CN114957194A - Method for improving yield of vinylene carbonate - Google Patents
Method for improving yield of vinylene carbonate Download PDFInfo
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- CN114957194A CN114957194A CN202210672479.8A CN202210672479A CN114957194A CN 114957194 A CN114957194 A CN 114957194A CN 202210672479 A CN202210672479 A CN 202210672479A CN 114957194 A CN114957194 A CN 114957194A
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 138
- 239000003112 inhibitor Substances 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 127
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 45
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- 239000012043 crude product Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- IBHWREHFNDMRPR-UHFFFAOYSA-N phloroglucinol carboxylic acid Natural products OC(=O)C1=C(O)C=C(O)C=C1O IBHWREHFNDMRPR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 17
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims abstract description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 16
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960005219 gentisic acid Drugs 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 126
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 123
- 239000000243 solution Substances 0.000 claims description 86
- 230000035484 reaction time Effects 0.000 claims description 37
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 20
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- -1 amine salt Chemical class 0.000 claims description 11
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 8
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 description 36
- 238000000926 separation method Methods 0.000 description 18
- 238000000605 extraction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000382 dechlorinating effect Effects 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 235000009048 phenolic acids Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for improving the yield of vinylene carbonate synthesis, which comprises the following steps: (1) in an organic solvent, taking chlorinated ethylene carbonate as a raw material, adding an organic amine dechlorination catalyst to perform dechlorination reaction, adding a polymerization inhibitor solution after the dechlorination reaction is performed for a period of time, and continuously performing the reaction to obtain a vinylene carbonate crude product; (2) extracting and separating the vinylene carbonate crude product by hot water to obtain a vinylene carbonate product; the polymerization inhibitor solution is prepared in advance by dissolving the polymerization inhibitor in the solvent, and the polymerization inhibitor is one or more of o-hydroxybenzoic acid, m-hydroxybenzoic acid, gentisic acid and phloroglucinol acid. The method can improve the crude yield of the VC product synthesized by the batch method to be more than or equal to 95 percent, and the crude yield of the VC product synthesized by the micro-reaction continuously to be more than or equal to 98 percent.
Description
Technical Field
The invention relates to the technical field of synthesis of lithium ion battery electrolyte additives, in particular to a method for improving the yield of intermittent and continuous synthesis of vinylene carbonate.
Background
Vinylene Carbonate (VC) is used as an organic film forming additive and an overcharge protection additive of the lithium ion battery electrolyte, and has good high-low temperature performance and an anti-swelling function. With the rapid increase of applications of lithium ion batteries in the fields of electric vehicles, energy storage and the like, the performance and stability of the lithium ion batteries become the focus of attention. A small amount of VC can be preferentially reduced and decomposed on the carbon negative electrode to form an SEI film with excellent performance in the charge and discharge processes of the battery, and the continuous decomposition of solvent molecules on the surface of the electrode is effectively inhibited, so that the performance of the carbon negative electrode is improved, and the energy density and the service life of the lithium ion battery are further improved. In addition, the polymer can also be used as a functional polymer material monomer, an elaborate chemical intermediate and the like, thereby having wide application prospect.
In the current industrial batch or continuous VC synthesis process, triethylamine (Et) is usually used 3 N) as dechlorinating agent, dechlorinating chloroethylene carbonate (CEC) to obtain VC and byproduct triethylamine hydrochloride (Et) 3 N-HCl), mild reaction conditions, simple operation and environmental protection. Patent DE-A19955944 reports that vinyl carbonate is used as a reaction solvent, and the reaction is carried out at 60 ℃ for 1.5 hours, wherein the VC yield of a product is 73%, and the reaction time is effectively shortened, but the melting point of the vinyl carbonate is higher, and the subsequent separation process is complicated. US 2009/0234141 adopts a solvent-free or small-amount solvent method, i.e. VC itself is used as a solvent to facilitate the separation of the product, the yield of the obtained product is 73%, the problem that the product VC is adsorbed on triethylamine hydrochloride and is difficult to purify from the mixture after the reaction is solved, but the VC concentration is too high, which causes the VC polymerization to be aggravated and reduces the VC yield. CN 108864031A adopts the mixture of p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol as a novel polymerization inhibitor in the process of catalyzing CEC dechlorination by triethylamine, thereby inhibiting polymerization side reaction, improving reaction selectivity and ensuring that the yield of crude products is 69%. CN 101407508A proposes that the yield of VC crude product is 65% with a mixture of ester, ether, hydrocarbon as organic solvent and BHT as polymerization inhibitor. CN 101161647A uses propylene carbonate as solvent, triethylamine is continuously added, and the yield of VC crude product is 60%. In addition, other methods may be adoptedSynthesis of VC by CEC dechlorination using solid catalyst and gas phase catalyst, as reported in US 2009/0176997 2 The method is used for preparing VC by directly dechlorinating CEC in a tubular reactor by using a catalyst, the yield is 69 percent, but the reaction temperature is higher, the product selectivity is lower, and the equipment and the production conditions are harsh. CN 105384720A reports that by using high-purity ammonia gas as dechlorinating agent and introducing ammonia gas at 70 ℃ for 3 hours, the yield of the vinylene carbonate crude product is 82%.
In the aspect of continuous VC synthesis process, CN 112174928A adopts CEC and Et 3 N is used as a raw material, dimethyl carbonate is used as a solvent, a multi-kettle series reactor is adopted for continuously producing VC, the feeding flow rate of the mixture is preferably 0.05-0.8 m/s, and the yield of VC obtained after reduced pressure rectification is 96.5%. CN 106749755B reports an enhanced mass transfer microchannel reactor, which is used for preparing VC, and the specific process comprises: 0.2mL/min of the mixture of CEC and dimethyl carbonate and 0.4mL/min Et 3 N is synchronously input into the micro-channel, the residence time is 250 seconds at 40 ℃, and the yield of the product is 94 percent after decompression and rectification. The method has high product yield, but small treatment capacity, and the triethylamine hydrochloride is easy to block a micro-channel and is not beneficial to industrial production.
The VC intermittent and continuous synthesis process reported at present is mostly characterized in that the raw material proportion and the used solvent are different, but the VC crude yield level before the VC is purified by reduced pressure distillation is only 60-80%. Because of lack of deep knowledge of VC polymerization side reaction mechanism, the types of the currently used polymerization inhibitors are structural polymerization inhibitors, the polymerization inhibition effect is not ideal, the product is unstable, the yield level is difficult to break through, the product separation difficulty is large, and the like.
Disclosure of Invention
In view of the above problems, the present invention provides a method for increasing the yield of vinylene carbonate synthesis, so that the yield of vinylene carbonate products is greater than or equal to 95% by a batch method and greater than or equal to 98% by a continuous method.
The technical scheme of the invention is as follows: a method for improving the yield of vinylene carbonate comprises the following steps:
(1) in an organic solvent, taking chlorinated ethylene carbonate as a raw material, adding an organic amine dechlorination catalyst to perform dechlorination reaction, adding a polymerization inhibitor solution after the dechlorination reaction is performed for a period of time, and continuously performing the reaction to obtain a vinylene carbonate crude product;
(2) extracting and separating the vinylene carbonate crude product by hot water to obtain a vinylene carbonate product;
the polymerization inhibitor solution is prepared in advance by dissolving the polymerization inhibitor in the solvent, and the polymerization inhibitor is one or more of o-hydroxybenzoic acid, m-hydroxybenzoic acid, gentisic acid and phloroglucinol acid.
The invention is further provided that the solvent is selected from one of chloroform, dimethyl carbonate or acetonitrile.
The invention is further set that the polymerization inhibitor consists of two parts of organic acid, namely phloroglucinol acid and at least one of o-hydroxybenzoic acid, m-hydroxybenzoic acid or gentisic acid, and the molar ratio of the two parts is 1: 7 to 10.
The invention further provides that the dechlorination catalyst is selected from one or more of triethylamine, tripropylamine, diethylamine, triethanolamine, isopropanolamine, pyridine, picoline and lutidine.
Preferably, the dechlorination catalyst is one or more of triethylamine, tripropylamine and picoline.
The invention further provides that, in the step (1), the dechlorination reaction can be batch synthesis or micro-reaction channel continuous synthesis.
The invention is further set that when the dechlorination reaction adopts batch synthesis, the reaction temperature is 50-70 ℃, the reaction time is 2-10 h, and the volume ratio of the chloroethylene carbonate to the solvent is 1: 2-5, wherein the mol ratio of the chloroethylene carbonate to the dechlorination catalyst is 1: 1-3, the molar weight of the polymerization inhibitor is 5-25% of the molar amount of the dechlorination catalyst, the mass fraction of the polymerization inhibitor solution is 30-50%, and the polymerization inhibitor solution is continuously added until the reaction time is over in a time period of 0.5-2.5 h after the reaction starts.
Preferably, the reaction temperature is 60 ℃ and the reaction time is 8 h.
Preferably, the volume ratio of the chloroethylene carbonate to the solvent is 1: 2.5.
preferably, the mol ratio of the chloroethylene carbonate to the dechlorination catalyst is 1: 1.5.
the invention further provides that when the solvent is acetonitrile, the molar quantity of the polymerization inhibitor is 10-25% of the molar quantity of the dechlorination catalyst, and in the time period of 20-40 min from the beginning of the reaction, the polymerization inhibitor solution is continuously added at the rate of 0.25-0.35 wt%/min until the end of the reaction time;
when the solvent is chloroform or dimethyl carbonate, the molar weight of the polymerization inhibitor is 5-10% of the molar amount of the dechlorination catalyst, and in the period of 50-70 min from the beginning of the reaction, the polymerization inhibitor solution is continuously added at the rate of 0.05-0.15 wt%/min until the reaction time is over.
The invention is further set that when the dechlorination reaction is continuously synthesized by adopting a micro-reaction channel, acetonitrile is used as a solvent to prepare a chloroethylene carbonate solution, a dechlorination catalyst solution and a polymerization inhibitor solution in advance, wherein in the chloroethylene carbonate solution, the mol ratio of chloroethylene carbonate to acetonitrile is 1: 3-8, wherein in the dechlorination catalyst solution, the volume ratio of the dosage of the dechlorination catalyst to the dosage of acetonitrile is 1: 1-3, the mass fraction of the polymerization inhibitor solution is 30-50%, the molar weight of the polymerization inhibitor is 1-3% of the molar amount of the dechlorination catalyst, and the molar ratio of the dechlorination catalyst to the chloroethylene carbonate is 1-1.5: 1.
preferably, in the chloroethylene carbonate solution, the mol ratio of chloroethylene carbonate to acetonitrile is 1: 5.
preferably, in the dechlorination catalyst solution, the volume ratio of the dechlorination catalyst to the acetonitrile is 1: 1.5.
preferably, the mole ratio of the dechlorination catalyst to the chloroethylene carbonate is 1.05: 1.
The invention is further set that the reaction temperature in the micro reaction channel is 50-70 ℃, the reaction time is 0.5-1 h, during the reaction, the chloroethylene carbonate solution is fed in one stream, the flow rate is 4-10 mL/min, the dechlorination catalyst solution is fed in the other stream, the flow rate is 4-8 mL/min, and during the reaction residence time of 10-20 min, the polymerization inhibitor solution is cut in through a three-way mixer, and the flow rate is 0.5-1 mL/min.
Preferably, the reaction temperature is 70 ℃, and the reaction time is 30-40 min.
Preferably, the polymerization inhibitor solution is cut in by a three-way mixer during the reaction residence time period of 15 min.
The invention is further set in the step (2), the vinylene carbonate crude product is extracted and separated in hot water of 60-75 ℃, the separated oil phase is the vinylene carbonate product insoluble in hot water, the water phase is the aqueous solution containing the organic amine salt by-product and the polymerization inhibitor, and the separated aqueous solution is separated out the polymerization inhibitor precipitate through cooling crystallization for recycling. In the hot water extraction process, when the extraction temperature is too low, the organic amine salt by-product is likely to precipitate, and when the temperature is too high, the vinylene carbonate may be polymerized, thereby affecting the yield.
Further, cooling the separated water solution, separating the polymerization inhibitor precipitate in time in the process of cooling to 30-35 ℃, and further recycling the polymerization inhibitor precipitate through acidification treatment.
The invention has the following beneficial effects:
(1) in the process of promoting dechlorination reaction by taking organic amine as a dechlorination catalyst, a proper organic acid polymerization inhibitor is added, the organic acid polymerization inhibitor has stronger proton affinity combined with triethylamine and simultaneously has a polymerization inhibition energy barrier lower than a main reaction energy barrier, so that the vinylene carbonate polymerization inhibition process is efficiently realized.
(2) The invention realizes the intermittent and continuous high-yield synthesis of vinylene carbonate by optimizing the addition amount and the addition time of the polymerization inhibitor, ensures that the VC yield by an intermittent method is more than or equal to 95 percent and the VC yield by a continuous method is more than or equal to 98 percent, is superior to the yield of the crude product for synthesizing VC reported at home and abroad at present, and the added organic polymerization inhibitor can be recycled by simple extraction and separation.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in further detail below, and it should be understood that the described embodiments are only further illustrations of the present invention, and should not be construed as limiting the scope of the present invention. Based on the examples of the present invention, those skilled in the art without any creative effort can make insubstantial improvements and modifications to the present invention, including further development and scale-up of the batch and continuous synthesis methods employed, and the use of polymerization inhibitors in a manner similar to the combination of phenolic acids, within the scope of the present invention.
Example 1 batch Synthesis Process
The reaction device is an intermittent reaction kettle, dimethyl carbonate is taken as a reaction solvent, and a dechlorination catalyst is triethylamine, wherein the molar ratio of the triethylamine to the raw material Chlorinated Ethylene Carbonate (CEC) is 1.5: 1, the volume ratio of dimethyl carbonate to CEC is 2.5: 1; the reaction temperature is 60 ℃, the reaction time is 8 hours, the yield of the crude product Vinylene Carbonate (VC) is 75 percent, and no polymerization inhibitor is added in the process. .
Example 2 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 60 ℃, the dechlorination catalyst is triethylamine, and the molar ratio of triethylamine to CEC is 1.5: 1, selecting dimethyl carbonate as a solvent, wherein the volume ratio of the dimethyl carbonate to the CEC is 2.5: 1, reaction time 8 hours. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the polymerization inhibitor is dissolved in the dimethyl carbonate, and the mass fraction of the polymerization inhibitor is 30 percent. Preparing a polymerization inhibitor solution according to the mol amount of 10 percent of triethylamine, dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.1wt percent/min after reacting for 1 hour until the reaction time is finished. The crude product after the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 96.8%.
Example 3 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 70 ℃, triethylamine and tripropylamine are mixed according to the molar ratio of 1:1 to form an organic amine dechlorination catalyst, and the molar ratio of the dechlorination catalyst to CEC is 2: 1, selecting chloroform as a solvent, wherein the volume ratio of chloroform to CEC is 5:1, reaction time 5 hours. The polymerization inhibitor is a combination of gentisic acid and phloroglucinol acid, and the molar ratio is 7: 1; the organic polymerization inhibitor is dissolved in chloroform, and the mass fraction of the organic polymerization inhibitor is 50 percent. Preparing a polymerization inhibitor solution according to 5 percent of the mol amount of the organic amine dechlorination catalyst, and dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.1wt percent/min after reacting for 1 hour till the reaction time is over. The crude product after the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 97.2%.
Example 4 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 50 ℃, triethylamine, isopropanolamine and picoline are mixed according to the molar ratio of 3:1:1 to form an organic amine dechlorination catalyst, and the molar ratio of the dechlorination catalyst to CEC is 3: and 1, selecting acetonitrile as a solvent, wherein the volume ratio of the acetonitrile to the CEC is 2: 1, reaction time 10 hours. The polymerization inhibitor is a combination of o-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 9: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction is 40%. Preparing a polymerization inhibitor solution according to the mol amount of 8 percent of the polymerization inhibitor of the organic amine, and dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.3wt percent/min after reacting for 1 hour until the reaction time is finished. The crude product after the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 95.2%.
Example 5 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 60 ℃, triethylamine, diethylamine and triethanolamine are mixed according to the molar ratio of 4:5:1 to form an organic amine dechlorination catalyst, and the molar ratio of the dechlorination catalyst to CEC is 1: and 1, selecting acetonitrile as a solvent, wherein the volume ratio of the acetonitrile to CEC is 4:1, reaction time 2 hours. The polymerization inhibitor is a combination of o-hydroxybenzoic acid, m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 3:6: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the organic polymerization inhibitor is 45 percent. Preparing a polymerization inhibitor solution according to the mol amount of 10 percent of the polymerization inhibitor which is the organic amine dechlorination catalyst, dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.3wt percent/min after reacting for 1 hour until the reaction time is over. The crude product after the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 96.0%.
Comparative example 1 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 60 ℃, the dechlorination catalyst is triethylamine, and the molar ratio of triethylamine to CEC is 1.5: 1, selecting dimethyl carbonate as a solvent, wherein the volume ratio of the dimethyl carbonate to the CEC is 2.5: 1, reaction time 8 hours. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the polymerization inhibitor is dissolved in the dimethyl carbonate, and the mass fraction of the polymerization inhibitor is 30 percent. And (3) preparing a polymerization inhibitor solution according to the molar amount of 10 percent of triethylamine, and dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.1wt percent/min after reacting for 20 minutes until the reaction time is finished. The crude product after the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 77.3%.
Comparative example 2 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 60 ℃, the dechlorination catalyst is triethylamine, and the molar ratio of triethylamine to CEC is 1.5: 1, selecting dimethyl carbonate as a solvent, wherein the volume ratio of dimethyl carbonate to CEC is 2.5: 1, reaction time 8 hours. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in the dimethyl carbonate, and the mass fraction of the organic polymerization inhibitor is 30 percent. Preparing a polymerization inhibitor solution according to the molar amount of 10 percent of the organic polymerization inhibitor of triethylamine, and dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.5wt percent/min after reacting for 20 minutes until the reaction time is finished. And (3) dissolving the crude product after the reaction in hot water at 60 ℃ for extraction and separation, wherein the yield of VC is 70.4%.
Comparative example 3 batch Synthesis Process
The reaction device is an intermittent reaction kettle, the reaction temperature of intermittent synthesis is 60 ℃, the dechlorination catalyst is triethylamine, and the molar ratio of triethylamine to CEC is 1.5: 1, selecting dimethyl carbonate as a solvent, wherein the volume ratio of the dimethyl carbonate to the CEC is 2.5: 1, reaction time 8 hours. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in the dimethyl carbonate, and the mass fraction of the organic polymerization inhibitor is 30 percent. Preparing a polymerization inhibitor solution according to the molar amount of 10 percent of the organic polymerization inhibitor of triethylamine, and dropwise adding the polymerization inhibitor solution into the reaction system at the speed of 0.5wt percent/min after reacting for 3 hours until the reaction time is finished. And (3) dissolving the crude product after the reaction in hot water at 75 ℃ for extraction separation, wherein the yield of VC is 78.8%.
EXAMPLE 6 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent is 1: 5; the organic amine dechlorination catalyst is a mixture of triethylamine and tripropylamine according to a molar ratio of 7:3, and the molar ratio of the organic amine to CEC is 1.05: 1; the volume ratio of the organic amine to the acetonitrile solvent is 1: 1.5; CEC solution is used as one feed, the feed flow is 4mL/min, organic amine solution is used as the other feed, the feed flow is 4mL/min, the reaction temperature is 60 ℃, the reaction time is 40 minutes, the VC yield of the crude product is 86%, and no polymerization inhibitor is added in the process.
EXAMPLE 7 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent is 1: 5; the organic amine dechlorination catalyst is a mixture of triethylamine and tripropylamine according to a molar ratio of 7:3, and the molar ratio of the organic amine to CEC is 1.05: 1; the volume ratio of the organic amine to the acetonitrile solvent is 1: 1.5; CEC solution was fed as one stream at a feed rate of 4mL/min, organic amine solution was fed as the other stream at a feed rate of 4mL/min, a reaction temperature of 70 ℃ and a reaction time of 40 minutes. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the polymerization inhibitor is 30 percent. And preparing a polymerization inhibitor solution according to the mol amount of 2 percent of the polymerization inhibitor of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 15 minutes, wherein the flow rate is 1 mL/min. And dissolving the crude product at the reaction outlet in hot water at 60 ℃ for extraction and separation, wherein the yield of VC is 99.1%.
EXAMPLE 8 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent in CEC solution is 1: 8; the organic amine dechlorination catalyst is triethylamine, and the molar ratio of the triethylamine to CEC is 1.5: 1; the volume ratio of triethylamine to acetonitrile solvent in the triethylamine solution is 1: 3; CEC solution as one feed with feed flow of 10mL/min, organic amine solution as the other feed with feed flow of 8mL/min, reaction temperature of 50 ℃ and reaction time of 1 hour. The polymerization inhibitor is a combination of gentisic acid and phloroglucinol acid, and the molar ratio is 7: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction is 50%. And preparing a polymerization inhibitor solution according to the mol amount of the polymerization inhibitor which is 3 percent of the mol amount of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 15 minutes, wherein the flow rate is 1 mL/min. The crude product at the outlet of the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 98.2%.
EXAMPLE 9 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent in CEC solution is 1: 3; the organic amine dechlorination catalyst is a mixture of triethylamine and tripropylamine according to a molar ratio of 1:1, and the molar ratio of the organic amine to CEC is 1: 1; the volume ratio of the organic amine to the acetonitrile solvent in the organic amine solution is 1: 1; CEC solution was fed as one stream at a feed rate of 5mL/min, organic amine solution was fed as the other stream at a feed rate of 4.5mL/min, a reaction temperature of 70 ℃ and a reaction time of 30 minutes. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the organic polymerization inhibitor is 30 percent. And preparing a polymerization inhibitor solution according to the mol amount of the polymerization inhibitor which is 1 percent of the molar amount of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 15 minutes, wherein the flow rate is 0.5 mL/min. The crude product at the outlet of the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 98.8%.
EXAMPLE 10 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent in CEC solution is 1: 6; the organic amine dechlorination catalyst is a mixture of triethylamine and triethanolamine according to a molar ratio of 4:1, and the molar ratio of the organic amine to CEC is 1.2: 1; the volume ratio of the organic amine to the acetonitrile solvent in the organic amine solution is 1: 2; CEC solution was fed as one stream at a feed rate of 4mL/min, organic amine solution was fed as the other stream at a feed rate of 4mL/min, a reaction temperature of 70 ℃ and a reaction time of 50 minutes. The polymerization inhibitor is a combination of m-hydroxybenzoic acid, o-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 6:3: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction is 40%. And preparing a polymerization inhibitor solution according to the mol amount of the polymerization inhibitor which is 3 percent of the mol amount of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 15 minutes, wherein the flow rate is 0.8 mL/min. The crude product at the outlet of the reaction is dissolved in hot water at 70 ℃ for extraction and separation, and the yield of VC is 98.4%.
Comparative example 4 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the micro-reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent is 1: 5; the organic amine dechlorination catalyst is a mixture of triethylamine and tripropylamine according to a molar ratio of 7:3, and the molar ratio of the organic amine to CEC is 1.05: 1; the volume ratio of the organic amine to the acetonitrile solvent is 1: 1.5; CEC solution was fed as one stream at a feed rate of 4mL/min, organic amine solution was fed as the other stream at a feed rate of 4mL/min, a reaction temperature of 70 ℃ and a reaction time of 40 minutes. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the organic polymerization inhibitor is 30 percent. Preparing a polymerization inhibitor solution according to the molar amount of 2 percent of the organic polymerization inhibitor of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 5 minutes, wherein the flow rate is 1 mL/min. And dissolving the crude product at the reaction outlet in hot water at 60 ℃ for extraction separation, wherein the yield of VC is 80%.
Comparative example 5 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent is 1: 5; the organic amine dechlorination catalyst is a mixture of triethylamine and tripropylamine according to a molar ratio of 7:3, and the molar ratio of the organic amine to CEC is 1.05: 1; the volume ratio of the organic amine to the acetonitrile solvent is 1: 1.5; CEC solution was fed as one stream at a feed rate of 4mL/min, organic amine solution was fed as the other stream at a feed rate of 4mL/min, a reaction temperature of 70 ℃ and a reaction time of 40 minutes. The polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the organic polymerization inhibitor is 30 percent. And preparing a polymerization inhibitor solution according to the mol amount of the polymerization inhibitor which is 3 percent of the molar amount of triethylamine, and cutting into the organic polymerization inhibitor solution through a three-way mixer within the reaction retention time of 30 minutes, wherein the flow rate is 1 mL/min. The crude product at the outlet of the reaction is dissolved in hot water at 70 ℃ for extraction separation, and the yield of VC is 84%.
Comparative example 6 micro-reaction channel Synthesis Process
The size of the micro-reaction channel is 1.8mm, the material of the reaction channel is a polytetrafluoroethylene tube, and in the micro-reaction continuous synthesis process, the volume ratio of CEC to acetonitrile solvent is 1: 5; the organic amine is a mixture of triethylamine and tripropylamine according to a molar ratio of 7:3, and the molar ratio of the organic amine to CEC is 1.05: 1; the volume ratio of the organic amine to the acetonitrile solvent is 1: 1.5; CEC solution was fed as one stream at a feed rate of 4mL/min, organic amine solution was fed as the other stream at a feed rate of 4mL/min, a reaction temperature of 70 ℃ and a reaction time of 40 minutes. The organic polymerization inhibitor is a combination of m-hydroxybenzoic acid and phloroglucinol acid, and the molar ratio is 10: 1; the organic polymerization inhibitor is dissolved in acetonitrile, and the mass fraction of the organic polymerization inhibitor is 30 percent. Preparing a polymerization inhibitor solution according to 1 percent of the molar amount of the organic polymerization inhibitor, and cutting into the organic polymerization inhibitor solution through a three-way mixer at the flow rate of 1mL/min within the reaction retention time of 1 minute. And dissolving the crude product at the reaction outlet in hot water at 75 ℃ for extraction separation, wherein the yield of VC is 80%.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (10)
1. A method for improving the yield of vinylene carbonate is characterized by comprising the following steps:
(1) in an organic solvent, taking chlorinated ethylene carbonate as a raw material, adding an organic amine dechlorination catalyst to perform dechlorination reaction, adding a polymerization inhibitor solution after the dechlorination reaction is performed for a period of time, and continuously performing the reaction to obtain a vinylene carbonate crude product;
(2) extracting and separating the vinylene carbonate crude product by hot water to obtain a vinylene carbonate product;
the polymerization inhibitor solution is prepared in advance by dissolving the polymerization inhibitor in the solvent, and the polymerization inhibitor is one or more of o-hydroxybenzoic acid, m-hydroxybenzoic acid, gentisic acid and phloroglucinol acid.
2. The method for increasing the yield of vinylene carbonate according to claim 1, wherein the solvent is selected from one of chloroform, dimethyl carbonate and acetonitrile.
3. The method for increasing the yield of vinylene carbonate according to claim 1, wherein the polymerization inhibitor is composed of two organic acid portions, namely phloroglucinol acid and at least one of o-hydroxybenzoic acid, m-hydroxybenzoic acid or gentisic acid, and the molar ratio of the two organic acid portions is 1: 7 to 10.
4. The method for improving the yield of vinylene carbonate (vinylene carbonate) according to claim 1, wherein the dechlorination catalyst is one or more of triethylamine, tripropylamine, diethylamine, triethanolamine, isopropanolamine, pyridine, picoline and lutidine;
preferably, the dechlorination catalyst is one or more of triethylamine, tripropylamine and picoline.
5. The method for increasing the yield of vinylene carbonate according to claim 1, wherein in step (1), the dechlorination reaction can be a batch synthesis or a micro-reaction channel continuous synthesis.
6. The method for improving the yield of vinylene carbonate according to claim 5, wherein when batch synthesis is adopted in the dechlorination reaction, the reaction temperature is 50-70 ℃, and the reaction time is 2-10 h; preferably, the reaction temperature is 60 ℃, and the reaction time is 8 h;
the volume ratio of the chloroethylene carbonate to the solvent is 1: 2-5, preferably 1: 2.5;
the mol ratio of the chloroethylene carbonate to the dechlorination catalyst is 1: 1-3, preferably 1: 1.5;
the molar weight of the polymerization inhibitor is 5-25% of the molar amount of the dechlorination catalyst, the mass fraction of the polymerization inhibitor solution is 30-50%, and the polymerization inhibitor solution is continuously added until the reaction time is over in a period of 0.5-2.5 h after the reaction starts.
7. The method for improving the yield of vinylene carbonate as claimed in claim 6, wherein when the solvent is acetonitrile, the molar amount of the polymerization inhibitor is 10-25% of the molar amount of the dechlorination catalyst, and the polymerization inhibitor solution is continuously added at a rate of 0.25-0.35 wt%/min at the beginning of the reaction for 20-40 min;
when the solvent is chloroform or dimethyl carbonate, the mol weight of the polymerization inhibitor is 5-10% of the mol amount of the dechlorination catalyst, and in the time period of 50-70 min from the beginning of the reaction, the polymerization inhibitor solution is continuously added at the rate of 0.05-0.15 wt%/min until the reaction time is over.
8. The method for improving the yield of vinylene carbonate according to claim 5, wherein when the dechlorination reaction is continuously synthesized by using a micro-reaction channel, a vinylene carbonate solution, a dechlorination catalyst solution and a polymerization inhibitor solution are prepared in advance by using acetonitrile as a solvent, wherein the vinylene carbonate solution has a molar ratio of the vinylene carbonate to the acetonitrile of 1: 3-8, preferably 1: 5; in the dechlorination catalyst solution, the volume ratio of the dechlorination catalyst to the acetonitrile is 1: 1-3, preferably 1: 1.5; the mass fraction of the polymerization inhibitor solution is 30-50%;
the molar amount of the polymerization inhibitor is 1-3% of the molar amount of the dechlorination catalyst; the mol ratio of the dechlorination catalyst to the chloroethylene carbonate is 1-1.5: 1, preferably 1.05: 1.
9. The method for improving the yield of vinylene carbonate according to claim 8, wherein the reaction temperature in the micro-reaction channel is 50-70 ℃, and the reaction time is 0.5-1 h; preferably, the reaction temperature is 70 ℃, and the reaction time is 30-40 min;
during reaction, the chloroethylene carbonate solution is fed into one flow of 4-10 mL/min, the dechlorination catalyst solution is fed into the other flow of 4-8 mL/min, and the polymerization inhibitor solution is cut into the chloroethylene carbonate solution through a three-way mixer at the flow of 0.5-1 mL/min within the reaction retention time of 10-20 min.
10. The method for improving the yield of the vinylene carbonate according to claim 1, wherein in the step (2), the vinylene carbonate crude product is extracted and separated in hot water at the temperature of 60-75 ℃, the separated oil phase is the vinylene carbonate product, the water phase is an aqueous solution containing the organic amine salt byproduct and the polymerization inhibitor, and the separated aqueous solution is subjected to temperature reduction crystallization to separate the polymerization inhibitor precipitate for recycling.
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