WO2023201999A1 - 一种电解液添加剂的生产方法及系统 - Google Patents

一种电解液添加剂的生产方法及系统 Download PDF

Info

Publication number
WO2023201999A1
WO2023201999A1 PCT/CN2022/124193 CN2022124193W WO2023201999A1 WO 2023201999 A1 WO2023201999 A1 WO 2023201999A1 CN 2022124193 W CN2022124193 W CN 2022124193W WO 2023201999 A1 WO2023201999 A1 WO 2023201999A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
crystallization
tower
carbonate
melting
Prior art date
Application number
PCT/CN2022/124193
Other languages
English (en)
French (fr)
Inventor
唐曦
康小玲
梁勇军
丁永良
郑伯川
张飞
李明全
贾凤刚
邓任军
常曲
黄杰
钟显威
刘晓花
陈孝建
Original Assignee
上海东庚化工技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202210438743.1A external-priority patent/CN114716402A/zh
Priority claimed from CN202210438949.4A external-priority patent/CN114874178A/zh
Priority claimed from CN202210438928.2A external-priority patent/CN114736185B/zh
Application filed by 上海东庚化工技术有限公司 filed Critical 上海东庚化工技术有限公司
Publication of WO2023201999A1 publication Critical patent/WO2023201999A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • 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
    • 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
    • C07D317/42—Halogen atoms or nitro radicals

Definitions

  • the present application relates to the field of organic synthesis technology, and in particular to an electrolyte production method and system.
  • the industrial production of vinylene carbonate is mainly divided into two steps: the first step is to generate monochloroethylene carbonate through the chlorination reaction of vinylene carbonate (using chlorine as the chlorinating agent under ultraviolet light irradiation), The second step is to remove chlorine atoms in monochloroethylene carbonate through dehalogenation agents such as triethylamine, ammonia, and alkali metal hydroxides to generate vinylene carbonate.
  • This method is used to synthesize vinylene carbonate with mild conditions, simple operation and easy control. It is a production method commonly used in industry at present.
  • the obtained crude vinylene carbonate with a purity of about 60% needs to be subjected to three-stage distillation (the first-stage distillation is carried out in a desolvation tower, and the first-stage distillation is After that, the purity of the product is about 97%.
  • the second-stage distillation is carried out in the light removal tower or the crude distillation tower. After the second-stage distillation treatment, the purity of the product is about 98%.
  • the third-stage rectification tower is carried out in the rectification tower.
  • the purity of the product is about 98.5%
  • the energy consumption is high (about 3600kg steam/t product)
  • the purity of the obtained product is only 98.5%, which cannot meet the application needs in the electronic field.
  • two more distillations are required to increase the purity of the product to about 99.5%. This further increases energy consumption (about 8000kg steam/t product) and leads to an enlarged production process. The economy is poor.
  • Fluoroethylene carbonate is synthesized by reacting a mixed gas of fluorine and nitrogen with ethylene carbonate. Its synthesis route is as follows:
  • the raw material used in this method is fluorine gas.
  • Fluorine gas is not only highly toxic, but also has high reactivity.
  • the reaction is violently exothermic, which can easily cause the pressure in the reaction vessel to be high and dangerous.
  • fluorine gas is highly corrosive, so it is harmful to the reaction equipment. The requirements are very high, the industrial risk is high, and the implementation is difficult.
  • ethylene carbonate As raw material, it is chlorinated with chlorine gas or other chlorinating reagents to generate monochloroethylene carbonate. After purification, the monochloroethylene carbonate reacts with the fluorinating reagent to obtain the target product fluorinated ethylene carbonate.
  • Its synthesis route is as follows:
  • This method does not involve toxic fluorine gas, greatly reduces safety costs, and the production process is easier to control. However, since it is a two-step reaction, the overall yield is low and the input of raw materials is large.
  • Fluorinated ethylene carbonate is obtained by anodic fluorination of 4-substituted arylthioethylene carbonate. This method can react under safe and relatively simple equipment conditions, but it is still in the laboratory theoretical research stage.
  • the most ideal synthesis process of fluorinated ethylene carbonate is currently the halogen exchange reaction method (Method 2).
  • Method 2 This process is a two-step reaction.
  • monochloroethylene carbonate excessive chlorine is used for intermittent reaction.
  • the reaction time is about 24 hours, which makes continuous production impossible, and the conversion rate of raw materials of ethylene carbonate and chlorine is not high, the yield of by-products is too high, and the economy is not good.
  • monochloroethylene carbonate After monochloroethylene carbonate is prepared, it needs to be purified before it can be used for the synthesis of fluorinated ethylene carbonate.
  • the purpose of purifying monochloroethylene carbonate is mainly to remove the by-product dichlorine by-product in the mixture.
  • the purified ethylene monochloride reacts with the fluorination reagent and solvent in the reaction kettle to generate fluorinated ethylene carbonate and mixed salt (solid fluorination reagent and potassium chloride). After filtration, the mother liquor is sent to the solvent recovery tower for recovery. After recovering the solvent, the crude fluoroethylene carbonate is purified by distillation/distillation to remove by-products such as difluoro substituents. At present, the purification process of fluoroethylene carbonate mostly adopts the distillation process. Although FEC with high purity can be obtained through multi-stage distillation, the purification of fluoroethylene carbonate by traditional distillation process not only consumes very high energy, but also suffers from process limitations. And the physical properties of the product make it difficult to obtain electronic grade fluoroethylene carbonate by distillation.
  • the first-level distillation is carried out in the desolvation tower. After the first-level distillation treatment, the purity of the product is about 97%.
  • the second-level distillation is carried out in the light removal tower or the crude distillation tower. After the second-level distillation treatment, the purity of the product is about 97%. 98%, the three-stage distillation tower is carried out in the distillation tower.
  • the purity of the product is about 98.5%
  • the energy consumption is high (about 3600kg steam/t product)
  • the obtained product The purity is only 98.5%, which cannot meet the application needs in the electronic field.
  • the present application provides a production method and production system of vinylene carbonate to reduce the energy consumption of vinylene carbonate production and reduce the amount of by-products produced.
  • the steps adopted in the production method are:
  • step S2 Place the monochloroethylene carbonate obtained in step S1 into a reaction kettle containing a solvent, an acid binding agent and a polymerization inhibitor for reaction, and wash the dechlorination reaction product with dimethyl carbonate for solid-liquid separation to obtain The liquid phase is treated in a desolvation tower and then melted and crystallized to obtain the vinylene carbonate.
  • the solvent is vinylene carbonate.
  • this application also provides a production method of vinylene carbonate, wherein the steps used in the production method include a chlorination reaction step, a dechlorination reaction step and a purification step.
  • the chlorination reaction step includes: using ethylene carbonate as the raw material, using chlorine as the chlorinating agent, performing the chlorination reaction under ultraviolet light irradiation, the molar ratio of chlorine to ethylene carbonate is (0.4-0.6): (2- 3).
  • vinylene carbonate prepared by the production method provided in the second aspect is also provided.
  • the vinylene carbonate prepared based on the production method provided in the second aspect can be used in related processes of lithium-ion batteries.
  • the production methods of vinylene carbonate provided in the first aspect and the second aspect also include the following contents:
  • the temperature of the chlorination reaction is 60-70°C, preferably 65-70°C.
  • the time of chlorination reaction is 1-2h, preferably 1.2-2h.
  • the liquid after the chlorination reaction is rectified, and the ethylene carbonate obtained by rectification is continued to be used as a raw material for the chlorination reaction.
  • the temperature of the distillation is 50-60°C, preferably 55-60°C.
  • triethylamine is used as the acid binding agent.
  • the polymerization inhibitor uses butyl p-cresol.
  • the molar ratio of solvent to monochloroethylene carbonate is 1: (1-1.5), preferably 1: (1.2-1.5).
  • the molar ratio of the acid binding agent to monochloroethylene carbonate is 1: (1-1.5), preferably 1: (1.2-1.5).
  • the mass ratio of the polymerization inhibitor to monochloroethylene carbonate is (0.1-0.5):100, preferably (0.2-0.5):100.
  • the temperature of the dechlorination reaction is 60-70°C, preferably 65-70°C; the time of the dechlorination reaction is 4-5h, preferably 4.5-5h.
  • the temperature is 30-40°C, preferably 35-40°C; the pressure is 6-10kPa, preferably 7-10kPa.
  • the method also includes the following steps: drying the solid phase obtained after washing with dimethyl carbonate, adding water and filtering, adding alkali to the liquid obtained by filtration for reaction, and then centrifuging to recover the triethylamine obtained by centrifugation, And continue to be used as raw material for dechlorination reaction.
  • the purification process includes melt crystallization.
  • a falling film crystallizer tube is used for melt crystallization.
  • the present application also provides a production system for vinylene carbonate, including a primary reaction unit, a secondary reaction unit and a purification unit.
  • the primary reaction unit includes at least one photolysis reaction tower, so The photolysis reaction tower is provided with an ethylene carbonate feed port, an air inlet, a liquid outlet and a gas outlet.
  • the secondary reaction unit includes at least one primary reaction kettle, and the reaction kettle is provided with a feed port and a discharge port. port, the purification unit includes a melting crystallizer, the discharge port of the last stage photolysis reaction tower is connected to the feed port of the first stage reactor, and the discharge port of the last stage reactor is connected to the melting crystallizer .
  • the first-level reaction unit also includes a deacidification tower, which is provided with an air inlet and an air outlet, which are located between the liquid outlet of the last-stage photolysis reaction tower and the first-stage reaction kettle. On the connecting pipe between the feed ports.
  • the first-level reaction unit further includes a rectification tower, which is located on the connecting pipeline between the deacidification tower and the first-level reaction kettle, one end of which is connected to the deacidification tower, and the third A liquid outlet and an ethylene carbonate outlet are provided at both ends.
  • the liquid outlet is connected to the feed inlet of the first-stage reactor, and the ethylene carbonate outlet is connected to the ethylene carbonate feed inlet of the photolysis reaction tower.
  • a first centrifugal device is provided between adjacent reaction kettles.
  • the first centrifugal device is provided with a liquid inlet, a liquid outlet and a solid outlet.
  • the liquid inlet and the liquid outlet are respectively connected to the discharge port of the upper-level reactor and the feed port of the next-level reactor.
  • the melting crystallizer adopts a falling film crystallizer.
  • the secondary reaction unit also includes a washing tower, located on the communication pipeline between the last-stage reaction kettle and the melting crystallizer, which is connected to the outlet of the last-stage reaction kettle, and is connected to the washing tower through a transmission assembly.
  • the solid outlet of the centrifugal device is provided with a liquid outlet and a solid discharge outlet, and the liquid outlet is connected to the melting crystallizer.
  • the production system also includes a triethylamine recovery unit.
  • the triethylamine recovery unit includes a drying device and a dissolving tank connected through a transmission assembly.
  • the drying device is connected to the solids in the washing tower through a transmission assembly.
  • Discharge port the dissolution tank is connected with a filtering device, the filtering device is provided with a liquid discharge port, the liquid discharge port is connected with a reaction tank, the reaction tank is connected with a second centrifugal device, and the second centrifugal device is provided with There is a triethylamine outlet, and the triethylamine outlet is connected to the feed port of the reaction kettle.
  • the purification unit further includes a desolvation tower connected to the liquid outlet end of the washing tower and the melting crystallizer.
  • the purification unit further includes a crude distillation tower, which is located on the communication pipeline between the desolvation tower and the melting crystallizer and communicates with the desolvation tower and the melting crystallizer.
  • the production system also includes a by-product recovery unit.
  • the by-product recovery unit includes a water absorption tower and an alkali absorption tower that are connected in sequence.
  • the water absorption tower is connected to the gas outlet of the last stage photolysis reaction tower.
  • the reaction tank is provided with a triethylamine outlet, and the triethylamine outlet is connected to the water absorption tower.
  • this application also provides an energy-saving production method and system for fluoroethylene carbonate.
  • the steps adopted in the production method are:
  • Chlorination reaction The chlorination reagent is first chlorinated with excess ethylene carbonate (ethylene carbonate) under the action of light to form monochloroethylene carbonate (ethylene carbonate).
  • the chlorination reaction products include monochloroethylene carbonate and unused ethylene carbonate. Reacted ethylene carbonate;
  • Fluorination reaction Add a fluorination reagent to the blend of monochloroethylene carbonate and ethylene carbonate, and use ethylene carbonate as the solvent to react to generate fluorinated ethylene carbonate (fluorinated ethylene carbonate);
  • Solid-liquid separation and purification The fluorinated reaction product is subjected to solid-liquid separation to obtain solid mixed salt and liquid, and the liquid is purified to obtain the target product fluorinated ethylene carbonate.
  • step S1 the molar ratio of chlorinated reagent to ethylene carbonate is (0.4-0.6): (2-3).
  • step S2 the molar ratio of the fluorination reagent to ethylene monochloride carbonate is (1-1.5):1, preferably (1-1.1):1.
  • ethylene carbonate reacts in a molten state.
  • the reaction temperature is 60-70°C and the reaction time is 1-2 hours.
  • the reaction is carried out under purple or blue light irradiation conditions.
  • the reaction temperature is 60-80°C and the reaction time is 7-9 hours.
  • the chlorination reagent is selected from chlorine gas.
  • the solid mixed salt includes MF and KCl; preferably, the solid mixed salt includes KF and KCl.
  • the solid mixed salt is stirred and dissolved with water, then the organic matter is removed, calcium chloride is added to stir the reaction, filtered after the reaction, the filter residue is washed and dried to obtain calcium fluoride, and the filtrate is distilled and crystallized to obtain Soluble chloride salt (potassium chloride).
  • activated carbon is used to adsorb the organic matter, and then calcium chloride is added to stir the reaction after filtering; or a filter bag or membrane is used to filter the organic matter, and then calcium chloride is added to stir the reaction.
  • the molar ratio of calcium chloride to fluoride ions is (1-1.02):1.
  • the calcium fluoride drying temperature is 140-160°C
  • continuous drying is 1-1.5 hours.
  • the liquid purification method includes the following steps:
  • falling film crystallization After the solvent ethylene carbonate in the liquid is removed, falling film crystallization is performed.
  • the falling film crystallization process includes several cycles of melting crystallization, and the melting crystallization includes the steps of crystallization, sweating, and melting in sequence.
  • the temperature is 110-130°C
  • the flow rate is 380-450Kg/m 3 /h
  • the pressure is 1-2kPa.
  • the material flow rate is 0.2-0.6m 3 /h and the pressure is 0.02-0.07MPa.
  • the crystallization step includes rapid cooling and slow cooling processes in sequence.
  • the rapid cooling temperature is 30-22°C and the slow cooling temperature is 22-0°C.
  • the crystallization time is 80-90 minutes.
  • the sweating step includes a rapid heating process and a slow heating process.
  • the rapid heating temperature is 0-18°C
  • the slow heating temperature is 18-22.5°C.
  • the sweating time is 40-50 minutes.
  • the temperature of the melting step is 30-35°C, and the melting time is 20-40 minutes.
  • the falling film crystallization process includes two or three melting crystallizations.
  • the two melting crystallizations are one-level melting crystallization and two-level melting crystallization.
  • the three-time melting crystallization is one-level melting crystallization, two-level melting crystallization, and three-level melting crystallization. level melt crystallization;
  • the first-level melting and crystallization includes first-level crystallization, first-level sweating, and first-level melting.
  • the first-level crystallization has a rapid cooling of 30-22°C, a slow cooling of 22-0°C, and a crystallization time of 80-90 minutes; a first-level sweating and rapid heating.
  • the temperature is 0 ⁇ 18°C, the temperature rises slowly to 18-22.5°C, and the sweating time is 40-50min; the first-level melting temperature is 30-35°C, and the melting time is 20-40 minutes; after the first-level melting is completed, the first-level product is obtained;
  • the secondary melting crystallization includes secondary crystallization, secondary sweating, and secondary melting.
  • the secondary crystallization has a rapid cooling of 30-22°C, a slow cooling of 22-5°C, and a crystallization time of 80-90 minutes; the secondary sweating has a rapid temperature rise.
  • the temperature is 5-18°C, the temperature rises slowly to 18-22.5°C, the sweating time is 40-50min; the secondary melting temperature is 30-35°C, the melting time is 20-40 minutes; after the secondary melting is completed, the secondary product is obtained;
  • the process parameter conditions of the third-level melting and crystallization step are the same as those of the second-level melting and crystallization. After the completion of the third-level melting and crystallization, a third-level product is obtained.
  • the falling film crystallization process also includes a first-level recovery, and the first-level recovery is to melt and crystallize the first-level product obtained from the first-level melt crystallization again.
  • the process parameter conditions of the first-level recovery step are the same as those of the first-level melting and crystallization step.
  • a multi-stage distillation step is also provided between the solvent removal and falling film crystallization steps; preferably, the multi-stage distillation is one-stage, two-stage distillation. Stage or tertiary distillation.
  • the temperature during distillation is 50-60°C
  • the flow rate is 40-70Kg/m 3 /h
  • the pressure is 5-6kPa.
  • the chlorination reaction includes a multi-stage photocatalytic chlorination reaction.
  • the chlorination reaction includes a two-stage photocatalytic chlorination reaction.
  • the by-product hydrogen chloride/chlorine mixed gas of the previous stage of chlorination reaction is passed into the subsequent stage of chlorination reaction as the raw material gas for the chlorination reaction.
  • the by-product hydrogen chloride/chlorine mixed gas of the chlorination reaction is absorbed by water and alkali to obtain hydrochloric acid and sodium hypochlorite as by-products respectively; preferably, a sodium hydroxide solution is used for alkali absorption, and the concentration of the sodium hydroxide solution is 20-30%.
  • the present invention provides an energy-saving production system for fluorinated ethylene carbonate, which includes a fluorinated primary reaction unit, a fluorinated secondary reaction unit and a fluorinated purification unit.
  • the fluorinated primary reaction unit includes multi-stage photolysis. Reaction tower and deacidification tower.
  • the photolysis reaction tower is a place where chlorinated reagent and ethylene carbonate carry out chlorination reaction to generate monochloroethylene carbonate.
  • the top of the photolysis reaction tower is provided with an exhaust port.
  • the exhaust port of the first-level photolysis reaction tower is connected to the next-level photolysis reaction tower, and the deacidification tower is connected to the photolysis reaction tower for removing excess Cl2 and HCl gas in the chlorination reaction product;
  • the secondary reaction unit includes a first reaction kettle and a centrifuge. The first reaction kettle is connected to the deacidification tower and is a place where monochloroethylene carbonate and fluorinating reagent carry out fluorination reaction to generate fluoroethylene carbonate.
  • the centrifuge is a place for solid-liquid separation of fluorinated reaction products;
  • the purification unit includes a desolvation tower and a falling film crystallization system, the desolvation tower is connected to the liquid outlet of the centrifuge, and is used to remove The solvent in the liquid separated by the centrifuge is used to purify fluoroethylene carbonate by the falling film crystallization system.
  • the falling film crystallization system includes a falling film crystallizer, a circulating heat preservation system cold and hot medium preheating device, and a crystallization circulation pump.
  • the falling film crystallizer is a purification site for fluoroethylene carbonate, and the circulating heat preservation system
  • the system's hot and cold medium preheating equipment is used to control and adjust the temperature of the cold and hot medium, and the crystallization circulation pump is used to circulate and transport the crystallization mother liquor.
  • the purification unit further includes a multi-stage rectification tower, which is arranged between the desolvation tower and the falling film crystallization system; preferably, the multi-stage rectification tower is one-stage, Level 2 or 3.
  • the outlet of the falling film crystallizer is connected to the inlet of the rectification tower.
  • the multi-stage photolysis reaction tower is a two-stage photolysis reaction tower.
  • the production system also includes a fluorinated first by-product recovery unit, the fluorinated first by-product recovery unit includes a water absorption tower and an alkali absorption tower, and an exhaust gas is provided at the top of the photolysis reaction tower.
  • the water absorption tower is connected to the exhaust port of the last stage photolysis reaction tower.
  • the water absorption tower is also provided with a process water inlet; the alkali absorption tower is connected to the water absorption tower.
  • the fluorinated first by-product recovery unit further includes a hydrochloric acid product tank, and the hydrochloric acid product tank is connected to the water absorption tower.
  • the fluorinated first by-product recovery unit further includes a sodium hypochlorite product tank, and the sodium hypochlorite product tank is connected to an alkali absorption tower.
  • the production system further includes a fluorinated second by-product recovery unit.
  • the fluorinated second by-product recovery unit includes a second reaction kettle, a first filter, a third reaction kettle, and a second reaction kettle, which are connected in series. filter and crystallization tower; the second reaction kettle is connected to the solid outlet of the centrifuge, and the second reaction kettle is provided with a water inlet; the first filter is placed with activated carbon and can filter the activated carbon, or, the The first filter is provided with an organic filter bag or filter membrane; the third reaction kettle is provided with a calcium chloride feed port; the second filter is used for solid-liquid separation; and the crystallization tower is used to separate the second The filtrate separated by the filter is distilled and crystallized.
  • the crystallization tower is provided with a water outlet, and the water outlet is connected to the water inlet of the second reaction kettle.
  • the first reaction kettle, the second reaction kettle, and the third reaction kettle are all stirred reaction kettles.
  • the solvent dimethyl carbonate used in the traditional dechlorination reaction step is adjusted to vinylene carbonate, thereby omitting the solvent removal step and reducing energy consumption.
  • the production method provided by this application can carry out continuous production as a whole, saving time; the by-products produced by each reaction step are promptly excluded from the system, avoiding further complications of reactions and intermediate processes, and improving the quality of the product. Yield and purity; it eliminates the residue of reactants, reduces the separation process, reduces the complexity and cost of production, and can control key technical indicators such as moisture to a low level.
  • the energy-saving production process of ultrapure fluorinated ethylene carbonate adds excess ethylene carbonate during the chlorination reaction, and uses unreacted ethylene carbonate as the solvent for the fluorination reaction, which not only enables continuous production , shorten the reaction time (chlorination reaction time 1-2h), reduce the loss of raw materials, reduce the generation of by-products such as dichlorides, increase the yield of the target product, ensure the utilization rate of raw materials, and also improve the efficiency of a single set of equipment Production capacity, the production capacity of a single set of equipment is increased by more than 5-10 times.
  • This application adopts falling film and melt crystallization technology in the purification process of fluoroethylene carbonate, which not only has a high single-pass crystallization yield and can achieve a product purity of more than 99.9, but also saves equipment investment and greatly reduces energy consumption.
  • FIG. 1 is a schematic diagram of the production of vinylene carbonate provided by this application.
  • FIG. 2 is a schematic diagram of the production of fluoroethylene carbonate provided by this application.
  • 1-primary reaction unit 11-first photolysis reaction tower, 12-second photolysis reaction tower, 13-deacidification tower, 14-distillation tower, 2-secondary reaction unit, 21-first reaction kettle , 22-First centrifugal device, 23-Second reaction kettle, 24-Wash tower, 3-Purification unit, 31-Desolvent tower, 32-Crude distillation tower, 33-Falling film crystallizer, 4-By-product recovery unit , 41-water washing tower, 42-alkali absorption tower, 5-triethylamine recovery unit, 51-drying device, 52-dissolving tank, 53-filtration device, 54-reaction tank, 55-second centrifugal device, 6-waste Liquid tank, 100-fluoro primary reaction unit, 200-fluoro secondary reaction unit, 300-fluoro purification unit, 304-fluoro distillation tower, 400-fluoro first by-product recovery unit, 403-hydrochloric acid Product tank, 404-sodium hypochlorite absorption tank
  • the production method of vinylene carbonate proposed in the first aspect of this application includes the following steps:
  • step S2 Place the chlorinated vinyl carbonate obtained in step S1 into a reaction kettle filled with vinylene carbonate, triethylamine and butyl p-cresol and perform a dechlorination reaction at 60-70°C for 4-5 hours.
  • the molar ratio of vinylene to monochloroethylene carbonate is 1: (1-1.5)
  • the molar ratio of triethylamine to monochloroethylene carbonate is 1: (1-1.5)
  • butyl p-cresol The mass ratio of monochloroethylene carbonate is (0.1-0.5):100.
  • the dechlorination reaction product is washed with dimethyl carbonate to obtain a solid phase and a liquid phase. After drying the liquid phase, water is added, and then filtered.
  • An alkali is added to the liquid obtained by solid-liquid separation for reaction, and then centrifuged to recover the centrifuged product. Triethylamine and continue to be used as the raw material for the dechlorination reaction.
  • the liquid phase obtained by washing the dechlorination reaction product is processed in a desolvation tower at a temperature of 30-40°C and a pressure of 6-10kPa, and then melts and crystallizes. The crystallization is carried out using a falling film crystallizer to obtain vinylene carbonate.
  • the production method of vinylene carbonate proposed in the second aspect of this application includes chlorination reaction, dechlorination reaction and purification steps:
  • the chlorination reaction is carried out under ultraviolet light irradiation and a temperature of 60-70°C for 1-2 hours.
  • the molar ratio of chlorine to ethylene carbonate is (0.4-0.6): (2 -3), recover hydrogen chloride gas and chlorine gas in the liquid after the chlorination reaction with water and alkali solution respectively.
  • Purification involves melt crystallization using a falling film crystallizer.
  • this application also provides a production system, including a primary reaction unit 1, a secondary reaction unit 2, a purification unit 3, a by-product recovery unit 4 and triethylamine recovery Unit 5.
  • the first-stage reaction unit includes at least one-stage photolysis reaction tower 11 and a deacidification tower 13.
  • the deacidification tower 13 is provided with a nitrogen inlet and a gas outlet, which are connected to the liquid outlet of the last-stage photolysis reaction tower 11.
  • the secondary reaction unit includes at least a primary reaction kettle 21 and a washing tower 24.
  • the reaction kettle is provided with a feed port and a discharge port.
  • the feed port of the first-stage reaction kettle 21 is connected to the deacidification tower 13, and the washing tower 24 is provided with an outlet. Liquid end and solids discharge port.
  • the triethylamine recovery unit 5 includes a drying device 51 and a dissolving tank 52 connected through a transmission assembly.
  • the dissolving tank 52 is connected to a filtering device 53.
  • the filtering device 53 is provided with a liquid discharge port.
  • the liquid discharge port is connected to a reaction tank 54.
  • the reaction tank 54 is connected to the second centrifugal device 22.
  • the second centrifugal device 22 is provided with a triethylamine outlet.
  • the triethylamine outlet is connected to the feed port of the reactor.
  • the drying device 51 is connected to the solid discharge port of the washing tower 24 through the transmission assembly.
  • the purification unit 3 includes a desolvation tower 31 and a falling film crystallizer 33 that are connected in sequence.
  • the desolvation tower 31 is connected to the liquid outlet of the washing tower 24 .
  • a rough distillation tower 32 is provided on the communication pipeline between the desolvation tower 31 and the falling film crystallizer 33 .
  • a first centrifugal device 21 is provided between adjacent reaction kettles.
  • the first centrifugal device 21 is provided with a liquid inlet, a liquid outlet and a solid outlet.
  • the liquid inlet and the liquid outlet are respectively connected to the discharge port of the upper stage reactor and the next stage.
  • the feed port of the reaction kettle, the solid outlet and the discharge port of the last stage reactor are connected to the washing tower 24.
  • the first reaction unit 1 also includes a rectification tower 14.
  • the rectification tower 14 is located on the connecting pipeline between the deacidification tower 13 and the first-stage reactor.
  • the first end of the rectification tower 14 is connected to the deacidification tower 13, and its first end is connected to the deacidification tower 13.
  • a liquid outlet and an ethylene carbonate outlet are provided at both ends.
  • the liquid outlet is connected to the feed inlet of the first-stage reactor 21, and the ethylene carbonate outlet is connected to the ethylene carbonate feed inlet of the photolysis reaction tower.
  • Vinylene carbonate is produced using a production system as shown in Figure 1.
  • the production system includes a primary reaction unit 1, a secondary reaction unit 2, a purification unit 3, a by-product recovery unit 4 and a triethylamine recovery unit 5.
  • the primary reaction unit 1 includes a first photolysis reaction tower 11, a second photolysis reaction tower 12, a deacidification tower 13 and a rectification tower 14.
  • the first photolysis reaction tower 11 and the second photolysis reaction tower 12 serve as chlorinated
  • a reaction vessel is provided with an ultraviolet light component and a temperature adjustment component.
  • the ultraviolet light component is used to provide ultraviolet light conditions for the chlorination reaction
  • the temperature adjustment component is used to adjust the temperature of the chlorination reaction.
  • the first photolysis reaction tower 11 and the second photolysis reaction tower 12 are both provided with an ethylene carbonate feed port, an air inlet, a liquid outlet and a gas outlet.
  • the first photolysis reaction tower can be The raw material molten ethylene carbonate is put into the tower 11 and the second photolysis reaction tower 12, and chlorine gas can be introduced into the first photolysis reaction tower 11 and the second photolysis reaction tower 12 through the air inlet.
  • the chlorine gas reaction can be further completed and the yield can be improved.
  • the upper part of the deacidification tower 13 is connected to the outlet of the second photolysis reaction tower 12 , and the lower part is connected to the rectification tower 14 .
  • the upper part of the deacidification tower 13 is provided with a gas outlet, and the lower part is provided with a nitrogen inlet. Nitrogen can be introduced into the deacidification tower 13 through the nitrogen inlet, and then chlorine, hydrogen chloride and other gases in the liquid obtained by the chlorination reaction are eliminated, thereby improving the efficiency of the deacidification tower 13.
  • the purity of the final product can also be reduced while reducing the energy consumption of subsequent purification processes.
  • the rectification tower 14 is used to remove unreacted ethylene carbonate in the chlorination reaction liquid. It is provided with a gas phase outlet, a liquid phase outlet and a waste liquid outlet.
  • the gas phase outlet is connected to the first photolysis reaction tower 11 and/or the second
  • the ethylene carbonate feed port of the photolysis reaction tower 12 is used to realize the recycling of ethylene carbonate.
  • the waste liquid outlet is connected to a waste liquid tank 6 which will not be described in detail here.
  • the secondary reaction unit 2 includes a first reaction kettle 21, a first centrifugal device 22, a second reaction kettle 23 and a washing tower 24.
  • the first reaction kettle 21 and the second reaction kettle 23 are dechlorination reaction vessels, and both are provided with a feed port, a discharge port and a temperature adjustment component.
  • the raw material removal agent triethylamine, the polymerization inhibitor butyl p-cresol and the solvent vinylene carbonate can be fed into the first reaction kettle 21 and the second reaction kettle 23 through the feed port.
  • the chlorination reaction liquid treated by the distillation tower 14 is fed into the first reaction kettle 21, and the liquid treated by the first centrifugal device 22 can also be fed into the second reaction kettle 23 through the feed port.
  • the temperature regulating component is used to regulate the temperature of the dechlorination reaction. By setting up a multi-stage reactor, the dechlorination reaction can be made more thorough and the yield can be increased.
  • the first centrifugal device 22 is provided with a liquid inlet, a liquid outlet and a solid outlet.
  • the liquid inlet and the liquid outlet are connected to the discharge port of the first reaction kettle 21 and the feed port of the second reaction kettle 23 respectively.
  • the first centrifuge device 22 adopts an automatic centrifuge.
  • the first end of the washing tower 24 is connected to the solid outlet of the first centrifugal device 22 through the transmission assembly, and the first end is also connected to the outlet of the second reaction kettle 23.
  • the first end of the washing tower 24 is also connected to dimethyl carbonate. Liquid inlet pipe. Through the dimethyl carbonate liquid inlet pipeline, dimethyl carbonate can be introduced into the washing tower 24. Dimethyl carbonate can dissolve vinylene carbonate, but cannot dissolve the dechlorination reaction product chlorinated triethylamine salt, thereby increasing the The purity of the final product.
  • the purification unit 3 includes a desolvation tower 31 and a falling film crystallizer 32 that are connected in sequence.
  • the falling film crystallizer 32 is connected to the lower part or bottom of the desolvation tower 31 through a circulation pump.
  • the detergent dimethyl carbonate can be removed through the desolvation tower 31 and the purity of the final product can be improved.
  • the purity of the final product can be improved through the falling film crystallizer 32 and energy consumption can be reduced.
  • the by-product recovery unit 4 includes a water absorption tower 41 and an alkali absorption tower 42 .
  • the first end of the water absorption tower 41 is connected to the gas outlet of the first photolysis reaction tower 11, the gas outlet of the second photolysis reaction tower 12 and the gas outlet of the deacidification tower 13.
  • the first end of the water absorption tower 41 is provided with a water inlet pipeline. Both ends are connected to the alkali absorption tower 42.
  • Water can be introduced into the water absorption tower 41 through the water inlet pipe, and the water can dissolve the chlorination reaction product hydrogen chloride to obtain hydrochloric acid.
  • the alkali absorption tower 42 is provided with a waste gas outlet, which is provided with an alkali liquid inlet pipeline.
  • the aqueous sodium hydroxide solution can be introduced into the alkali absorption tower 42.
  • the aqueous sodium hydroxide solution can be mixed with the aqueous sodium hydroxide solution that has not participated in chlorination.
  • the reacted chlorine gas reacts to form sodium hypochlorite.
  • the triethylamine recovery unit 5 includes a drying device 51 and a dissolving tank 52 connected through a transmission assembly.
  • the dissolving tank 52 is connected to a filtering device 53.
  • the filtering device 53 is provided with a liquid discharge port.
  • the liquid discharge port is connected to a reaction tank 54.
  • the reaction tank 54 is connected to a second centrifugal device 55, and the second centrifugal device 55 is provided with a triethylamine outlet, and the triethylamine outlet is connected to the feed inlet of the first reaction kettle 21 and/or the second reaction kettle 22.
  • the drying device 51 is connected to the second end of the washing tower 24 through a transmission assembly, and is provided with a dimethyl carbonate discharge port.
  • the drying device 51 is used to dry the triethylamine chloride salt solid washed by the washing tower 24 and remove the detergent dimethyl carbonate attached to its surface.
  • the drying device 51 can use a blast dryer, and the blast dryer is The existing technology will not be described again here.
  • the dissolving tank 52 is connected with a water inlet pipeline, through which water can be passed into the dissolving tank 52 to dissolve the flocculent organic matter and other impurities attached to the solid surface of the chlorinated triethylamine salt, and then pass through the filtering device connected to the dissolving tank 52 53 was filtered and removed.
  • the reaction tank 54 is provided with a solid alkali inlet.
  • the material sodium hydroxide can be put into the reaction tank 54 through the solid alkali inlet, so that the chlorinated triethylamine salt entering the reaction tank 54 and the sodium hydroxide can undergo a displacement reaction to generate triethyl. amine.
  • Triethylamine has low solubility in water and can be separated by the second centrifugal device 55 connected to the reaction tank.
  • the triethylamine obtained after separation can be sent to the first reaction kettle 21 and/or the second reaction kettle 21 through the triethylamine outlet.
  • Reactor 22 realizes the recovery and reuse of triethylamine.
  • the production system shown in Figure 1 is used to produce vinylene carbonate.
  • the specific steps are as follows:
  • Ethylene carbonate preheated to a molten state is put into the first photolysis reaction tower 11 and the second photolysis reaction tower 12, and is passed into the first photolysis reaction tower 11 and the second photolysis reaction tower 12 through the air inlet.
  • the chlorine and ethylene carbonate in the first photolysis reaction tower 11 Esters account for 2/3 of their respective total amounts.
  • the chlorination reaction liquid is obtained, and the switch valve and water on the pipeline between the gas outlet of the first photolysis reaction tower 11 and the gas outlet of the second photolysis reaction tower 12 and the first end of the water absorption tower 41 are opened.
  • the switch valve on the pipeline between the second end of the absorption tower 41 and the alkali absorption tower 42 is used to pass water into the water absorption tower 41 and a sodium hydroxide aqueous solution with a concentration of 30wt% into the alkali absorption tower 42.
  • Hydrochloric acid is obtained by dissolving the hydrogen chloride gas, the product of the chlorination reaction, and the sodium hydroxide aqueous solution reacts with chlorine gas that does not participate in the chlorination reaction to generate sodium hypochlorite.
  • the content of dichloroethylene carbonate is in accordance with "Q1327HG003-2019 Chlorinated Ethylene Carbonate"
  • the ester> is detected in countercurrent contact, and then the chlorine and hydrogen chloride in the liquid are discharged to obtain crude monochloroethylene carbonate (CEC) liquid phase.
  • CEC monochloroethylene carbonate
  • the temperature adjustment component is opened, the materials in the first reaction kettle 21 are heated to 60°C, and the high-purity chloroethylene carbonate and triethylamine entering the first reaction kettle 21 are processed in the presence of vinylene carbonate.
  • the removal reaction was carried out for 4 hours to obtain the removal reaction product (containing chlorinated triethylamine salt).
  • the on-off valve on the pipeline between the first reaction kettle 21 and the first centrifugal device 22 is opened, and the reaction product is removed and enters the first centrifugal device 22 for centrifugal treatment to obtain liquid and solid.
  • the on-off valve on the pipeline between the liquid outlet of the first centrifugal device 22 and the second reaction kettle 23 is opened, and the liquid obtained by centrifugation enters the second reaction kettle 23.
  • the temperature adjustment component is opened and the second reaction kettle is The materials in 23 are heated to 60°C, and the unreacted materials are continued to undergo removal reaction in the second reactor 21 for 4 hours to obtain the removal reaction product (containing chlorinated triethylamine salt).
  • Dimethyl carbonate dimethyl carbonate can dissolve vinylene carbonate but cannot dissolve chlorinated triethylamine salt, thereby removing the chlorinated triethylamine salt and improving the purity of the final product.
  • the transmission component between the washing tower 24 and the drying device 51 is started, and the chlorotriethylamine salt solid with dimethyl carbonate and flocculent organic matter attached is dried by the drying device 51 and then the attached dimethyl carbonate is removed.
  • Dimethyl carbonate enters the washing tower 24 through the pipeline to realize recycling of dimethyl carbonate.
  • the on-off valve on the pipeline between the reaction pool 54 and the second centrifugal device 55 is opened, the mixed liquid enters the second centrifugal device 55, and is separated to obtain triethylamine after filtration, and the second centrifugal device 55 is opened to react with the first centrifugal device 55.
  • the on-off valve on the pipeline between the kettle 21 and/or the second reaction kettle 22 allows the triethylamine liquid to enter the first reaction kettle 21 and/or the second reaction kettle 22 through the triethylamine outlet to continue to participate in the removal reaction to achieve Recycling and reuse of triethylamine.
  • the desolvating tower 31 can remove the detergent dimethyl carbonate through distillation.
  • the temperature of the desolvation treatment is 30°C and the pressure is 6kPa.
  • the pipeline between the desolvation tower 31 and the falling film crystallizer 32 is opened, and the liquid treated by the desolvation tower 31 (purity is 97%, taking the processing capacity of 10kg as an example) enters the falling film crystallizer 33 for melting Crystallization and melting crystallization include crystallization, sweating and melting steps, specifically:
  • S2 Material pre-cooling: start the crystallization circulation pump, transport the VC crystallization raw materials in the raw material tank to the falling film crystallizer for circulation, control the circulation material flow to 0.2-0.6m 3 /h, the pressure to 0.02-0.07MPa, the motor
  • the frequency is 13-18Hz, which quickly reduces the temperature of circulating materials to 20-25°C;
  • Crystallization process Gradually reduce the temperature of the circulating hot and cold medium by 1°C-3°C at a rate of 0.1°C-2°C/min, control the crystallization time at 80-90min, stop the crystallization circulation pump, discharge the mother liquor and weigh it to obtain 3kg of mother liquor, take a sample and measure
  • the purity of the mother liquor is 91%.
  • the mother liquor can be filled and stored to accumulate a certain amount and then directly crystallized to obtain 1.7kg of recovery liquid and 1.3kg of residual liquid.
  • the purity of the recovery liquid product can reach about 98%.
  • the recovery liquid can be used with the next product with a purity of 97%.
  • VC crystallization raw materials are crystallized and purified together, and the residual liquid can be sent to the distillation unit;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes. After sweating is completed, the sweat liquid is discharged and weighed to obtain 0.5Kg. The purity of the sweat liquid is 99.2% after sampling. The sweat liquid can be filled and stored and added to the next crystallization raw material with a purity of 97%;
  • Melting process Gradually adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the first-level crystallized product is discharged and weighed to obtain 6.5kg. Samples are taken to measure the first-level crystallization. Product purity is 99.4%;
  • Crystallization process 6.5kg of the first-level crystallized product with a purity of 99.4% is sent to the falling film crystallizer for circulation, and the temperature of the circulating hot and cold medium is gradually reduced by 1°C-3°C at a rate of 0.1°C-2°C/min for crystallization. Control the crystallization time to 80-90 minutes, stop the crystallization circulation pump, discharge and weigh to get 0.9kg of the secondary mother liquor. The purity of the secondary mother liquor is 99.3% after sampling. The secondary mother liquor can be used together with the next VC crystallization raw material with a purity of 97%. Perform crystallization and purification;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the secondary sweating liquid is discharged and weighed to obtain 0.6Kg.
  • the purity of the secondary sweating liquid is 99.3% according to the sampling measurement.
  • the secondary sweating liquid can be crystallized and purified together with the next VC crystallization raw material with a purity of 99.4%;
  • Melting process Gradually adjust the temperature of the cold and hot media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the secondary crystallized product is discharged and weighed to obtain 5kg (using the recovery liquid, primary and secondary The weight of the product after sweating was 8.7kg), and the secondary crystallization product was sampled and measured (the vinylene carbonate crystals on the wall of the crystallization tube of the falling film crystallizer during the first crystallization process were melted and then recycled and crystallized again. The purity of vinylene carbonate crystals on the wall of the crystallizer tube of the membrane crystallizer was 99.99%.
  • Vinylene carbonate is produced according to the method of this example and is scaled up to 3000t of product for calculation.
  • the energy consumption is 2350kg steam/t vinylene carbonate final product. In the purification process, the energy consumption is 1700kg steam/t vinylene carbonate.
  • the energy consumption of the final product is calculated according to "GB/T 2589-2020 General Principles for Comprehensive Energy Consumption Calculation".
  • the production system is different from Example 1 in that: the temperature of the desolvation treatment is 40°C and the pressure is 10kPa; the communication pipeline between the desolvation tower 31 and the falling film crystallizer 32 A rough distillation tower 33 is provided, and the falling film crystallizer 32 is connected to the lower part or bottom of the rough distillation tower 33 via a circulation pump. Impurities such as the polymerization inhibitor butyl p-cresol and polyvinylene carbonate can be removed through distillation through the crude distillation tower 33, thereby further improving the purity of the final product.
  • the temperature of the crude distillation treatment is 55°C and the pressure is 2kPa; the purity of the material after being processed by the crude distillation tower 32 is 98%;
  • the molar ratio of the total amount of chlorine to the total amount of ethylene carbonate in the first photolysis reaction tower 11 and the second photolysis reaction tower 12 is 0.6:3, and the total amount of triethylamine and high-purity chloroethylene carbonate (CEC)
  • the molar ratio of the total amount is 1:1.5, the molar ratio of the total amount of vinylene carbonate to the total amount of high-purity chloroethylene carbonate is 1:1.5, and the molar ratio of the total amount of butyl-p-cresol to the total amount of high-purity chloroethylene carbonate is 1:1.5.
  • the mass ratio of the amounts is 0.5:100, the temperature of the chlorination reaction is 70°C, the time of the chlorination reaction is 2h, the content of dichloroethylene carbonate in the chlorination reaction liquid is 0.63wt%; the temperature of the dechlorination reaction is 70 °C, the dechlorination reaction time is 5h;
  • the temperature is 60°C;
  • S2 Material pre-cooling: start the crystallization circulation pump, transport the VC crystallization raw materials in the raw material tank to the falling film crystallizer for circulation, control the circulation material flow to 0.2-0.6m 3 /h, the pressure to 0.02-0.07MPa, the motor
  • the frequency is 13-18Hz, which quickly reduces the temperature of circulating materials to 20-25°C;
  • Crystallization process Reduce the temperature of the circulating hot and cold medium to 1°C-3°C step by step at 0.1°C-2°C/min. Control the crystallization time at 80-90min. Stop the crystallization circulation pump and discharge the mother liquor to weigh 1.8kg. Direct crystallization yields 1.2kg recovery liquid and 0.6kg residual liquid. The purity of the recovery liquid product can reach about 98.5%. The recovery liquid can be crystallized and purified together with the next VC crystallization raw material with a purity of 98%. The residual liquid can be sent to the secondary refiner. distillation unit;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the first-level sweat liquid is discharged and weighed to obtain 0.3kg.
  • the purity of the first-level sweat liquid is 99.5% after sampling and measurement.
  • the first-level sweat liquid can be filled and stored and added to the next crystallization raw material with a purity of 98%;
  • Melting process Gradually adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the first-level crystallized product is discharged and weighed to obtain 7.9kg. Samples are taken to measure the first-level crystallization. Product purity is 99.4%;
  • Crystallization process 7.9kg of the first-level crystallized product with a purity of 99.4% is sent to the falling film crystallizer for circulation, and the temperature of the circulating hot and cold medium is gradually reduced by 1°C-3°C at a rate of 0.1°C-2°C/min for crystallization. Control the crystallization time to 80-90 minutes, stop the crystallization circulation pump, discharge and weigh to get 1.6kg of the secondary mother liquor. The purity of the secondary mother liquor is 98.6% after sampling. The secondary mother liquor can be used together with the next VC crystallization raw material with a purity of 98%. Perform crystallization and purification;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the secondary sweat liquid is discharged and weighed to obtain 0.5Kg.
  • the purity of the secondary sweat liquid is 99.3% measured by sampling.
  • the secondary sweat liquid can be crystallized and purified together with the next primary crystallization product with a purity of 99.4%;
  • Melting process Gradually adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the secondary crystallized product is discharged and weighed to obtain 5.8kg. Samples are taken to measure the secondary crystallization. Product purity is 99.99%;
  • Crystallization process 5.8kg of secondary crystallized product with a purity of 99.99% is sent to the falling film crystallizer for circulation, and the temperature of the circulating cold and hot medium is gradually reduced by 1°C-3°C at a rate of 0.1°C-2°C/min for crystallization. Control the crystallization time to 80-90 minutes, stop the crystallization circulation pump, discharge and weigh to get 0.9kg of the third-level mother liquor. The purity of the third-level mother liquor is 99.92% by sampling. The third-level mother liquor can be used with the next first-level crystallization product with a purity of 99.4%. Crystallization and purification together;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the third-level sweat liquid is discharged and weighed to obtain 0.7Kg.
  • the purity of the third-level sweat liquid is 99.95% after sampling.
  • the third-level sweat liquid can be crystallized and purified together with the next second-level crystallization product with a purity of 99.99%;
  • Melting process Gradually adjust the temperature of the cold and hot media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the third-level crystallized product is discharged and weighed to obtain 4.2kg (recovery liquid, second and third levels). The product weight after utilization of the first-, second- and third-level mother liquor, first-, second- and third-level sweat liquids is about 7.3kg), and the purity of the second-level crystallized product was measured by sampling to be 99.995%;
  • the energy consumption required to purify the crude VC product with a purity of 60% into high-purity VC with a purity of 99.995% is 2500kg of steam per ton of product.
  • the rapid cooling of first-level crystallization is 35-22°C, and the slow cooling is 22-0°C;
  • the rapid cooling of the second and third-stage crystallization is 35-22°C, and the slow cooling is 22-5°C.
  • the first-level crystallization has a rapid temperature rise of 0-18°C and a slow temperature rise of 18-22.5°C;
  • the second and third-level crystallization has a rapid temperature rise of 5-18°C and a slow temperature rise of 18-22.5°C.
  • Vinylene carbonate is produced according to the method of this example and is scaled up to 3000t product for calculation.
  • the energy consumption is 3120kg steam/t vinylene carbonate final product.
  • the energy consumption is 2500kg steam/t vinylene carbonate. final product.
  • the difference between this embodiment and Embodiment 2 is that: the molar ratio of the total amount of chlorine to the total amount of ethylene carbonate in the first photolysis reaction tower 11 and the second photolysis reaction tower 12 is 0.5:2.5, and triethylamine
  • the molar ratio of the total amount of vinylene carbonate to the total amount of high-purity chloroethylene carbonate is 1:1.2
  • the molar ratio of the total amount of vinylene carbonate to the total amount of high-purity chloroethylene carbonate is 1:1.2, the total amount of butyl-p-cresol
  • the mass ratio of the amount to the total amount of high-purity chlorinated ethylene carbonate is 0.3:100, the temperature of the chlorination reaction is 64°C, the time of the chlorination reaction is 1.5h, and the content of dichloroethylene carbonate in the chlorination reaction liquid is 0.71wt%; the temperature of the dechlorination reaction is 64°C, and the time of the dechlorination reaction is 4.5h
  • S2 Material pre-cooling: start the crystallization circulation pump, transport the VC crystallization raw materials in the raw material tank to the falling film crystallizer for circulation, control the circulation material flow to 0.2-0.6m 3 /h, the pressure to 0.02-0.07MPa, the motor
  • the frequency is 13-18Hz, which quickly reduces the temperature of circulating materials to 20-25°C;
  • Crystallization process Reduce the temperature of the circulating hot and cold medium to 1°C-3°C step by step at 0.1°C-2°C/min. Control the crystallization time at 80-90min. Stop the crystallization circulation pump and discharge the mother liquor to weigh 1.8kg. Direct crystallization yields 1.2kg recovery liquid and 0.6kg residual liquid. The purity of the recovery liquid product can reach about 98.5%. The recovery liquid can be crystallized and purified together with the next VC crystallization raw material with a purity of 98%. The residual liquid can be sent to the secondary refiner. distillation unit;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the first-level sweat liquid is discharged and weighed to obtain 0.3kg.
  • the purity of the first-level sweat liquid is 99.5% after sampling and measurement.
  • the first-level sweat liquid can be filled and stored and added to the next crystallization raw material with a purity of 98%;
  • Melting process Gradually adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the first-level crystallized product is discharged and weighed to obtain 7.9kg. Samples are taken to measure the first-level crystallization. Product purity is 99.4%;
  • Crystallization process 7.9kg of the first-level crystallized product with a purity of 99.4% is sent to the falling film crystallizer for circulation, and the temperature of the circulating hot and cold medium is gradually reduced by 1°C-3°C at a rate of 0.1°C-2°C/min for crystallization. Control the crystallization time to 80-90 minutes, stop the crystallization circulation pump, discharge and weigh to get 1.6kg of the secondary mother liquor. The purity of the secondary mother liquor is 98.6% after sampling. The secondary mother liquor can be used together with the next VC crystallization raw material with a purity of 98%. Perform crystallization and purification;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the secondary sweat liquid is discharged and weighed to obtain 0.5Kg.
  • the purity of the secondary sweat liquid is 99.3% measured by sampling.
  • the secondary sweat liquid can be crystallized and purified together with the next primary crystallization product with a purity of 99.4%;
  • Melting process Gradually adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the secondary crystallized product is discharged and weighed to obtain 5.8kg. Samples are taken to measure the secondary crystallization. Product purity is 99.99%;
  • Crystallization process 5.8kg of secondary crystallized product with a purity of 99.99% is sent to the falling film crystallizer for circulation, and the temperature of the circulating cold and hot medium is gradually reduced by 1°C-3°C at a rate of 0.1°C-2°C/min for crystallization. Control the crystallization time to 80-90 minutes, stop the crystallization circulation pump, discharge and weigh to get 0.9kg of the third-level mother liquor. The purity of the third-level mother liquor is 99.92% by sampling. The third-level mother liquor can be used with the next first-level crystallization product with a purity of 99.4%. Crystallization and purification together;
  • Sweating process Gradually increase the temperature of the circulating cold and hot media to 18°C-23°C at a rate of 0.1°C-2°C/min, keep the temperature of the cold and hot media of the falling film crystallization circulating insulation system unchanged, and control the sweating time to 40-50 minutes.
  • the third-level sweat liquid is discharged and weighed to obtain 0.7Kg.
  • the purity of the third-level sweat liquid is 99.95% after sampling.
  • the third-level sweat liquid can be crystallized and purified together with the next second-level crystallization product with a purity of 99.99%;
  • Melting process Gradually adjust the temperature of the cold and hot media of the falling film crystallization system to 30-35°C to melt the crystallized product. Control the melting time for 30 minutes. After the melting is completed, the third-level crystallized product is discharged and weighed to obtain 4.2kg (recovery liquid, second and third levels). The product weight after utilization of the first-, second- and third-level mother liquor, first-, second- and third-level sweat liquids is about 7.3kg), and the purity of the second-level crystallized product was measured by sampling to be 99.995%;
  • the energy consumption required to purify the crude VC product with a purity of 60% into high-purity VC with a purity of 99.995% is 2500kg of steam per ton of product.
  • the rapid cooling of first-level crystallization is 35-22°C, and the slow cooling is 22-0°C;
  • the rapid cooling of the second and third-stage crystallization is 35-22°C, and the slow cooling is 22-5°C.
  • the first-level crystallization has a rapid temperature rise of 0-18°C and a slow temperature rise of 18-22.5°C;
  • the second and third-level crystallization has a rapid temperature rise of 5-18°C and a slow temperature rise of 18-22.5°C.
  • Vinylene carbonate is produced according to the method of this example, and is scaled up to 3000t product for calculation.
  • the energy consumption is 3230kg steam/t vinylene carbonate final product. Among them, in the purification process, the energy consumption is 2550kg steam/t vinylene carbonate. final product.
  • Example 2 The difference between this comparative example and Example 2 is that the solvent added to the reaction kettle is dimethyl carbonate instead of vinylene carbonate, and the moles of the total amount of dimethyl carbonate and the total amount of high-purity chloroethylene carbonate The ratio is 5:1.
  • Vinylene carbonate is produced according to the method of this comparative example and scaled up to 3000t product for calculation.
  • the energy consumption is 4800kg steam/t product vinylene carbonate final product (the purity of the secondary crystallized product is 99.97%). Among them, in the purification process, The energy consumption is 3900kg steam/t vinylene carbonate final product.
  • This application also proposes a production method of fluoroethylene carbonate in the third aspect, and its synthesis route is as follows:
  • fluoroethylene carbonate is produced through the following steps:
  • Chlorination reaction The chlorination reagent is first chlorinated with excess ethylene carbonate under the irradiation of light (violet or blue light) to form monochloroethylene carbonate.
  • the reaction temperature is 60-70°C and the reaction time is 1-2 Hours, the chlorination reaction product includes monochloroethylene carbonate and unreacted ethylene carbonate;
  • Fluorination reaction Add a fluorination reagent to the blend of monochloroethylene carbonate and ethylene carbonate, and use ethylene carbonate as the solvent to react to generate fluorinated ethylene carbonate.
  • the reaction temperature is 60-80°C. Time is 7-9 hours;
  • Solid-liquid separation and purification The fluorinated reaction product is subjected to solid-liquid separation to obtain solid mixed salt and liquid, and the liquid is purified to obtain the target product fluorinated ethylene carbonate.
  • the molar ratio of chlorination reagent to ethylene carbonate is (0.4-0.6): (2-3).
  • the molar ratio of the fluorinating reagent to vinyl chloride carbonate is (1-1.5):1, preferably (1-1.1):1.
  • KF is used as the fluorination reagent, so the obtained solid mixed salt includes the fluorination reagent and potassium chloride.
  • Solid-liquid separation and purification the solid mixed salt treatment method is: add the solid mixed salt to water, stir and dissolve, and then use activated carbon to absorb the organic matter, or use a filter bag or filter membrane to filter the organic matter to remove the organic matter, and then add calcium chloride, calcium chloride
  • the molar ratio to fluoride ions is (1-1.02): 1. Stir and react for 0.5-1h. After the reaction, filter, wash and dry the filter residue to obtain calcium fluoride.
  • the drying method is continuous drying. The drying temperature is 140-160°C. Stay The time is 1-1.5 hours, and the filtrate is distilled and crystallized to obtain potassium chloride.
  • the liquid purification method includes the following steps:
  • falling film crystallization After the solvent ethylene carbonate in the liquid is removed, falling film crystallization is performed.
  • the falling film crystallization process includes several cycles of melting crystallization, and the melting crystallization includes the steps of crystallization, sweating, and melting in sequence.
  • the temperature is 110-130°C
  • the flow rate is 380-450Kg/m 3 /h
  • the pressure is 1-2kPa.
  • the material flow rate during falling film crystallization is 0.2-0.6m 3 /h, and the pressure is 0.02-0.07MPa.
  • the crystallization step includes rapid cooling and slow cooling processes in sequence.
  • the rapid cooling temperature is 30-22°C
  • the slow cooling temperature is 22-0°C
  • the crystallization time is 80-90 minutes.
  • the sweating step includes a rapid heating process and a slow heating process.
  • the rapid heating temperature is 0-18°C
  • the slow heating temperature is 18-22.5°C
  • the sweating time is 40-50 minutes.
  • the temperature of the melting step is 30-35°C, and the melting time is 20-40 minutes.
  • the falling film crystallization process includes two or three melting crystallizations.
  • the two melting crystallizations are one-level melting crystallization and two-level melting crystallization in sequence.
  • the three-melting crystallization is one-level melting crystallization, two-level melting crystallization and three-level melting crystallization.
  • the first-level melting crystallization includes first-level crystallization, first-level sweating, and first-level melting.
  • the first-level crystallization has a rapid cooling of 30-22°C, a slow cooling of 22-0°C, and a crystallization time of 80-90 minutes; a first-level sweating and rapid heating.
  • the temperature is 0-18°C, the temperature rises slowly to 18-22.5°C, and the sweating time is 40-50 minutes; the first-level melting temperature is 30-35°C, and the melting time is 20-40 minutes; after the first-level melting is completed, the first-level product is obtained;
  • the secondary melting crystallization includes secondary crystallization, secondary sweating, and secondary melting.
  • the secondary crystallization has a rapid cooling of 30-22°C, a slow cooling of 22-5°C, and a crystallization time of 80-90 minutes; the secondary sweating has a rapid temperature rise.
  • the temperature is 5-18°C, the temperature rises slowly to 18-22.5°C, the sweating time is 40-50min; the secondary melting temperature is 30-35°C, the melting time is 20-40 minutes; after the secondary melting is completed, the secondary product is obtained;
  • the process parameter conditions of the third-level melting and crystallization step are the same as those of the second-level melting and crystallization. After the completion of the third-level melting and crystallization, a third-level product is obtained.
  • the falling film crystallization process also includes a first-level recovery.
  • the first-level recovery is to melt and crystallize the first-level product obtained from the first-level melt crystallization again.
  • the process parameter conditions of the first-level recovery step are the same as those of the first-level melting and crystallization step.
  • a multi-stage distillation step is provided between the solvent removal and falling film crystallization steps, preferably one-stage, two-stage or three-stage distillation.
  • the temperature during distillation is 50-60°C
  • the flow rate is 40-70Kg/m 3 /h
  • the pressure is 5-6kPa.
  • the chlorination reaction of the present invention includes a multi-stage photocatalytic chlorination reaction, preferably a two-stage photocatalytic chlorination reaction. Specifically, the by-product hydrogen chloride/chlorine mixed gas of the previous stage of chlorination reaction is passed into the subsequent stage of chlorination reaction as the raw material gas for the chlorination reaction.
  • the by-product hydrogen chloride/chlorine mixed gas of the chlorination reaction of the present invention is absorbed by water and alkali to obtain hydrochloric acid and sodium hypochlorite by-products respectively; preferably, a sodium hydroxide solution is used for alkali absorption, and the concentration of the sodium hydroxide solution is 20- 30%.
  • the invention also provides a fluoroethylene carbonate production system, which produces fluoroethylene carbonate according to the above energy-saving fluoroethylene carbonate production process.
  • the production system includes a fluorinated primary reaction unit 100, a fluorinated secondary reaction unit 200 and a purification unit 300.
  • the fluorinated primary reaction unit 100 includes a multi-stage photolysis reaction tower 11 and a deacidification tower 12.
  • the photolysis reaction tower 11 is a place where the chlorination reagent and ethylene carbonate perform a chlorination reaction to generate monochloroethylene carbonate, as shown in Figure 2
  • the multi-stage photolysis reaction tower 11 shown is a two-stage photolysis reaction tower 11, but is not limited to this.
  • the first-stage photolysis reaction tower 11 is provided with an ethylene carbonate feed port and a chlorine reagent feed port.
  • the top of the photolysis reaction tower 11 is provided with an exhaust port, which is used to discharge excess hydrogen chloride/chlorine gas mixture. Gas, the exhaust port of the previous stage photolysis reaction tower 11 is connected with the subsequent stage photolysis reaction tower 11.
  • the deacidification tower 12 is connected to the photolysis reaction tower 11 and is used to remove excess chlorine and hydrogen chloride gas in the chlorination reaction product; in Figure 2, the deacidification tower 12 is connected to the discharge ports at the bottom of the two photolysis reaction towers 11.
  • the top of the deacidification tower 12 is provided with an exhaust port for discharging hydrogen chloride/chlorine gas mixture, and the bottom is provided with an ethylene carbonate/monochloroethylene carbonate blend liquid outlet, and is also provided with a nitrogen inlet, which can blow away chlorine by introducing nitrogen. Replace hydrogen chloride and remaining chlorine in the reactants so that they can be discharged and recycled.
  • the fluorinated secondary reaction unit 200 includes a first reaction kettle 21 and a first centrifugal device 22.
  • the first reaction kettle 21 is a place where monochloroethylene carbonate and fluorinating reagent perform fluorination reaction to generate fluorinated ethylene carbonate.
  • the first reaction kettle 21 is connected to the ethylene carbonate/monochloroethylene carbonate blend outlet of the deacidification tower 12, and is provided with a fluorination reagent feed port; the first centrifugal device 22 performs solid-liquid processing for the fluorination reaction product
  • the first centrifugal device 22 is provided with a solid outlet and a liquid outlet.
  • the fluorinated reaction product is solid-liquid separated in the first centrifugal device 22.
  • the liquid, that is, the ethylene carbonate/monochloroethylene carbonate blend liquid passes through the liquid outlet.
  • the solid mixed salt enters the second by-product recovery unit through the solid outlet.
  • the purification unit 300 includes a desolvation tower 31 and a falling film crystallization system.
  • the desolvation tower 31 is connected to the liquid outlet of the first centrifugal device 22 and is used to remove the solvent in the liquid separated by the first centrifugal device 22.
  • the falling film crystallization system Used to purify fluoroethylene carbonate.
  • the falling film crystallization system includes a falling film crystallizer 33, a cold and hot medium preheating device of the circulating insulation system, and a crystallization circulation pump.
  • the falling film crystallizer 33 is a purification place for fluoroethylene carbonate, and the cold and hot medium preheating equipment of the circulating insulation system is used.
  • Thermal equipment is used to control and adjust the temperature of hot and cold media, and the crystallization circulation pump is used to circulate and transport the crystallization mother liquor.
  • the purification unit 300 also includes a multi-stage fluorinated distillation tower 304.
  • the multi-stage fluorinated distillation tower 304 is arranged between the desolvation tower 31 and the falling film crystallization system.
  • the fluorinated distillation towers 304 are connected in series in sequence.
  • the first-stage fluorinated distillation tower 304 is The feed port of the distillation tower 304 is connected to the discharge port of the desolvation tower 31, and the discharge port of the last stage fluorine-substituted distillation tower 304 is connected to the feed port of the falling film crystallizer 33; preferably, the multi-stage
  • the distillation tower 302 is one-stage, two-stage or three-stage.
  • the purification unit 300 shown in Figure 2 is provided with a first-stage fluorinated distillation tower 304.
  • the outlet of the falling film crystallizer 33 is also connected to the inlet of the rectification tower 302 to return the crystallization mother liquor to the fluorine rectification tower 304 for distillation and purification.
  • the energy-saving production system of fluorinated ethylene carbonate of the present invention also includes a first fluorinated by-product recovery unit 400.
  • the first fluorinated by-product recovery unit 400 includes a water absorption tower 41, an alkali absorption tower 42, a hydrochloric acid product tank 403, and an alkali absorption tower.
  • Tower 42 is connected, and the water absorption tower 41 is connected with the exhaust port of the last stage photolysis reaction tower 11 and the exhaust port of the deacidification tower 12.
  • the water absorption tower 41 is also equipped with a process water inlet and a hydrochloric acid product tank.
  • the first fluorinated by-product recovery unit 400 is used to recover hydrogen chloride/chlorine mixed gas.
  • the hydrogen chloride/chlorine mixed gas first enters the water absorption tower 41, and the hydrogen chloride is dissolved by water to form hydrochloric acid, which is collected in the hydrochloric acid product tank 403; then it enters The remaining chlorine gas enters the alkali absorption tower 42 and reacts with the sodium hydroxide solution to generate sodium hypochlorite, which is collected in the sodium hypochlorite product tank, and the remaining unreacted waste gas is discharged.
  • the fluorinated ethylene carbonate production system of the present invention also includes a fluorinated first by-product recovery unit 500.
  • the fluorinated first by-product recovery unit 500 includes a second reaction kettle 23, a first filter 502, and a second reaction kettle 23 connected in series in sequence.
  • the second reaction kettle 23 is provided with a water inlet, and the solid mixed salt is in the second reaction kettle.
  • the first filter 502 is placed with activated carbon and can filter the activated carbon, or the first filter 502 is provided with an organic filter bag or filter membrane, and the solid mixed salt (fluorination reagent and potassium chloride) obtained by centrifugation ) may contain a certain amount of organic matter, so activated carbon is used to adsorb the organic matter and then filter to remove the organic matter, or a filter bag or filter membrane that can filter organic matter is directly used to remove the organic matter;
  • the third reaction kettle 503 is equipped with a calcium chloride feed port, and the second The filter 504 is used for solid-liquid separation, and the second filter 504 is provided with a filtrate outlet.
  • the crystallization tower 505 is connected to the filtrate outlet of the second filter 504 and is used for distilling and crystallizing the filtrate separated by the second filter 504.
  • the mixed salt liquid is stirred and reacted with calcium chloride in the third reaction kettle 503 to generate calcium fluoride, which is then filtered through the second filter 504 to obtain the by-product calcium fluoride.
  • the obtained filtrate is distilled and crystallized in the crystallization tower 505 to obtain the by-product Potassium chloride.
  • the crystallization tower 505 is provided with a water outlet, and the water outlet is connected to the water inlet of the second reaction kettle 23 .
  • the first reaction kettle 21, the second reaction kettle 23, and the third reaction kettle 503 are all stirred reaction kettles.
  • the fluoroethylene carbonate production system in this embodiment is provided with a first-stage distillation tower.
  • Chlorination reaction Chlorine and ethylene carbonate are chlorinated in a photolysis reaction tower under light irradiation at a molar ratio of 0.5:2 to generate monochloroethylene carbonate.
  • the reaction temperature is 65°C and the reaction time is 2 hours.
  • the chlorination reaction product includes monochloroethylene carbonate and unreacted ethylene carbonate.
  • the chlorination reaction product in the photolysis reaction tower is sent to the deacidification tower, and nitrogen gas is blown to blow away the excess hydrogen chloride and chlorine to obtain an EC/FEC blend composed of monochloroethylene carbonate and unreacted ethylene carbonate.
  • the excess hydrogen chloride/chlorine mixed gas in the deacidification tower and the excess hydrogen chloride/chlorine mixed gas in the photolysis reaction tower are absorbed by water and alkali to obtain by-products hydrochloric acid and sodium hypochlorite.
  • Fluorination reaction Add fluorination reagent to the blend of monochloroethylene carbonate and ethylene carbonate.
  • the molar ratio of fluorination reagent to monochloroethylene carbonate is 1.3:1.
  • the reaction generates fluoroethylene carbonate.
  • the reaction temperature was 75°C and the reaction time was 7 hours.
  • Solid-liquid separation and purification The fluorination reaction product is subjected to solid-liquid separation to obtain solid mixed salt (fluorination reagent and potassium chloride) and liquid.
  • the liquid is purified to obtain high-purity fluoroethylene carbonate product.
  • the purification process is as follows:
  • S1 Pour 8L of crude fluoroethylene carbonate primary distillation into the raw material tank, start the falling film crystallization system, and control the temperature of the cold and hot media at 23-30°C through the hot and cold medium preheating equipment of the circulation insulation system;
  • S3 Adjust the temperature of the hot and cold media in the falling film crystallization system.
  • the first-level crystallization rapidly cools to 30-22°C and slowly cools to 22-0°C.
  • Control the crystallization time at 80-90 minutes, stop the crystallization circulation pump, and discharge the mother liquor for weighing and sampling. ;
  • S4 Sweating adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the first-level sweating has a rapid temperature rise of 0-18°C and a slow temperature rise of 18-22.5°C.
  • the sweating time is controlled to 40-50min. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • S5 Adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C, perform first-level melting, control the melting time for 30 minutes, and discharge the first-level product for weighing and sampling after the melting is completed.
  • S7 Sweating adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the second-level sweating quickly heats up to 5-18°C and slowly heats up to 18-22.5°C.
  • the sweating time is controlled to 40-50 minutes. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • the purity of the FEC primary distillation crude product is 92.5%
  • the purity of the primary product is 98%
  • the purity of the secondary product is 99.5%
  • the purity of the primary recovery product is 95%.
  • the energy consumption in step (3) is 900kg steam per ton of product.
  • the fluoroethylene carbonate production system in this embodiment is equipped with a three-stage distillation tower.
  • the fluoroethylene carbonate production system of this embodiment is used to purify the liquid obtained in step 3 of Example 1 to obtain a high-purity fluoroethylene carbonate product.
  • the purification process is as follows:
  • S1 Pour 8L of crude fluoroethylene carbonate primary distillation into the raw material tank, start the falling film crystallization system, and control the temperature of the hot and cold medium at 23-30°C through the hot and cold medium preheating equipment of the circulation insulation system;
  • S3 Adjust the temperature of the hot and cold media in the falling film crystallization system.
  • the first-level crystallization rapidly cools to 30-22°C and slowly cools to 22-0°C.
  • Control the crystallization time at 80-90 minutes, stop the crystallization circulation pump, and discharge the mother liquor for weighing and sampling. ;
  • S4 Sweating adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the first-level sweating has a rapid temperature rise of 0-18°C and a slow temperature rise of 18-22.5°C.
  • the sweating time is controlled to 40-50min. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • S5 Adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C, perform first-level melting, control the melting time for 30 minutes, and discharge the first-level product for weighing and sampling after the melting is completed.
  • S7 Sweating adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the second-level sweating quickly heats up to 5-18°C and slowly heats up to 18-22.5°C.
  • the sweating time is controlled to 40-50 minutes. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • the purity of the crude product of the third-stage distillation of fluoroethylene carbonate is 98%
  • the purity of the first-level product is 99%
  • the purity of the second-level product is 99.9%
  • the purity of the first-level recovered product is 98%.
  • the energy consumption in step (3) is 2.5t steam per ton of product.
  • the fluoroethylene carbonate production system in this embodiment is provided with a secondary distillation tower.
  • the fluoroethylene carbonate production system of this embodiment is used to purify the liquid obtained in step 3 of Example 1 to obtain a high-purity fluoroethylene carbonate product.
  • the purification process is as follows:
  • S1 Pour 8L of crude fluoroethylene carbonate primary distillation into the raw material tank, start the falling film crystallization system, and control the temperature of the cold and hot media at 23-30°C through the hot and cold medium preheating equipment of the circulation insulation system;
  • S3 Adjust the temperature of the hot and cold media in the falling film crystallization system.
  • the first-level crystallization rapidly cools to 30-22°C and slowly cools to 22-0°C.
  • Control the crystallization time at 80-90 minutes, stop the crystallization circulation pump, and discharge the mother liquor for weighing and sampling. ;
  • S4 Sweating adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the first-level sweating has a rapid temperature rise of 0-18°C and a slow temperature rise of 18-22.5°C.
  • the sweating time is controlled to 40-50min. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • S5 Adjust the temperature of the hot and cold media of the falling film crystallization system to 30-35°C, perform first-level melting, control the melting time for 30 minutes, and discharge the first-level product for weighing and sampling after the melting is completed.
  • Sweat adjusts the temperature of the hot and cold media of the falling film crystallization system.
  • the second-level sweating quickly heats up to 5-18°C and slowly heats up to 18-22.5°C. Control the sweating time to 40-50min. After sweating is completed, the sweating liquid is discharged, weighed and sampled;
  • S9 Third-level melting and crystallization: The process parameter conditions of the step are the same as the second-level melting and crystallization. After the third-level melting is completed, the third-level product is obtained.
  • the purity of the crude product of the secondary distillation of fluoroethylene carbonate is 95%
  • the purity of the first-level product is 98%
  • the purity of the second-level product is 99.5%
  • the purity of the third-level product is 99.99%
  • the purity of the first-level recovered product is 96%.
  • the energy consumption in step (3) is 2.2t steam per ton of product.
  • Chlorination reaction Chlorine and ethylene carbonate are chlorinated in a photolysis reaction tower under light irradiation at a molar ratio of 0.4:2 to generate monochloroethylene carbonate.
  • the reaction temperature is 60°C and the reaction time is 2 hours.
  • the chlorination reaction product includes monochloroethylene carbonate and unreacted ethylene carbonate.
  • the chlorination reaction product in the photolysis reaction tower is sent to the deacidification tower, and nitrogen gas is blown to blow away the excess hydrogen chloride and chlorine to obtain an EC/FEC blend composed of monochloroethylene carbonate and unreacted ethylene carbonate.
  • the excess hydrogen chloride/chlorine mixed gas in the deacidification tower and the excess hydrogen chloride/chlorine mixed gas in the photolysis reaction tower are absorbed by water and alkali to obtain by-products hydrochloric acid and sodium hypochlorite.
  • Fluorination reaction Add fluorination reagent to the blend of monochloroethylene carbonate and ethylene carbonate. The molar ratio of fluorination reagent to monochloroethylene carbonate is 1:1. The reaction generates fluoroethylene carbonate. The reaction temperature was 60°C and the reaction time was 9 hours.
  • Solid-liquid separation and purification The fluorinated reaction product is subjected to solid-liquid separation to obtain solid mixed salt (fluorination reagent and potassium chloride) and liquid. The liquid is purified to obtain high-purity fluorinated ethylene carbonate product, and the solid mixed salt is recovered and processed. The by-products calcium fluoride and potassium chloride are obtained.
  • Chlorination reaction Chlorine and ethylene carbonate are chlorinated in a photolysis reaction tower under light irradiation at a molar ratio of 0.6:2.5 to generate monochloroethylene carbonate.
  • the reaction temperature is 70°C and the reaction time is 1 hour.
  • the chlorination reaction product includes monochloroethylene carbonate and unreacted ethylene carbonate.
  • the chlorination reaction product in the photolysis reaction tower is sent to the deacidification tower, and nitrogen gas is blown to blow away the excess hydrogen chloride and chlorine to obtain an EC/FEC blend composed of monochloroethylene carbonate and unreacted ethylene carbonate.
  • the excess hydrogen chloride/chlorine mixed gas in the deacidification tower and the excess hydrogen chloride/chlorine mixed gas in the photolysis reaction tower are absorbed by water and alkali to obtain by-products hydrochloric acid and sodium hypochlorite.
  • Fluorination reaction Add fluorination reagent to the blend of monochloroethylene carbonate and ethylene carbonate.
  • the molar ratio of fluorination reagent to monochloroethylene carbonate is 1.5:1.
  • the reaction generates fluoroethylene carbonate.
  • the reaction temperature was 80°C and the reaction time was 8 hours.
  • Solid-liquid separation and purification The fluorinated reaction product is subjected to solid-liquid separation to obtain solid mixed salt (fluorination reagent and potassium chloride) and liquid. The liquid is purified to obtain high-purity fluorinated ethylene carbonate product, and the solid mixed salt is recovered and processed. The by-products calcium fluoride and potassium chloride are obtained.
  • the liquid obtained in step 3 of Example 1 is purified to obtain a high-purity fluoroethylene carbonate product.
  • the purification process is as follows:
  • the crude fluoroethylene carbonate (85%) reaches 92.5% through one-stage distillation, 95% through two-stage distillation, and 98% purity of the third-stage distillation product.
  • the energy consumption is 1.5t steam per ton of product. If it is processed through 5
  • the purity of the sub-distillation product is 99.5%, and its energy consumption is 3t of steam per ton of product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供了一种电解液添加剂的生产方法及系统。通过氯代反应、脱氯反应和纯化三个步骤制得碳酸亚乙烯酯，通过降低反应过程中氯气与碳酸乙烯酯的比例，显著降低了反应能耗。又通过氯代反应、氟代反应和固液分离提纯三个步骤制得氟代碳酸乙烯酯，在反应过程中采用加入过量碳酸乙烯酯的方法，以提高反应的连续性，减少副产物的生成，提高了氟代碳酸乙烯酯的制备效率。本申请提供的生产方法制得的碳酸亚乙烯酯和氟代碳酸乙烯酯均具有高纯度的特点，均可在锂电池电解液的相关工艺中使用。

Description

一种电解液添加剂的生产方法及系统 技术领域
本申请涉及有机合成技术领域，尤其涉及一种电解液的生产方法及系统。
背景技术
近几年，随着各国对环保的高度重视，锂电池产业和新能源汽车等下游行业规模的不断扩大以及锂电池对安全性、循环寿命和能量密度要求的提升，电解液添加剂的需求量逐年增加。电解液中目前用量最大的还是碳酸亚乙烯酯、氟代碳酸乙烯酯。
碳酸亚乙烯酯的工业化生产主要分为两个步骤：第一步为通过碳酸亚乙烯酯的氯代反应(以氯气为氯化剂，在紫外光照射下进行)生成一氯代碳酸乙烯酯，第二步为通过三乙胺、氨气、碱金属的氢氧化物等脱卤剂脱除一氯代碳酸乙烯酯中的氯原子生成碳酸亚乙烯酯。采用该方法合成碳酸亚乙烯酯，条件温和，操作简便，易于控制，是目前工业上普遍采用的生产方法。
然而，采用该方法生产高纯碳酸亚乙烯酯，需将得到的纯度约为60％的碳酸亚乙烯酯粗品进行三级精馏处理(一级蒸馏于脱溶塔中进行，经一级蒸馏处理后，产品的纯度约为97％，二级蒸馏于脱轻塔或粗馏塔中进行，经二级蒸馏处理后，产品的纯度约为98％，三级精馏塔于精馏塔中进行，经三级精馏处理后，产品的纯度约为98.5％)，能耗较高(约为3600kg蒸汽/t产品)，且得到的产品纯度仅为98.5％，无法满足电子领域的应用需要，为进一步提高产品的纯度，需继续进行两次精馏处理，方能将产品的纯度提高至99.5％左右，这进一步增加了能耗(约为8000kg蒸汽/t产品)，导致进行放大化生产过程的经济性较差。
氟代碳酸乙烯酯合成路线有以下几种方法：
方法一：直接氟气反应法
用氟气和氮气的混合气体与碳酸乙烯酯进行反应合成氟代碳酸乙烯酯。其合成路线如下所示：
该方法使用的原料为氟气，氟气不仅毒性大，而且反应活性高，反应剧烈放热，很容易导致反应容器内的压力偏高，出现危险，而且氟气腐蚀性强，因此对反应设备要求很高，工业上危险性较高，实现难度较高。
方法二：卤素交换反应法
以碳酸乙烯酯为原料，经氯气或其他氯化试剂氯化生成一氯碳酸乙烯酯，一氯碳酸乙烯酯纯化后和氟化试剂发生反应，得到目标产物氟代碳酸乙烯酯。其合成路线如下所示：
该方法不涉及有毒的氟气，安全成本大大降低，生产工艺更易于控制。但由于是两步反应，总收率较低，原料投入大。
方法三：电化学氟化法
通过阳极氟化4-取代芳硫基碳酸乙烯酯得到氟代碳酸乙烯酯。该方法能在安全和设 备相对简单的条件下反应，但还处在实验室理论研究阶段。
综上，目前最为理想的氟代碳酸乙烯酯合成工艺为卤素交换反应法(方法二)，该工艺为两步反应，在一氯碳酸乙烯酯制备部分，选用氯气过量的方式，进行间歇反应，反应时间为24h左右，无法连续生产，且碳酸乙烯酯、氯气原料转化率不高，副产物产率太高，经济性不好。一氯碳酸乙烯酯制备好后，需要纯化后才能用于氟代碳酸乙烯酯的合成，一氯碳酸乙烯酯纯化的目的主要是除去混合物中的副产品二氯副产物。纯化后的一氯碳酸乙烯酯与氟化试剂及溶剂在反应釜中反应，生成氟代碳酸乙烯酯及混合盐(固体氟化试剂与氯化钾)，经过过滤后母液送入溶剂回收塔回收溶剂，回收溶剂后将氟代碳酸乙烯酯粗品通过蒸馏/精馏的方式进行提纯，以除去二氟类取代物等副产物。目前氟代碳酸乙烯酯的提纯过程多采用精馏工艺，虽然经过多级精馏能够得到纯度很高的FEC，但是传统精馏工艺提纯氟代碳酸乙烯酯不仅能耗非常高，而且由于工艺限制和产品物性特性，使得精馏难以得到电子级氟代碳酸乙烯酯。
发明内容
发明人在研究过程中发现，为提高碳酸亚乙烯酯的纯度，在实际生产过程中，需将第二步反应得到的纯度约为60％的碳酸亚乙烯酯粗品进行三级精馏处理(一级蒸馏于脱溶塔中进行，经一级蒸馏处理后，产品的纯度约为97％，二级蒸馏于脱轻塔或粗馏塔中进行，经二级蒸馏处理后，产品的纯度约为98％，三级精馏塔于精馏塔中进行，经三级精馏处理后，产品的纯度约为98.5％)，能耗较高(约为3600kg蒸汽/t产品)，且得到的产品纯度仅为98.5％，无法满足电子领域的应用需要，为进一步提高产品的纯度，需继续进行两次精馏处理，方能将产品的纯度提高至99.5％左右，这进一步增加了能耗(约为8000kg蒸汽/t产品)。
为了解决上述问题，第一方面，本申请提供了一种碳酸亚乙烯酯的生产方法及生产系统，以降低碳酸亚乙烯酯的生产能耗，降低副产物产生量。其中，生产方法采用的步骤为：
S1：以碳酸乙烯酯和氯气为原料，于紫外光照射下进行氯代反应，得到中间产物一氯代碳酸乙烯酯。
S2：将步骤S1得到的一氯代碳酸乙烯酯置于装有溶剂、缚酸剂和阻聚剂的反应釜中进行反应，用碳酸二甲酯洗涤脱氯反应产物进行固液分离，得到的液相经脱溶塔处理后熔融结晶，即得所述碳酸亚乙烯酯，所述溶剂采用碳酸亚乙烯酯。
第二方面，本申请还提供了一种碳酸亚乙烯酯的生产方法，其中，生产方法采用的步骤包括氯代反应步骤，脱氯反应步骤和纯化步骤。其中，氯代反应步骤包括：以碳酸乙烯酯为原料，以氯气为氯化剂，在紫外光照射下进行氯代反应，氯气与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)。
基于第二方面提供的生产方法，还提供了由第二方面内容提供的生产方法制得的碳酸亚乙烯酯。基于第二方面内容提供的生产方法制得的碳酸亚乙烯酯，可以应用于锂离子电池的相关工艺中。
在第一方面和第二方面提供的碳酸亚乙烯酯的生产方法中，还包括以下内容：
可选地，氯代反应的温度为60-70℃，优选为65-70℃。氯代反应的时间为1-2h，优选为1.2-2h。
可选地，将氯代反应后液体进行精馏，精馏得到的碳酸乙烯酯作为氯代反应原料继续使用。
可选地，所述精馏的温度为50-60℃，优选为55-60℃。
可选地，缚酸剂采用三乙胺。
可选地，阻聚剂采用丁基对甲酚。
可选地，溶剂与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)，优选为1：(1.2-1.5)。
可选地，缚酸剂与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)，优选为1：(1.2-1.5)。
可选地，阻聚剂与一氯代碳酸乙烯酯的质量比为(0.1-0.5)：100，优选为(0.2-0.5)：100。
可选地，脱氯反应的温度为60-70℃，优选为65-70℃；脱氯反应的时间为4-5h，优选为4.5-5h。
可选地，脱溶塔处理过程中，温度为30-40℃，优选为35-40℃；压力为6-10kPa，优选为7-10kPa。
可选地，还包括以下步骤：将碳酸二甲酯洗涤后得到的固相干燥后加入水后过滤，向过滤所得液体中加入碱进行反应，随后进行离心，回收离心处理得到的三乙胺，并作为脱氯反应的原料继续使用。
可选地，纯化过程包括熔融结晶。
可选地，采用降膜结晶管进行熔融结晶。
适应于上述生产方法，本申请还提供一种碳酸亚乙烯酯的生产系统，包括一级反应单元、二级反应单元和提纯单元，所述一级反应单元包括至少一级光解反应塔，所述光解反应塔设置有碳酸乙烯酯进料口、进气口、出液口和出气口，所述二级反应单元包括至少一级反应釜，所述反应釜设置有进料口和出料口，所述提纯单元包括熔融结晶器，所述最后一级光解反应塔的出料口连通第一级反应釜的进料口，最后一级反应釜的出料口连通所述熔融结晶器。
在本发明提供的碳酸亚乙烯酯的生产系统中，还包括以下内容：
可选地，所述一级反应单元还包括脱酸塔，所述脱酸塔设置有进气口和出气口，其位于最后一级光解反应塔的出液口与第一级反应釜的进料口之间的连通管路上。
可选地，所述一级反应单元还包括精馏塔，所述精馏塔位于所述脱酸塔与第一级反应釜之间的连通管路上，其一端连通所述脱酸塔，第二端设置有液体出口和碳酸乙烯酯出口，所述液体出口连通第一级反应釜的进料口，所述碳酸乙烯酯出口连通所述光解反应塔的碳酸乙烯酯进料口。
可选地，当二级反应单元包括若干级反应釜时，相邻反应釜之间设置有第一离心装置，所述第一离心装置设置有液体进口、液体出口和固体出口，所述液体进口和液体出口分别连通上一级反应釜的出料口和下一级反应釜的进料口。
可选地，所述熔融结晶器采用降膜结晶器。
可选地，所述二级反应单元还包括洗涤塔，位于最后一级反应釜与熔融结晶器之间的连通管路上，其连通最后一级反应釜的出料口，通过传输组件连接所述离心装置的固体出口，并设置有出液端和固体排出口，所述出液端连通所述熔融结晶器。
可选地，所述生产系统还包括三乙胺回收单元，所述三乙胺回收单元包括通过传输 组件相连接的干燥装置和溶解池，所述干燥装置通过传输组件连通所述洗涤塔的固体排出口，所述溶解池连通有过滤装置，所述过滤装置设置有液体排出口，所述液体排出口连通有反应池，所述反应池连通有第二离心装置，所述第二离心装置设置有三乙胺出口，所述三乙胺出口连通反应釜的进料口。
可选地，所述提纯单元还包括脱溶塔，所述脱溶塔连通所述洗涤塔的出液端和熔融结晶器。
可选地，所述提纯单元还包括粗馏塔，所述粗镏塔位于所述脱溶塔与熔融结晶器之间的连通管路上，并连通所述脱溶塔和熔融结晶器。
可选地，所述生产系统还包括副产回收单元，所述副产回收单元包括依次连通的水吸收塔和碱吸收塔，所述水吸收塔连通最后一级光解反应塔的出气口所述反应池设置有三乙胺出口，所述三乙胺出口连通所述水吸收塔。
第三方面，本申请还提供了一种氟代碳酸乙烯酯节能生产方法及系统。其中，生产方法采用的步骤为：
氯代反应：氯代试剂先与过量的碳酸乙烯酯(碳酸乙烯酯)在光的作用下氯化生成一氯碳酸乙烯酯(碳酸乙烯酯)，氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯；
氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，以碳酸乙烯酯为溶剂，反应生成氟代碳酸乙烯酯(氟代碳酸乙烯酯)；
固液分离、提纯：氟代反应产物经固液分离得到固体混合盐和液体，将液体提纯得到目标产品氟代碳酸乙烯酯。
可选地，所述步骤S1中，氯代试剂与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)。
可选地，所述步骤S2中，氟化试剂与一氯碳酸乙烯酯的摩尔比为(1-1.5)：1，优选为(1-1.1)：1。
可选地，氯代反应过程中，碳酸乙烯酯以熔融态进行反应。
可选地，氯代反应过程中，反应温度为60-70℃，反应时间为1-2小时。
可选地，氯代反应过程中，反应在紫光或蓝光照射条件下进行。
可选地，氟代反应过程中，反应温度为60-80℃，反应时间为7-9小时。
可选地，氯代反应过程中，所述氯代试剂选自氯气。
可选地，氟代反应过程中，所述氟化试剂为碱金属氟化物，通式为MF，其中，M＝Na，K，Rb，Cs。
可选地，固液分离、提纯过程中，所述固体混合盐包括MF和KCl；优选地，所述固体混合盐包括KF和KCl。
可选地，固液分离、提纯过程中，所述固体混合盐加水搅拌溶解，然后除去有机物，加入氯化钙搅拌反应，反应结束后过滤，滤渣洗涤后干燥得到氟化钙，滤液蒸馏结晶得到可溶性氯盐(氯化钾)。
可选地，固液分离、提纯过程中，采用活性炭吸附有机物，过滤后再加入氯化钙搅拌反应；或者采用过滤袋或滤膜过滤有机物，再加入氯化钙搅拌反应。
可选地，固液分离、提纯过程中，氯化钙与氟离子的摩尔比为(1-1.02)：1。
可选地，固液分离、提纯过程中，氟化钙干燥温度为140-160℃，连续干燥，停留时 间为1-1.5小时。
可选地，固液分离、提纯过程中，液体的提纯方法包括如下步骤：
将液体中的溶剂碳酸乙烯酯脱除后，进行降膜结晶，降膜结晶过程包括若干次循环的熔融结晶，所述熔融结晶依次包括结晶、发汗、熔融步骤。
可选地，脱除溶剂碳酸乙烯酯时温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
可选地，降膜结晶时物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa。
可选地，所述结晶步骤依次包括快速降温和缓慢降温过程，结晶时快速降温温度为30-22℃，缓慢降温温度为22-0℃。
可选地，结晶时间为80-90min。
可选地，所述发汗步骤包括快速升温和缓慢升温过程，发汗时快速升温温度为0-18℃，缓慢升温温度为18-22.5℃。
可选地，发汗时间为40-50min。
可选地，所述熔融步骤温度为30-35℃，熔融时间为20-40分钟。
可选地，所述降膜结晶过程包括两次或三次熔融结晶，两次熔融结晶依次为一级熔融结晶、二级熔融结晶，三次熔融结晶依次为一级熔融结晶、二级熔融结晶、三级熔融结晶；
所述一级熔融结晶包括一级结晶、一级发汗、一级熔融，一级结晶快速降温为30～22℃，缓慢降温为22-0℃，结晶时间为80-90min；一级发汗快速升温为0～18℃，缓慢升温为18-22.5℃，发汗时间为40-50min；一级熔融温度为30-35℃，熔融时间为20-40分钟；一级熔融完成后得到一级产品；
所述二级熔融结晶包括二级结晶、二级发汗、二级熔融，二级结晶快速降温为30-22℃，缓慢降温为22-5℃，结晶时间在80-90min；二级发汗快速升温为5-18℃，缓慢升温为18-22.5℃，发汗时间为40-50min；二级熔融温度为30-35℃，熔融时间为20-40分钟；二级熔融完成后得到二级产品；
所述三级熔融结晶步骤工艺参数条件与所述二级熔融结晶相同，三级熔融完成后得到三级产品。
可选地，所述降膜结晶过程还包括一级回收，所述一级回收为将第一级熔融结晶得到的一级产品再次进行熔融结晶。
可选地，所述一级回收步骤工艺参数条件与所述一级熔融结晶步骤相同。
可选地，固液分离、提纯过程中，液体提纯过程中，溶剂脱除与降膜结晶步骤之间还设有多级精馏步骤；优选地，所述多级精馏为一级、二级或三级精馏。
可选地，精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
可选地，所述氯代反应包括多级光催化氯代反应，优选地，所述氯代反应包括二级光催化氯代反应。
可选地，前一级氯代反应的副产物氯化氢/氯气混合气体通入后一级氯代反应中，作为氯代反应的原料气。
可选地，所述氯代反应的副产物氯化氢/氯气混合气体经水吸收、碱吸收分别得盐酸、次氯酸钠副产品；优选地，采用氢氧化钠溶液进行碱吸收，所述氢氧化钠溶液的浓度为 20-30％。
本发明另一方面提供一种氟代碳酸乙烯酯节能生产系统，包括氟代一级反应单元、氟代二级反应单元和氟代提纯单元，所述氟代一级反应单元包括多级光解反应塔和脱酸塔，所述光解反应塔为氯代试剂与碳酸乙烯酯进行氯代反应生成一氯碳酸乙烯酯的场所，所述光解反应塔的顶部设有排气口，前一级光解反应塔的排气口与后一级光解反应塔相连通，所述脱酸塔与所述光解反应塔相连，用于除去氯代反应产物中多余的Cl2和HCl气体；所述二级反应单元包括第一反应釜和离心机，所述第一反应釜与所述脱酸塔相连，为一氯碳酸乙烯酯与氟化试剂进行氟代反应生成氟代碳酸乙烯酯的场所，所述离心机为氟代反应产物进行固液分离的场所；所述提纯单元包括脱溶塔和降膜结晶系统，所述脱溶塔与所述离心机的液体出口相连，用于脱除离心机分离出的液体中的溶剂，所述降膜结晶系统用于提纯氟代碳酸乙烯酯。
可选地，所述降膜结晶系统包括降膜结晶器、循环保温系统冷热媒预热设备、结晶循环泵，所述降膜结晶器为氟代碳酸乙烯酯的提纯场所，所述循环保温系统冷热媒预热设备用于控制调节冷热媒温度，所述结晶循环泵用于将循环输送结晶母液。
可选地，所述提纯单元还包括多级精馏塔，所述多级精馏塔设置于脱溶塔和降膜结晶系统之间；优选地，所述多级精馏塔为一级、二级或三级。
可选地，所述降膜结晶器的出料口与所述精馏塔的进口相连。
可选地，所述多级光解反应塔为二级光解反应塔。
可选地，所述生产系统还包括氟代第一副产回收单元，所述氟代第一副产回收单元包括水吸收塔和碱吸收塔，所述光解反应塔的顶部设有排气口，所述水吸收塔与最末一级光解反应塔的排气口相连通，所述水吸收塔还设有工艺水进口；所述碱吸收塔与水吸收塔相连。
可选地，所述氟代第一副产回收单元还包括盐酸产品罐，所述盐酸产品罐与水吸收塔相连。
可选地，所述氟代第一副产回收单元还包括次氯酸钠产品罐，所述次氯酸钠产品罐与碱吸收塔相连。
可选地，所述生产系统还包括氟代第二副产回收单元，所述氟代第二副产回收单元包括依次串联的第二反应釜、第一过滤器、第三反应釜、第二过滤器、结晶塔；所述第二反应釜与所述离心机的固体出口相连，所述第二反应釜设有进水口；所述第一过滤器放置有活性炭并能过滤活性炭，或者，所述第一过滤器中设有有机物过滤袋或滤膜；所述第三反应釜设有氯化钙进料口，所述第二过滤器用于固液分离，所述结晶塔用于将第二过滤器分离出的滤液蒸馏结晶。
可选地，所述结晶塔设有出水口，所述出水口与所述第二反应釜的进水口相连。
可选地，所述第一反应釜、第二反应釜、第三反应釜均为搅拌式反应釜。
由以上技术可知，本申请提供的一种电解液添加剂的生产方法及系统具有以下有益效果：
(1)本申请通过将传统的脱氯反应步骤中采用的溶剂碳酸二甲酯调整为碳酸亚乙烯酯，省略了溶剂脱除步骤，降低了能耗。
(2)本申请提供的生产方法，能够在整体上进行连续生产，节约了时间；将每步反 应产生的副产品及时排除在体系之外，避免反应及中间过程的进一步复杂化，提高了产品的产率和纯度；杜绝了反应物的残留，减少了分离工序，降低了生产的复杂性和成本，能够将水分等关键技术指标控制到较低水平。
(3)采用本申请的方法进行生产，制得的碳酸亚乙烯酯的纯度高。
(4)本申请提供的超纯氟代碳酸乙烯酯节能生产工艺在氯代反应时加入了过量的碳酸乙烯酯，并以未反应的碳酸乙烯酯为氟代反应的溶剂，不仅可以实现连续生产，缩短反应时间(氯代反应时间1-2h)，并且减少了原料损耗，降低了二氯代物等副产物的生成，提高了目标产物收率，保证了原料利用率，还提升了单套设备产能，单套设备产能提高5-10倍以上。
(5)本申请提供的超纯氟代碳酸乙烯酯节能生产方法在氟代碳酸乙烯酯合成过程中会产生副产物KCL，同时有过量的未能完全反应的氟化试剂，这种混合盐会严重影响氟代碳酸乙烯酯后续的纯化。本发明采用氯化钙处理废盐，将难处理的固废物质变成可外售的氯化钾、氟化钙，这样原料利用率高，无固废产生，几乎全部制成产物、副产物售卖，保障了经济性。
(6)本申请在氟代碳酸乙烯酯提纯过程中采用降膜和熔融结晶技术，不仅结晶单程收率高，能产品纯度达到99.9以上，还能节省设备投资，大大降低能耗。
附图说明
为了更清楚地说明本申请的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，对于本领域普通技术人员而言，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请提供的碳酸亚乙烯酯的生产示意图；
图2为本申请提供的氟代碳酸乙烯酯的生产示意图。
图示说明：
1-一级反应单元，11-第一光解反应塔，12-第二光解反应塔，13-脱酸塔，14-精馏塔，2-二级反应单元，21-第一反应釜，22-第一离心装置，23-第二反应釜，24-洗涤塔，3-提纯单元，31-脱溶塔，32-粗镏塔，33-降膜结晶器，4-副产回收单元，41-水洗塔，42-碱吸收塔，5-三乙胺回收单元，51-干燥装置，52-溶解池，53-过滤装置，54-反应池，55-第二离心装置，6-废液罐，100-氟代一级反应单元，200-氟代二级反应单元，300-氟代提纯单元，304-氟代精馏塔，400-氟代第一副产回收单元，403-盐酸产品罐，404-次氯酸钠吸收罐，5-氟代第二副产回收单元，24-第三反应釜，502-第一过滤器，503-第三反应釜，504-第二过滤器，505-结晶塔。
具体实施方式
下面将详细地对实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下实施例中描述的实施方式并不代表与本申请相一致的所有实施方式。仅是与权利要求书中所详述的、本申请的一些方面相一致的系统和方法的示例。
本申请在第一方面中提出的碳酸亚乙烯酯的生产方法包括以下步骤：
S1：以碳酸乙烯酯和氯气为原料，于紫外光照射下进行氯代反应，得到中间产物一 氯代碳酸乙烯酯。
S2.将步骤S1得到的氯代碳酸乙烯酯置于装有碳酸亚乙烯酯、三乙胺和丁基对甲酚的反应釜中于60-70℃温度下进行脱氯反应4-5h，碳酸亚乙烯酯与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)，三乙胺与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)，丁基对甲酚与一氯代碳酸乙烯酯的质量比为(0.1-0.5)：100。用碳酸二甲酯洗涤脱氯反应产物，得到固相和液相，将液相干燥后加入水，随后过滤，向固液分离所得液体中加入碱进行反应，随后进行离心，回收离心处理得到的三乙胺，并作为脱氯反应的原料继续使用，洗涤脱氯反应产物得到的液相于温度为30-40℃，压力为6-10kPa条件下于脱溶塔中进行处理后熔融结晶，熔融结晶采用降膜结晶管进行，即得碳酸亚乙烯酯。
本申请在第二方面中提出的碳酸亚乙烯酯的生产方法包括氯代反应、脱氯反应以及纯化步骤：
以碳酸乙烯酯为原料，以氯气为氯化剂，于紫外光照射且60-70℃温度下进行氯代反应1-2h，氯气与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)，分别用水和碱液回收氯代反应后液体中的氯化氢气体和氯气。
向氯代反应液体中加入脱除剂三乙胺和阻聚剂丁基对甲酚，于60-70℃温度下进行脱氯反应4-5h，脱除剂与氯代反应液体中含有的氯代碳酸乙烯酯的摩尔比为1：(1-1.5)，阻聚剂与氯代反应液体中含有的氯代碳酸乙烯酯的质量比为(0.1-0.5)：100。
纯化包括熔融结晶，熔融结晶采用降膜借结晶器进行。
适用于第一方面和第二方面的生产方法，本申请还提供了一种生产系统，包括一级反应单元1、二级反应单元2、提纯单元3、副产回收单元4和三乙胺回收单元5。
一级反应单元包括至少一级光解反应塔11和脱酸塔13，脱酸塔13设置有氮气进口和出气口，其连通最后一级光解反应塔11的出液口。
二级反应单元包括至少一级反应釜21和洗涤塔24，反应釜设置有进料口和出料口，第一级反应釜21的进料口连通脱酸塔13，洗涤塔24设置有出液端和固体排出口。
三乙胺回收单元5包括通过传输组件相连接的干燥装置51和溶解池52，溶解池52连通有过滤装置53，过滤装置53设置有液体排出口，液体排出口连通有反应池54，反应池54连通有第二离心装置22，第二离心装置22设置有三乙胺出口，三乙胺出口连通反应釜的进料口，干燥装置51通过传输组件连通洗涤塔24的固体排出口。
提纯单元3包括依次连通的脱溶塔31和降膜结晶器33，脱溶塔31连通洗涤塔24的出液端。
脱溶塔31和降膜结晶器33之间的连通管路上设置有粗镏塔32。
相邻反应釜之间设置有第一离心装置21，第一离心装置21设置有液体进口、液体出口和固体出口，液体进口和液体出口分别连通上一级反应釜的出料口和下一级反应釜的进料口，固体出口和最后一级反应釜的出料口连通洗涤塔24。
第一反应单元1还包括精馏塔14，精馏塔14位于脱酸塔13与第一级反应釜之间的连通管路上，精馏塔14的第一端连通脱酸塔13，其第二端设置有液体出口和碳酸乙烯酯出口，液体出口连通第一级反应釜21的进料口，碳酸乙烯酯出口连通光解反应塔的碳酸乙烯酯进料口。
下面结合图1通过具体的实施例以详细说明本申请提供的生产方法及系统。
实施例1
采用如图1所示生产系统生产碳酸亚乙烯酯，该生产系统包括一级反应单元1、二级反应单元2、提纯单元3、副产回收单元4和三乙胺回收单元5。
一级反应单元1包括第一光解反应塔11、第二光解反应塔12、脱酸塔13和精馏塔14，第一光解反应塔11和第二光解反应塔12作为氯代反应的容器，其内设置有紫外光组件和温度调节组件，紫外光组件用于为氯代反应提供紫外光条件，温度调节组件用于调节氯代反应的温度。
第一光解反应塔11和第二光解反应塔12均设置有碳酸乙烯酯进料口、进气口、出液口和出气口，通过碳酸乙烯酯进料口能够向第一光解反应塔11和第二光解反应塔12中投入原料熔融态碳酸乙烯酯，通过进气口能够向第一光解反应塔11和第二光解反应塔12中通入氯气。通过设置多级光解反应塔能够进一步使氯气反应完全，提高收率。
脱酸塔13的上部连通第二光解反应塔12的出料口，其下部连通精馏塔14。脱酸塔13的上部设置有气体出口，其下部设置有氮气进口，通过氮气进口能够向脱酸塔13中通入氮气，进而将氯代反应所得液体中的氯气、氯化氢等气体排除出去，提高终产品的纯度，同时还能够降低后续提纯工序的能耗。
精馏塔14用于脱除氯代反应液体中未反应完全的碳酸乙烯酯，其设置有气相出口、液相出口和废液出口，气相出口连通第一光解反应塔11和/或第二光解反应塔12的碳酸乙烯酯进料口，以实现碳酸乙烯酯的循环利用。废液出口连通有废液罐6此处不再赘述。
二级反应单元2包括第一反应釜21、第一离心装置22、第二反应釜23和洗涤塔24。
第一反应釜21和第二反应釜23为脱氯反应容器，二者均设置有进料口、出料口和温度调节组件。通过进料口能够向第一反应釜21和第二反应釜23中送入原料脱除剂三乙胺、阻聚剂丁基对甲酚和溶剂碳酸亚乙烯酯，通过进料口还能够向第一反应釜21中送入经精馏塔14处理后的氯代反应液体，通过进料口还能够向第二反应釜23中送入经第一离心装置22处理所得液体。温度调节组件用于调节脱氯反应的温度。通过设置多级反应釜，能够使脱氯反应更彻底，提高收率。
第一离心装置22设置有液体进口、液体出口和固体出口，液体进口和液体出口分别连通第一反应釜21的出料口和第二反应釜23的进料口。第一离心装置22采用自动离心机。
洗涤塔24的第一端通过传输组件连接第一离心装置22的固体出口，其第一端还连通第二反应釜23的出料口，洗涤塔24的第一端还连通有碳酸二甲酯进液管路。通过碳酸二甲酯进液管路，能够向洗涤塔24中通入碳酸二甲酯，碳酸二甲酯能够溶解碳酸亚乙烯酯，而不能溶解脱氯反应产物氯代三乙胺盐，进而提高终产品的纯度。
提纯单元3包括依次连通的脱溶塔31和降膜结晶器32，降膜结晶器32经循环泵连通脱溶塔31的下部或底部。通过脱溶塔31能够脱除洗涤剂碳酸二甲酯，提高终产品的纯度，通过降膜结晶器32能够提高终产品的纯度，降低能耗。通过将降膜结晶器32经循环泵连通脱溶塔32的下部或底部，能够将部分未熔融结晶的碳酸亚乙烯酯经脱溶塔31蒸馏后再次进入降膜结晶器33中熔融结晶，提高收率。
副产回收单元4包括水吸收塔41和碱吸收塔42。水吸收塔41的第一端连通第一光解反应塔11的出气口、第二光解反应塔12的出气口及脱酸塔13的气体出口，其第一端 设置有进水管路，第二端连通碱吸收塔42。通过进水管路能够向水吸收塔41内通入水，水能够溶解氯代反应产物氯化氢进而得到盐酸。碱吸收塔42设置有废气出口，其设置有碱液进液管路，通过碱液进液管路能够向碱吸收塔42内通入氢氧化钠水溶液，氢氧化钠水溶液能够与未参与氯代反应的氯气反应生成次氯酸钠。
三乙胺回收单元5包括通过传输组件相连接的干燥装置51和溶解池52，溶解池52连通有过滤装置53，过滤装置53设置有液体排出口，液体排出口连通有反应池54，反应池54连通有第二离心装置55，第二离心装置55设置有三乙胺出口，三乙胺出口连通第一反应釜21和/或第二反应釜22的进料口。
干燥装置51通过传输组件与洗涤塔24的第二端相连接，其设置有碳酸二甲酯排料口。干燥装置51用于对经洗涤塔24洗涤的氯代三乙胺盐固体进行干燥处理，除去其表面附着的洗涤剂碳酸二甲酯，干燥装置51可以采用鼓风干燥机，鼓风干燥机为现有技术，此处不再赘述。
溶解池52连通有进水管路，通过进水管路能够向溶解池52中通入水，溶解氯代三乙胺盐固体表面附着的絮状有机物等杂质，进而通过与其溶解池52相连通的过滤装置53过滤除去。
反应池54设置有固碱进口，通过固碱进口能够向反应池54中投放物料氢氧化钠，进而使进入反应池54内的氯代三乙胺盐与氢氧化钠进行置换反应，生成三乙胺。三乙胺在水中的溶解度较低，可通过与反应池连通的第二离心装置55进行分离，分离后得到的三乙胺可通过三乙胺出口送入第一反应釜21和/或第二反应釜22，实现三乙胺的回收再利用。
以上所有连通管路上均设置有开关阀。
采用如图1所示生产系统生产碳酸亚乙烯酯，具体步骤如下：
向第一光解反应塔11和第二光解反应塔12中投入预先加热至熔融状态的碳酸乙烯酯，通过进气口向第一光解反应塔11和第二光解反应塔12中通入氯气；第一光解反应塔11和第二光解反应塔12中的氯气总量与碳酸乙烯酯总量的摩尔比为0.4：1，第一光解反应塔11内的氯气和碳酸乙烯酯分别占各自总量的2/3。
打开紫外光组件和温度调节组件，将第一光解反应塔11中的碳酸乙烯酯加热至60℃，紫外光波长为365nm，1-2h后，打开第一光解反应塔11与第二光解反应塔12之间的管路上的开关阀，打开紫外光组件和温度调节组件，将第二光解反应塔12中的碳酸乙烯酯加热至60℃，紫外光波长为365nm。氯气和碳酸乙烯酯在紫外光照射下进行氯代反应，由于碳酸乙烯酯过量，故二氯代碳酸乙烯酯的生成量极少，即本实施例通过降低氯气与碳酸乙烯酯的比例降低高沸点物质二氯代碳酸乙烯酯的生成量，进而显著降低了后续纯化过程中的能耗，同时，提高了原料转化率。
1h后，得到氯代反应液体，打开第一光解反应塔11的出气口及第二光解反应塔12的出气口与水吸收塔41的第一端之间的管路上的开关阀及水吸收塔41的第二端与碱吸收塔42之间的管路上的开关阀，并向水吸收塔41中通入水，向碱吸收塔42中通入浓度为30wt％的氢氧化钠水溶液，水溶解氯代反应产物氯化氢气体得到盐酸，氢氧化钠水溶液与未参与氯代反应的氯气反应生成次氯酸钠。
在此过程中，打开第一光解反应塔11的出液口及第二反应釜12的出液口与脱酸塔 13之间的管路上的开关阀，打开脱酸塔13与水吸收塔41之间的管路上的开关阀，并向脱酸塔13内通入氮气，自下部进入脱酸塔13的氮气与自上部进入脱酸塔13的液体(进入脱酸塔13的氯代反应液体中，二氯代碳酸乙烯酯含量为0.76wt％，现有技术，二氯代碳酸乙烯酯含量约为7wt％-8wt％，二氯代碳酸乙烯酯含量按照《Q1327HG003-2019氯代碳酸乙烯酯》进行检测逆流接触，进而将液体中的氯气和氯化氢排出，得到一氯代碳酸乙烯酯(CEC)液相粗品。
接着，打开脱酸塔13与精馏塔14之间的管路上的开关阀，一氯代碳酸乙烯酯液相粗品于温度为50℃，压力为1kPa条件下在精馏塔14中进行精馏后脱除未反应完全的碳酸乙烯酯，得到高纯氯代碳酸乙烯酯；在此过程中，打开精馏塔14的气相出口与第一光解反应塔11和/或第二光解反应塔12之间的管路上的开关阀，碳酸乙烯酯经管路循环至第一光解反应塔11和/或第二光解反应塔12。
精馏完成后，打开精馏塔14与第一反应釜21之间的管路上的开关阀，并向第一反应釜21和第二反应釜22中送入脱除剂三乙胺、阻聚剂丁基对甲酚和溶剂碳酸亚乙烯酯，第一反应釜21和第二反应釜22中的三乙胺总量与高纯氯代碳酸乙烯酯总量的摩尔比为1：1，碳酸亚乙烯酯总量与高纯氯代碳酸乙烯酯总量的摩尔比为1：1，丁基对甲酚总量与高纯氯代碳酸乙烯酯总量的质量比为0.1：100。
在此过程中，打开温度调节组件，将第一反应釜21内的物料加热至60℃，进入第一反应釜21的高纯氯代碳酸乙烯酯与三乙胺在碳酸亚乙烯酯存在下进行脱除反应4h，得到脱除反应产物(含氯代三乙胺盐)。
接着，打开第一反应釜21与第一离心装置22之间的管路上的开关阀，脱除反应产物进入第一离心装置22进行离心处理，得到液体和固体。
随后，打开第一离心装置22的液体出口与第二反应釜23之间的管路上的开关阀，离心所得液体进入第二反应釜23，在此过程中，打开温度调节组件将第二反应釜23内的物料加热至60℃，未反应完的物料在第二反应釜21中继续进行脱除反应4h，得到脱除反应产物(含氯代三乙胺盐)。
然后，打开第二反应釜23与洗涤塔24之间的管路上的开关阀，启动第一离心装置22的固体出口与洗涤塔24之间的传输组件，并向洗涤塔24中通入洗涤剂碳酸二甲酯，碳酸二甲酯能够溶解碳酸亚乙烯酯，不能溶解氯代三乙胺盐，进而除去氯代三乙胺盐，提高终产品的纯度。
随后，启动洗涤塔24与干燥装置51之间的传输组件，附着有碳酸二甲酯及絮状有机物的氯代三乙胺盐固体经干燥装置51干燥后脱除其附着的碳酸二甲酯，碳酸二甲酯则经管路进入洗涤塔24，实现碳酸二甲酯的循环利用。
接着，启动干燥装置51与溶解池52之间的传输组件，并向溶解池52中通入水，随后打开溶解池52与过滤装置53之间管路上的开关阀，液体混合物进入过滤装置53经过滤处理后除去氯代三乙胺盐附着的絮状有机物。
然后，打开过滤装置53与反应池54之间的管路上的开关阀，并向反应池中投放物料氢氧化钠，含氯代三乙胺盐的液体进入反应池54中，并与氢氧化钠发生置换反应，生成三乙胺。
随后，打开反应池54与第二离心装置55之间管路上的开关阀，混合液体进入第二 离心装置55中，经过滤处理后分离得到三乙胺，打开第二离心装置55与第一反应釜21和/或第二反应釜22之间的管路上的开关阀，三乙胺液体经三乙胺出口进入第一反应釜21和/或第二反应釜22中继续参与脱除反应，实现三乙胺的回收再利用。
打开洗涤塔24与脱溶塔31之间的管路上的开关阀，洗涤后液体(纯度为60％)进入脱溶塔31中，脱溶塔31能够通过蒸馏脱除洗涤剂碳酸二甲酯。脱溶处理的温度为30℃，压力为6kPa。
随后，打开脱溶塔31与降膜结晶器32之间的管路，经脱溶塔31处理后的液体(纯度为97％，以处理量10kg为例)进入降膜结晶器33中进行熔融结晶，熔融结晶包括结晶、发汗和熔融步骤，具体为：
S1：设备预热：
将10kg纯度为97％的待处理VC结晶原料(温度为30-35℃)倒入原料罐中，启动降膜结晶器和循环冷热媒预热设备，将循环冷热媒温度控制在20-25℃；
S2：物料预冷：启动结晶循环泵，将原料罐中VC结晶原料输送至降膜结晶器后进行循环输送，控制循环物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz，使循环物料温度迅速降低至20-25℃；
S3：进行第一次降膜结晶：
结晶过程：以0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃，控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重得到3kg母液，取样测得母液纯度为91％，母液可灌装存储积累一定量后直接结晶得到1.7kg回收液和1.3kg残液，回收液产品纯度可达98％左右，回收液可以与下一次纯度为97％的VC结晶原料一起进行结晶提纯，残液可以送至精馏单元；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发汗液排出称重得到0.5Kg，取样测得发汗液纯度为99.2％，发汗液可灌装储存加入下一次纯度为97％的结晶原料中；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将一级结晶产品排出称重得到6.5kg，取样测得一级结晶产品纯度为99.4％；
S4：进行第二次降膜结晶：
结晶过程：将6.5kg纯度为99.4％的一级结晶产品送入降膜结晶器中进行循环，以0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃进行结晶，控制结晶时间在80-90min，停止结晶循环泵，排出称重得到0.9kg二级母液，取样测得二级母液纯度为99.3％，二级母液可以与下一次纯度为97％的VC结晶原料一起进行结晶提纯；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发二级发汗液排出称重得到0.6Kg，取样测得二级发汗液纯度为99.3％，二级发汗液可以与下一次纯度为99.4％的VC结晶原料一起进行结晶提纯；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将二级结晶产品排出称重得到5kg(利用回收液、一二级发汗液 后产品重量为8.7kg)，取样测得二级结晶产品(第一次结晶过程中降膜结晶器的结晶管的管壁上的碳酸亚乙烯酯结晶物熔融后再次循环结晶得到的降膜结晶器的结晶管的管壁上的碳酸亚乙烯酯结晶物)纯度为99.99％。
按照本实施例的方式生产碳酸亚乙烯酯，放大至3000t产品进行计算，能耗为2350kg蒸汽/t碳酸亚乙烯酯终产品，其中，纯化工序中，能耗为1700kg蒸汽/t碳酸亚乙烯酯终产品，能耗根据《GB/T 2589-2020综合能耗计算通则》进行计算。
本实施例中，纯度按照《GB/T 27801-2011碳酸亚乙烯酯》进行检测。
实施例2
如图2所示生产系统，本实施例与实施例1的不同之处在于：脱溶处理的温度为40℃，压力为10kPa；脱溶塔31和降膜结晶器32之间的连通管路上设置有粗镏塔33，降膜结晶器32经循环泵连通粗镏塔33的下部或底部。通过粗镏塔33能够通过蒸馏去除阻聚剂丁基对甲酚及聚碳酸亚乙烯酯等杂质，进一步提高终产品的纯度。粗馏处理的温度为55℃，压力为2kPa；经粗馏塔32处理后物料的纯度为98％；
第一光解反应塔11和第二光解反应塔12中的氯气总量与碳酸乙烯酯总量的摩尔比为0.6：3，三乙胺总量与高纯氯代碳酸乙烯酯(CEC)总量的摩尔比为1：1.5，碳酸亚乙烯酯总量与高纯氯代碳酸乙烯酯总量的摩尔比为1：1.5，丁基对甲酚总量与高纯氯代碳酸乙烯酯总量的质量比为0.5：100，氯代反应的温度为70℃，氯代反应的时间为2h，氯代反应液体中二氯代碳酸乙烯酯含量为0.63wt％；脱氯反应的温度为70℃，脱氯反应的时间为5h；
精馏塔14中，温度为60℃；
S1：将10kg纯度为98％的待处理VC结晶原料(温度为30-35℃)倒入原料罐中，启动降膜结晶器和循环冷热媒预热设备，将循环冷热媒温度控制在20-23℃；
S2：物料预冷：启动结晶循环泵，将原料罐中VC结晶原料输送至降膜结晶器后进行循环输送，控制循环物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz，使循环物料温度迅速降低至20-25℃；
S3：进行第一次降膜结晶：
结晶过程：以0.1℃-2℃/min逐级将循环冷热媒温度降低至1℃-3℃，控制，控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重得到1.8kg直接结晶得到1.2kg回收液和0.6kg残液，回收液产品纯度可达98.5％左右，回收液可以与下一次纯度为98％的VC结晶原料一起进行结晶提纯，残液可以送至二级精馏单元；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将一级发汗液排出称重得到0.3kg，取样测得一级发汗液纯度为99.5％，一级发汗液可灌装储存加入下一次纯度为98％的结晶原料中；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将一级结晶产品排出称重得到7.9kg，取样测得一级结晶产品纯度为99.4％；
S4：进行第二次降膜结晶：
结晶过程：将7.9kg纯度为99.4％的一级结晶产品送入降膜结晶器中进行循环，以 0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃进行结晶，控制结晶时间在80-90min，停止结晶循环泵，排出称重得到1.6kg二级母液，取样测得二级母液纯度为98.6％，二级母液可以与下一次纯度为98％的VC结晶原料一起进行结晶提纯；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发二级发汗液排出称重得到0.5Kg，取样测得二级发汗液纯度为99.3％，二级发汗液可以与下一次纯度为99.4％的一级结晶产品一起进行结晶提纯；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将二级结晶产品排出称重得到5.8kg，取样测得二级结晶产品纯度为99.99％；
S4：进行第三次降膜结晶：
结晶过程：将5.8kg纯度为99.99％的二级结晶产品送入降膜结晶器中进行循环，以0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃进行结晶，控制结晶时间在80-90min，停止结晶循环泵，排出称重得到0.9kg三级母液，取样测得三级母液纯度为99.92％，三级母液可以与下一次纯度为99.4％的一级结晶产品一起进行结晶提纯；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发三级级发汗液排出称重得到0.7Kg，取样测得三级发汗液纯度为99.95％，三级发汗液可以与下一次纯度为99.99％的二级结晶产品一起进行结晶提纯；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将三级结晶产品排出称重得到4.2kg(回收液、二、三级母液、一、二、三发汗液利用后产品重量约7.3kg)，取样测得二级结晶产品纯度为99.995％；
上述将纯度为60％的VC粗品提纯到纯度为99.995％的高纯VC所需能耗为每吨产品2500kg蒸汽。
结晶过程温度调节：
一级结晶快速降温为35-22℃，缓慢降温为22-0℃；
二、三级结晶快速降温为35-22℃，缓慢降温为22-5℃。
发汗调节降膜结晶系统冷热媒温度：
一级结晶快速升温为0-18℃，缓慢升温为18-22.5℃；
二、三级结晶快速升温为5-18℃，缓慢升温为18-22.5℃。
保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
按照本实施例的方式生产碳酸亚乙烯酯，放大至3000t产品进行计算，能耗为3120kg蒸汽/t碳酸亚乙烯酯终产品，其中，纯化工序中，能耗为2500kg蒸汽/t碳酸亚乙烯酯终产品。
实施例3
本实施例与实施例2的不同之处在于：第一光解反应塔11和第二光解反应塔12中的氯气总量与碳酸乙烯酯总量的摩尔比为0.5：2.5，三乙胺总量与高纯氯代碳酸乙烯酯总量的摩尔比为1：1.2，碳酸亚乙烯酯总量与高纯氯代碳酸乙烯酯总量的摩尔比为1： 1.2，丁基对甲酚总量与高纯氯代碳酸乙烯酯总量的质量比为0.3：100，氯代反应的温度为64℃，氯代反应的时间为1.5h，氯代反应液体中二氯代碳酸乙烯酯含量为0.71wt％；脱氯反应的温度为64℃，脱氯反应的时间为4.5h随后；粗馏处理的温度为60℃，压力为4kPa；
S1：将10kg纯度为98％的待处理VC结晶原料(温度为30-35℃)倒入原料罐中，启动降膜结晶器和循环冷热媒预热设备，将循环冷热媒温度控制在20-23℃；
S2：物料预冷：启动结晶循环泵，将原料罐中VC结晶原料输送至降膜结晶器后进行循环输送，控制循环物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz，使循环物料温度迅速降低至20-25℃；
S3：进行第一次降膜结晶：
结晶过程：以0.1℃-2℃/min逐级将循环冷热媒温度降低至1℃-3℃，控制，控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重得到1.8kg直接结晶得到1.2kg回收液和0.6kg残液，回收液产品纯度可达98.5％左右，回收液可以与下一次纯度为98％的VC结晶原料一起进行结晶提纯，残液可以送至二级精馏单元；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将一级发汗液排出称重得到0.3kg，取样测得一级发汗液纯度为99.5％，一级发汗液可灌装储存加入下一次纯度为98％的结晶原料中；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将一级结晶产品排出称重得到7.9kg，取样测得一级结晶产品纯度为99.4％；
S4：进行第二次降膜结晶：
结晶过程：将7.9kg纯度为99.4％的一级结晶产品送入降膜结晶器中进行循环，以0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃进行结晶，控制结晶时间在80-90min，停止结晶循环泵，排出称重得到1.6kg二级母液，取样测得二级母液纯度为98.6％，二级母液可以与下一次纯度为98％的VC结晶原料一起进行结晶提纯；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发二级发汗液排出称重得到0.5Kg，取样测得二级发汗液纯度为99.3％，二级发汗液可以与下一次纯度为99.4％的一级结晶产品一起进行结晶提纯；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将二级结晶产品排出称重得到5.8kg，取样测得二级结晶产品纯度为99.99％；
S4：进行第三次降膜结晶：
结晶过程：将5.8kg纯度为99.99％的二级结晶产品送入降膜结晶器中进行循环，以0.1℃-2℃/min逐级将循环冷热媒温度降低1℃-3℃进行结晶，控制结晶时间在80-90min，停止结晶循环泵，排出称重得到0.9kg三级母液，取样测得三级母液纯度为99.92％，三级母液可以与下一次纯度为99.4％的一级结晶产品一起进行结晶提纯；
发汗过程：以0.1℃-2℃/min逐级将循环冷热媒温度升高至18℃-23℃，保持降膜结 晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发三级级发汗液排出称重得到0.7Kg，取样测得三级发汗液纯度为99.95％，三级发汗液可以与下一次纯度为99.99％的二级结晶产品一起进行结晶提纯；
熔融过程：逐级调节降膜结晶系统冷热媒温度至30-35℃以熔融结晶产品，控制熔融时间30min，熔融完成后将三级结晶产品排出称重得到4.2kg(回收液、二、三级母液、一、二、三发汗液利用后产品重量约7.3kg)，取样测得二级结晶产品纯度为99.995％；
上述将纯度为60％的VC粗品提纯到纯度为99.995％的高纯VC所需能耗为每吨产品2500kg蒸汽。
结晶过程温度调节：
一级结晶快速降温为35-22℃，缓慢降温为22-0℃；
二、三级结晶快速降温为35-22℃，缓慢降温为22-5℃。
发汗调节降膜结晶系统冷热媒温度：
一级结晶快速升温为0-18℃，缓慢升温为18-22.5℃；
二、三级结晶快速升温为5-18℃，缓慢升温为18-22.5℃。
保持降膜结晶循环保温系统冷热媒温度不变，控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
按照本实施例的方式生产碳酸亚乙烯酯，放大至3000t产品进行计算，能耗为3230kg蒸汽/t碳酸亚乙烯酯终产品，其中，纯化工序中，能耗为2550kg蒸汽/t碳酸亚乙烯酯终产品。
对比例1
本对比例与实施例2的不同之处在于：向反应釜中加入的溶剂为碳酸二甲酯而非碳酸亚乙烯酯，碳酸二甲酯总量与高纯氯代碳酸乙烯酯总量的摩尔比为5：1。
按照本对比例的方式生产碳酸亚乙烯酯，放大至3000t产品进行计算，能耗为4800kg蒸汽/t产品碳酸亚乙烯酯终产品(二级结晶产品纯度为99.97％)，其中，纯化工序中，能耗为3900kg蒸汽/t碳酸亚乙烯酯终产品。
本申请还在第三方面提出了氟代碳酸乙烯酯的生产方法，其合成路线如下：
Figure PCTCN2022124193-appb-000001
具体通过以下步骤生产氟代碳酸乙烯酯：
(1)氯代反应：氯代试剂先与过量的碳酸乙烯酯在光(紫光或蓝光)的照射下氯化生成一氯碳酸乙烯酯，反应温度为60-70℃，反应时间为1-2小时，氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯；
(2)氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，以碳酸乙烯酯为溶剂，反应生成氟代碳酸乙烯酯，反应温度为60-80℃，反应时间为7-9小时；
(3)固液分离、提纯：氟代反应产物经固液分离得到固体混合盐和液体，将液体提纯得到目标产品氟代碳酸乙烯酯。
氯代反应中，氯代试剂与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)。
氟代反应中，氟化试剂与一氯碳酸乙烯酯的摩尔比为(1-1.5)：1，优选为(1-1.1)： 1。
氯代反应中，碳酸乙烯酯以熔融态进行反应。
氟代反应中，氟化试剂为碱金属氟化物，通式为MF，其中，M＝Na，K，Rb，Cs。以下实施例中，氟化试剂均采用KF，因此所得固体混合盐包括氟代试剂和氯化钾。
固液分离、提纯，固体混合盐处理方式为：将固体混合盐加水搅拌溶解，然后采用活性炭吸附有机物，或者采用过滤袋或滤膜过滤有机物，以除去有机物，再加入氯化钙，氯化钙与氟离子的摩尔比为(1-1.02)：1，搅拌反应0.5-1h，反应结束后过滤，滤渣洗涤后干燥得到氟化钙，干燥方式为连续干燥，干燥温度为140-160℃，停留时间为1-1.5小时滤液蒸馏结晶得到氯化钾。
固液分离、提纯中，液体的提纯方法包括如下步骤：
将液体中的溶剂碳酸乙烯酯脱除后，进行降膜结晶，降膜结晶过程包括若干次循环的熔融结晶，所述熔融结晶依次包括结晶、发汗、熔融步骤。
其中，脱除溶剂碳酸乙烯酯时温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
其中，降膜结晶时物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa。
其中，所述结晶步骤依次包括快速降温和缓慢降温过程，结晶时快速降温温度为30-22℃，缓慢降温温度为22-0℃，结晶时间为80-90min。
其中，所述发汗步骤包括快速升温和缓慢升温过程，发汗时快速升温温度为0-18℃，缓慢升温温度为18-22.5℃，发汗时间为40-50min。
其中，所述熔融步骤温度为30-35℃，熔融时间为20-40分钟。
所述降膜结晶过程包括两次或三次熔融结晶，两次熔融结晶依次为一级熔融结晶、二级熔融结晶，三次熔融结晶依次为一级熔融结晶、二级熔融结晶、三级熔融结晶；
所述一级熔融结晶包括一级结晶、一级发汗、一级熔融，一级结晶快速降温为30-22℃，缓慢降温为22-0℃，结晶时间为80-90min；一级发汗快速升温为0-18℃，缓慢升温为18-22.5℃，发汗时间为40-50min；一级熔融温度为30-35℃，熔融时间为20-40分钟；一级熔融完成后得到一级产品；
所述二级熔融结晶包括二级结晶、二级发汗、二级熔融，二级结晶快速降温为30-22℃，缓慢降温为22-5℃，结晶时间在80-90min；二级发汗快速升温为5-18℃，缓慢升温为18-22.5℃，发汗时间为40-50min；二级熔融温度为30-35℃，熔融时间为20-40分钟；二级熔融完成后得到二级产品；
所述三级熔融结晶步骤工艺参数条件与所述二级熔融结晶相同，三级熔融完成后得到三级产品。
所述降膜结晶过程还包括一级回收，所述一级回收为将第一级熔融结晶得到的一级产品再次进行熔融结晶。具体的，所述一级回收步骤工艺参数条件与所述一级熔融结晶步骤相同。
所述步骤(3)中，液体提纯过程中，溶剂脱除与降膜结晶步骤之间还设有多级精馏步骤，优为一级、二级或三级精馏。具体的，精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
本发明的氯代反应包括多级光催化氯代反应，优选为二级光催化氯代反应。具体的， 前一级氯代反应的副产物氯化氢/氯气混合气体通入后一级氯代反应中，作为氯代反应的原料气。
本发明的氯代反应的副产物氯化氢/氯气混合气体经水吸收、碱吸收分别得盐酸、次氯酸钠副产品；优选地，采用氢氧化钠溶液进行碱吸收，所述氢氧化钠溶液的浓度为20-30％。
本发明还提供了一种氟代碳酸乙烯酯生产系统，根据上述的氟代碳酸乙烯酯节能生产工艺生产氟代碳酸乙烯酯。如图2所示，所述生产系统包括氟代一级反应单元100、氟代二级反应单元200和提纯单元300。
氟代一级反应单元100包括多级光解反应塔11和脱酸塔12，光解反应塔11为氯代试剂与碳酸乙烯酯进行氯代反应生成一氯碳酸乙烯酯的场所，图2所示的多级光解反应塔11为二级光解反应塔11，但不局限于此。第一级光解反应塔11上设有碳酸乙烯酯进料口和氯代试剂进料口，光解反应塔11的顶部设有排气口，排气口用于排出多余的氯化氢/氯气混合气，前一级光解反应塔11的排气口与后一级光解反应塔11相连通。脱酸塔12与光解反应塔11相连，用于除去氯代反应产物中多余的氯气和氯化氢气体；图2中，脱酸塔12与两个光解反应塔11底部的出料口相连，脱酸塔12的顶部设有用于排出氯化氢/氯气混合气的排气口，底部设有碳酸乙烯酯/一氯代碳酸乙烯酯共混液出口，还设有氮气进口，通入氮气能吹走氯代反应物中的氯化氢和剩余氯气，以便于将其排出并进行回收处理。
氟代二级反应单元200包括第一反应釜21和第一离心装置22，第一反应釜21为一氯碳酸乙烯酯与氟化试剂进行氟代反应生成氟代碳酸乙烯酯的场所，具体的，第一反应釜21与脱酸塔12的碳酸乙烯酯/一氯代碳酸乙烯酯共混液出口相连，并设有氟化试剂进料口；第一离心装置22为氟代反应产物进行固液分离的场所，第一离心装置22设有固体出口和液体出口，氟代反应产物在第一离心装置22中进行固液分离，液体即碳酸乙烯酯/一氯代碳酸乙烯酯共混液经液体出口进入提纯单元300，固体混合盐经固体出口进入第二副产物回收单元。
提纯单元300包括脱溶塔31和降膜结晶系统，脱溶塔31与第一离心装置22的液体出口相连，用于脱除第一离心装置22分离出的液体中的溶剂，降膜结晶系统用于提纯氟代碳酸乙烯酯。
具体的，降膜结晶系统包括降膜结晶器33、循环保温系统冷热媒预热设备、结晶循环泵，降膜结晶器33为氟代碳酸乙烯酯的提纯场所，循环保温系统冷热媒预热设备用于控制调节冷热媒温度，结晶循环泵用于将循环输送结晶母液。
提纯单元300还包括多级氟代精馏塔304，多级氟代精馏塔304设置于脱溶塔31和降膜结晶系统之间，氟代精馏塔304依次串联，第一级氟代精馏塔304进料口与脱溶塔31的出料口相连，最末一级精氟代精馏塔304的出料口与降膜结晶器33的进料口相连；优选地，多级精馏塔302为一级、二级或三级。图2所示的提纯单元300设有一级氟代精馏塔304。
降膜结晶器33的出料口还与精馏塔302的进口相连，以将结晶母液送回氟代精馏塔304中进行精馏提纯。
本发明的氟代碳酸乙烯酯节能生产系统还包括氟代第一副产回收单元400，氟代第一 副产回收单元400包括水吸收塔41、碱吸收塔42、盐酸产品罐403、碱吸收塔42相连，水吸收塔41与最末一级光解反应塔11的排气口、脱酸塔12的排气口相连通，另外，水吸收塔41还设有工艺水进口，盐酸产品罐403与水吸收塔41底部的出料口相连；碱吸收塔42与水吸收塔41顶部的排气口相连，碱吸收塔42底部的出料口连接次氯酸钠产品罐。氟代第一副产回收单元400用于回收氯化氢/氯气混合气，具体过程如下：氯化氢/氯气混合气先进入水吸收塔41，氯化氢被水溶解形成盐酸，收集于盐酸产品罐403中；然后进入剩余的氯气进入碱吸收塔42，与氢氧化钠溶液反应生成次氯酸钠，收集于次氯酸钠产品罐中，其余未反应的废气排出。进一步地，本发明的氟代碳酸乙烯酯生产系统还包括氟代第一副产回收单元500，氟代第一副产回收单元500包括依次串联的第二反应釜23、第一过滤器502、第三反应釜503、第二过滤器504、结晶塔505；第二反应釜23与第一离心装置22的固体出口相连，第二反应釜23设有进水口，固体混合盐在第二反应釜23被水溶解；第一过滤器502放置有活性炭，并且能过滤活性炭，或者，第一过滤器502中设有有机物过滤袋或滤膜，离心得到的固体混合盐(氟化试剂和氯化钾)可能带有一定量的有机物，因此采用活性炭吸附有机物再过滤以去除有机物，或者直接用能过滤有机物的过滤袋或滤膜除去有机物；第三反应釜503设有氯化钙进料口，第二过滤器504用于固液分离，第二过滤器504设有滤液出口，所述结晶塔505与第二过滤器504的滤液出口相连，用于将第二过滤器504分离出的滤液蒸馏结晶。混合盐液体在第三反应釜503与氯化钙搅拌反应，生成氟化钙，然后经第二过滤器504过滤后，得到副产氟化钙，所得滤液在结晶塔505蒸馏结晶，得到副产氯化钾。
结晶塔505设有出水口，出水口与第二反应釜23的进水口相连。
另外，本发明的生产系统中，第一反应釜21、第二反应釜23、第三反应釜503均为搅拌式反应釜。
下面通过具体的实施例来对本发明进行进一步详细地说明。
实施例4
本实施例中的氟代碳酸乙烯酯生产系统设有一级精馏塔。
本实施例中氟代碳酸乙烯酯的生产过程具体如下：
1、氯代反应：氯气与碳酸乙烯酯按照0.5:2的摩尔比在光照射下在光解反应塔中氯化生成一氯碳酸乙烯酯，反应温度为65℃，反应时间为2小时，所得氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯。
将光解反应塔中的氯代反应产物送入脱酸塔中，通入氮气吹走多余的氯化氢和氯气，得到由一氯碳酸乙烯酯及未反应的碳酸乙烯酯组成的EC/FEC共混液，脱酸塔中多余的氯化氢/氯气混合气体与光解反应塔中多余的氯化氢/氯气混合气体一起经水吸收和碱吸收，得到副产盐酸和次氯酸钠。
2、氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，氟化试剂与一氯碳酸乙烯酯的摩尔比为1.3：1，反应生成氟代碳酸乙烯酯，反应温度为75℃，反应时间为7小时。
3、固液分离、提纯：氟代反应产物经固液分离得到固体混合盐(氟化试剂和氯化钾)和液体。
将液体提纯得到高纯氟代碳酸乙烯酯产品，提纯过程具体如下：
(1)脱除碳酸乙烯酯：温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
(2)氟代碳酸乙烯酯一级精馏：精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
(3)2+1降膜结晶，即二次熔融结晶+一级回收，具体操作步骤如下：
S1：将8L的氟代碳酸乙烯酯一级精馏粗品倒入原料罐中，启动降膜结晶系统，通过循环保温系统冷热媒预热设备将冷热媒温度控制在23-30℃；
S2：启动结晶循环泵，控制流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz；
S3：调节降膜结晶系统冷热媒温度，一级结晶快速降温为30-22℃，缓慢降温为22-0℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S4：发汗调节降膜结晶系统冷热媒温度，一级发汗快速升温为0-18℃，缓慢升温为18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S5：调节降膜结晶系统冷热媒温度为30-35℃，进行一级熔融，控制熔融时间30min，熔融完成后将一级产品排出称重取样。
S6：调节降膜结晶系统冷热媒温度，二级结晶快速降温为30-22℃，缓慢降温为22-5℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S7：发汗调节降膜结晶系统冷热媒温度，二级发汗快速升温为5-18℃，缓慢升温为18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S8：调节降膜结晶系统冷热媒温度为30-35℃，进行二级熔融，控制熔融时间30min，熔融完成后将二级产品排出称重取样。
S9：将一级产品进行一级回收，一级回收操作步骤按一级熔融结晶操作步骤进行。
经检测，FEC一级精馏粗品纯度为92.5％，一级产品纯度为98％，二级产品纯度为99.5％，一级回收产品纯度95％。步骤(3)能耗为900kg蒸汽每吨产品。
2)回收处理固体混合盐(氟化试剂和氯化钾)，处理方式具体如下：
将固体混合盐(氟化试剂和氯化钾)加水搅拌溶解，然后采用活性炭吸附有机物，再将活性炭过滤，以除去有机物，在滤液中加入氯化钙，氯化钙与氟离子的摩尔比为1.02：1，搅拌反应1h，反应结束后过滤，滤渣洗涤后干燥得到氟化钙，干燥方式为连续干燥，干燥温度为150℃，停留时间为1小时左右，滤液蒸馏结晶得到氯化钾。
实施例5
本实施例中的氟代碳酸乙烯酯生产系统设有三级精馏塔。采用本实施例的氟代碳酸乙烯酯生产系统将实施例1步骤3所得的液体提纯得到高纯氟代碳酸乙烯酯产品，提纯过程具体如下：
(1)脱除碳酸乙烯酯：温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
(2)氟代碳酸乙烯酯三级精馏：精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
(3)2+1降膜结晶，即二次熔融结晶+一级回收，具体操作步骤如下：
S1：将8L的氟代碳酸乙烯酯一级精馏粗品倒入原料罐中，启动降膜结晶系统，通过 循环保温系统冷热媒预热设备将冷热媒温度控制在23-30℃；
S2：启动结晶循环泵，控制流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz；
S3：调节降膜结晶系统冷热媒温度，一级结晶快速降温为30-22℃，缓慢降温为22-0℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S4：发汗调节降膜结晶系统冷热媒温度，一级发汗快速升温为0-18℃，缓慢升温为18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S5：调节降膜结晶系统冷热媒温度为30-35℃，进行一级熔融，控制熔融时间30min，熔融完成后将一级产品排出称重取样。
S6：调节降膜结晶系统冷热媒温度，二级结晶快速降温为30-22℃，缓慢降温为22-5℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S7：发汗调节降膜结晶系统冷热媒温度，二级发汗快速升温为5-18℃，缓慢升温为18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S8：调节降膜结晶系统冷热媒温度为30-35℃，进行二级熔融，控制熔融时间30min，熔融完成后将二级产品排出称重取样。
S9：将一级产品进行一级回收，一级回收操作步骤按一级熔融结晶操作步骤进行。
经检测，氟代碳酸乙烯酯三级精馏粗品纯度为98％，一级产品纯度为99％，二级产品纯度为99.9％，一级回收产品纯度98％。步骤(3)能耗为2.5t蒸汽每吨产品。
实施例6
本实施例中的氟代碳酸乙烯酯生产系统设有二级精馏塔。采用本实施例的氟代碳酸乙烯酯生产系统将实施例1步骤3所得的液体提纯得到高纯氟代碳酸乙烯酯产品，提纯过程具体如下：
(1)脱除碳酸乙烯酯：温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
(2)FEC二级精馏：精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
(3)3+1降膜结晶，即三次熔融结晶+一级回收，具体操作步骤如下：
S1：将8L的氟代碳酸乙烯酯一级精馏粗品倒入原料罐中，启动降膜结晶系统，通过循环保温系统冷热媒预热设备将冷热媒温度控制在23-30℃；
S2：启动结晶循环泵，控制流量为0.2-0.6m 3/h，压力为0.02-0.07MPa，电机频率为13-18Hz；
S3：调节降膜结晶系统冷热媒温度，一级结晶快速降温为30-22℃，缓慢降温为22-0℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S4：发汗调节降膜结晶系统冷热媒温度，一级发汗快速升温为0-18℃，缓慢升温为18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S5：调节降膜结晶系统冷热媒温度为30-35℃，进行一级熔融，控制熔融时间30min，熔融完成后将一级产品排出称重取样。
S6：调节降膜结晶系统冷热媒温度，二级结晶快速降温为30-22℃，缓慢降温为22-5℃；控制结晶时间在80-90min，停止结晶循环泵，将母液排出称重取样；
S7：发汗调节降膜结晶系统冷热媒温度，二级发汗快速升温为5-18℃，缓慢升温为 18-22.5℃；控制发汗时间为40-50min，发汗完成将发汗液排出称重取样；
S8：调节降膜结晶系统冷热媒温度为30-35℃，进行二级熔融，控制熔融时间30min，熔融完成后将二级产品排出称重取样。
S9：三级熔融结晶：步骤工艺参数条件与所述二级熔融结晶相同，三级熔融完成后得到三级产品。
S10：将一级产品进行一级回收，一级回收操作步骤按一级熔融结晶操作步骤进行。
经检测，氟代碳酸乙烯酯二级精馏粗品纯度为95％，一级产品纯度为98％，二级产品纯度为99.5％三级产品纯度为99.99％，一级回收产品纯度为96％。步骤(3)能耗为2.2t蒸汽每吨产品。
实施例7
本实施例中氟代碳酸乙烯酯的生产过程具体如下：
1、氯代反应：氯气与碳酸乙烯酯按照0.4：2的摩尔比在光照射下在光解反应塔中氯化生成一氯碳酸乙烯酯，反应温度为60℃，反应时间为2小时，所得氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯。
将光解反应塔中的氯代反应产物送入脱酸塔中，通入氮气吹走多余的氯化氢和氯气，得到由一氯碳酸乙烯酯及未反应的碳酸乙烯酯组成的EC/FEC共混液，脱酸塔中多余的氯化氢/氯气混合气体与光解反应塔中多余的氯化氢/氯气混合气体一起经水吸收和碱吸收，得到副产盐酸和次氯酸钠。
2、氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，氟化试剂与一氯碳酸乙烯酯的摩尔比为1：1，反应生成氟代碳酸乙烯酯，反应温度为60℃，反应时间为9小时。
3、固液分离、提纯：氟代反应产物经固液分离得到固体混合盐(氟化试剂和氯化钾)和液体，将液体提纯得到高纯氟代碳酸乙烯酯产品，固体混合盐回收处理得到副产氟化钙和氯化钾。
实施例8
本实施例中氟代碳酸乙烯酯的生产过程具体如下：
1、氯代反应：氯气与碳酸乙烯酯按照0.6：2.5的摩尔比在光照射下在光解反应塔中氯化生成一氯碳酸乙烯酯，反应温度为70℃，反应时间为1小时，所得氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯。
将光解反应塔中的氯代反应产物送入脱酸塔中，通入氮气吹走多余的氯化氢和氯气，得到由一氯碳酸乙烯酯及未反应的碳酸乙烯酯组成的EC/FEC共混液，脱酸塔中多余的氯化氢/氯气混合气体与光解反应塔中多余的氯化氢/氯气混合气体一起经水吸收和碱吸收，得到副产盐酸和次氯酸钠。
2、氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，氟化试剂与一氯碳酸乙烯酯的摩尔比为1.5：1，反应生成氟代碳酸乙烯酯，反应温度为80℃，反应时间为8小时。
3、固液分离、提纯：氟代反应产物经固液分离得到固体混合盐(氟化试剂和氯化钾)和液体，将液体提纯得到高纯氟代碳酸乙烯酯产品，固体混合盐回收处理得到副产氟化钙和氯化钾。
对比例2
将实施例1步骤3所得的液体提纯得到高纯氟代碳酸乙烯酯产品，提纯过程具体如下：
(1)脱除碳酸乙烯酯：温度为110～130℃，流量为380-450Kg/m 3/h，压力为1-2kPa。
(2)氟代碳酸乙烯酯精馏：精馏时温度为50-60℃，流量40-70Kg/m 3/h，压力为5-6kPa。
氟代碳酸乙烯酯粗品(85％)经一级精馏达到92.5％，二级精馏达到95％，三级精馏产品纯度达98％，能耗为1.5t蒸汽每吨产品，如果经5次精馏产品纯度为99.5％，其能耗为3t蒸汽每吨产品。
对比实施例4-6及对比例可知，在氟代碳酸乙烯酯提纯过程中，采用降膜结晶技术，在得到高纯氟代碳酸乙烯酯产品的同时，能够有效降低能耗。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (30)

  1. 一种碳酸亚乙烯酯的生产方法，其特征在于，包括以下步骤：
    S1.以碳酸乙烯酯和氯气为原料，于紫外光照射下进行氯代反应，得到中间产物一氯代碳酸乙烯酯；
    S2.将步骤S1得到的一氯代碳酸乙烯酯置于装有溶剂、缚酸剂和阻聚剂的反应釜中进行脱氯反应，用碳酸二甲酯洗涤脱氯反应产物，将得到的液相经脱溶塔处理后熔融结晶，即得所述碳酸亚乙烯酯，所述溶剂采用碳酸亚乙烯酯。
  2. 根据权利要求1所述的生产方法，其特征在于，还包括以下步骤：将氯代反应后液体进行精馏，精馏得到的碳酸乙烯酯作为氯代反应原料继续使用；
    和/或，步骤S2中，所述缚酸剂采用三乙胺；
    和/或，步骤S2中，所述阻聚剂采用丁基对甲酚。
  3. 根据权利要求1所述的生产方法，其特征在于，步骤S2中，所述溶剂与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)；
    和/或，步骤S2中，所述缚酸剂与一氯代碳酸乙烯酯的摩尔比为1：(1-1.5)；
    和/或，步骤S2中，所述阻聚剂与一氯代碳酸乙烯酯的质量比为(0.1-0.5)：100。
  4. 根据权利要求1所述的生产方法，其特征在于，步骤S2中，所述脱氯反应的温度为60-70℃，脱氯反应的时间为4-5h；
    和/或，步骤S2中，所述脱溶塔处理过程中，温度为30-40℃，压力为6-10kPa。
  5. 根据权利要求1所述的生产方法，其特征在于，步骤S2中，还包括以下步骤：将碳酸二甲酯洗涤后得到的固相干燥后加入水后过滤，向过滤所得液体中加入碱进行反应，随后进行离心，回收离心处理得到的三乙胺，并作为脱氯反应的原料继续使用；
    和/或，步骤S2中，采用降膜结晶管进行熔融结晶。
  6. 一种碳酸亚乙烯酯的生产系统，其特征在于，包括一级反应单元、二级反应单元和提纯单元，所述一级反应单元包括至少一级光解反应塔，所述光解反应塔设置有碳酸乙烯酯进料口、进气口、出液口和出气口，所述二级反应单元包括至少一级反应釜，所述反应釜设置有进料口和出料口，所述提纯单元包括熔融结晶器，所述最后一级光解反应塔的出料口连通第一级反应釜的进料口，最后一级反应釜的出料口连通所述熔融结晶器。
  7. 根据权利要求6所述的生产系统，其特征在于，所述一级反应单元还包括脱酸塔，所述脱酸塔设置有进气口和出气口，其位于最后一级光解反应塔的出液口与第一级反应釜的进料口之间的连通管路上；
    和/或，当二级反应单元包括若干级反应釜时，相邻反应釜之间设置有第一离心装置，所述第一离心装置设置有液体进口、液体出口和固体出口，所述液体进口和液体出口分别连通上一级反应釜的出料口和下一级反应釜的进料口；
    和/或，所述熔融结晶器采用降膜结晶器。
  8. 根据权利要求7所述的生产系统，其特征在于，所述一级反应单元还包括精馏塔，所述精馏塔位于所述脱酸塔与第一级反应釜之间的连通管路上，其一端连通所述脱酸塔，第二端设置有液体出口和碳酸乙烯酯出口，所述液体出口连通第一级反应釜的进 料口，所述碳酸乙烯酯出口连通所述光解反应塔的碳酸乙烯酯进料口；
    和/或，所述二级反应单元还包括洗涤塔，所述洗涤塔位于最后一级反应釜与熔融结晶器之间的连通管路上，其连通最后一级反应釜的出料口，通过传输组件连接所述离心装置的固体出口，并设置有出液端和固体排出口，所述出液端连通所述熔融结晶器。
  9. 根据权利要求8所述的生产系统，其特征在于，所述提纯单元还包括脱溶塔，所述脱溶塔连通所述洗涤塔的出液端和熔融结晶器；
    和/或，还包括三乙胺回收单元，所述三乙胺回收单元包括通过传输组件相连接的干燥装置和溶解池，所述干燥装置通过传输组件连通所述洗涤塔的固体排出口，所述溶解池连通有过滤装置，所述过滤装置设置有液体排出口，所述液体排出口连通有反应池，所述反应池连通有第二离心装置，所述第二离心装置设置有三乙胺出口，所述三乙胺出口连通反应釜的进料口。
  10. 根据权利要求9所述的生产系统，其特征在于，还包括副产回收单元，所述副产回收单元包括依次连通的水吸收塔和碱吸收塔，所述水吸收塔连通最后一级光解反应塔的出气口；
    和/或，所述提纯单元还包括粗馏塔，所述粗镏塔位于所述脱溶塔与熔融结晶器之间的连通管路上，并连通所述脱溶塔和熔融结晶器。
  11. 一种碳酸亚乙烯酯的生产方法，其特征在于，包括氯代反应步骤、脱氯反应步骤和纯化步骤，所述氯代反应包括：以碳酸乙烯酯为原料，以氯气为氯化剂，于紫外光照射下进行氯代反应，所述氯气与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)。
  12. 根据权利要求11所述的生产方法，其特征在于，所述氯代反应的温度为60-70℃，氯代反应的时间为1-2h。
  13. 根据权利要求11所述的生产方法，其特征在于，还包括以下步骤：分别用水和碱液回收氯代反应后液体中的氯化氢气体和氯气。
  14. 根据权利要求11所述的生产方法，其特征在于，所述脱氯反应：向氯代反应液体中加入脱除剂和阻聚剂，进行脱氯反应。
  15. 根据权利要求14所述的生产方法，其特征在于，所述脱除剂为三乙胺。
  16. 根据权利要求14所述的生产方法，其特征在于，所述阻聚剂为丁基对甲酚。
  17. 根据权利要求11所述的生产方法，其特征在于，所述纯化包括熔融结晶。
  18. 根据权利要求17所述的生产方法，其特征在于，采用降膜结晶器进行熔融结晶。
  19. 权利要求11-18任一项所述的生产方法制得的碳酸亚乙烯酯。
  20. 权利要求11-18任一项所述的生产方法制得的碳酸亚乙烯酯在锂离子电池中的应用。
  21. 一种氟代碳酸乙烯酯节能生产工艺，其特征在于，包括如下步骤：
    (1)氯代反应：氯代试剂先与过量的碳酸乙烯酯(EC)在光的作用下氯化生成一氯碳酸乙烯酯(CEC)，氯代反应产物包括一氯碳酸乙烯酯及未反应的碳酸乙烯酯；
    (2)氟代反应：在一氯碳酸乙烯酯与碳酸乙烯酯的共混液中加入氟化试剂，以碳酸乙烯酯为溶剂，反应生成氟代碳酸乙烯酯(FEC)；
    (3)固液分离、提纯：氟代反应产物经固液分离得到固体混合盐和液体，将液体 提纯得到目标产品氟代碳酸乙烯酯。
  22. 根据权利要求21所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述步骤(1)中，氯代试剂与碳酸乙烯酯的摩尔比为(0.4-0.6)：(2-3)；
    和/或，所述步骤(2)中，氟化试剂与一氯碳酸乙烯酯的摩尔比为(1-1.5)：1；
    和/或，所述步骤(1)中，碳酸乙烯酯以熔融态进行反应；
    和/或，所述步骤(1)中，反应温度为60-70℃，反应时间为1-2小时；
    和/或，所述步骤(1)中，反应在紫光或蓝光照射条件下进行；
    和/或，所述步骤(2)中，反应温度为60-80℃，反应时间为7-9小时。
  23. 根据权利要求21所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述步骤(1)中，所述氯代试剂选自Cl2；所述步骤(2)中，所述氟化试剂为碱金属氟化物，通式为MF，其中，M＝Na，K，Rb，Cs；所述步骤(3)中，所述固体混合盐包括MF和KCl。
  24. 根据权利要求21所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述步骤(3)中，所述固体混合盐加水搅拌溶解，然后除去有机物，加入氯化钙搅拌反应，反应结束后过滤，滤渣洗涤后干燥得到氟化钙，滤液蒸馏结晶得到可溶性氯盐(氯化钾)。
  25. 根据权利要求21所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述步骤(3)中，液体的提纯方法包括如下步骤：
    将液体中的溶剂碳酸乙烯酯脱除后，进行降膜结晶，降膜结晶过程包括若干次循环的熔融结晶，所述熔融结晶依次包括结晶、发汗、熔融步骤。
  26. 根据权利要求25所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：脱除溶剂碳酸乙烯酯时温度为110-130℃，流量为380-450Kg/m 3/h，压力为1-2kPa；
    和/或，降膜结晶时物料流量为0.2-0.6m 3/h，压力为0.02-0.07MPa；
    和/或，所述结晶步骤依次包括快速降温和缓慢降温过程，结晶时快速降温温度为30-22℃，缓慢降温温度为22-0℃；
    和/或，结晶时间为80-90min；
    和/或，所述发汗步骤包括快速升温和缓慢升温过程，发汗时快速升温温度为0-18℃，缓慢升温温度为18-22.5℃；
    和/或，发汗时间为40-50min；
    和/或，所述熔融步骤温度为30-35℃，熔融时间为20-40分钟。
  27. 根据权利要求26所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述降膜结晶过程包括两次或三次熔融结晶，两次熔融结晶依次为一级熔融结晶、二级熔融结晶，三次熔融结晶依次为一级熔融结晶、二级熔融结晶、三级熔融结晶；
    所述一级熔融结晶包括一级结晶、一级发汗、一级熔融，一级结晶快速降温为30-22℃，缓慢降温为22-0℃，结晶时间为80-90min；一级发汗快速升温为0-18℃，缓慢升温为18-22.5℃，发汗时间为40-50min；一级熔融温度为30-35℃，熔融时间为20-40分钟；一级熔融完成后得到一级产品；
    所述二级熔融结晶包括二级结晶、二级发汗、二级熔融，二级结晶快速降温为30-22℃，缓慢降温为22-5℃，结晶时间在80-90min；二级发汗快速升温为5-18℃，缓慢 升温为18-22.5℃，发汗时间为40-50min；二级熔融温度为30-35℃，熔融时间为20-40分钟；二级熔融完成后得到二级产品；
    所述三级熔融结晶步骤工艺参数条件与所述二级熔融结晶相同，三级熔融完成后得到三级产品。
  28. 根据权利要求21所述的氟代碳酸乙烯酯节能生产工艺，其特征在于：所述降膜结晶过程还包括一级回收，所述一级回收为将第一级熔融结晶得到的一级产品再次进行熔融结晶；
    和/或，所述步骤(3)中，液体提纯过程中，溶剂脱除与降膜结晶步骤之间还设有多级精馏步骤；
    和/或，所述氯代反应包括多级光催化氯代反应；
    和/或，所述氯代反应的副产物HCl/Cl2混合气体经水吸收、碱吸收分别得盐酸、次氯酸钠副产品。
  29. 一种氟代碳酸乙烯酯生产系统，其特征在于，包括一级反应单元、二级反应单元和提纯单元，所述一级反应单元包括多级光解反应塔和脱酸塔，所述光解反应塔为氯代试剂与碳酸乙烯酯进行氯代反应生成一氯碳酸乙烯酯的场所，所述光解反应塔的顶部设有排气口，前一级光解反应塔的排气口与后一级光解反应塔相连通，所述脱酸塔与所述光解反应塔相连，用于除去氯代反应产物中多余的Cl2和HCl气体；所述二级反应单元包括第一反应釜和离心机，所述第一反应釜与所述脱酸塔相连，为一氯碳酸乙烯酯与氟化试剂进行氟代反应生成氟代碳酸乙烯酯的场所，所述离心机为氟代反应产物进行固液分离的场所；所述提纯单元包括脱溶塔和降膜结晶系统，所述脱溶塔与所述离心机的液体出口相连，用于脱除离心机分离出的液体中的溶剂，所述降膜结晶系统用于提纯氟代碳酸乙烯酯。
  30. 根据权利要求29所述的氟代碳酸乙烯酯生产系统，其特征在于：所述降膜结晶系统包括降膜结晶器、循环保温系统冷热媒预热设备、结晶循环泵，所述降膜结晶器为氟代碳酸乙烯酯的提纯场所，所述循环保温系统冷热媒预热设备用于控制调节冷热媒温度，所述结晶循环泵用于将循环输送结晶母液；
    和/或，所述生产系统还包括第一副产回收单元，所述第一副产回收单元包括水吸收塔和碱吸收塔，所述光解反应塔的顶部设有排气口，所述水吸收塔与最末一级光解反应塔的排气口相连通，所述水吸收塔还设有工艺水进口；所述碱吸收塔与水吸收塔相连；
    和/或，所述生产系统还包括第二副产回收单元，所述第二副产回收单元包括依次串联的第二反应釜、第一过滤器、第三反应釜、第二过滤器、结晶塔。
PCT/CN2022/124193 2022-04-21 2022-10-09 一种电解液添加剂的生产方法及系统 WO2023201999A1 (zh)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN202210438743.1A CN114716402A (zh) 2022-04-21 2022-04-21 一种高纯碳酸亚乙烯酯及其生产方法与应用
CN202210438928.2 2022-04-21
CN202210438949.4 2022-04-21
CN202210438949.4A CN114874178A (zh) 2022-04-21 2022-04-21 一种碳酸亚乙烯酯的生产方法及生产系统
CN202210438743.1 2022-04-21
CN202210438928.2A CN114736185B (zh) 2022-04-21 2022-04-21 一种超纯氟代碳酸乙烯酯节能生产工艺及系统

Publications (1)

Publication Number Publication Date
WO2023201999A1 true WO2023201999A1 (zh) 2023-10-26

Family

ID=88418994

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/124193 WO2023201999A1 (zh) 2022-04-21 2022-10-09 一种电解液添加剂的生产方法及系统

Country Status (1)

Country Link
WO (1) WO2023201999A1 (zh)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066965A (zh) * 2007-06-01 2007-11-07 张家港市华盛化学有限公司 氟代环状碳酸酯的制备方法
CN101161647A (zh) * 2007-11-26 2008-04-16 中国海洋石油总公司 一种锂离子电池用碳酸亚乙烯酯的制备方法
CN101171242A (zh) * 2005-05-12 2008-04-30 赛拓有限责任公司 碳酸亚乙烯酯的生产方法
CN101200461A (zh) * 2007-11-27 2008-06-18 张家港市华盛化学有限公司 高纯氯代环状碳酸酯的制备方法
CN101676282A (zh) * 2008-09-16 2010-03-24 中国科学院福建物质结构研究所 一种氟代碳酸乙烯酯的合成方法
CN108084144A (zh) * 2018-01-23 2018-05-29 长园华盛(泰兴)锂电材料有限公司 一种碳酸亚乙烯酯的生产工艺
CN110655499A (zh) * 2018-06-29 2020-01-07 东营市海科新源化工有限责任公司 一种采用降膜结晶耦合精馏提纯电池级碳酸亚乙烯酯的方法和系统
CN112300111A (zh) * 2020-11-10 2021-02-02 湖北省宏源药业科技股份有限公司 一种氟代碳酸乙烯酯固渣的处理方法
CN215137056U (zh) * 2021-07-26 2021-12-14 山东海科创新研究院有限公司 一种氟代碳酸乙烯酯的纯化装置
CN114716402A (zh) * 2022-04-21 2022-07-08 上海东庚化工技术有限公司 一种高纯碳酸亚乙烯酯及其生产方法与应用
CN114736185A (zh) * 2022-04-21 2022-07-12 上海东庚化工技术有限公司 一种超纯氟代碳酸乙烯酯节能生产工艺及系统
CN217149037U (zh) * 2022-04-21 2022-08-09 上海东庚化工技术有限公司 一种碳酸亚乙烯酯生产系统
CN114874178A (zh) * 2022-04-21 2022-08-09 上海东庚化工技术有限公司 一种碳酸亚乙烯酯的生产方法及生产系统
CN217499114U (zh) * 2022-04-21 2022-09-27 上海东庚化工技术有限公司 一种氟代碳酸乙烯酯生产系统
CN115353504A (zh) * 2022-08-30 2022-11-18 福建中盛宏业新材科技股份公司 一种超纯氟代碳酸乙烯酯及其制备方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101171242A (zh) * 2005-05-12 2008-04-30 赛拓有限责任公司 碳酸亚乙烯酯的生产方法
CN101066965A (zh) * 2007-06-01 2007-11-07 张家港市华盛化学有限公司 氟代环状碳酸酯的制备方法
CN101161647A (zh) * 2007-11-26 2008-04-16 中国海洋石油总公司 一种锂离子电池用碳酸亚乙烯酯的制备方法
CN101200461A (zh) * 2007-11-27 2008-06-18 张家港市华盛化学有限公司 高纯氯代环状碳酸酯的制备方法
CN101676282A (zh) * 2008-09-16 2010-03-24 中国科学院福建物质结构研究所 一种氟代碳酸乙烯酯的合成方法
CN108084144A (zh) * 2018-01-23 2018-05-29 长园华盛(泰兴)锂电材料有限公司 一种碳酸亚乙烯酯的生产工艺
CN110655499A (zh) * 2018-06-29 2020-01-07 东营市海科新源化工有限责任公司 一种采用降膜结晶耦合精馏提纯电池级碳酸亚乙烯酯的方法和系统
CN112300111A (zh) * 2020-11-10 2021-02-02 湖北省宏源药业科技股份有限公司 一种氟代碳酸乙烯酯固渣的处理方法
CN215137056U (zh) * 2021-07-26 2021-12-14 山东海科创新研究院有限公司 一种氟代碳酸乙烯酯的纯化装置
CN114716402A (zh) * 2022-04-21 2022-07-08 上海东庚化工技术有限公司 一种高纯碳酸亚乙烯酯及其生产方法与应用
CN114736185A (zh) * 2022-04-21 2022-07-12 上海东庚化工技术有限公司 一种超纯氟代碳酸乙烯酯节能生产工艺及系统
CN217149037U (zh) * 2022-04-21 2022-08-09 上海东庚化工技术有限公司 一种碳酸亚乙烯酯生产系统
CN114874178A (zh) * 2022-04-21 2022-08-09 上海东庚化工技术有限公司 一种碳酸亚乙烯酯的生产方法及生产系统
CN217499114U (zh) * 2022-04-21 2022-09-27 上海东庚化工技术有限公司 一种氟代碳酸乙烯酯生产系统
CN115353504A (zh) * 2022-08-30 2022-11-18 福建中盛宏业新材科技股份公司 一种超纯氟代碳酸乙烯酯及其制备方法

Similar Documents

Publication Publication Date Title
CN108002355B (zh) 一种双氟磺酰亚胺锂盐的制备方法
CA2677304C (en) Method of manufacturing phosphorous pentafluoride and hexafluorophosphate
WO2018184379A1 (zh) 一种高纯氟代碳酸乙烯酯的制备方法
CN114736185B (zh) 一种超纯氟代碳酸乙烯酯节能生产工艺及系统
CN114874178A (zh) 一种碳酸亚乙烯酯的生产方法及生产系统
KR101283843B1 (ko) 탄산리튬의 정제 방법
CN103071365A (zh) 酰氯化反应尾气的治理方法
CN114917848A (zh) 一种合成硫酸乙烯酯的装置和方法
CN217149037U (zh) 一种碳酸亚乙烯酯生产系统
CN217499114U (zh) 一种氟代碳酸乙烯酯生产系统
CN103908870A (zh) 一种酰氯化反应尾气的治理方法
CN114716402A (zh) 一种高纯碳酸亚乙烯酯及其生产方法与应用
CN115724444A (zh) 一种六氟磷酸锂的生产方法
CN115304039B (zh) 一种双氯磺酰亚胺的提纯装置及方法
CN103936047B (zh) 一种无水氯化铝的制备方法
WO2023201999A1 (zh) 一种电解液添加剂的生产方法及系统
CN115448268B (zh) 一种双氟磺酰亚胺锂的生产方法及生产系统
CN217756905U (zh) 一种双氟磺酰亚胺锂制备工艺系统
CN103708518A (zh) 一种无水氯化铝制备方法
CN112010792B (zh) 一种高纯度二苯砜的生产方法
CN112724047B (zh) 一种制备三氟甲磺酰氟的装置及方法
CA3158831A1 (en) Production of lithium hydroxide and lithium carbonate
CN115487522A (zh) 氟化氢提纯系统及工艺
CN110759362B (zh) 一种含六氟磷酸锂晶体和水分的组合物
CN113860331A (zh) 利用废液为原料合成高活性氟化钾并联产氟化钠的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22938222

Country of ref document: EP

Kind code of ref document: A1