CN213977486U - Co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene - Google Patents
Co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene Download PDFInfo
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- CN213977486U CN213977486U CN202022928677.5U CN202022928677U CN213977486U CN 213977486 U CN213977486 U CN 213977486U CN 202022928677 U CN202022928677 U CN 202022928677U CN 213977486 U CN213977486 U CN 213977486U
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Abstract
The utility model relates to a co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene, which comprises a reaction system, a rectification pre-separation system and an azeotrope-like extraction separation system; the raw material premixer adopts a falling film evaporation premixer to promote the rapid and sufficient vaporization of the liquid material 1,1,1, 3-tetrachloropropane and enhance the mixing effect of various gas-phase materials. The rectification pre-separation system adopts a three-tower continuous rectification mode to realize the high-efficiency separation of reaction by-product hydrogen chloride, high-boiling-point substances and excessive hydrogen fluoride. The azeotrope-like extraction separation system realizes the liquid-liquid two-phase extraction separation of azeotrope-like substances. The utility model discloses a production device of specific structure and relation of connection carries out the coproduction of 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene, has that reaction condition is mild, and reaction rate is high, and atomic economy is good, and product quality is stable, advantages such as product proportion is adjustable to can realize full flow automatic control, save the manual work.
Description
Technical Field
The utility model relates to a preparation facilities of fluorine-containing alkene, fluorine-containing chloro alkene especially relates to a coproduction device of 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene.
Background
3,3, 3-trifluoropropene is a basic raw material for synthesizing high value-added organic compounds such as 2-bromo-3, 3, 3-trifluoropropene (BTP), fluorosilicone rubber and the like. The 2-bromine-3, 3, 3-trifluoropropene is degradable bromohydrocarbon, is a novel clean efficient fire extinguishing agent, has ozone consumption potential (0.0028) and global warming potential (0.005) far lower than Halon series fire extinguishing agents (7.1 and 1890), is easy to degrade in the environment, has the advantages of rapid fire extinguishing, cleanness, high efficiency, non-conductivity and the like when being used as the fire extinguishing agent, and is a new substitute of the traditional Halon fire extinguishing agent. The fluorosilicone rubber not only has the performance of resisting high and low temperatures (-55-205 ℃) of the silicon rubber, but also has the characteristics of fuel oil resistance, chemical corrosion resistance and the like of the fluororubber, and is one of the synthetic rubbers with the best comprehensive performance in the world at present. The composite material is widely applied to the fields of aviation, aerospace, automobiles, medicine and the like.
2-chloro-3, 3, 3-trifluoropropene is an important precursor compound for the synthesis of the refrigerant HFO-1234 yf. Ozone depleting chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs) are being phased out according to the montreal protocol. In addition to ozone depletion issues, global warming is another important environmental issue. HFC-134a which is widely applied to automobile air conditioners, household electrical appliances and industrial and commercial refrigeration equipment at present and applied to the industries of foaming, fire extinguishing, aerosol, cleaning and the like has high global warming potential (GWP 1300) and long atmospheric service life, and a large amount of use can cause global warming, and the countdown phase is also entered. Therefore, the research and popularization of compounds that can simultaneously meet low ozone depletion standards and have low global warming potential has been the focus of the fluorocarbon industry. Among them, HFO-1234yf has been identified as a potential refrigerant, and HFO-1234yf can be used as a polymerization monomer and a comonomer of a rubber material with high thermal stability and high elasticity in addition to being used as a refrigerant, and has a large market capacity. With the wide popularization of HFC-1234yf, the 2-chloro-3, 3, 3-trifluoropropene used as a raw material is bound to generate great economic value and social value.
Currently, among the known production methods of 3,3, 3-trifluoropropene, the production using hydrofluorination is the most common method, for example, U.S. Pat. No. 4, 4465786A discloses a method for producing 3,3, 3-trifluoropropene by fluorinating 1,1,1, 3-tetrachloropropane, and a method for prolonging the life of the catalyst by adding a small amount of hexachloroethane and chlorine gas to the raw material, but the addition of hexachloroethane increases the difficulty of material purification. U.S. Pat. No. 3,9096489 also uses 1,1,1, 3-tetrachloropropane as raw material and hydrogen fluoride as fluorinating agent, and prepares 3,3, 3-trifluoropropene by catalytic fluorination in the presence of zinc/chromium oxide catalyst, and the preparation process of the catalyst in the method is difficult, requires high-temperature calcination above 500 ℃, and has high requirements on equipment. U.S. Pat. No. 4,08 describes a process for preparing 3,3, 3-trifluoropropene from one or more of 1,1,1, 3-tetrachloropropane, 1,1, 3-trichloropropene and 3,3, 3-trichloropropene by fluorination using hydrogen fluoride as a fluorinating agent under catalysis of a nitrogen-based catalyst to obtain 3,3, 3-trifluoropropene, which catalyst has the problems of difficult separation from the product, difficult regeneration and difficult industrial production. The preparation of 3,3, 3-trifluoropropene disclosed in US patent 10689316 employs a two-step process, the first step of which is a catalytic fluorination starting from 1,1,1, 3-tetrachloropropane, using HF as fluorinating agent, at a temperature of 20 ℃ to 100 ℃ to produce a liquid phase reaction product comprising 1-chloro-3, 3, 3-trifluoropropane. The second step is the dehydrochlorination of 1-chloro-3, 3, 3-trifluoropropane carried out at 250-350 deg.C under the action of catalyst to produce 3,3, 3-trifluoropropene. Although the difficulty of material separation is reduced by the two-step method, the number of operation steps is increased, the equipment investment is increased, and the industrial production is not facilitated.
Known methods for preparing 2-chloro-3, 3, 3-trifluoropropene include methods of fluorination with anhydrous hydrogen fluoride. For example, patent WO2008/054781 reports a process comprising fluorination of 1,1,2, 3-tetrachloropropene in the gas phase in the presence of a chromium-based catalyst. Since the catalytic activity tends to deteriorate as the reaction proceeds, if the reaction is continued for a longer time, the catalytic activity is decreased, resulting in a decrease in the selectivity of 2-chloro-3, 3, 3-trifluoropropene. U.S. Pat. No. 4,9902671 discloses at least one of 1,1,2, 3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,1,2, 3-pentachloropropaneA compound is used as raw material, under the existence of fluorinated chromium oxide catalyst and stabilizing agent such as benzenediol, the gas-phase fluorination reaction is carried out to prepare 2-chloro-3, 3, 3-trifluoropropene, the method introduces stabilizing agent to prolong the service life of catalyst to some extent, but the addition of stabilizing agent makes the separation of product become more complicated. Chinese patent CN109651077 discloses a method for preparing 2-chloro-3, 3, 3-trifluoropropene, comprising: reacting anhydrous hydrogen fluoride with at least one chlorine-containing compound selected from chloropropanes and chloropropenes represented by a specific formula in a gas phase in the presence of a chromium atom-containing fluorination catalyst while heating, the reaction being carried out in the presence of molecular chlorine and under conditions such that the water content in the reaction system is less than 300 ppm. Chinese patent CN10847339A takes 2, 3-dichloro-1, 1, 1-trifluoropropane, 1,1,1,2, 3-pentachloropropane, 2,3,3, 3-tetrachloropropene and/or 1,1,2, 3-tetrachloropropene as raw materials and uses a fluorination catalyst AlF3Or fluorinated alumina, with HF in the gas phase to form a 2-chloro-3, 3, 3-trifluoropropene-based product. The two Chinese patents only pay attention to the preparation of 2-chloro-3, 3, 3-trifluoropropene, and other products such as 3,3, 3-trifluoropropene in the products are not effectively utilized, so that the atom economy is poor, and the total yield is not high. US patent 20140147343 discloses a catalyst-free process for preparing 2-chloro-3, 3, 3-trifluoropropene by low-temperature fluorination using hydrogen fluoride. The method is not suitable for industrial production due to slow reaction rate, long reaction time, severe high-pressure reaction conditions and the like.
Although some reports on the preparation methods of 3,3, 3-trifluoropropene or 2-chloro-3, 3, 3-trifluoropropene have been published, no reports on the co-production of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene have been published yet, and more importantly, the methods have problems such as difficult separation, no regeneration of the catalyst, poor reaction atom economy, low yield, more reaction steps, complex reaction system, slow reaction rate, long reaction time, severe high-pressure reaction conditions, low product quality, difficulty in realizing industrial continuous large-scale production and the like. The device which has the advantages of mild reaction conditions, environment-friendly process, high reaction rate, good atom economy, stable product quality and adjustable product proportion and can be used for industrial continuous large-scale co-production of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene is urgently needed to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the problems that the prior preparation technology of 3,3, 3-trifluoropropene or 2-chloro-3, 3, 3-trifluoropropene is difficult to realize high atom utilization rate, the requirement on a preparation device is high, the production cost is high, and the like. The utility model provides a reaction condition is mild, technology environmental protection, reaction rate is high, atom economy is good, product quality is stable, the continuous large-scale coproduction 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene of industrialization of product proportion adjustable.
The technical scheme of the utility model as follows:
a co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene comprises a reaction system, a rectification pre-separation system and an azeotrope-like extraction separation system;
the reaction system comprises a premixer, a reactor and a reaction cooler, wherein a discharge port at the bottom of the premixer is communicated with a feed port at the side bottom of the reactor, and a discharge port at the top of the reactor is communicated with a feed port of the reaction cooler;
the rectifying pre-separating system comprises a multi-stage rectifying device, each stage of rectifying device comprises a rectifying tower and a rectifying tower condenser communicated with the top of the rectifying tower, and a discharge hole of the reaction cooler is communicated with a feed inlet of the first stage of rectifying tower;
the azeotrope-like extraction separation system comprises a static mixer, a phase separation condenser, a phase separator and a multi-stage rectification device, wherein each stage of rectification device comprises a rectification tower and a rectification tower condenser communicated with the top of the rectification tower; the discharge hole of the last-stage condenser in the rectification pre-separation system is communicated with the feed inlet of a static mixer, the discharge hole of the static mixer is communicated with the feed inlet of a phase separator through a phase separation condenser, and the discharge hole at the bottom of the phase separator is communicated with the feed inlet of a first-stage rectification tower of the azeotrope-like extraction separation system; the bottom of the last stage of rectifying tower of the azeotrope-like extraction and separation system is communicated with a 2-chloro-3, 3, 3-trifluoropropene crude product tank through a 2-chloro-3, 3, 3-trifluoropropene alkaline washing tower, and the discharge port of the condenser of the last stage of rectifying tower of the azeotrope-like extraction and separation system is communicated with the 3,3, 3-trifluoropropene crude product tank through the 3,3, 3-trifluoropropene alkaline washing tower.
According to the utility model discloses, it is preferred, reaction system in still include hydrogen fluoride metering tank, liquid chlorine metering tank, tetrachloropropane metering tank, hydrogen fluoride measuring pump, liquid chlorine measuring pump, tetrachloropropane measuring pump, hydrogen fluoride vaporizer, liquid chlorine vaporizer, tetrachloropropane preheater, hydrogen fluoride measuring tank through hydrogen fluoride measuring pump and hydrogen fluoride vaporizer bottom feed inlet intercommunication, hydrogen fluoride vaporizer top discharge gate and premixer top gas phase feed inlet intercommunication, liquid chlorine metering tank through liquid chlorine measuring pump and liquid chlorine vaporizer bottom feed inlet intercommunication, liquid chlorine vaporizer top discharge gate and premixer top gas phase feed inlet intercommunication, tetrachloropropane metering tank through tetrachloropropane measuring pump and tetrachloropropane preheater bottom feed inlet intercommunication, tetrachloropropane preheater top discharge gate and premixer side top liquid feed inlet intercommunication.
According to the utility model, preferably, the multistage rectifying device in the rectifying pre-separation system is a three-stage rectifying device, and comprises a rectifying tower I, a rectifying tower I condenser, a rectifying tower II condenser, a rectifying tower III and a rectifying tower III condenser, wherein a discharge port at the top of the reactor is communicated with a feed port in the middle of the rectifying tower I through a reaction cooler; a gas phase discharge port at the top of a rectification I tower is communicated with a feed inlet of a condenser of a rectification I tower, a discharge port at the bottom of the rectification I tower is externally connected with a valve pipeline, waste liquid is continuously output, a gas phase discharge port of the condenser of the rectification I tower is communicated with a gas phase feed port at the middle of a rectification II tower, a liquid phase discharge port of the condenser of the rectification I tower is communicated with a liquid phase return port at the top of the side of the rectification I tower, a liquid phase feed port at the middle of the rectification II tower is communicated with a pipeline between the liquid phase discharge port of the condenser of the rectification I tower and the liquid phase return port at the top of the side of the rectification I tower, a gas phase discharge port at the top of the rectification II tower is communicated with a feed inlet of the condenser of the rectification II tower, a liquid phase discharge port of the condenser of the rectification II tower is communicated with the liquid phase return port at the side of the top of the rectification II tower, a discharge port at the bottom of the rectification II tower is communicated with a feed port of the middle of the rectification III tower, a gas phase discharge port at the top of the rectification III tower is communicated with a liquid phase return port at the side of the condenser of the rectification III tower.
According to the utility model, preferably, a discharge port at the bottom of the rectification III tower in the rectification pre-separation system is communicated with a feed port of a hydrogen fluoride vaporizer through a hydrogen fluoride recovery pump;
preferably, a pipeline between the liquid phase discharge port of the condenser of the rectification column III and the liquid phase feed back port at the top of the rectification column III is communicated with the feed port of the static mixer.
According to the utility model discloses, it is preferred, class azeotrope extraction piece-rate system in still include the light phase jar, the light phase discharge gate in phase separator top and light phase jar feed inlet intercommunication, light phase jar discharge gate is through light phase pump of beating material and rectification III tower middle part feed inlet intercommunication.
According to the utility model, preferably, the multi-stage rectification device in the azeotrope-like extraction separation system is a two-stage rectification device, comprising a rectification IV tower and a rectification IV tower condenser, a discharge port at the bottom of the phase separator is communicated with a feed port in the middle of the rectification IV tower through a heavy phase material-pumping pump, a gas-phase discharge port at the top of the rectification IV tower is communicated with a feed port of the rectification IV tower condenser, a liquid-phase discharge port of the rectification IV tower condenser is communicated with a liquid-phase return port at the top of the rectification IV tower side, a pipeline between the liquid-phase discharge port of the rectification IV tower condenser and the liquid-phase return port at the top of the rectification IV tower is communicated with a feed port of a static mixer, a discharge port at the bottom of the rectification IV tower is communicated with a feed port in the middle of the rectification V tower, a gas-phase discharge port at the top of the rectification V tower is communicated with a feed port of the rectification V tower condenser, and a liquid-phase discharge port of the rectification V tower condenser is communicated with a liquid-phase return port at the top of the rectification V tower side;
preferably, a pipeline between a liquid phase discharge port of a condenser of the rectification V tower and a liquid phase return port at the top of the side of the rectification V tower is communicated with a feed inlet at the middle lower part of the 3,3, 3-trifluoropropene alkali wash tower, a discharge port at the top of the 3,3, 3-trifluoropropene alkali wash tower is communicated with a feed inlet at the top of a crude product tank of the 3,3, 3-trifluoropropene, and a valve pipeline is connected outside a discharge port at the bottom of the 3,3, 3-trifluoropropene alkali wash tower to continuously output waste alkali liquor.
According to the utility model, preferably, the bottom discharge port of the rectifying V tower is communicated with the side top feed inlet of the 2-chloro-3, 3, 3-trifluoropropene crude product tank through the tower bottom cooler, the top of the 2-chloro-3, 3, 3-trifluoropropene crude product tank is externally connected with the 2-chloro-3, 3, 3-trifluoropropene input valve pipeline, the bottom discharge port of the 2-chloro-3, 3, 3-trifluoropropene crude product tank is communicated with the middle upper feed inlet of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower through the 2-chloro-3, 3, 3-trifluoropropene crude product pump, the pipeline between the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower is communicated with the feed inlet of the static mixer through the valve, and a discharge hole at the top of the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower is externally connected with a valve pipeline, and waste alkali liquor is continuously output.
According to the utility model discloses, preferred, hydrogen fluoride vaporizer, liquid chlorine vaporizer, tetrachloropropane preheater all be equipped with and press from both sides the cover, let in steam heating in pressing from both sides the cover.
According to the utility model discloses, it is preferred, the premixer adopt falling film evaporation premixer, promote the quick abundant vaporization of liquid material, strengthen the mixed effect of each gaseous phase material, falling film evaporation premixer outside be equipped with and press from both sides the cover, let in the conduction oil heating in pressing from both sides the cover.
According to the utility model, preferably, the reactor is a fixed bed tubular reactor; preferably, the lower end enclosure of the fixed bed tubular reactor is provided with a jacket, and heat conducting oil is introduced into the jacket for heating, so that the feeding temperature is further increased to the reaction temperature.
According to the utility model discloses, rectification pre-separation system adopt three continuous rectification's of rectification I tower, rectification II tower, rectification III tower separation mode, realize the high-efficient separation of reaction by-product hydrogen chloride, high boiling thing and excessive hydrogen fluoride.
According to the utility model discloses, preferably, rectification II tower condenser adopt-15 ℃ to-35 ℃ frozen salt solution cooling, strengthen the cooling effect of other materials except hydrogen chloride, further preferably, frozen salt solution temperature is-30 ℃ to-35 ℃.
According to the utility model discloses, preferably, the phase separation condenser adopt-15 ℃ to-35 ℃ freezing salt solution cooling, further preferably, freezing salt solution temperature is-30 ℃ to-35 ℃.
According to the utility model discloses, preferably, the phase separator be equipped with the cover that presss from both sides, let in the cooling of frozen salt solution, frozen salt solution temperature be-15 ℃ to-35 ℃, further preferably, frozen salt solution temperature be-30 ℃ to-35 ℃.
According to the utility model discloses, preferably, 3,3, 3-trifluoropropene caustic wash tower well upper portion even have alkali lye input pipeline, 2-chlorine-3, 3, 3-trifluoropropene caustic wash tower well lower part even have alkali lye input pipeline.
According to the utility model discloses, utilize above-mentioned device coproduction 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene's method, including the step as follows:
(1) reaction process
a) Pumping hydrogen fluoride to a hydrogen fluoride vaporizer for preheating by a hydrogen fluoride metering tank, b) pumping liquid chlorine to the liquid chlorine vaporizer for preheating by a liquid chlorine metering tank, c) pumping 1,1,1, 3-tetrachloropropane to a tetrachloropropane preheater for preheating by a tetrachloropropane metering tank, and simultaneously and continuously introducing the preheated materials in the steps a), b) and c) into a falling film evaporation premixer; the hydrogen fluoride gas is excessively introduced, so that the vaporization partial pressure of the 1,1,1, 3-tetrachloropropane is effectively reduced, the 1,1,1, 3-tetrachloropropane is rapidly vaporized in the premixer, the premixer adopts a falling film evaporation premixer, and the continuous rapid vaporization and the full mixing of the mixed materials in the premixer are promoted; continuously introducing the vaporized and mixed materials into a fixed bed tubular reactor filled with a catalyst for reaction; after the reaction is finished, continuously discharging the mixed material from a discharge hole of the reactor, cooling the mixed material by a reaction cooler, and then feeding the cooled mixed material into a rectification pre-separation system;
the reaction process carried out in a fixed bed tubular reactor has the following main reaction equation:
chlorine gas is added to the reaction process to produce 2-chloro-3, 3, 3-trifluoropropene, and the possible reaction equation is as follows:
(2) pre-separation by rectification
Continuously feeding the cooled mixed material from a middle feeding hole of a rectifying tower I, rectifying at positive pressure, condensing the tower top material by circulating water at 5-10 ℃ in a rectifying tower I condenser, refluxing, extracting a mixture of hydrogen fluoride, chlorine, 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene, continuously introducing the mixture into a middle liquid phase feeding hole of a rectifying tower II, continuously introducing uncondensed components of the rectifying tower I condenser, which are mainly hydrogen chloride and a small amount of chlorine, into a middle gas phase feeding hole of the rectifying tower II, continuously discharging high-boiling-point substances at the bottom of the rectifying tower I, taking the high-boiling-point substances as waste liquid, and transferring and burning the waste liquid; continuous positive pressure rectification is carried out in a rectification II tower, materials at the top of the tower flow back after being condensed by frozen saline water at the temperature of minus 30 ℃ to minus 35 ℃ in a rectification II tower condenser, and hydrogen chloride and a small amount of chlorine are extracted and enter a hydrogen chloride absorption device; continuously discharging a mixture of hydrogen fluoride, 3,3, 3-trifluoropropene, 2-chloro-3, 3, 3-trifluoropropene and the like from the bottom of a rectification II tower, continuously inputting the mixture into a rectification III tower, rectifying at positive pressure, condensing the materials at the top of the tower by circulating water at 5-10 ℃ in a condenser of the rectification III tower, refluxing, extracting an azeotrope-like mixture, entering an azeotrope-like extraction separation system, continuously discharging hydrogen fluoride from the bottom of the rectification III tower, and pumping the hydrogen fluoride to a hydrogen fluoride vaporizer for use by a hydrogen fluoride recovery pump;
(3) azeotrope-like extraction separation
Introducing an azeotrope-like mixture extracted from the top of a rectifying tower III into a static mixer, pumping a certain amount of 2-chloro-3, 3, 3-trifluoropropene into the static mixer from a crude product tank of the 2-chloro-3, 3, 3-trifluoropropene, fully mixing the 2-chloro-3, 3, 3-trifluoropropene as an extractant with the azeotrope-like mixture, cooling by a phase separation condenser with frozen brine at-30 to-35 ℃, then entering a phase separator for standing and phase separation, introducing the frozen brine at-30 to-35 ℃ into a jacket of the phase separator for cooling and maintaining a certain positive pressure, discharging a light component phase from the upper part of the phase separator after the phase separation is completed, entering a light phase tank, pumping the light phase into a rectifying tower III by a light phase material-pumping pump for applying, wherein the recombination phase separation comprises the 3,3, 3-trifluoropropene and the 2-chloro-3, 3, 3-trifluoropropene and a small amount of hydrogen fluoride are discharged from the bottom of a phase separator, and are pumped to a rectification IV tower through a heavy phase material pump, the rectification IV tower is subjected to positive pressure rectification, the materials at the tower top are condensed by circulating water at the temperature of 5-10 ℃ in a rectification IV tower condenser and then flow back, the extracted azeotrope-like mixture is introduced into a static mixer for application, the mixture of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene discharged from the tower bottom of the rectification IV tower enters a rectification V tower, the mixture is subjected to positive pressure rectification, the materials at the tower top are condensed by the circulating water at the temperature of 5-10 ℃ in a rectification V tower condenser and then flow back, the extracted 3,3, 3-trifluoropropene crude product is continuously introduced into a 3, 3-trifluoropropene alkali washing tower for alkali washing, the 2-chloro-3, 3, 3-trifluoropropene crude product is continuously output from the tower bottom of the rectification V tower, the 2-chloro-3, 3-trifluoropropene crude product is cooled by circulating water at the tower bottom cooler and then enters 2-chloro-3, 3, 3-trifluoropropene crude product tank;
feeding a 3,3, 3-trifluoropropene crude product from a feed inlet at the middle lower part of a 3,3, 3-trifluoropropene alkali wash tower, feeding alkali liquor from a feed inlet at the middle upper part of the 3,3, 3-trifluoropropene alkali wash tower, wherein positive pressure exists in the alkali wash tower, 3,3, 3-trifluoropropene is fully alkali washed, discharging from a discharge outlet at the top of the 3,3, 3-trifluoropropene alkali wash tower, feeding the discharged material into a 3,3, 3-trifluoropropene crude product tank, further rectifying and purifying to obtain a 3,3, 3-trifluoropropene product, and continuously discharging waste alkali liquor from the bottom of the 3,3, 3-trifluoropropene alkali wash tower for transfer treatment; pumping part of the 2-chloro-3, 3, 3-trifluoropropene crude product in the 2-chloro-3, 3, 3-trifluoropropene crude product tank to a static mixer for mixing and extracting, and washing the other part with alkali; feeding 2-chloro-3, 3, 3-trifluoropropene from a feed inlet at the middle upper part of a 2-chloro-3, 3, 3-trifluoropropene alkali wash tower, feeding alkali liquor from a feed inlet at the middle lower part of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower, and feeding positive pressure in the alkali wash tower to fully alkali wash the 2-chloro-3, 3, 3-trifluoropropene from a discharge outlet at the bottom of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower, further rectifying and purifying to obtain a 2-chloro-3, 3, 3-trifluoropropene product, and continuously discharging waste alkali liquor from the top of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower for transfer treatment.
According to the utility model, the temperature in the falling film evaporation premixer in the step (1) is 240-300 ℃, and the working pressure is 1.0-1.3 MPa;
preferably, the molar ratio of the chlorine to the 1,1,1, 3-tetrachloropropane is (1-5): 100, the chlorine inhibits the decomposition of the raw material 1,1,1, 3-tetrachloropropane, inhibits the carbon deposition of the fluorination catalyst, prolongs the service life of the catalyst, and the output ratio of the product 2-chloro-3, 3, 3-trifluoropropene can be regulated and controlled by regulating the introduction amount of the chlorine;
preferably, the molar ratio of the hydrogen fluoride to the 1,1,1, 3-tetrachloropropane is (10-50): 1, the hydrogen fluoride is excessive, the partial pressure of vaporization of the 1,1,1, 3-tetrachloropropane is reduced, the 1,1,1, 3-tetrachloropropane is ensured to be rapidly vaporized, and the hydrogen fluoride and the chlorine are fully mixed;
preferably, the reaction temperature is 240-300 ℃, and the reaction pressure is 1.0-1.3 MPa.
According to the utility model, the working pressure of the rectifying tower I and the rectifying tower II in the step (2) is 1.0-1.2MPa, and the working pressure of the rectifying tower III is 0.8-1.0 MPa. The azeotrope-like composition comprises hydrogen fluoride, 3,3, 3-trifluoropropene, and 2-chloro-3, 3, 3-trifluoropropene.
According to the utility model, the working pressure of the phase separator in the step (3) is 0.6-0.8MPa, the working pressure of the rectifying IV tower is 0.6-1.0MPa, the working pressure of the rectifying V tower is 0.5-0.8MPa, the working pressure of the 3,3, 3-trifluoropropene alkali washing tower is 0.6-0.8MPa, and the working pressure of the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower is 0.4-0.6 MPa; the alkali liquor is 5-15 wt% potassium hydroxide aqueous solution.
The utility model is not elaborated, and is processed according to the conventional technology in the field.
The utility model has the advantages that:
1. the utility model discloses premixer adopts falling film evaporation premixer, promotes the quick abundant vaporization of liquid material 1,1,1, 3-tetrachloropropane, simultaneously, strengthens the mixed effect of each gaseous phase material.
2. The utility model discloses separation system is in advance rectified to rectification adopts the mode of three tower continuous rectification, realizes the high-efficient separation of reaction by-product hydrogen chloride, high boiling thing and excessive hydrogen fluoride.
3. When the utility model is used, the liquid 2-chlorine-3, 3, 3-trifluoropropene and the liquid 3,3, 3-trifluoropropene are mutually soluble, and the principle that the liquid hydrogen fluoride is insoluble is adopted, the 2-chlorine-3, 3, 3-trifluoropropene which is one of reaction products is taken as an extracting agent, 3,3, 3-trifluoropropene and the 2-chlorine-3, 3, 3-trifluoropropene are dissolved in an azeotrope-like mixture, and the liquid-liquid two-phase extraction separation of the azeotrope-like mixture is realized.
4. The utility model provides an when the apparatus for producing of specific structure and relation of connection produces, it is mild to have reaction condition, and reaction rate is high, and atom economy is good, and product quality is stable, advantages such as product proportion is adjustable to can realize full flow automatic control, save the manual work, be fit for 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene's industrial coproduction.
Drawings
FIG. 1 is a schematic view of a co-production apparatus for 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene of the present invention.
Wherein: 1. a hydrogen fluoride measuring tank, a liquid chlorine measuring tank and a tetrachloropropane measuring tank. 4. Hydrogen fluoride metering pump, 5, liquid chlorine metering pump, 6, tetrachloropropane metering pump, 7, hydrogen fluoride vaporizer, 8, liquid chlorine vaporizer, 9, tetrachloropropane preheater, 10, premixer, 11, reactor, 12, reaction cooler, 13, rectification column I, 14, rectification column I condenser, 15, rectification column II, 16, rectification column II condenser, 17, rectification column III, 18, rectification column III condenser, 19, hydrogen fluoride recovery pump, 20, static mixer, 21, phase separation condenser, 22, phase separator, 23, light phase tank, 24, light phase feed pump, 25, heavy phase feed pump, 26, rectification column IV, 27, rectification column IV condenser, 28, rectification column V, 29, rectification column V condenser, 30, column bottom cooler, 31, 2-chlorine-3, 3, 3-trifluoropropene crude tank, 32, 2-chlorine-3, a 3, 3-trifluoropropene crude product feeding pump, a 33, 3,3, 3-trifluoropropene alkali washing tower, a 34, 3,3, 3-trifluoropropene crude product tank and a 35, 2-chloro-3, 3, 3-trifluoropropene alkali washing tower.
Detailed Description
For further understanding of the present invention, preferred embodiments of the present invention will be described below with reference to examples, but it should be understood that these descriptions are only for the purpose of further illustrating the features and advantages of the present invention, and are not intended to limit the claims of the present invention.
Example 1:
a co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene comprises a reaction system, a rectification pre-separation system and an azeotrope-like extraction separation system;
the reaction system comprises a premixer 10, a reactor 11 and a reaction cooler 12, wherein a discharge hole at the bottom of the premixer 10 is communicated with a feed hole at the side bottom of the reactor 11, and a discharge hole at the top of the reactor 11 is communicated with a feed hole of the reaction cooler 12;
the rectifying pre-separating system comprises a multi-stage rectifying device, each stage of rectifying device comprises a rectifying tower and a rectifying tower condenser communicated with the top of the rectifying tower, and a discharge hole of the reaction cooler 12 is communicated with a feed inlet of the first stage of rectifying tower;
the azeotrope-like extraction separation system comprises a static mixer 20, a phase separation condenser 21, a phase separator 22 and a multi-stage rectification device, wherein each stage of rectification device comprises a rectification tower and a rectification tower condenser communicated with the top of the rectification tower; the discharge hole of the last-stage condenser in the rectification pre-separation system is communicated with the feed hole of a static mixer 20, the discharge hole of the static mixer 20 is communicated with the feed hole of a phase separator 22 through a phase separation condenser 21, and the discharge hole of the phase separator 22 is communicated with the feed hole of a first-stage rectification tower of an azeotrope-like extraction separation system; the bottom of the last stage of rectifying tower of the azeotrope-like extraction and separation system is communicated with a 2-chloro-3, 3, 3-trifluoropropene crude product tank 31 and a 2-chloro-3, 3, 3-trifluoropropene alkaline washing tower 35 through the crude product tank 31, and the discharge port of the last stage of rectifying tower condenser of the azeotrope-like extraction and separation system is communicated with a 3,3, 3-trifluoropropene crude product tank 34 through a 3,3, 3-trifluoropropene alkaline washing tower 33.
The multistage rectifying device in the rectifying pre-separation system in the embodiment is a three-stage rectifying device, and comprises a rectifying tower I13, a rectifying tower I condenser 14, a rectifying tower II 15, a rectifying tower II condenser 16, a rectifying tower III 17 and a rectifying tower III condenser 18, wherein a discharge port at the top of a reactor 11 is communicated with a feed port in the middle of the rectifying tower I13 through a reaction cooler 12; the top gas phase discharge hole of the rectifying tower I13 is communicated with the feed inlet of a rectifying tower I condenser 14, the bottom discharge hole of the rectifying tower I13 is externally connected with a valve pipeline for continuously outputting waste liquid, the gas phase discharge hole of the rectifying tower I condenser 14 is communicated with the middle gas phase feed inlet of a rectifying tower II 15, the liquid phase discharge hole of the rectifying tower I condenser 14 is communicated with the side top liquid phase feed back hole of the rectifying tower I13, the middle liquid phase feed inlet of the rectifying tower II 15 is communicated with a pipeline between the liquid phase discharge hole of the rectifying tower I condenser 14 and the side top liquid phase feed back hole of the rectifying tower I13, the top gas phase discharge hole of the rectifying tower II condenser 15 is communicated with the feed inlet of the rectifying tower II condenser 16, the liquid phase discharge hole of the rectifying tower II condenser 16 is communicated with the side top liquid phase feed back hole of the rectifying tower II 15, the bottom discharge hole of the rectifying tower II condenser 15 is communicated with the middle feed inlet of a rectifying tower III 17, the top gas phase discharge hole of the rectifying tower III condenser 18 is communicated with the rectifying tower III condenser 18, a liquid phase discharge port of a condenser 18 of the rectification III tower is communicated with a liquid phase feed back port at the top of the side of the rectification III tower 17.
Example 2:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 1, except that:
the reaction system also comprises a hydrogen fluoride metering tank 1, a liquid chlorine metering tank 2, a tetrachloropropane metering tank 3, a hydrogen fluoride metering pump 4, a liquid chlorine metering pump 5, a tetrachloropropane metering pump 6, a hydrogen fluoride vaporizer 7, a liquid chlorine vaporizer 8 and a tetrachloropropane preheater 9, the hydrogen fluoride metering tank 1 is communicated with a bottom feed inlet of a hydrogen fluoride vaporizer 7 through a hydrogen fluoride metering pump 4, a top discharge outlet of the hydrogen fluoride vaporizer 7 is communicated with a top gas phase feed inlet of a premixer 10, a liquid chlorine metering tank 2 is communicated with a bottom feed inlet of the liquid chlorine vaporizer 8 through a liquid chlorine metering pump 5, a top discharge outlet of the liquid chlorine vaporizer 8 is communicated with a top gas phase feed inlet of the premixer 10, a tetrachloropropane metering tank 3 is communicated with a bottom feed inlet of a tetrachloropropane preheater 9 through a tetrachloropropane metering pump 6, and a top discharge outlet of the tetrachloropropane preheater 9 is communicated with a side top liquid feed inlet of the premixer 10.
Example 3:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 2, except that:
a discharge hole at the bottom of a rectification III tower 17 in the rectification pre-separation system is communicated with a feed hole of a hydrogen fluoride vaporizer 7 through a hydrogen fluoride recovery pump 19; a pipeline between a liquid phase discharge port of a condenser 18 of the rectification column III and a liquid phase feed back port at the top of the rectification column III 17 is communicated with a feed port of a static mixer 20.
Example 4:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 2, except that:
the azeotrope-like extraction separation system also comprises a light phase tank 23, a light phase discharge port at the top of the phase separator 22 is communicated with a feed port of the light phase tank 23, and a discharge port of the light phase tank 23 is communicated with a feed port in the middle of the rectification III tower 17 through a light phase material pumping pump 24.
Example 5:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 2, except that:
the multi-stage rectifying device in the azeotrope-like extraction separation system is a two-stage rectifying device and comprises a rectifying IV tower 26 and a rectifying IV tower condenser 27, a discharge port at the bottom of the phase separator 22 is communicated with a feed port in the middle of the rectification IV tower 26 through a heavy phase material pumping pump 25, a gas phase discharge port at the top of the rectification IV tower 26 is communicated with a feed port of the rectification IV tower condenser 27, a liquid phase discharge port of the rectification IV tower condenser 27 is communicated with a liquid phase return port at the side top of the rectification IV tower 27, a pipeline between the liquid phase discharge port of the rectification IV tower condenser 27 and the liquid phase return port at the side top of the rectification IV tower 26 is communicated with a feed port of the static mixer 20, a discharge port at the bottom of the rectification IV tower 26 is communicated with a feed port in the middle of the rectification V tower 28, a gas phase discharge port at the top of the rectification V tower 28 is communicated with a feed port of the rectification V tower condenser 29, and a liquid phase discharge port of the rectification V tower condenser 29 is communicated with a liquid phase return port at the side top of the rectification V tower 28;
a pipeline between a liquid phase discharge port of a condenser 29 of the rectification V tower and a liquid phase return port at the top of the side of the rectification V tower 28 is communicated with a feed inlet at the middle lower part of a 3,3, 3-trifluoropropene alkaline washing tower 33, a discharge port at the top of the 3,3, 3-trifluoropropene alkaline washing tower 33 is communicated with a feed inlet at the top of a crude product tank 34 of the 3,3, 3-trifluoropropene alkaline washing tower 33, and a valve pipeline is externally connected with a discharge port at the bottom of the 3,3, 3-trifluoropropene alkaline washing tower 33 to continuously output waste alkali liquor.
Example 6:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 5, except that:
a discharge port at the bottom of the rectifying V-tower 28 is communicated with a feed port at the side top of a 2-chloro-3, 3, 3-trifluoropropene crude product tank 31 through a tower bottom cooler 30, a 2-chloro-3, 3, 3-trifluoropropene input valve pipeline is externally connected to the top of the 2-chloro-3, 3, 3-trifluoropropene crude product tank 31, a feed port at the middle upper part of the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower 35 is communicated with a discharge port at the bottom of the 2-chloro-3, 3, 3-trifluoropropene crude product tank 31 through a 2-chloro-3, 3, 3-trifluoropropene crude product pump 32, a pipeline between the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower 35 and a feed port of the static mixer 20 through a valve, a discharge hole at the top of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower 35 is externally connected with a valve pipeline to continuously output waste alkali liquor.
Example 7:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 6, except that:
the hydrogen fluoride vaporizer 7, the liquid chlorine vaporizer 8 and the tetrachloropropane preheater 9 are all provided with jackets, and steam is introduced into the jackets for heating; the premixer 10 adopts a falling film evaporation premixer 10 to promote the liquid material to be quickly and fully vaporized and strengthen the mixing effect of various gas phase materials, a jacket is arranged outside the falling film evaporation premixer 10, and heat conducting oil is introduced into the jacket for heating; the reactor 11 is a fixed bed tubular reactor 11, the condenser 16 of the rectifying II tower is cooled by freezing saline water at a temperature of between 15 ℃ below zero and 30 ℃ below zero, the cooling effect of other materials except hydrogen chloride is enhanced, the jacket of the phase separation condenser 21 is cooled by freezing saline water at a temperature of between 15 ℃ below zero and 35 ℃ below zero, the phase separator 22 is provided with a jacket, the freezing saline water is introduced for cooling, and the temperature of the freezing saline water is between 15 ℃ below zero and 35 ℃ below zero.
Example 8:
a co-production plant of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene as described in example 7, except that:
the lower end socket of the fixed bed tubular reactor 11 is provided with a jacket, heat conducting oil is introduced into the jacket for heating, the feeding temperature is further increased to the reaction temperature, the condenser 16 of the rectification II tower is cooled by frozen brine at-30 ℃ to-35 ℃, the cooling effect of other materials except hydrogen chloride is further enhanced, the material loss is reduced, the yield is improved, the jacket of the phase separation condenser 21 is cooled by the frozen brine at-30 ℃ to-35 ℃, the jacket of the phase separator 20 is cooled by the frozen brine at-30 ℃ to-35 ℃, the middle upper part of the 3,3, 3-trifluoropropene alkali washing tower 33 is connected with an alkali liquor input pipeline, and the middle lower part of the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower 35 is connected with an alkali liquor input pipeline.
When 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene are co-produced by using the production apparatus described in examples 1 to 8, the fluorination catalyst used in the reaction process is a chromium-based fluorination catalyst, and the method comprises the following steps:
(1) reaction process
a) Pumping hydrogen fluoride to a hydrogen fluoride vaporizer 7 by a hydrogen fluoride metering tank 1 for preheating, b) pumping liquid chlorine to a liquid chlorine vaporizer 8 by a liquid chlorine metering tank 2 for preheating, c) pumping 1,1,1, 3-tetrachloropropane to a tetrachloropropane preheater 9 by a tetrachloropropane metering tank 3 for preheating, simultaneously and continuously introducing the materials preheated in the steps a), b) and c) into a falling film evaporation premixer 10, wherein the temperature in the falling film evaporation premixer 10 is 240-300 ℃, the working pressure is 1.0-1.3MPa, wherein the mol ratio of chlorine to 1,1,1, 3-tetrachloropropane is (1-5): 100, chlorine inhibits the decomposition of the raw material 1,1,1, 3-tetrachloropropane, inhibits the carbon deposition of the fluorination catalyst, prolongs the service life of the catalyst, and adjusts the chlorine input, the output proportion of the product 2-chloro-3, 3, 3-trifluoropropene can be regulated and controlled; the molar ratio of hydrogen fluoride to 1,1,1, 3-tetrachloropropane is (10-50): 1, hydrogen fluoride gas is excessively introduced, the partial pressure of vaporization of 1,1,1, 3-tetrachloropropane is effectively reduced, 1,1, 3-tetrachloropropane is rapidly vaporized in the premixer, the premixer adopts the falling film evaporation premixer 10, and continuous rapid vaporization and full mixing in the mixed material premixer are realized. The vaporized and mixed materials are continuously introduced into a fixed bed tubular reactor 11 filled with a catalyst for reaction, the reaction temperature is 240-300 ℃, the reaction pressure is 1.0-1.3MPa, chlorine is added in the reaction process to generate 2-chloro-3, 3, 3-trifluoropropene, and after the reaction is finished, the mixed materials are continuously discharged from a discharge port of the fixed bed tubular reactor 11, cooled by a reaction cooler 12 and then enter a rectification pre-separation system.
(2) Pre-separation by rectification
And continuously feeding the cooled mixed material from a middle feeding hole of a rectifying tower I13, rectifying under positive pressure at the pressure of 1.0-1.2MPa, condensing the tower top material through circulating water at 145-10 ℃ in a rectifying tower I condenser, refluxing, extracting hydrogen fluoride, chlorine, 3,3, 3-trifluoropropene and a 2-chloro-3, 3, 3-trifluoropropene mixture, continuously introducing the hydrogen fluoride, chlorine, the 3, 3-trifluoropropene and the 2-chloro-3, 3, 3-trifluoropropene mixture into a middle liquid phase feeding hole of a rectifying tower II 15, continuously introducing uncondensed components of a rectifying tower I condenser 14, mainly hydrogen chloride and a small amount of chlorine into a middle gas phase feeding hole of the rectifying tower II 15, continuously discharging high-boiling substances at the bottom of the rectifying tower I13, taking the high-boiling substances as waste liquid, and performing transfer incineration treatment. And (3) continuously carrying out positive pressure rectification on the rectification II tower 15 under the pressure of 1.0-1.2MPa, condensing the materials at the top of the tower by using frozen saline water at the temperature of 16-30-35 ℃ in a rectification II tower condenser, refluxing, and extracting hydrogen chloride and a small amount of chlorine to enter a hydrogen chloride absorption device. And continuously discharging the mixture of hydrogen fluoride, 3,3, 3-trifluoropropene, 2-chloro-3, 3, 3-trifluoropropene and the like from the bottom of a rectification II tower 15, continuously inputting the mixture into a rectification III tower 17, rectifying under positive pressure at the pressure of 0.8-1.0MPa, condensing the tower top material by circulating water at 185-10 ℃ in a rectification III tower condenser, refluxing, collecting azeotrope-like mixture hydrogen fluoride, 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene, and feeding the mixture into an azeotrope-like extraction separation system, continuously discharging the hydrogen fluoride from the bottom of the rectification III tower 17, and pumping the hydrogen fluoride back to a hydrogen fluoride vaporizer 7 for use by a hydrogen fluoride recovery pump 19.
(3) Azeotrope-like extraction separation
Introducing an azeotrope-like mixture extracted from the tower top of the rectifying tower III 17 into a static mixer 20, pumping a certain amount of 2-chloro-3, 3, 3-trifluoropropene from a crude 2-chloro-3, 3, 3-trifluoropropene tank 31 into the static mixer 20, 2-chloro-3, 3, 3-trifluoropropene as an extractant to be fully mixed with the azeotrope-like mixture, cooling by a frozen brine at the temperature of between 21 and 30 ℃ below zero and 35 ℃ below zero in a phase separation condenser, allowing the mixture to enter a phase separator 22 for standing and phase separation, allowing the phase separator 22 to jacket to introduce the frozen brine at the temperature of between 30 ℃ below zero and 35 ℃ below zero to cool and maintain the pressure at 0.6 to 0.8MPa, discharging a light component phase from the upper part of the phase separator 22 after phase separation, allowing the light component phase to enter a light phase tank 23, pumping the light phase to the rectifying tower III 17 by a light phase pumping pump 24, and performing recombination phase separation including 3,3, 3-trifluoropropene, 2-chloro-3, 3, 3-trifluoropropene and a small amount of hydrogen fluoride are discharged from the bottom of a phase separator 22, pumped to a rectification IV tower 26 by a heavy phase material pump 25, rectified at positive pressure with the pressure of 0.6-1.0MPa, materials at the tower top are condensed by circulating water at 275-10 ℃ in a rectification IV tower condenser and then refluxed, an extracted azeotrope-like mixture is led into a static mixer 20 for use, a 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene mixture discharged from the tower bottom of the rectification IV tower 26 is led into a rectification V tower 28, rectified at positive pressure with the pressure of 0.5-0.8MP, materials at the tower top are condensed by circulating water at 295-10 ℃ in a rectification V tower condenser and then refluxed, a 3, 3-trifluoropropene crude product is continuously led into a 3,3,3, 3-trifluoropropene alkaline washing tower 33 for alkaline washing, and 2-chloro-3 is continuously output from the rectification V tower 28, and cooling the 3, 3-trifluoropropene crude product by circulating water at 305-10 ℃ through a tower bottom cooler, and then feeding the cooled crude product into a 2-chloro-3, 3, 3-trifluoropropene crude product tank 31.
Feeding a 3,3, 3-trifluoropropene crude product from a feed inlet at the middle lower part of a 3,3, 3-trifluoropropene alkali washing tower 33, feeding a 5 wt% -15 wt% potassium hydroxide aqueous solution from a feed inlet at the middle upper part of the 3,3, 3-trifluoropropene alkali washing tower 33, fully alkali washing the 3,3, 3-trifluoropropene alkali washing tower 33 at the working pressure of 0.6-0.8MPa, discharging the 3,3, 3-trifluoropropene from a discharge outlet at the top of the 3,3, 3-trifluoropropene alkali washing tower 33, feeding the discharged material into a 3,3, 3-trifluoropropene crude product tank 34, further rectifying and purifying to obtain a 3,3, 3-trifluoropropene product, and continuously discharging waste alkali liquor from the bottom of the 3,3, 3-trifluoropropene alkali washing tower 33 for transfer treatment. One part of the 2-chloro-3, 3, 3-trifluoropropene crude product in the 2-chloro-3, 3, 3-trifluoropropene crude product tank 31 is pumped to a static mixer 20 for mixing and extraction, and the other part is subjected to alkali washing treatment. Feeding 2-chloro-3, 3, 3-trifluoropropene from a feed inlet at the middle upper part of a 2-chloro-3, 3, 3-trifluoropropene alkali wash tower 35, feeding 5 wt% -15 wt% of potassium hydroxide aqueous solution from a feed inlet at the middle lower part of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower 35, discharging 2-chloro-3, 3, 3-trifluoropropene from a discharge outlet at the bottom of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower 35 after fully alkali washing at the working pressure of 0.4-0.6MPa, further rectifying and purifying to obtain 2-chloro-3, 3, 3-trifluoropropene products, continuously discharging waste alkali liquor from the top of the 2-chloro-3, 3, 3-trifluoropropene alkali wash tower 35, and (5) transferring.
Comparative example 1
As described in example 1, except that: the reaction premixer 10 adopts a traditional mixer, the reactor 11 adopts a traditional stirring reaction kettle, and the batch reaction is carried out. The rectification pre-separation adopts a common batch type rectification tower for rectification separation. The method is characterized in that equipment such as a static mixer 20, a phase separation condenser 21, a phase separator 22, a light phase tank 23, a light phase material pumping pump 24, a heavy phase material pumping pump 25 and the like is not used, materials extracted from the top of a rectifying column III directly enter a rectifying column IV, and the liquid-liquid two-phase extraction separation of azeotrope-like substances is realized without adopting the means of 2-chloro-3, 3, 3-trifluoropropene extraction and phase separation.
Test examples
The production apparatuses of example 1 and comparative example 1 were used to co-produce 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene, and the respective yields and total yields of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene, respectively, were calculated, based on 1,1,1, 3-tetrachloropropane, and the results are shown in table 1.
TABLE 1
| Number/item | Yield of 3,3, 3-trifluoropropene% | Yield of 2-chloro-3, 3, 3-trifluoropropene% | The total yield of the product is% |
| Example 1 | 92.5 | 4.5 | 97 |
| Comparative example 1 | 87.5 | 0 | 87.5 |
As can be seen from Table 1, the utility model relates to a 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene's coproduction device has realized the coproduction of 3,3, 3-trifluoropropene and 2-chlorine-3, 3, 3-trifluoropropene, and 3,3, 3-trifluoropropene yield also obviously improves simultaneously, and the total yield is improved to 97% by 87.5%, and atom economy is good, when raising the benefit, has reduced the production of waste material, more does benefit to the environmental protection.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. It will be apparent to persons skilled in the relevant art that various changes in form and detail can be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene is characterized by comprising a reaction system, a rectification pre-separation system and an azeotrope-like extraction separation system;
the reaction system comprises a premixer, a reactor and a reaction cooler, wherein a discharge port at the bottom of the premixer is communicated with a feed port at the side bottom of the reactor, and a discharge port at the top of the reactor is communicated with a feed port of the reaction cooler;
the rectifying pre-separating system comprises a multi-stage rectifying device, each stage of rectifying device comprises a rectifying tower and a rectifying tower condenser communicated with the top of the rectifying tower, and a discharge hole of the reaction cooler is communicated with a feed inlet of the first stage of rectifying tower;
the azeotrope-like extraction separation system comprises a static mixer, a phase separation condenser, a phase separator and a multi-stage rectification device, wherein each stage of rectification device comprises a rectification tower and a rectification tower condenser communicated with the top of the rectification tower; the discharge hole of the last-stage condenser in the rectification pre-separation system is communicated with the feed inlet of a static mixer, the discharge hole of the static mixer is communicated with the feed inlet of a phase separator through a phase separation condenser, and the discharge hole at the bottom of the phase separator is communicated with the feed inlet of a first-stage rectification tower of the azeotrope-like extraction separation system; the bottom of the last stage of rectifying tower of the azeotrope-like extraction and separation system is communicated with a 2-chloro-3, 3, 3-trifluoropropene crude product tank through a 2-chloro-3, 3, 3-trifluoropropene alkaline washing tower, and the discharge port of the condenser of the last stage of rectifying tower of the azeotrope-like extraction and separation system is communicated with the 3,3, 3-trifluoropropene crude product tank through the 3,3, 3-trifluoropropene alkaline washing tower.
2. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 1, wherein the reaction system further comprises a hydrogen fluoride metering tank, a liquid chlorine metering tank, a tetrachloropropane metering tank, a hydrogen fluoride metering pump, a liquid chlorine metering pump, a tetrachloropropane metering pump, a hydrogen fluoride vaporizer, a liquid chlorine vaporizer, and a tetrachloropropane preheater, wherein the hydrogen fluoride metering tank is communicated with a bottom feed inlet of the hydrogen fluoride vaporizer through the hydrogen fluoride metering pump, a top discharge outlet of the hydrogen fluoride vaporizer is communicated with a top gas phase feed inlet of the premixer, the liquid chlorine metering tank is communicated with a bottom feed inlet of the liquid chlorine vaporizer through the liquid chlorine metering pump, a top discharge outlet of the liquid chlorine vaporizer is communicated with a top gas phase feed inlet of the premixer, and the tetrachloropropane metering tank is communicated with a bottom metering pump of the tetrachloropropane preheater through the tetrachloropropane metering pump, and a discharge hole at the top of the tetrachloropropane preheater is communicated with a liquid feed hole at the top of the side of the premixer.
3. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 1, wherein the multi-stage distillation apparatus in the distillation pre-separation system is a three-stage distillation apparatus comprising a distillation column I, a distillation column I condenser, a distillation column II condenser, a distillation column III and a distillation column III condenser, and the discharge port at the top of the reactor is communicated with the feed port at the middle part of the distillation column I through a reaction cooler; a gas phase discharge port at the top of a rectification I tower is communicated with a feed inlet of a condenser of a rectification I tower, a discharge port at the bottom of the rectification I tower is externally connected with a valve pipeline, waste liquid is continuously output, a gas phase discharge port of the condenser of the rectification I tower is communicated with a gas phase feed port at the middle of a rectification II tower, a liquid phase discharge port of the condenser of the rectification I tower is communicated with a liquid phase return port at the top of the side of the rectification I tower, a liquid phase feed port at the middle of the rectification II tower is communicated with a pipeline between the liquid phase discharge port of the condenser of the rectification I tower and the liquid phase return port at the top of the side of the rectification I tower, a gas phase discharge port at the top of the rectification II tower is communicated with a feed inlet of the condenser of the rectification II tower, a liquid phase discharge port of the condenser of the rectification II tower is communicated with the liquid phase return port at the side of the top of the rectification II tower, a discharge port at the bottom of the rectification II tower is communicated with a feed port of the middle of the rectification III tower, a gas phase discharge port at the top of the rectification III tower is communicated with a liquid phase return port at the side of the condenser of the rectification III tower.
4. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 3, wherein the rectification pre-separation system comprises a rectification column III with a bottom outlet connected to a feed inlet of a hydrogen fluoride vaporizer via a hydrogen fluoride recovery pump;
and a pipeline between the liquid phase discharge port of the condenser of the rectifying tower III and the liquid phase feed back port at the top of the rectifying tower III is communicated with the feed inlet of the static mixer.
5. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 1, wherein the azeotrope-like extraction separation system further comprises a light phase tank, a light phase discharge port at the top of the phase separator is communicated with a light phase tank feed port, and a light phase tank discharge port is communicated with a middle feed port of the rectification column III via a light phase material-pumping pump.
6. The apparatus for co-production of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 1, wherein the multi-stage distillation apparatus in the azeotrope-like extraction separation system is a two-stage distillation apparatus comprising a distillation IV column, a distillation IV column condenser, a distillation V column condenser, a bottom discharge port of the phase separator is communicated with a middle feed port of the distillation IV column via a heavy phase pump, a top gas phase discharge port of the distillation IV column is communicated with a feed port of the distillation IV column condenser, a liquid phase discharge port of the distillation IV column condenser is communicated with a side top liquid phase return port of the distillation IV column, a pipeline between the liquid phase discharge port of the distillation IV column condenser and the side top liquid phase return port of the distillation IV column is communicated with a feed port of the static mixer, and the bottom discharge port of the distillation IV column is communicated with a middle feed port of the distillation V column, and a gas phase discharge port at the top of the rectifying V-shaped tower is communicated with a feed port of a condenser of the rectifying V-shaped tower, and a liquid phase discharge port of the condenser of the rectifying V-shaped tower is communicated with a liquid phase feed back port at the top of the rectifying V-shaped tower.
7. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 6, wherein a pipeline between a liquid phase discharge port of a condenser of the rectification V-column and a top liquid phase feed back port of the rectification V-column is communicated with a feed port at the middle and lower part of the 3,3, 3-trifluoropropene caustic scrubber, and a top discharge port of the 3,3, 3-trifluoropropene caustic scrubber is communicated with a feed port at the top of the crude 3,3, 3-trifluoropropene tank.
8. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 6, wherein a bottom outlet of the rectifying V-column is communicated with a side top inlet of the crude 2-chloro-3, 3, 3-trifluoropropene tank via a bottom cooler, a top of the crude 2-chloro-3, 3, 3-trifluoropropene tank is externally connected with a 2-chloro-3, 3, 3-trifluoropropene inlet valve pipeline, a bottom outlet of the crude 2-chloro-3, 3, 3-trifluoropropene tank is communicated with a middle upper inlet of the 2-chloro-3, 3, 3-trifluoropropene caustic scrubber via a crude 2-chloro-3, 3, 3-trifluoropropene material pump, which is between 2-chloro-3, the pipeline between the 3, 3-trifluoropropene crude product feeding pump and the 2-chloro-3, 3, 3-trifluoropropene alkali washing tower is communicated with the feed inlet of the static mixer through a valve.
9. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 2, wherein the hydrogen fluoride vaporizer, the liquid chlorine vaporizer, and the tetrachloropropane preheater are each provided with a jacket.
10. The apparatus for co-producing 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene according to claim 2, wherein the premixer is a falling film evaporation premixer, the outside of which is jacketed.
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| CN202022928677.5U CN213977486U (en) | 2020-12-09 | 2020-12-09 | Co-production device of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene |
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