WO2022135562A1 - 一种偏氯乙烯的连续化制备系统及方法 - Google Patents

一种偏氯乙烯的连续化制备系统及方法 Download PDF

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WO2022135562A1
WO2022135562A1 PCT/CN2021/141197 CN2021141197W WO2022135562A1 WO 2022135562 A1 WO2022135562 A1 WO 2022135562A1 CN 2021141197 W CN2021141197 W CN 2021141197W WO 2022135562 A1 WO2022135562 A1 WO 2022135562A1
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reactor
vinylidene chloride
continuous preparation
reaction
supergravity
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French (fr)
Chinese (zh)
Inventor
张亮亮
周黎旸
初广文
林金元
童继红
陈建峰
张一栋
吴志刚
余云飞
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ZHEJIANG QUZHOU JUSU CHEMICAL INDUSTRY Co Ltd
Beijing University of Chemical Technology
Juhua Group Corp
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ZHEJIANG QUZHOU JUSU CHEMICAL INDUSTRY Co Ltd
Beijing University of Chemical Technology
Juhua Group Corp
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Priority to US18/258,616 priority Critical patent/US12134081B2/en
Priority to JP2023538078A priority patent/JP2024501820A/ja
Priority to EP21909557.7A priority patent/EP4268950A4/en
Publication of WO2022135562A1 publication Critical patent/WO2022135562A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1856—Stationary reactors having moving elements inside placed in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/28—Moving reactors, e.g. rotary drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00038—Processes in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow

Definitions

  • the invention relates to the field of preparation of vinylidene chloride, and more particularly, to a continuous preparation system and method of vinylidene chloride.
  • vinylidene chloride is the main monomer for the production of polyvinylidene chloride (PVDC) resin and PVDC latex, and an important intermediate for the production of chlorofluorocarbon substitutes. and other industries also have an important position and are widely used.
  • PVDC polyvinylidene chloride
  • Its polymers are used in fibers, modified resins, coatings, adhesives, fire retardant coatings, food and chemical packaging materials.
  • the 1,1,2-trichloroethane liquid-phase saponification method is mainly used in China, but the existing 1,1,2-trichloroethane saponification reaction process is backward, resulting in low equipment production capacity and high energy consumption.
  • the purity of VDC is low, and the by-product chloroacetylene is easily generated.
  • chloroacetylene is extremely unstable, easily decomposed, spontaneously combusted, and even explodes when the concentration accumulates, posing a certain threat to safety production. Therefore, it is necessary to improve the system for preparing vinylidene chloride by continuous reaction, so as to improve the production capacity of the equipment and ensure the safety of the production process.
  • saponification can be divided into sodium hydroxide method, calcium hydroxide method and ammonium hydroxide method according to the different alkalis used.
  • calcium hydroxide method is widely used because the cost is low, the generation amount of chloroacetylene is relatively low, and the reaction is relatively safe, so it is widely used, and its reaction equation is as follows:
  • the current main industrial production process is to react 1,1,2-trichloroethane and calcium hydroxide solution in a large stirred tank, and then rectify and separate light and heavy components through a multi-stage rectification tower to obtain refined vinylidene chloride Calcium chloride solution for products and by-products.
  • Chinese patent CN 200310122646.9 reported a method for preparing vinylidene chloride in series using multi-stage stirred tanks to achieve high conversion.
  • Chinese patent CN 201780050736.1 reports a reactor equipment, using a stirred tank equipped with multi-stage impellers to improve the reactivity of the reaction.
  • the above methods all have problems such as high content of by-products, low conversion rate, and high total organic carbon (TOC) value in CaCl 2 wastewater, and there is no good solution in the industry.
  • TOC total organic carbon
  • one aspect of the present invention provides a continuous preparation system of vinylidene chloride, comprising:
  • the first supergravity reactor its liquid inlet is communicated with the liquid inlet pipeline of trichloroethane and lye, and its gas inlet is communicated with the water vapor pipeline;
  • Reactor its inlet is communicated with the liquid outlet of the first supergravity reactor, the gas inlet is communicated with the gas outlet of the first supergravity reactor, and the reactor is connected to an external product through the first branch pipeline tank connection;
  • a second hypergravity reactor the liquid outlet of which is in communication with the liquid inlet of the reactor, and the gas inlet is in communication with the gas outlet of the reactor;
  • the condensation circulation pipeline forms a condensation circuit with the gas outlet and the gas inlet of the second supergravity reactor.
  • reaction kettle is communicated with the liquid inlet of the first supergravity reactor through a second branch pipeline, and the continuous preparation system further includes:
  • the second valve is located on the second branch pipeline.
  • it also includes:
  • a valve controller coupled with the first valve and/or the second valve, is used to control the opening and closing degrees of the corresponding valves.
  • it also includes:
  • Detector to detect the flow of trichloroethane and lye in the liquid inlet pipeline
  • the processor determines the opening and closing degree of the corresponding valve according to the flow rate.
  • the first hypergravity reactor and the second hypergravity reactor are rotating packed beds.
  • an oleophobic packing is provided in the rotating packed bed.
  • the oleophobic filler is formed with a plurality of penetrating micropores.
  • the micropores are of micro-nano scale.
  • the gas inlet of the first supergravity reactor is located on the side wall of the first supergravity reactor and is disposed toward the inside of the packing.
  • the present invention further provides a continuous preparation method of vinylidene chloride, the continuous preparation method comprising: preparing vinylidene chloride by using the above-mentioned continuous preparation system.
  • the invention provides a continuous preparation system and method of vinylidene chloride.
  • the invention couples two-stage hypergravity reactors, and adopts steam stripping to remove the product vinylidene chloride and water vapor from the reaction system in the form of azeotrope. Steamed out, the purity of the product obtained in this way is relatively high.
  • the water vapor is supplemented by an external water vapor source, and on the other hand, it can be reused through the reaction cycle to form a water vapor cycle, which can ensure the amount of water vapor without the need for A large amount of water vapor;
  • the azeotrope is combined with the multi-stage supergravity reactor, aiming at the characteristics of the azeotrope in the reaction system of the present invention, the gas phase mass transfer and liquid phase mass transfer efficiency of the azeotrope is greatly improved, and then The overall conversion rate of the reaction is higher, and at the same time, based on the combination of stripping and hypergravity, the trichloroethane and the lye are rapidly mixed and mass-transferred, and the product vinylidene chloride is quickly distilled from the reaction system in the form of an azeotrope (based on The rapid diffusion of water vapor), so that the reaction has been carried out in the direction of generating vinylidene chloride, and the conversion rate has been significantly improved.
  • FIG. 1 shows a schematic structural diagram of a continuous production system of vinylidene chloride in an embodiment of the present invention.
  • the inventors of the present invention have found that the current mainstream production process for preparing vinylidene chloride is as follows: trichloroethane and calcium hydroxide solution are reacted in a large stirred tank, and then the light and heavy components are rectified and separated through a multi-stage rectifying tower to obtain refined The resulting vinylidene chloride product and by-product calcium chloride solution, but there are many shortcomings, such as low product conversion rate, easy occurrence of multiple side reactions, etc., there is still no better solution in the industry, and researchers in the industry do not. Knowing the reasons for its insufficiency, research progress has been stagnant.
  • the reason for the above deficiency is that the gas-liquid mixing in the stirring tank is poor, resulting in insufficient contact between the oil and water phases, and the calcium hydroxide is easily adhered, and the pressure drop in the reactor is large, which cannot be timely.
  • the transfer of the product leads to low conversion rate, and it is easy to cause equipment blockage; and due to the poor mixing effect of oil and water two-phase, resulting in local excess of alkali, and the reaction time is long, and multiple side reactions are prone to occur.
  • 1,1,2-trichloroethane and calcium hydroxide suspension are completely immiscible, 1,1,2-trichloroethane is a typical organic, oil phase liquid, while calcium hydroxide is slightly soluble in water, It takes the form of an aqueous suspension in water.
  • the organic matter is agglomerated in the form of large oil droplets or even stratified directly, and part of the calcium hydroxide that is not dissolved in water can also be used as an adsorption nucleus in the reactor, and the oil droplets are in the calcium hydroxide micronucleus. Surface agglomeration and coating. Due to the poor mixing effect of organic matter and aqueous solution, the actual contact area of the two reactants is small, resulting in low reaction rate and long reaction time. According to research, the current mainstream process reaction time is as long as 10 hours.
  • the total organic carbon (TOC) value in CaCl2 wastewater is high. Due to the poor mixing and separation effect in the traditional stirred tank, the reaction of the reactant trichloroethane is incomplete, and the vinylidene chloride generated by the reaction cannot be extracted in time and the lye to generate chloroacetylene, which makes the TOC value in the CaCl2 wastewater on the high side, which increases the The cost of subsequent wastewater treatment. According to the survey, the TOC value in the CaCl2 wastewater from the current mainstream process is about 150mg/L.
  • the present invention provides a new continuous preparation system, as shown in Figure 1, which specifically includes:
  • the first supergravity reactor 8 its liquid inlet is communicated with the liquid inlet pipeline of trichloroethane 1 and lye 2, and its gas inlet is communicated with the water vapor pipeline;
  • Reactor 9 its inlet is communicated with the liquid outlet of the first supergravity reactor 8, the gas inlet is communicated with the gas outlet of the first supergravity reactor 8, and the reactor 9 is connected with the first branch pipe through the first branch pipeline.
  • An external product storage tank 15 is communicated;
  • the second hypergravity reactor 10 its liquid outlet communicates with the liquid inlet of the reactor 9, and the gas inlet communicates with the gas outlet of the reactor 9;
  • the condensation circulation pipeline forms a condensation circuit with the gas outlet and the gas inlet of the second supergravity reactor 10 (for example, a condenser 12 is included on the condensation circuit).
  • two-stage supergravity reactors are coupled, and the product vinylidene chloride and water vapor are steamed from the reaction system in the form of azeotrope by means of steam stripping.
  • it is supplemented by an external water vapor source, and on the other hand, it can be reused through the reaction cycle to form a water vapor cycle, which can ensure the amount of water vapor and does not require a large amount of water vapor; further, the use of azeotrope combined with multi-stage supergravity
  • the reactor according to the characteristics of the azeotrope in the reaction system of the present invention, greatly improves the gas phase mass transfer and liquid phase mass transfer efficiency of the azeotrope, thereby making the overall conversion rate of the reaction higher, and based on the combination of stripping and hypergravity , so that trichloroethane and lye are rapidly mixed and mass-transferred, and the product vinylidene chloride is quickly evaporated from the reaction system in the form of an a
  • the conversion rate is significantly improved.
  • the test device proves that the present invention can stabilize the purity of vinylidene chloride products above 98% (mass fraction), reduce the TOC value of chlorinated salt wastewater to below 100mg/L, reduce material consumption and follow-up The cost of saline wastewater treatment.
  • the present invention innovatively adopts the method of utilizing air stripping, and uses the water vapor required by the system itself to be reused as the air stripping gas, so that on the one hand, the equipment cost will not be increased, only the pipeline needs to be modified, and the other
  • the air stripping method is adopted to quickly discharge the product in the form of azeotrope, and then the product can be quickly transferred, so that the reaction is always carried out in the direction of producing vinylidene chloride, and the conversion rate is significantly improved.
  • the reactor is communicated with the liquid inlet of the first supergravity reactor through a second branch pipeline, and the present invention further includes:
  • the second valve is located on the second branch pipeline.
  • the flow rate returned to the first hypergravity reactor and the flow rate of the product storage tank can be adjusted, thereby controlling the reaction balance of the entire reaction system and improving the overall reaction conversion rate .
  • it also includes:
  • a valve controller coupled with the first valve and/or the second valve, is used to control the opening and closing degrees of the corresponding valves.
  • valve opening and closing degree can be automatically controlled by the valve controller, so that manual control is not required.
  • the present invention also includes:
  • Detector to detect the flow of trichloroethane and lye in the liquid inlet pipeline
  • the processor determines the opening and closing degree of the corresponding valve according to the flow rate.
  • the flow rate of the raw material inlet can be detected by a detector, and then the valve opening and closing degree can be adjusted according to the flow feedback, that is, the adjustment in this embodiment is controlled based on the overall flow rate, which is targeted and can be automatically and dynamically adjusted.
  • the condensation circulation pipeline may further include a plurality of condensers, which will not be described in detail in the present invention.
  • the hypergravity reactor can be selected specifically, and the first hypergravity reactor and the second hypergravity reactor are rotating packed beds.
  • the steam stripping emphasizes the dispersion and mixing of the gas phase, and uses the filler in the rotating packed bed to carry out mass transfer and mixing, which greatly enhances the overall dispersion effect and air stripping effect.
  • the stator and rotor are used for liquid reaction, and then Increase the collision area of the liquid and improve the efficiency of the liquid phase reaction.
  • the first hypergravity reactor is a rotating packed bed, and an oleophobic packing is arranged in the rotating packed bed.
  • hypergravity technology is a typical process intensification technology. It has been successfully applied to various industrial processes to enhance mass transfer, heat transfer and micro-mixing and has achieved excellent results. It is characterized by small equipment footprint, The residence time is short, the mass transfer efficiency is high, and the reaction is fast and efficient.
  • the invention combines the supergravity technology and the stripping technology, and applies them to the preparation process of vinylidene chloride.
  • the reaction system is fully turbulent, efficient mass transfer and heat exchange, the product vinylidene chloride and water vapor are evaporated from the reaction system in the form of azeotrope, and the water vapor is passed into the first supergravity reactor to quickly take away the reaction generated.
  • the vinylidene chloride can make the reaction proceed in the direction favorable for the production of vinylidene chloride, so that the occurrence of side reactions can be suppressed to a great extent. And because the residence time of the product in the system is greatly shortened, the self-aggregation problem of the product is effectively solved.
  • FIG. 1 The continuous preparation system of the present invention will be described in detail below by taking FIG. 1 as an example.
  • a process system for preparing vinylidene chloride by continuous reaction characterized in that it includes: a first supergravity reactor (8), a stirred tank (9), a second supergravity reactor Reactor (10), condenser (12), No. 1 storage tank (3), No. 2 storage tank (4), regulating tank (15), circulating pump (11), No. 1 pump (5), No. 2 pump (6); No. 1 storage tank (3) and No. 2 storage tank (4) are respectively connected to the liquid inlet of the first supergravity reactor (8) through No. 1 pump (5) and No.
  • the liquid outlet of the gravity reactor (8) is connected to the inlet of the stirred tank liquid (9); the liquid outlet of the stirred tank (9) is connected to the circulation pump inlet (11); the circulation pump outlet (11) is connected to the liquid of the first supergravity reactor (8) Inlet; a bypass is provided between the outlet of the circulating pump (11) and the liquid inlet of the first supergravity reactor (8), and the bypass is the outlet of the circulating pump connected to the liquid inlet of the regulating tank (15); the liquid outlet of the regulating tank (15)
  • the by-product outlet (16) is connected; the neutralizer inlet (14) is connected to the liquid inlet of the regulating tank (15); the water vapor inlet (7) is connected to the gas inlet of the first supergravity reactor (8); the gas of the first supergravity reactor is connected (8) the outlet is connected to the gas inlet of the stirred tank (9); the gas outlet of the stirred tank (9) is connected to the gas inlet of the second supergravity reactor (10); the gas outlet of the second supergravity reactor
  • the process method matched with the above-mentioned process system is specifically as follows: the reaction feed liquid is broken into tiny droplets and emulsion droplets in the first supergravity reactor, rapidly mixed in the reactor, and in the second supergravity reactor, The gasified crude product and the reflux condensate are fully contacted, and the heat and mass transfer are rapid, so that the light components and the heavy components are efficiently separated. More specifically, it mainly includes the following steps:
  • the raw material 1,1,2-trichloroethane and lye are continuously added into the first supergravity reactor according to a certain proportion, fully mixed, and react quickly; at the same time, water vapor is continuously fed into the first supergravity reactor, Exchange heat with the reactant liquid.
  • the product vinylidene chloride and part of unreacted trichloroethane in the feed liquid in the first supergravity reactor are carried out by steam from the top of the first supergravity reactor after being heated and gasified, and then removed from the stirred tank The bottom of the stirred tank is passed into the stirred tank; the remaining feed liquid in the first supergravity reactor flows out from the bottom of the reactor, and then flows into the stirred tank from the top of the stirred tank.
  • the above-mentioned liquid discharged from the bottom of the stirred tank (mainly the mixed solution of by-product chloride salt and trichloroethane and alkali that has not been fully reacted) is divided into two shares according to a certain proportion, and one is used as a circulating liquid, which is passed through a circulating pump. It is recycled back to the first supergravity reactor, and another solution of chloride salt as a by-product is neutralized by hydrochloric acid and produced.
  • the above-mentioned gas (mainly water vapor and vaporized vinylidene chloride and a small amount of entrained trichloroethane) discharged from the top of the stirred tank is passed into the second supergravity reactor, and in the second supergravity reactor and reflux
  • the condensate is fully contacted and mixed, and the heavy component is liquefied under the cooling of the reflux liquid of the second supergravity reactor, discharged from the bottom of the second supergravity reactor, and passed into the above-mentioned stirred tank as a circulating liquid; the light component is gasified by gasification.
  • the state is discharged from the top of the second hypergravity reactor.
  • the above-mentioned light component gas discharged from the top of the second supergravity reactor becomes the liquid of product vinylidene chloride after the condenser, then this liquid is divided into two shares with a certain proportion, and one is passed into the first as a circulating liquid In the two supergravity reactors, as the above-mentioned reflux condensate, one is extracted as a vinylidene chloride product.
  • the supergravity field level in the first supergravity reactor is 30-1500g, more preferably 50-300g.
  • the reaction temperature in the first supergravity reactor is 50-100°C.
  • the lye solution includes but is not limited to calcium hydroxide solution, sodium hydroxide solution, ammonia water or a mixture thereof; the molar ratio of 1,1,2-trichloroethane to lye solution is 1.1-2:1, more preferably It is 1.1 to 1.7:1.
  • the amount of water vapor continuously fed into the first supergravity reactor is 110-160Kg/(t VDC).
  • the vacuum degree of the control system is 60-100Kpa, more preferably 70-90Kpa.
  • the flow ratio of the circulating liquid and the produced liquid into which the liquid discharged from the bottom of the stirred tank is divided is 2 to 10:1, more preferably 4 to 8:1.
  • the light component gas discharged from the top of the second supergravity reactor passes through the condenser and becomes the product of vinylidene chloride.
  • the flow ratio of the circulating liquid and the product produced liquid is 3-4:1.
  • the first hypergravity reactor in the present invention can quickly mix and break into tiny droplets and emulsion droplets with two reaction solutions of oil phase and water phase on the one hand, and then fully contact, and when using lye as When the calcium hydroxide suspension is used, it can effectively prevent pipeline blockage; on the other hand, through the continuous shearing and crushing of the supergravity filler, the oil droplets covering the calcium hydroxide particles are destroyed, so that the calcium hydroxide as the raw material of the reactant is fully peeled off.
  • the second supergravity reactor in the present invention can effectively promote the contact and separation of gas and liquid, thereby obtaining a vinylidene chloride product with higher purity.
  • the first and second supergravity reactors are efficiently coupled, and can achieve good results in the process of continuous reaction to prepare vinylidene chloride.
  • the reaction efficiency is improved and the reaction time is shortened.
  • the system in the present invention integrates reaction, separation and purification, and can realize rapid and uniform mixing and reaction of 1,1,2-trichloroethane solution and calcium hydroxide solution in the first hypergravity reactor, and then enter the stirring tank for further After separation and purification, gas-liquid two-phase rapid contact and separation occurs in the secondary supergravity reactor to obtain a high-purity vinylidene chloride product. Therefore, after adopting the system and method of the present invention, the reaction rate can be greatly improved, and it is conservatively believed that the reaction time is shortened by more than three times compared with the traditional stirred tank, which is beneficial to the later production capacity improvement.
  • the first and second supergravity reactors in the present invention can achieve a significant increase in the reaction and separation rates, and the reaction time can be significantly shortened. Since the reaction rates of the above-mentioned side reactions are all relatively slow, the reaction time is shortened, which can effectively suppress the formation of by-products. At the same time, the distribution of the alkali concentration is relatively uniform, which can effectively avoid the partial chlorine in the product caused by the local high alkali concentration in the traditional stirred tank. The overreaction of ethylene to form chloroacetylene.
  • the water vapor is introduced into the first supergravity reactor to quickly take away the vinylidene chloride produced by the reaction, so that the reaction proceeds in the direction favorable for the production of vinylidene chloride, so that the occurrence of side reactions can be suppressed to a great extent.
  • the residence time of the product in the system is greatly shortened, the self-aggregation problem of the product is effectively solved.
  • the purity of vinylidene chloride is improved.
  • the system in the present invention integrates reaction, separation and purification.
  • the second hypergravity reactor in the present invention can realize full reverse contact separation and purification of gas-liquid two-phase, and the condensed liquid phase is partially returned to the secondary hypergravity reactor.
  • the liquid phase at the outlet of the secondary hypergravity reactor is recycled back to the primary hypergravity reactor for reaction, so the effect of purifying vinylidene chloride can be well achieved.
  • the invention can stabilize the purity of the vinylidene chloride product at more than 98% (mass fraction).
  • the system in the present invention integrates reaction, separation and purification. Compared with the traditional stirred tank reactor, the steam stripping process is carried out in the first supergravity reactor. The liquid is highly fragmented, the gas-liquid contact area is greatly increased, and the water vapor separation effect can be greatly improved, thereby reducing the steam consumption.
  • the water vapor After passing through the first supergravity reactor, the water vapor entrains the vaporized vinylidene chloride and a small amount of trichloroethane into the second supergravity reactor, and then contacts the refluxed condensate in countercurrent, and under the action of the filler, the liquid It is highly crushed, the gas-liquid contact area is greatly increased, the light components in the liquid are gasified, the heavy components in the gas are condensed, and then the gas and liquid are quickly separated to obtain high-purity vinylidene chloride products.
  • the thermal and kinetic energy of the steam is fully utilized.
  • the system in the present invention integrates reaction, separation and purification, and can reduce the total volume of the device by more than three times compared with the traditional single stirred tank or multi-stage serial stirred tank reactor. At the same time, due to the efficient separation effect of the present invention, the comprehensive energy consumption per unit product is about two times lower than that of the traditional stirred tank reactor.
  • the system in the present invention integrates reaction, separation and purification, and the first hypergravity reactor in the present invention can realize the full mixing reaction between the two liquid phases, so that the reaction of trichloroethane is completed; the second hypergravity reactor in the present invention
  • the reactor can realize the purification and purification of vinylidene chloride and the further reflux reaction of 1,1,2-trichloroethane. All of these significantly improve the conversion rate of 1,1,2-trichloroethane, and at the same time, the content of by-products is significantly reduced, so that the TOC value of chlorinated salt wastewater can be reduced to below 100mg/L, reducing material consumption and subsequent salt-containing wastewater treatment the cost of.
  • the present invention is exemplified below with specific scenarios.
  • the present invention uses a continuous reaction system for preparing vinylidene chloride, wherein the feed molar ratio ( ⁇ ) of 1,1,2-trichloroethane and calcium hydroxide solution is 1.4:1, the reaction temperature (T) is 80°C, and the first The super-gravity level (G 1 ) of the first super-gravity reactor is 200 g, the super-gravity level (G 2 ) of the second super-gravity reactor is 200 g, and the reaction vacuum degree (P) is 90 Kpa.
  • the flow ratio ( ⁇ ) of the circulating liquid and the produced liquid divided by the effluent at the bottom of the stirring tank is 5:1, and the flow ratio ( ⁇ ) of the reflux condensate and the produced product liquid divided by the liquid at the condenser outlet is 4:1, and the total test time (t) was 150 min, the measured conversion rate was 99.95%, the VDC selectivity was 99.1%, the VDC purity was 98.5%, the water vapor consumption (Q) was 130Kg/(t VDC), and the TOC value in the CaCl 2 wastewater was 98 mg/ L.
  • Embodiment 2 ⁇ 16 technological process and steps are the same as embodiment 1, and the process condition and operating condition of each embodiment and corresponding experimental result refer to table 1 for details, and the meanings of the letters listed in the header are the same as in embodiment 1.
  • examples 1 to 7 are within the scope of the process parameters claimed by the present invention. From the results of the examples, it can be concluded that the present invention can not only improve the reaction efficiency, shorten the reaction time, reduce the size of the device, but also inhibit the Side reactions occur, reduce the content of by-products, improve the purity of vinylidene chloride, reduce steam consumption, and reduce the TOC value of CaCl 2 wastewater.
  • the present invention also provides a continuous preparation method of vinylidene chloride, the continuous preparation method comprises: using the continuous preparation system as described above to prepare vinylidene chloride.
  • the invention provides a continuous preparation method of vinylidene chloride.
  • the invention couples two-stage hypergravity reactors, and adopts steam stripping to steam the product vinylidene chloride and water vapor from the reaction system in the form of azeotrope. , the purity of the product obtained in this way is relatively high.
  • the water vapor is supplemented by an external water vapor source, and on the other hand, it can be reused through the reaction cycle to form a water vapor cycle, which can ensure the amount of water vapor and does not require a large amount of water.
  • the azeotrope is combined with the multi-stage hypergravity reactor, aiming at the characteristics of the azeotrope in the reaction system of the present invention, the gas phase mass transfer and liquid phase mass transfer efficiency of the azeotrope is greatly improved, and the reaction
  • the overall conversion rate is higher, and at the same time, based on the combination of stripping and supergravity, the trichloroethane and the lye are rapidly mixed and mass-transferred, and the product vinylidene chloride is quickly distilled from the reaction system in the form of an azeotrope (based on water vapor).
  • the rapid diffusion of vinylidene chloride) the reaction is always carried out in the direction of generating vinylidene chloride, and the conversion rate is significantly improved.
  • the test device proves that the present invention can stabilize the purity of vinylidene chloride products above 98% (mass fraction), so that the chloride salt
  • the TOC value of wastewater is reduced to below 100mg/L, which reduces material consumption and the cost of subsequent treatment of salty wastewater.

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