can reuse and keep catalyst activity constant, selectivity is more than 98%, and transformation frequency reaches 5000h
-1More than.
(method of carbon dioxide and epoxy second or propane carbonate synthesis second or propylene ester, PetroChina Company Ltd. 2010-09-08) adopt continuous circular response device to CN101824022; With carbonate and alkyl imidazole salt or Fixanol ionic liquid is catalyst, and reaction pressure is 1.0-5MPa, reaction temperature 100-200 ℃; Reaction time 1-5h; Through catalysis carbon dioxide and epoxy second or propane carbonate synthesis second or propylene ester, catalytic activity is high, and catalyst loss is little; The oxirane conversion ratio is 96-99%, and selectivity is 97-99%.(a kind of method for preparing ethylene carbonate, PetroChina Company Ltd. 2009-09-22) adopt continuous circular response device to CN101838257; With carbonate and alkyl imidazole salt ion liquid is catalyst, and reaction pressure is 1-4MPa, reaction temperature 100-180 ℃; Reaction time 1-5h, the admixture of gas that the ethene oxidation is obtained contacts preparation ethylene carbonate under the effect of catalyst with the ethylene carbonate ester solution, need not separation, rectifying; Catalytic activity is high; Catalyst loss is little, and the oxirane conversion ratio is 96%-99%, and selectivity is 97%-99%.
US2009/0286998 (Process for the preparation of alkylene carbonate and/or alkylene glycol; Shell oil company; 2009-10-19) invented the continuity circulation catalytic reactor device of a kind of catalytically synthesizing cyclic carbonate ester and dihydroxylic alcohols, reactor assembly is divided into two parts: a part is the zoneofoxidation of alkene; Another part is the oxide of alkene and the catalytic domain of carbon dioxide catalytically synthesizing cyclic carbonate ester; The separation and the purifying that wherein also comprise product; What the ethene oxidation was adopted is to be the catalyst of main immobilized alundum (Al with silver, and the catalyst that cycloaddition is adopted is iodide.
In the prior art, adopt oxirane and carbon dioxide addition reaction to prepare ethylene carbonate, it is too high to be the cost that intermittent operation and catalyst expend; Use homogeneous catalyst catalytic synthesis of C vinyl acetate to have the problem of separating catalyst from product, thereby make catalysqt deactivation.
Summary of the invention
The technical process that the objective of the invention is to overcome the problem of prior art existence and provide a kind of heterogeneous catalysis to prepare ethylene carbonate is that a kind of energy consumption is low, continuity is reacted, the simple preparation method of technological operation.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of preparation method with the inorganic carrier solid-carried catalyst may further comprise the steps:
(a) under nitrogen or inert gas shielding, the N-vinyl imidazole is mixed with anhydrous organic solvent, and drip halide, 60～80 ℃ of following heated and stirred reaction 12～48h; Solvent is removed in decompression distillation, and vacuum drying obtains functional vinyl imidazole ionic liquid; N-vinyl imidazole and anhydrous organic solvent amount ratio are 1: 2～4g/ml; N-vinyl imidazole and halid mol ratio are 1: 1～2.
Preferably, anhydrous organic solvent is a kind of in absolute ethyl alcohol, anhydrous acetonitrile, absolute methanol or the anhydrous dimethyl formamide (DMF);
Said halide is a kind of in chlorethanol, chlorethamin, chloroethanes, bromoethanol, bromine ethamine, bromoethane, iodohydrin, iodine ethamine, the iodoethane, i.e. general formula X CH
2CH
2Z, wherein X represents halogens, X=Cl, Br, I; Z represents function functional group, Z=OH, NH
2, H;
The functional vinyl imidazole ionic liquid that obtains is: bromination 3-vinyl-1-hydroxyethyl imidazole salt, bromination 3-vinyl-1-aminoethyl imidazole salts, bromination 3-vinyl-1-ethyl imidazol(e) salt, chlorination 3-vinyl-1-hydroxyethyl imidazole salt, chlorination 3-vinyl-1-aminoethyl imidazole salts, chlorination 3-vinyl-1-ethyl imidazol(e) salt, iodate 3-vinyl-1-hydroxyethyl imidazole salt, iodate 3-vinyl-1-hydroxyethyl imidazole salt or iodate 3-vinyl-1-hydroxyethyl imidazole salt.
(b) the functional vinyl imidazole ionic liquid, methacrylic acid or acrylic acid, styrene, hydroxy-ethyl acrylate or the hydroxypropyl acrylate that obtain of step (a) is monomer, and the weight ratio of monomer is 1: 0.4～0.6: 0.05～0.2: 0.5～2; Add entry and mix, the amount ratio of vinyl imidazole ionic liquid and water is 1: 5～7;
Weight with mixed liquor is benchmark; Added 1～3% initator, 0.5%～2% 1 waterside sodium phosphite, 0.5 ‰～2 ‰ TBABs and 1 ‰～2 ‰ lauryl sodium sulfate copolymer-1s 6～30 hours, the quadripolymer that obtains is functional imidazol ion liquid high polymer; Its structure is one of formula I～formula IV:
Wherein X=Cl, Br, I; Z=OH, NH
2, H;
Specifically, the used monomer of described quadripolymer is one of following combination:
(1) vinyl imidazole ionic liquid, styrene, methacrylic acid, hydroxy-ethyl acrylate;
(2) vinyl imidazole ionic liquid, styrene, methacrylic acid, hydroxypropyl acrylate;
(3) vinyl imidazole ionic liquid, styrene, acrylic acid, hydroxy-ethyl acrylate;
(4) vinyl imidazole ionic liquid, styrene, acrylic acid, hydroxypropyl acrylate;
Described initator is a kind of in ammonium persulfate and the azodiisobutyronitrile;
(c) the functional imidazol ion liquid high polymer of step (b) stirs and is coated on the inorganic carrier, and dry back (80～100 ℃ of oven dry down) obtains the continual multi-phase agent; Inorganic carrier is preferably 4A molecular sieve α-Al
2O
3Or SiO
2, particle diameter is 0.5～2mm.Functional imidazol ion liquid high polymer and inorganic carrier weight ratio are 1: 2～4.
The inorganic particle of this immobilized imidazol ion liquid high polymer, but catalysis carbon dioxide and oxirane addition reaction be used for continual multi-phase and prepare ethylene carbonate, preparation technology's step comprises:
In fixed-bed reactor, with N
2Be carrier gas; After oxirane that feeds and the carbon dioxide mix under the effect of above-mentioned heterogeneous continuous catalyst; 1～6Mpa, 80～150 ℃ of following reactions 1～6 hour; The ethylene carbonate that generates separates with the solution absorption device through high-pressure gas-liquid separator, and unreacted carbon dioxide and the circulation of oxirane mixture feed in the fixed-bed reactor, reuse same catalyst and proceed reaction.
The liquid that being used in the solution absorption device absorbs ethylene carbonate is the ethylene carbonate aqueous solution of ester of distilled water or 2wt%～10wt%.Product is used gas Chromatographic Determination.
Compare with existing technology of preparing, technical method of the present invention has very big novelty and economy:
(1) catalyst of oxirane of the present invention and carbon dioxide addition reaction is that imidazol ion liquid high polymer is coated in the solid particle on the inorganic carrier; Building-up process is simple, and cost is lower, and catalyst activity is higher; Lose for a short time, realized the technical process of heterogeneous catalytic method synthesizing ethylene carbonate;
(2) the present invention adopts the fixed-bed reactor continued operation; Through the gas-solid heterogeneous catalytic reaction, process need not other organic solvents just can obtain the product ethylene carbonate in raw material oxirane and the carbon dioxide access equipment, practices thrift cost; Simple to operate, be fit to large-scale industrialization production; The oxirane conversion ratio can reach 97%, and selectivity can reach 98%;
(3) unreacted raw material can continue reaction through being circulated in the reaction unit, has economic benefits;
(4) catalytic activity reused after 10 times of catalyst is still very high, and the productive rate of ethylene carbonate is still 90%.
Description of drawings
The thermogravimetric curve figure of Fig. 1 catalyst imidazol ion liquid high polymer
The infrared spectrum of Fig. 2 catalyst imidazol ion liquid high polymer
Fig. 3 catalyst imidazol ion liquid high polymer
1HNMR schemes (nucleus magnetic hydrogen spectrum, D
2O is a solvent)
The SEM figure of Fig. 4 catalyst
The specific embodiment:
Below in conjunction with embodiment the present invention is done further detailed, complete explanation.Except that specifying, described umber is weight portion.Methacrylic acid can replace with acrylic acid, and hydroxy-ethyl acrylate replaces with hydroxypropyl acrylate, and effect is identical.
(1) immobilized synthesizing on inorganic particle of catalyst-imidazol ion liquid high polymer:
(a) get a there-necked flask, feed N
2Protection adds 9.41gN-vinyl imidazole (0.1mol), 30g absolute ethyl alcohol heated and stirred, slowly drips 12.52g bromoethanol (0.1mol) again, and behind 70 ℃ of following heated and stirred reaction 24h, decompression distillation, vacuum drying get the vinyl imidazole ionic liquid.
(b) 10 parts of vinyl imidazole ionic liquid, 5 parts of methacrylic acids, 1 part of styrene, 10 parts of hydroxy-ethyl acrylates add after 65 parts distilled water mixes again; Weight with said mixture is benchmark, 80 ℃ under the effect of 2% initiator ammonium persulfate, 1% 1 waterside sodium phosphite, 1 ‰ TBABs, 2 ‰ lauryl sodium sulfate copolyreaction 2h make imidazol ion liquid high polymer.
Thermogravimetric curve figure, infrared spectrum reach
1HNMR schemes (nucleus magnetic hydrogen spectrum, D
2O is a solvent) shown in Fig. 1～3.
(c) the imidazol ion liquid high polymer that makes is coated under mechanical agitation on the 4A molecular sieve, and both weight ratios are 1: 3; 80 ℃ of dry catalyst in baking oven at last.Its SEM figure is as shown in Figure 4.
(2) addition reaction of carbon dioxide and oxirane: in the fixed-bed reactor; 0.5mL/min after the 30mL/min carbon dioxide mix of oxirane and feeding under the above-mentioned synthetic catalyst action of 3g; With N2 is carrier gas, and pressure is 4MPa, after temperature is 120 ℃ of reaction 6h; The ethylene carbonate that generates separates (liquid in the solution absorption device is distilled water) through high-pressure gas-liquid separator with the solution absorption device; Unreacted carbon dioxide and oxirane mixing circulation feed and continue reaction in the fixed-bed reactor, reuse same catalyst reaction and carry out, and product is used gas chromatography determination.The conversion ratio of oxirane is 97%, and selectivity is 98%; It is 90% that the conversion ratio of oxirane after 10 times is used in repetition catalysis, and selectivity is 97%.
(1) immobilized synthesizing on inorganic particle of catalyst-imidazol ion liquid high polymer:
(a) get a there-necked flask, feed N
2Protection adds 9.41g N-vinyl imidazole (0.1mol), 30ml absolute ethyl alcohol heated and stirred, slowly drips 12.42g bromine ethamine (0.1mol) again, and behind 70 ℃ of following heated and stirred reaction 24h, decompression distillation, vacuum drying get the vinyl imidazole ionic liquid.
(b) 10 parts of vinyl imidazole ionic liquid, 5 parts of methacrylic acids, 1 part of styrene, 10 parts of hydroxy-ethyl acrylates add after 65 parts distilled water mixes again; Weight with said mixture is benchmark, 80 ℃ under the effect of 2% initiator ammonium persulfate, 1% 1 waterside sodium phosphite, 1 ‰ TBABs, 2 ‰ lauryl sodium sulfate copolyreaction 2h make imidazol ion liquid high polymer.
(c) the imidazol ion liquid high polymer that makes is coated under mechanical agitation on the 4A molecular sieve, and both weight ratios are 1: 3 80 ℃ of dry catalyst I I of getting in baking oven at last.
(2) addition reaction of carbon dioxide and oxirane: in the fixed bed micro-reaction device, after the 20mL/min carbon dioxide mix of 1mL/min oxirane and feeding under the effect of 3g catalyst, with N
2Be carrier gas; At pressure is 4MPa; After temperature is 120 ℃ of reaction 6h; The ethylene carbonate that generates separates (liquid in the solution absorption device is distilled water) through high-pressure gas-liquid separator with the solution absorption device, continue to reuse same catalyst reaction in unreacted carbon dioxide and the oxirane mixing circulation feeding fixed-bed reactor and carry out, and product is used gas chromatography determination.The conversion ratio of oxirane is 87%, and selectivity is 90%; It is 85% that the conversion ratio of oxirane after 10 times is used in repetition catalysis, and selectivity is 97%.
Embodiment 3
(1) catalyst---immobilized synthesizing on inorganic particle of imidazol ion liquid high polymer:
(a) get a there-necked flask, feed N
2Protection adds 9.41gN-vinyl imidazole (0.1mol), 30 parts of absolute ethyl alcohol heated and stirred, slowly drips 12.42g bromoethane (0.1mol) again, and behind 70 ℃ of following heated and stirred reaction 24h, decompression distillation, vacuum drying get the vinyl imidazole ionic liquid.
(b) 10 parts of vinyl imidazole ionic liquid, 5 parts of methacrylic acids, 1 part of styrene, 10 parts of hydroxy-ethyl acrylates add after 65 parts distilled water mixes again; Weight with said mixture is benchmark, 80 ℃ under the effect of 2% initiator ammonium persulfate, 1% 1 waterside sodium phosphite, 1 ‰ TBABs, 2 ‰ lauryl sodium sulfate copolyreaction 2h make imidazol ion liquid high polymer.
(c) the imidazol ion liquid high polymer that makes is coated under mechanical agitation on the 4A molecular sieve, and both weight ratios are 1: 3; 90 ℃ of dry catalyst in baking oven at last.
(2) addition reaction of carbon dioxide and oxirane: in the fixed bed micro-reaction device, 2mL/min oxirane with feed after the 15mL/min carbon dioxide mix under the effect of 3g catalyst, with N
2Be carrier gas; At pressure is 4MPa; After temperature is 120 ℃ of reaction 6h; The ethylene carbonate that generates separates (liquid in the solution absorption device is distilled water) through high-pressure gas-liquid separator with the solution absorption device, continue to reuse same catalyst reaction in unreacted carbon dioxide and the oxirane mixing circulation feeding fixed-bed reactor and carry out.Product is used gas chromatography determination, and the conversion ratio of oxirane is 80%, and selectivity is 87%; It is 75% that the conversion ratio of oxirane after 10 times is used in repetition catalysis, and selectivity is 86%.
What this embodiment and embodiment 1 were different is: used halide is chlorethanol in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 78%, and selectivity is 90%.
Embodiment 5
What this embodiment and tool embodiment 1 were different is: used halide is chlorethamin in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 75%, and selectivity is 92%.
What this embodiment and embodiment 1 were different is: used halide is chloroethanes in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 60%, and selectivity is 81%.
Embodiment 7
What this embodiment and embodiment 1 were different is: used halide is iodohydrin in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 82%, and selectivity is 93%.
Embodiment 8
What this embodiment and embodiment 1 were different is: used halide is iodine ethamine in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 76%, and selectivity is 90%.
Embodiment 9
What this embodiment and embodiment 1 were different is: used halide is iodoethane in the building-up process of catalyst; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 64%, and selectivity is 87%.
Embodiment 10
What this embodiment and embodiment 1 were different is: immobilized inorganic carrier is α-Al of particle diameter 1mm in the building-up process of catalyst
2O
3, other steps are identical with embodiment 1, obtain the ethylene carbonate ester products at last and use gas chromatography determination, and the conversion ratio of oxirane is 95%, and selectivity is 98%.
Embodiment 11
What this embodiment and embodiment 1 were different is: immobilized inorganic carrier is the SiO of particle diameter 1mm in the building-up process of catalyst
2, the imidazol ion liquid high polymer that makes in the step (c) and the weight ratio of 4A molecular sieve are 1: 2; Other steps are identical with embodiment 1, obtain the ethylene carbonate ester products at last and use gas chromatography determination, and the conversion ratio of oxirane is 93%, and selectivity is 95%.
Embodiment 12
What this embodiment and embodiment 1 were different is: reaction pressure is 3MPa in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 89%, and selectivity is 91%.
Embodiment 13
What this embodiment and embodiment 1 were different is: reaction pressure is 6MPa in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 95%, and selectivity is 98%.
Embodiment 14
What this embodiment and embodiment 1 were different is: reaction pressure is 1MPa in the addition reaction of oxirane and carbon dioxide, and the imidazol ion liquid high polymer that makes in the step (c) and the weight ratio of 4A molecular sieve are 1: 4; Other steps are identical with embodiment 1, obtain the ethylene carbonate ester products at last and use gas chromatography determination, and the conversion ratio of oxirane is 70%, and selectivity is 78%.
Embodiment 15
What this embodiment and embodiment 1 were different is: reaction temperature is 130 ℃ in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 94%, and selectivity is 97%.
Embodiment 16
What this embodiment and embodiment 1 were different is: reaction temperature is 150 ℃ in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 81%, and selectivity is 93%.
Embodiment 17
What this embodiment and embodiment 1 were different is: reaction temperature is 100 ℃ in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 83%, and selectivity is 92%.
Embodiment 18
What this embodiment and embodiment 1 were different is: reaction temperature is 80 ℃ in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 65%, and selectivity is 81%.
Embodiment 19
What this embodiment and embodiment 1 were different is: the reaction time is 4h in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 92%, and selectivity is 97%.
What this embodiment and embodiment 1 were different is: the reaction time is 2h in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 76%, and selectivity is 85%.
Embodiment 21
What this embodiment and embodiment 1 were different is: the reaction time is 1h in the addition reaction of oxirane and carbon dioxide; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination, the conversion ratio of oxirane is 67%, and selectivity is 84%.
Embodiment 22
What present embodiment and embodiment 1 were different is: it is 10wt% ethylene carbonate aqueous solution of ester that the addition reaction of oxirane and carbon dioxide finishes the used absorption liquid in back; Other steps are identical with embodiment 1; Obtain the ethylene carbonate ester products at last and use gas chromatography determination; The conversion ratio of oxirane is 97%, and selectivity is 98%.
Claims (8)
1. continual multi-phase agent is characterized in that the preparation method may further comprise the steps:
(a) under nitrogen or inert gas shielding, the N-vinyl imidazole is mixed with anhydrous organic solvent, and drip halide, 60～80 ℃ of following heated and stirred reaction 12～48h; Solvent is removed in decompression distillation, and vacuum drying obtains the vinyl imidazole ionic liquid; N-vinyl imidazole and anhydrous organic solvent amount ratio are 2～4g/ml, the N-vinyl imidazole with halid mol ratio be 1～2;
Said halide general formula is XCH
2CH
2Z, wherein X=Cl, Br or I; Z=OH, NH
2Or H;
(b) vinyl imidazole ionic liquid, methacrylic acid or acrylic acid, styrene and the hydroxy-ethyl acrylate or the hydroxypropyl acrylate that obtain with step (a) are monomer, and the weight ratio of monomer is 1: 0.4～0.6: 0.05～0.2: 0.5～2; Add entry and mix, the amount ratio of vinyl imidazole ionic liquid and water is 1: 5～7;
Weight with mixed liquor is benchmark; Added 1～3% initator, 0.5%～2% 1 waterside sodium phosphite, 0.5 ‰～2 ‰ TBABs and 1 ‰～2 ‰ lauryl sodium sulfate copolymer-1s 6～30 hours, the quadripolymer that obtains is functional imidazol ion liquid high polymer; Its structure is one of formula I～formula IV:
(formula III)
Wherein X=Cl, Br, I; Z=OH, NH
2, H;
(c) the functional imidazol ion liquid high polymer of step (b) stirs and is coated on the inorganic carrier, and oven dry obtains the continual multi-phase agent.
2. the said continual multi-phase agent of claim 1 is characterized in that the initator described in the step (a) is ammonium persulfate or azodiisobutyronitrile.
3. the said continual multi-phase agent of claim 1 is characterized in that, the anhydrous organic solvent described in the step (a) is a kind of in absolute ethyl alcohol, anhydrous acetonitrile, absolute methanol or the anhydrous dimethyl formamide.
4. the said continual multi-phase agent of claim 1 is characterized in that, monomer vinyl imidazol ion liquid, methacrylic acid or acrylic acid, styrene and hydroxy-ethyl acrylate described in the step (b) or hydroxypropyl acrylate amount ratio are 1: 0.5: 0.1: 1.
5. the said continual multi-phase agent of claim 1 is characterized in that, said inorganic carrier is 4A molecular sieve α-Al
2O
3Or SiO
2, particle diameter is 0.5～2mm; Said functional imidazol ion liquid high polymer and inorganic carrier weight ratio are 1: 2～4.
6. each said continual multi-phase agent of claim 1～5 is used to prepare ethylene carbonate.
7. a continual multi-phase prepares the method for ethylene carbonate, it is characterized in that, and be fixed catalyst with each said continual multi-phase agent of claim 1～4, in fixed-bed reactor, with N
2Be carrier gas; Behind the oxirane and carbon dioxide mix that feeds; 1～6Mpa, 80～150 ℃ of following reactions 1～6 hour; The ethylene carbonate that generates separates with the solution absorption device through high-pressure gas-liquid separator, and unreacted carbon dioxide and the circulation of oxirane mixture feed in the fixed-bed reactor.
8. the said continual multi-phase of claim 7 prepares the method for ethylene carbonate, it is characterized in that, the liquid that is used to absorb ethylene carbonate in the solution absorption device is the ethylene carbonate aqueous solution of ester of distilled water or 2%～10%.
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| CN105777543A (en) * | 2016-04-07 | 2016-07-20 | 奥克化学扬州有限公司 | Chain-shaped carbonate ester preparing and dihydric alcohol coproduction method and technology system |
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