CN217499114U - Fluoroethylene carbonate production system - Google Patents
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- CN217499114U CN217499114U CN202220965486.2U CN202220965486U CN217499114U CN 217499114 U CN217499114 U CN 217499114U CN 202220965486 U CN202220965486 U CN 202220965486U CN 217499114 U CN217499114 U CN 217499114U
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Abstract
The utility model belongs to the technical field of lithium battery electrolyte material preparation, and specifically discloses a fluoroethylene carbonate production system, which comprises a first-stage reaction unit, a second-stage reaction unit and a purification unit, wherein the first-stage reaction unit comprises a multi-stage photolysis reaction tower and a deacidification tower; the second-stage reaction unit comprises a first reaction kettle for carrying out the fluorination reaction and a centrifuge for carrying out solid-liquid separation on the fluorination reaction product; the purification unit comprises a desolventizing tower and a falling film crystallization system, wherein the desolventizing tower is connected with a liquid outlet of the centrifuge and used for removing the solvent, and the falling film crystallization system is used for purifying the fluoroethylene carbonate. The system adopts a falling film crystallization system to replace a rectifying tower, so that the high-purity FEC product is ensured to be obtained, and the once-through yield of crystallization is improved, thereby reducing energy consumption and saving equipment investment; the FEC can be continuously produced by adopting the system, and the process capacity is easy to enlarge and industrialize.
Description
Technical Field
The utility model relates to a lithium cell electrolyte material preparation technical field especially relates to a fluoroethylene carbonate production system.
Background
In recent years, with the high importance of various countries on environmental protection, the scale of the downstream industries such as the lithium battery industry and new energy automobiles is continuously enlarged, the requirements of the lithium battery on safety, cycle life and energy density are improved, and the demand of the electrolyte additive is increased year by year. The most used electrolyte is the conventional additives such as Vinylene Carbonate (VC), fluoroethylene carbonate (FEC) and Phenylsulfone (PS).
The most ideal FEC synthesis process at present is a halogen exchange reaction method, and the synthesis route is as follows:
the method takes Ethylene Carbonate (EC) as a raw material, chloridizes the raw material by chlorine or other chlorinating reagents to generate monochloroethylene carbonate (CEC), and reacts with a fluorinating reagent after CEC purification to obtain a target product fluoroethylene carbonate (FEC).
Although the method does not relate to toxic fluorine gas, the safety cost is greatly reduced, and the production process is easy to control. However, since the method is a two-step reaction, Cl is selected in the CEC preparation section 2 An excessive mode, intermittent reaction is carried out, the reaction time is about 24 hours, continuous production cannot be realized, and EC and Cl are added 2 The conversion rate of raw materials is not high, the yield of byproducts is too high, and the economical efficiency is not good. Meanwhile, CEC is prepared and then purified to remove the byproduct dichloro byproduct from the mixture before it can be used for FEC synthesis. Reacting the purified CEC with a fluorination reagent (KF) and a solvent in a reaction kettle to generate FEC and mixed salts (solid KF and KCl), filtering, feeding the mother liquor into a solvent recovery tower to recover the solvent, and purifying the FEC crude product in a distillation/rectification mode after the solvent is recovered to remove byproducts such as difluoro substitutes and the like. At present, most of FEC purification processes adopt a rectification process, although high-purity FEC can be obtained through multi-stage rectification, the energy consumption of FEC purification by the traditional rectification process is very high, and electronic-grade FEC is difficult to obtain through rectification due to process limitation and product physical property characteristics.
Therefore, if an FEC production process which can be continuously produced, has a high raw material utilization rate, low byproducts, low energy consumption, good economy, and can achieve a product purity above an electronic level and can be industrially produced can be developed, and a new FEC production system is designed, efficient, energy-saving, and economical FEC production can be better achieved.
SUMMERY OF THE UTILITY MODEL
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a fluoroethylene carbonate production system, which can better realize FEC efficient, energy-saving, economical production, and is easy to be industrialized.
In order to achieve the above and other related objects, the present invention provides a fluoroethylene carbonate production system, comprising a first-stage reaction unit, a second-stage reaction unit and a purification unit, wherein the first-stage reaction unit comprises a multi-stage photolysis reaction tower and a deacidification tower, the photolysis reaction tower performs a chlorination reaction with ethylene carbonate for generating chlorinated reagentsA place of chloroethylene carbonate, the top of photolysis reaction tower is equipped with the gas vent, and the gas vent and the back one-level photolysis reaction tower of preceding one-level photolysis reaction tower are linked together, deacidify the tower with the photolysis reaction tower links to each other for get rid of unnecessary Cl in the chlorination reaction product 2 And HCl gas; the second-stage reaction unit comprises a first reaction kettle and a centrifugal machine, the first reaction kettle is connected with the deacidification tower and is a place where chloroethylene carbonate and a fluorination reagent perform a fluorination reaction to generate fluoroethylene carbonate, and the centrifugal machine is a place where a fluorination reaction product performs solid-liquid separation; the purification unit comprises a desolventizing tower and a falling film crystallization system, the desolventizing tower is connected with a liquid outlet of the centrifugal machine and used for removing the solvent in the liquid separated by the centrifugal machine, and the falling film crystallization system is used for purifying fluoroethylene carbonate.
Further, falling film crystallization system includes falling film crystallizer, circulation heat preservation system heat medium preheating equipment, crystallization circulating pump, the falling film crystallizer is the purification place of fluoroethylene carbonate, circulation heat preservation system heat medium preheating equipment is used for controlling and adjusting the heat medium temperature, the crystallization circulating pump is used for circulating the mother liquor of carrying crystallization.
Further, the purification unit also comprises a multi-stage rectifying tower which is arranged between the desolventizing tower and the falling film crystallization system; preferably, the multistage rectifying tower is one-stage, two-stage or three-stage.
Further, a discharge hole of the falling film crystallizer is connected with an inlet of the rectifying tower.
Further, the multistage photolysis reaction tower is a second-stage photolysis reaction tower.
Further, the production system further comprises a first byproduct recovery unit, the first byproduct recovery unit comprises a water absorption tower and an alkali absorption tower, the top of the photolysis reaction tower is provided with an exhaust port, the water absorption tower is communicated with the exhaust port of the last stage of photolysis reaction tower, and the water absorption tower is further provided with a process water inlet; the alkali absorption tower is connected with the water absorption tower.
Further, the first byproduct recovery unit further comprises a hydrochloric acid product tank, and the hydrochloric acid product tank is connected with the water absorption tower.
Further, the first byproduct recovery unit further comprises a sodium hypochlorite product tank, and the sodium hypochlorite product tank is connected with the alkali absorption tower.
Further, the production system also comprises a second byproduct recovery unit, wherein the second byproduct recovery unit comprises a second reaction kettle, a first filter, a third reaction kettle, a second filter and a crystallization tower which are sequentially connected in series; the second reaction kettle is connected with a solid outlet of the centrifuge and is provided with a water inlet; the first filter is provided with activated carbon and can filter the activated carbon, or an organic matter filter bag or a filter membrane is arranged in the first filter; the third reaction kettle is provided with a calcium chloride feed inlet, the second filter is used for solid-liquid separation, and the crystallization tower is used for distilling and crystallizing filtrate separated by the second filter.
Further, the crystallization tower is provided with a water outlet, and the water outlet is connected with a water inlet of the second reaction kettle.
Further, the first reaction kettle, the second reaction kettle and the third reaction kettle are all stirring type reaction kettles.
As mentioned above, the fluoroethylene carbonate production system of the present invention has the following advantages:
the utility model provides a fluoroethylene carbonate production system is according to the integrated development thinking of upper and lower stream, links such as follow raw materials, product, solid useless, improve and optimize process system equipment composition and configuration mode, substitute or substitute partial rectifying column completely through introducing falling liquid film crystal system, on the basis of guaranteeing to obtain high-purity FEC product, further improve crystallization one-way yield, reduce the energy consumption, save equipment investment; by arranging the first recovery unit and the second recovery unit, not only can a high-purity FEC product be obtained in the production process, but also KCl, NaCl, NaClO, CaF2 and industrial hydrochloric acid which have high additional values and can be sold outside can be obtained, the solid waste problem in the FEC production process is thoroughly solved, and the utilization rate of resources is improved. By adopting the production system, the continuous production of the FEC can be realized, the process capacity is easy to enlarge, the industrialization is easy to realize, and the market demand can be better met.
Drawings
Fig. 1 shows a schematic structural diagram of a fluoroethylene carbonate production system according to an embodiment of the present invention.
Description of reference numerals:
the device comprises a primary reaction unit L1, a photolysis reaction tower 101, an acid removal tower 102, a secondary reaction unit L2, a first reaction kettle 201, a centrifuge 202, a purification unit L3, a desolventizing tower 301, a rectification tower 302, a falling film crystallizer 303, a first byproduct recovery unit L4, a water absorption tower 401, an alkali absorption tower 402, a hydrochloric acid product tank 403, an alkali absorption tower 404, a second byproduct recovery unit L5, a second reaction kettle 501, a first filter 502, a third reaction kettle 503, a second filter 504 and a crystallization tower 505.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The present invention can also be implemented or applied through other different specific embodiments, and various details in the present specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.
The utility model provides a fluoro ethylene carbonate production system. As shown in FIG. 1, the production system comprises a primary reaction unit L1, a secondary reaction unit L2, and a purification unit L3.
The first-stage reaction unit L1 includes a multi-stage photolysis tower 101 and a deacidification tower 102, the photolysis tower 101 is a place where the chlorination reagent and the ethylene carbonate perform the chlorination reaction to generate the ethylene carbonate monochloride, and the multi-stage photolysis tower 101 shown in fig. 1 is a two-stage photolysis tower 101, but is not limited thereto. The first-stage photolysis reaction tower 101 is provided with a ethylene carbonate feed port and a chlorinated reagent feed port, the top of the photolysis reaction tower 101 is provided with an exhaust port, and the exhaust port is used for exhausting redundant HCl/Cl 2 The mixed gas, the exhaust port of the previous photolysis reaction tower 101 is communicated with the next photolysis reaction tower 101. The deacidification tower 102 is connected with the photolysis reaction tower 101 and is used for removing redundant chlorination reaction productsCl of 2 And HCl gas; in FIG. 1, the deacidification tower 102 is connected with the discharge holes at the bottom of the two photolysis reaction towers 101, and the top of the deacidification tower 102 is provided with a device for discharging HCl/Cl 2 The bottom of the mixed gas exhaust port is provided with an EC/CEC mixed liquid outlet and a nitrogen inlet, and HCl and residual Cl in the chlorinated reactant can be blown away by introducing nitrogen 2 So that it can be discharged and recovered.
The secondary reaction unit L2 includes a first reaction kettle 201 and a centrifuge 202, the first reaction kettle 201 is a place where vinyl monochlorocarbonate and a fluorination reagent perform a fluorination reaction to generate vinyl fluorocarbonate, specifically, the first reaction kettle 201 is connected to an EC/FEC blend outlet of the deacidification tower 102, and is provided with a fluorination reagent feed inlet; the centrifuge 202 is a place where the solid-liquid separation is performed on the fluoro reaction product, the centrifuge 202 is provided with a solid outlet and a liquid outlet, the fluoro reaction product is subjected to the solid-liquid separation in the centrifuge 202, the liquid, namely the EC/FEC blending liquid enters the purification unit L3 through the liquid outlet, and the solid mixed salt enters the second byproduct recovery unit through the solid outlet.
Purification unit L3 includes desolventizing tower 301 and falling film crystallization system, and desolventizing tower 301 is connected with the liquid outlet of centrifuge 202 for removing solvent in the liquid separated by centrifuge 202, and falling film crystallization system is used for purifying fluoroethylene carbonate.
Specifically, the falling film crystallization system comprises a falling film crystallizer 303, a circulation heat preservation system cooling and heating medium preheating device (not shown in the figure) and a crystallization circulating pump (not shown in the figure), the falling film crystallizer 303 is a purification place of fluoroethylene carbonate, the circulation heat preservation system cooling and heating medium preheating device is used for controlling and adjusting the temperature of the cooling and heating medium, and the crystallization circulating pump is used for circularly conveying crystallization mother liquor.
Further, the purification unit L3 further includes a multi-stage rectification tower 302, the multi-stage rectification tower 302 is disposed between the desolventizing tower 301 and the falling film crystallization system, the multi-stage rectification towers 302 are sequentially connected in series, a feed port of the first-stage rectification tower 302 is connected with a feed port of the desolventizing tower 301, and a feed port of the last-stage rectification tower 302 is connected with a feed port of the falling film crystallizer 303; preferably, multi-stage rectification column 302 is one, two, or three stage. The purification unit L3 shown in fig. 1 is provided with a primary rectification column 302.
Further, the discharge port of the falling film crystallizer 303 is also connected with the inlet of the rectifying tower 302, so that the crystallization mother liquor is sent back to the rectifying tower 302 for rectification and purification.
Further, the utility model discloses a fluoroethylene carbonate production system still includes first coproduction recovery unit L4, and first coproduction recovery unit L4 includes that water absorption tower 401, alkali absorption tower 402, hydrochloric acid product jar 403, alkali absorption tower 402 link to each other, and water absorption tower 401 is linked together with the gas vent of the last level photolysis reaction tower 101 (shown in FIG. 1 as second level photolysis reaction tower 101), the gas vent of deacidification tower 102, and in addition, water absorption tower 401 still is equipped with the process water import, and hydrochloric acid product jar 403 links to each other with the discharge gate of water absorption tower 401 bottom; the alkali absorption tower 402 is connected with an exhaust port at the top of the water absorption tower 401, and a discharge port at the bottom of the alkali absorption tower 402 is connected with a sodium hypochlorite product tank. The first byproduct recovery unit L4 is used for recovering HCl/Cl 2 The specific process of the mixed gas is as follows HCl/Cl 2 The mixed gas firstly enters a water absorption tower 401, HCl is dissolved by water to form hydrochloric acid, and the hydrochloric acid is collected in a hydrochloric acid product tank 403; then into the remaining Cl 2 Enters an alkali absorption tower 402, reacts with sodium hydroxide solution to generate sodium hypochlorite, is collected in a sodium hypochlorite product tank, and the rest unreacted waste gas is discharged. Further, the fluoroethylene carbonate production system of the present invention further comprises a second byproduct recovery unit L5, wherein the second byproduct recovery unit L5 comprises a second reaction kettle 501, a first filter 502, a third reaction kettle 503, a second filter 504, and a crystallization tower 505, which are connected in series in sequence; the second reaction kettle 501 is connected with a solid outlet of the centrifuge 202, the second reaction kettle 501 is provided with a water inlet, and the solid mixed salt is dissolved by water in the second reaction kettle 501; 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 matter filter bag or filter membrane, the solid mixed salt (KF and KCl) obtained by centrifugation may have a certain amount of organic matter, so the organic matter is removed by adsorbing the organic matter with activated carbon and then filtering, or the organic matter is removed directly with the filter bag or filter membrane capable of filtering the organic matter; the third reaction kettle 503 is provided with a calcium chloride feed inlet, the second filter 504 is used for solid-liquid separation, and the second filter 504 is provided with a filtrate outlet, and the crystallization tower 505 is connected with 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 a third reaction kettle 503 to generate calcium fluoride, then the calcium fluoride is filtered by a second filter 504 to obtain a byproduct calcium fluoride, and the obtained filtrate is distilled and crystallized in a crystallization tower 505 to obtain a byproduct potassium chloride.
Further, the crystallization tower 505 is provided with a water outlet, and the water outlet is connected with the water inlet of the second reaction kettle 501.
Additionally, the utility model discloses an among the production system, first reation kettle 201, second reation kettle 501, third reation kettle 503 are stirring formula reation kettle.
The utility model provides a production system is applicable to following fluoro ethylene carbonate production technology, the production technology step includes:
(1) chlorination reaction: chlorination reagent (Cl) 2 ) Firstly, chlorinating the Ethylene Carbonate (EC) with excessive Ethylene Carbonate (EC) under the irradiation of light (purple light or blue light) to generate monochloroethylene carbonate (CEC), wherein the reaction temperature is 60-70 ℃, the reaction time is 1-2 hours, and the chlorination reaction product comprises monochloroethylene carbonate and unreacted ethylene carbonate;
(2) and (3) fluoro reaction: adding a fluorination reagent into a blending solution of monochloroethylene carbonate and ethylene carbonate, taking the ethylene carbonate as a solvent, and reacting to generate fluoroethylene carbonate (FEC), wherein the reaction temperature is 60-80 ℃, and the reaction time is 7-9 hours;
(3) solid-liquid separation and purification: and (3) carrying out solid-liquid separation on the fluoro reaction product to obtain solid mixed salt and liquid, and purifying the liquid to obtain the target product fluoroethylene carbonate.
Specifically, in the step (1), the molar ratio of the chlorinated reagent to the ethylene carbonate is (0.4-0.6): (2-3).
Specifically, in the step (2), the molar ratio of the fluorinating agent to the ethylene monochlorocarbonate is (1-1.5): 1, preferably (1-1.1): 1.
specifically, in the step (1), ethylene carbonate is reacted in a molten state.
Specifically, in the step (2), the fluorinating reagent is alkali metal fluoride and has a general formula of MF, wherein M ═ Na, K, Rb and Cs. In the following examples, KF was used as the fluorinating agent, and thus the solid mixed salt obtained included KF and KCl.
Specifically, in the step (3), the solid mixed salt treatment mode is as follows: adding water into the solid mixed salt, stirring and dissolving, then adsorbing the organic matters by using activated carbon, or filtering the organic matters by using a filter bag or a filter membrane to remove the organic matters, and then adding calcium chloride, wherein the molar ratio of the calcium chloride to the fluorine ions is (1-1.02): 1, stirring and reacting for 0.5-1 h, filtering after the reaction is finished, washing filter residues, and drying to obtain calcium fluoride, wherein the drying mode is continuous drying, the drying temperature is 140-160 ℃, the retention time is 1-1.5 hours, and the filtrate is distilled and crystallized to obtain potassium chloride.
Specifically, in the step (3), the liquid purification method comprises the following steps:
removing a solvent ethylene carbonate ester in the liquid, and then carrying out falling film crystallization, wherein the falling film crystallization process comprises a plurality of times of circulating melt crystallization, and the melt crystallization sequentially comprises the steps of crystallization, sweating and melting.
Wherein the temperature for removing the solvent ethylene carbonate is 110-130 ℃, and the flow rate is 380-450 Kg/m 3 The pressure is 1-2 kPa.
Wherein the material flow is 0.2-0.6 m during falling film crystallization 3 The pressure is 0.02-0.07 MPa.
The crystallization step sequentially comprises a rapid cooling process and a slow cooling process, wherein the rapid cooling temperature is 30-22 ℃ during crystallization, the slow cooling temperature is 22-0 ℃, and the crystallization time is 80-90 min.
The sweating step comprises a rapid heating process and a slow heating process, wherein the rapid heating temperature is 0-18 ℃ during sweating, the slow heating temperature is 18-22.5 ℃, and the sweating time is 40-50 min.
Wherein the temperature of the melting step is 30-35 ℃, and the melting time is 20-40 minutes.
Preferably, the falling film crystallization process comprises two or three times of melt crystallization, wherein the two times of melt crystallization are first-stage melt crystallization and second-stage melt crystallization in sequence, and the three times of melt crystallization are first-stage melt crystallization, second-stage melt crystallization and third-stage melt crystallization in sequence;
the primary melting crystallization comprises primary crystallization, primary sweating and primary melting, wherein the primary crystallization is rapidly cooled to 30-22 ℃, the primary crystallization is slowly cooled to 22-0 ℃, and the crystallization time is 80-90 min; the first-stage sweating rapid temperature rise is 0-18 ℃, the slow temperature rise is 18-22.5 ℃, and the sweating time is 40-50 min; the primary melting temperature is 30-35 ℃, and the melting time is 20-40 minutes; obtaining a first-grade product after the first-grade melting is finished;
the secondary melting crystallization comprises secondary crystallization, secondary sweating and secondary melting, wherein the temperature of the secondary crystallization is quickly reduced to 30-22 ℃, the temperature of the secondary crystallization is slowly reduced to 22-5 ℃, and the crystallization time is 80-90 min; rapidly heating to 5-18 ℃ for secondary sweating, slowly heating to 18-22.5 ℃, and sweating for 40-50 min; the secondary melting temperature is 30-35 ℃, and the melting time is 20-40 minutes; obtaining a secondary product after the secondary melting is finished;
and the process parameter conditions of the third-stage melting crystallization step are the same as those of the second-stage melting crystallization step, and a third-stage product is obtained after the third-stage melting is completed.
Further, the falling film crystallization process also comprises primary recovery, wherein the primary recovery is to perform melt crystallization on a primary product obtained by the primary melt crystallization again. Specifically, the process parameter conditions of the first-stage recovery step are the same as those of the first-stage melt crystallization step.
Further, in the step (3), in the liquid purification process, a multi-stage rectification step, preferably a primary, secondary or tertiary rectification step, is further arranged between the solvent removal step and the falling film crystallization step. Specifically, the temperature during rectification is 50-60 ℃, and the flow rate is 40-70 Kg/m 3 The pressure is 5-6 kPa.
The chlorination reaction in the FEC production process includes a multi-stage photocatalytic chlorination reaction, preferably a two-stage photocatalytic chlorination reaction. In particular, HCl/Cl as a by-product of the preceding chlorination reaction 2 And introducing the mixed gas into the subsequent chlorination reaction to serve as raw material gas of the chlorination reaction.
HCl/Cl byproduct of chlorination reaction in FEC production process 2 Mixed gas (es)The body is absorbed by water and alkali to obtain hydrochloric acid and sodium hypochlorite byproducts respectively; preferably, a sodium hydroxide solution is adopted for alkali absorption, and the concentration of the sodium hydroxide solution is 20-30%.
The FEC production process has the following advantages:
1. the production process adds excessive EC during chlorination reaction, takes unreacted EC as a solvent for fluorination reaction, can realize continuous production, shortens the reaction time (chlorination reaction time is 1-2h), reduces the raw material loss, reduces the generation of byproducts such as dichlorinated products and the like, improves the yield of a target product, ensures the utilization rate of raw materials, improves the productivity of a single set of equipment, and improves the productivity of the single set of equipment by more than 5-10 times.
2. KCL is generated as a byproduct in the FEC synthesis process, excessive KF which is not completely reacted exists, and the subsequent purification of FEC is seriously influenced by the mixed salt. The utility model adopts CaCl 2 Treating waste salt to convert hard-to-treat solid waste into KCL and CaF 2 Therefore, the raw material utilization rate is high, no solid waste is generated, almost all products and byproducts are prepared for sale, and the economy is guaranteed.
3. The falling film and melting crystallization technology is adopted in the FEC purification process, so that the single-pass yield of crystallization is high, the product purity can reach more than 99.9, the equipment investment can be saved, and the energy consumption is greatly reduced.
The advantages of the system of the present invention in producing FEC are verified below by specific examples.
Example 1
The FEC production system in this embodiment is provided with a first-stage rectifying tower.
The FEC production process in this embodiment is as follows:
1. chlorination reaction: cl 2 Chlorinated with Ethylene Carbonate (EC) in a molar ratio of 0.5:2 under irradiation of light in a photolysis reaction tower to produce monochloroethylene carbonate (CEC) at 65 ℃ for 2 hours, and the obtained chlorinated reaction products comprise monochloroethylene carbonate and unreacted ethylene carbonate.
Produced by chlorination reaction in a photolysis reaction towerThe mixture is sent into a deacidification tower, and nitrogen is introduced to blow away excessive HCl and Cl 2 To obtain EC/FEC blending liquid consisting of vinyl monochlorocarbonate and unreacted vinyl carbonate, and removing redundant HCl/Cl in an acid tower 2 Mixing the gas with the excessive HCl/Cl in the photolysis reaction tower 2 The mixed gas is absorbed by water and alkali to obtain hydrochloric acid and sodium hypochlorite as by-products.
2. And (3) fluoro reaction: adding a fluorinating agent (KF) into a blending liquid of the monochloroethylene carbonate and the ethylene carbonate, wherein the molar ratio of the fluorinating agent to the monochloroethylene carbonate is 1.3: 1, generating fluoroethylene carbonate (FEC) by the reaction, wherein the reaction temperature is 75 ℃ and the reaction time is 7 hours.
3. Solid-liquid separation and purification: and (3) carrying out solid-liquid separation on the fluorination reaction product to obtain solid mixed salt (KF and KCl) and liquid.
1) Purifying the liquid to obtain a high-purity fluoroethylene carbonate product, wherein the purification process is as follows:
(1) and removing ethylene carbonate: the temperature is 110-130 ℃, and the flow rate is 380-450 Kg/m 3 The pressure is 1-2 kPa.
(2) FEC first-stage rectification: the temperature is 50-60 ℃ during rectification, and the flow is 40-70 Kg/m 3 The pressure is 5-6 kPa.
(3) 2+1 falling film crystallization, namely secondary melt crystallization and primary recovery, and comprises the following specific operation steps:
s1: pouring 8L of FEC primary-rectification crude product into a raw material tank, starting a falling film crystallization system, and controlling the temperature of a cooling and heating medium at 23-30 ℃ through cooling and heating medium preheating equipment of a circulating heat preservation system;
s2: starting a crystallization circulating pump, and controlling the flow rate to be 0.2-0.6 m 3 The pressure is 0.02-0.07 MPa, and the motor frequency is 13-18 Hz;
s3: adjusting the temperature of a cooling medium of a falling film crystallization system, wherein the temperature of a primary crystallization is quickly reduced to 30-22 ℃, and the temperature of a primary crystallization is slowly reduced to 22-0 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s4: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, wherein the temperature is quickly increased to 0-18 ℃ by primary sweating, and is slowly increased to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s5: adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, performing primary melting, controlling the melting time for 30min, discharging a primary product after the melting is finished, weighing and sampling.
S6: adjusting the temperature of a cooling medium of the falling film crystallization system, rapidly cooling the secondary crystallization to 30-22 ℃, and slowly cooling to 22-5 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s7: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, rapidly heating to 5-18 ℃ by secondary sweating, and slowly heating to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s8: and adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, carrying out secondary melting, controlling the melting time to be 30min, discharging the secondary product after the melting is finished, weighing and sampling.
S9: and primary recovery is carried out on the primary product, and the primary recovery operation step is carried out according to the primary melting crystallization operation step.
Through detection, the purity of the FEC primary rectification crude product is 92.5%, the purity of the primary product is 98%, the purity of the secondary product is 99.5%, and the purity of the primary recovery product is 95%.
The energy consumption of the step (3) is 900kg of steam per ton of product.
2) Recovering and processing solid mixed salt (KF and KCl) in the following specific way:
adding water into solid mixed salt (KF and KCl), stirring for dissolving, adsorbing organic matters by using activated carbon, filtering the activated carbon to remove the organic matters, adding calcium chloride into the filtrate, wherein the molar ratio of the calcium chloride to fluoride ions is 1.02: 1, stirring and reacting for 1h, filtering after the reaction is finished, washing filter residues, drying to obtain calcium fluoride, continuously drying in a drying mode, keeping the drying temperature at 150 ℃ for about 1 hour, and distilling and crystallizing the filtrate to obtain potassium chloride.
Example 2
The FEC production system in this embodiment is provided with a three-stage rectification column.
The FEC production system of this embodiment is adopted to purify the liquid obtained in step 3 of example 1 to obtain a high-purity fluoroethylene carbonate product, and the purification process is specifically as follows:
(1) and removing ethylene carbonate: the temperature is 110-130 ℃, and the flow rate is 380-450 Kg/m 3 The pressure is 1-2 kPa.
(2) And FEC three-stage rectification: the temperature is 50-60 ℃ during rectification, and the flow is 40-70 Kg/m 3 The pressure is 5-6 kPa.
(3) 2+1 falling film crystallization, namely secondary melt crystallization and primary recovery, and comprises the following specific operation steps:
s1: pouring 8L of FEC primary-rectification crude product into a raw material tank, starting a falling film crystallization system, and controlling the temperature of a cooling and heating medium at 23-30 ℃ through cooling and heating medium preheating equipment of a circulating heat preservation system;
s2: starting a crystallization circulating pump, and controlling the flow rate to be 0.2-0.6 m 3 The pressure is 0.02-0.07 MPa, and the motor frequency is 13-18 Hz;
s3: adjusting the temperature of a cooling medium of a falling film crystallization system, wherein the temperature of a primary crystallization is quickly reduced to 30-22 ℃, and the temperature of a primary crystallization is slowly reduced to 22-0 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s4: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, wherein the temperature is quickly increased to 0-18 ℃ by primary sweating, and is slowly increased to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s5: and adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, carrying out primary melting, controlling the melting time to be 30min, discharging the primary product after the melting is finished, weighing and sampling.
S6: adjusting the temperature of a cooling medium of the falling film crystallization system, rapidly cooling the secondary crystallization to 30-22 ℃, and slowly cooling to 22-5 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s7: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, rapidly heating to 5-18 ℃ by secondary sweating, and slowly heating to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s8: and adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, carrying out secondary melting, controlling the melting time to be 30min, discharging the secondary product after the melting is finished, weighing and sampling.
S9: and primary recovery is carried out on the primary product, and the primary recovery operation step is carried out according to the primary melting crystallization operation step.
Through detection, the purity of the FEC tertiary rectification crude product is 98%, the purity of the primary product is 99%, the purity of the secondary product is 99.9%, and the purity of the primary recovery product is 98%.
The energy consumption of the step (3) is 2.5t of steam per ton of product.
Example 3
The FEC production system in this embodiment is provided with a secondary rectification column.
The FEC production system of this embodiment is adopted to purify the liquid obtained in step 3 of example 1 to obtain a high-purity fluoroethylene carbonate product, and the purification process is specifically as follows:
(1) and removing ethylene carbonate: the temperature is 110-130 ℃, and the flow rate is 380-450 Kg/m 3 The pressure is 1 to 2 kPa.
(2) FEC second-stage rectification: the temperature is 50-60 ℃ during rectification, and the flow is 40-70 Kg/m 3 The pressure is 5-6 kPa.
(3) And 3+1 falling film crystallization, namely three-time melt crystallization and primary recovery, and comprises the following specific operation steps:
s1: pouring 8L of FEC primary-rectification crude product into a raw material tank, starting a falling film crystallization system, and controlling the temperature of a cooling and heating medium at 23-30 ℃ through cooling and heating medium preheating equipment of a circulating heat preservation system;
s2: starting a crystallization circulating pump, and controlling the flow rate to be 0.2-0.6 m 3 The pressure is 0.02-0.07 MPa, and the motor frequency is 13-18 Hz;
s3: adjusting the temperature of a cooling medium of a falling film crystallization system, wherein the temperature of a primary crystallization is quickly reduced to 30-22 ℃, and the temperature of a primary crystallization is slowly reduced to 22-0 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s4: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, wherein the temperature is quickly increased to 0-18 ℃ by primary sweating, and is slowly increased to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s5: and adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, carrying out primary melting, controlling the melting time to be 30min, discharging the primary product after the melting is finished, weighing and sampling.
S6: adjusting the temperature of a cooling medium of the falling film crystallization system, rapidly cooling the secondary crystallization to 30-22 ℃, and slowly cooling to 22-5 ℃; controlling the crystallization time to be 80-90 min, stopping a crystallization circulating pump, discharging the mother liquor, weighing and sampling;
s7: adjusting the temperature of a cooling medium of a falling film crystallization system by sweating, rapidly heating to 5-18 ℃ by secondary sweating, and slowly heating to 18-22.5 ℃; controlling the sweating time to be 40-50 min, and discharging, weighing and sampling the sweating liquid after the sweating is finished;
s8: and adjusting the temperature of a cooling medium of the falling film crystallization system to be 30-35 ℃, carrying out secondary melting, controlling the melting time to be 30min, discharging the secondary product after the melting is finished, weighing and sampling.
S9: three-stage melt crystallization: the technological parameter conditions of the steps are the same as those of the second-level melting crystallization, and a third-level product is obtained after the third-level melting is finished.
S10: and primary recovery is carried out on the primary product, and the primary recovery operation step is carried out according to the primary melting crystallization operation step.
Through detection, the purity of the FEC secondary rectification crude product is 95%, the purity of the primary product is 98%, the purity of the secondary product is 99.5%, the purity of the tertiary product is 99.99%, and the purity of the primary recovery product is 96%.
The energy consumption of the step (3) is 2.2t of steam per ton of product.
Comparative example 1
The FEC production system in this comparative example was equipped with a five-stage rectification column, and was not equipped with a falling film crystallization system.
And (3) purifying the liquid obtained in the step 3 of the example 1 to obtain a high-purity fluoroethylene carbonate product, wherein the purification process is as follows:
(1) and removing ethylene carbonate:the temperature is 110-130 ℃, and the flow rate is 380-450 Kg/m 3 The pressure is 1-2 kPa.
(2) FEC rectification: the temperature is 50-60 ℃ during rectification, and the flow rate is 40-70 Kg/m 3 The pressure is 5-6 kPa.
The purity of the FEC crude product (85%) is up to 92.5% by primary rectification, 95% by secondary rectification and 98% by tertiary rectification, the energy consumption is 1.5t steam per ton product, and if the purity of the FEC crude product is 99.5% by 5 times of rectification, the energy consumption is 3t steam per ton product.
Comparing examples 1-3 and comparative example 1, it can be seen that, in the FEC purification process, the falling film crystallization system is used to replace part of the rectifying tower, so that high-purity FEC product can be obtained and energy consumption can be effectively reduced. It is further concluded that energy consumption can be reduced to a greater extent if all the rectification columns are replaced by falling film crystallization systems.
The above embodiments are merely illustrative of the principles and effects of the present invention, and are not to be construed as limiting the invention. It will be apparent to those skilled in the art that modifications and variations can be made to the above-described embodiments without departing from the spirit and scope of the invention, and it is intended that all equivalent modifications and variations be covered by the appended claims without departing from the spirit and scope of the invention.
Claims (10)
1. The utility model provides a fluoro ethylene carbonate production system, its characterized in that, includes one-level reaction unit, second grade reaction unit and purification unit, one-level reaction unit includes multistage photolysis reaction tower and deacidification tower, the photolysis reaction tower carries out the place that the chlorination produced a chlorine ethylene carbonate for chloro reagent and ethylene carbonate, the top of photolysis reaction tower is equipped with the gas vent, and the gas vent and the back one-level photolysis reaction tower of preceding one-level photolysis reaction tower are linked together, deacidification tower with the photolysis reaction tower links to each other for detach unnecessary Cl among the chloro reaction product 2 And HCl gas; the second-stage reaction unit comprises a first reaction kettle and a centrifugal machine, the first reaction kettle is connected with the deacidification tower and is monochloro carbonic acidThe method comprises the following steps of (1) carrying out a fluoro reaction on vinyl ester and a fluorinating reagent to generate fluoroethylene carbonate, wherein the centrifuge is used for carrying out solid-liquid separation on a fluoro reaction product; the purification unit comprises a desolventizing tower and a falling film crystallization system, the desolventizing tower is connected with a liquid outlet of the centrifugal machine and used for removing the solvent in the liquid separated by the centrifugal machine, and the falling film crystallization system is used for purifying fluoroethylene carbonate.
2. The fluoroethylene carbonate production system according to claim 1, wherein: the falling film crystallization system comprises a falling film crystallizer, a circulation heat preservation system cooling and heating medium preheating device and a crystallization circulating pump, the falling film crystallizer is a purification place of fluoroethylene carbonate, the circulation heat preservation system cooling and heating medium preheating device is used for controlling and adjusting the temperature of the cooling and heating medium, and the crystallization circulating pump is used for circularly conveying crystallization mother liquor.
3. The fluoroethylene carbonate production system according to claim 2, wherein: the purification unit also comprises a multistage rectifying tower which is arranged between the desolventizing tower and the falling film crystallization system.
4. The fluoroethylene carbonate production system of claim 3, wherein: and the discharge hole of the falling film crystallizer is connected with the inlet of the rectifying tower.
5. The fluoroethylene carbonate production system of claim 1, wherein: the multistage photolysis reaction tower is a second-stage photolysis reaction tower.
6. The fluoroethylene carbonate production system of claim 1, wherein: the production system further comprises a first byproduct recovery unit, the first byproduct recovery unit comprises a water absorption tower and an alkali absorption tower, the top of the photolysis reaction tower is provided with an exhaust port, the water absorption tower is communicated with the exhaust port of the last stage of photolysis reaction tower, and the water absorption tower is further provided with a process water inlet; the alkali absorption tower is connected with the water absorption tower.
7. The fluoroethylene carbonate production system of claim 6, wherein: the first byproduct recovery unit further comprises a hydrochloric acid product tank, and the hydrochloric acid product tank is connected with the water absorption tower.
8. The fluoroethylene carbonate production system of claim 6, wherein: the first byproduct recovery unit further comprises a sodium hypochlorite product tank, and the sodium hypochlorite product tank is connected with the alkali absorption tower.
9. The fluoroethylene carbonate production system according to claim 1, wherein: the production system also comprises a second byproduct recovery unit, wherein the second byproduct recovery unit comprises a second reaction kettle, a first filter, a third reaction kettle, a second filter and a crystallization tower which are sequentially connected in series; the second reaction kettle is connected with a solid outlet of the centrifuge and is provided with a water inlet; the first filter is provided with activated carbon and can filter the activated carbon, or an organic matter filter bag or a filter membrane is arranged in the first filter; the third reaction kettle is provided with a calcium chloride feed inlet, the second filter is used for solid-liquid separation, and the crystallization tower is used for distilling and crystallizing the filtrate separated by the second filter.
10. The fluoroethylene carbonate production system of claim 9, wherein: the crystallization tower is provided with a water outlet, and the water outlet is connected with the water inlet of the second reaction kettle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114736185A (en) * | 2022-04-21 | 2022-07-12 | 上海东庚化工技术有限公司 | Energy-saving production process and system for ultrapure fluoroethylene carbonate |
| WO2023201999A1 (en) * | 2022-04-21 | 2023-10-26 | 上海东庚化工技术有限公司 | Production method and system for electrolyte additive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736185A (en) * | 2022-04-21 | 2022-07-12 | 上海东庚化工技术有限公司 | Energy-saving production process and system for ultrapure fluoroethylene carbonate |
| WO2023201999A1 (en) * | 2022-04-21 | 2023-10-26 | 上海东庚化工技术有限公司 | Production method and system for electrolyte additive |
| CN114736185B (en) * | 2022-04-21 | 2024-01-02 | 上海东庚化工技术有限公司 | Energy-saving production process and system for ultra-pure fluoroethylene carbonate |
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