Continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone

Abstract

The utility model provides a continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone. The continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone comprises a raw material continuous supply unit, a first continuous chlorination reaction unit, a ring-opening reaction unit, a ring-closing reaction unit and a second continuous chlorination reaction unit. According to the technical scheme provided by the utility model, through the continuous synthesis device, the continuous production of 2-chloro-1-(1-chlorocyclopropyl) ethanone can be realized, and the labor cost is reduced; the continuous reactor has a relatively large heat exchange area, reaction heat can be quickly removed, accurate temperature control is realized, and the reaction selectivity is high; a gas-liquid two-phase contact interface in the continuous reactor is large, the reaction rate is high, and process amplification is easy to carry out. According to the continuous device, each reaction unit and each auxiliary unit also realize automation, and the reaction conditions are stable, so that the quality of a product prepared by the continuous device is relatively stable and uniform.

Description

TECHNICAL FIELD

[0001] The utility model relates to a chemical industry machinery technical field, and specifically, relate to a kind of continuous device of synthesis 2-chloro-1-(1-chlorocyclopropyl) ethanone. BACKGROUND

[0002] 2-chloro-1-(1-chlorocyclopropyl) ethanone, a liquid organic matter, is an important organic synthesis intermediate, often used as raw material for drug and pesticide synthesis, and has a wide range of applications in the field of pharmacy.

[0003] For example, 2-chloro-1-(1-chlorocyclopropyl) ethanone is one of the key intermediates for the synthesis of the fungicide prothioconazole. Prothioconazole has a more extensive fungicidal spectrum than other triazole fungicides, with the advantages of high efficacy, low toxicity and low residue. It is also safe for crops, people and the environment, and has many other advantages, making it one of the most promising triazole fungicides.

[0004] The key applications of 2-chloro-1-(1-chlorocyclopropyl) ethanone in the field of pharmacy have prompted the development of synthesis processes. Currently, there are several processes for the production of 2-chloro-1-(1-chlorocyclopropyl) ethanone in industrial production: (1) using a mixture of sulfuryl chloride and methanol as a chlorinating reagent, and reacting with 1-acetyl-1-chlorocyclopropane in dichloromethane solution; (2) using hydrochloric acid and hydrogen peroxide as chlorinating reagents, and generating the product in the presence of a catalyst and a phase transfer catalyst; (3) adding dichloromethane and methanol into the kettle, and passing in chlorine gas as a chlorinating reagent to react with 1-acetyl-1-chlorocyclopropane; (4) using a microchannel as a reactor, and generating the product from 1-acetyl-1-chlorocyclopropane in the presence of a solvent or without a solvent.

[0005] However, the above-mentioned processes for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone have one or more of the following disadvantages: (1) the reaction process using chlorine gas as a chlorinating reagent is mainly carried out in a batch kettle reactor, which results in a long chlorination reaction time; after the reaction is completed, the acidic and corrosive gases such as chlorine and hydrogen chloride in the system are directly extracted under negative pressure, which leads to a large investment in equipment and a large amount of acidic waste gas; (2) the reaction process using chlorine gas as a chlorinating reagent can produce products with high purity and yield when using a microchannel reactor, but it is only suitable for small-scale reactions and cannot be applied to industrial large-scale production.

[0006] In summary, the above-mentioned disadvantages of the existing synthesis process of 2-chloro-1-(1-chlorocyclopropyl) ethanone make its cost relatively high, which limits the application of its related derivatives. UTILITY MODEL CONTENT

[0007] The utility model discloses a main purpose provides a kind of continuous device of synthesis 2-chloro-1-(1-chlorocyclopropyl) ethanone, to solve the synthesis preparation cost of 2-chloro-1-(1-chlorocyclopropyl) ethanone in prior art, poor safety problem.

[0008] In order to achieve the above object, according to one aspect of the utility model, a kind of continuous device of synthesis 2-chloro-1-(1-chlorocyclopropyl) ethanone, comprising: raw material continuous supply unit, first continuous chlorination reaction unit, ring-opening reaction unit, ring-closing reaction unit and second continuous chlorination reaction unit;

[0009] Wherein, first continuous chlorination reaction unit has raw material inlet, first continuous chlorination reactor, first continuous gas-liquid separation device and first product outlet, raw material inlet is communicated with raw material continuous supply unit;

[0010] Ring-opening reaction unit includes second continuous feeding module, second continuous reaction module and second product outlet, second continuous feeding module includes first product continuous feeding module and concentrated hydrochloric acid continuous feeding module, wherein, first product continuous feeding module and first product outlet are communicated;

[0011] Ring-closing reaction unit includes third continuous feeding module and third continuous reaction module and third product outlet;Third continuous feeding module second product continuous feeding module, sodium hydroxide continuous feeding module and tetrabutylammonium bromide continuous feeding module, second product continuous feeding module is communicated with second product outlet;

[0012] Second continuous chlorination reaction unit has 1-(1-chlorocyclopropyl) ethanone inlet, second continuous chlorination reactor, first continuous purification device and 2-chloro-1-(1-chlorocyclopropyl) ethanone product outlet, 1-(1-chlorocyclopropyl) ethanone inlet is communicated with product outlet.

[0013] Further, first continuous chlorination reaction unit includes first temperature control device, and first temperature control device includes heating element, cooling element, temperature sensor, temperature controller and software control system, first temperature control device is set to first continuous chlorination reactor and can be pre-cooled to-5-0 ℃ or controlled to 0-10 ℃;

[0014] Second continuous chlorination reaction unit includes second temperature control device, and second temperature control device includes heating element, cooling element, temperature sensor, temperature controller and software control system, second temperature control device is set to second continuous chlorination reactor and can be pre-cooled to 10-25 ℃ or controlled to 20-35 ℃;

[0015] First continuous purification device includes second continuous gas-liquid separation device, water washing device, liquid-liquid separation device and first continuous rectification device arranged in sequence.

[0016] Further, the raw material continuous supply unit comprises an alpha-acetyl-gamma-butyrolactone supply device and a chlorine gas supply device.

[0017] The alpha-acetyl-gamma-butyrolactone supply device comprises an alpha-acetyl-gamma-butyrolactone storage tank and an alpha-acetyl-gamma-butyrolactone pre-cooler.

[0018] The chlorine gas supply device comprises a chlorine gas storage tank and a chlorine gas pre-cooler.

[0019] Further, the chlorine gas supply device is a gaseous raw material supply device, and the first continuous chlorination reactor is any one of a continuous gas-liquid reactor, a coil reactor and a micro-channel reactor.

[0020] Further, the chlorine gas supply device is a liquid raw material supply device, and the first continuous chlorination reactor is any one of a dynamic tubular reactor, a coil reactor and a micro-channel reactor.

[0021] Further, the first continuous chlorination reaction unit further comprises a first mixing device, the first mixing device comprises a material inlet and a material outlet, the material inlet is in communication with the raw material inlet, and the material outlet is in communication with the first continuous chlorination reactor.

[0022] Further, the first continuous purification device comprises a third continuous gas-liquid separation device, a falling film evaporator and a third continuous rectification device arranged in sequence.

[0023] Further, the second continuous chlorination reaction unit further comprises a second mixing device, the second mixing device is in communication with the second continuous chlorination reactor, and the second mixing device is arranged to uniformly mix 1-(1-chlorocyclopropyl) ethanone and other raw materials and pass them into the second continuous chlorination reactor.

[0024] Further, the second continuous chlorination reaction unit further comprises a gaseous chlorine gas inlet, and the second continuous chlorination reactor is any one of a continuous gas-liquid reactor, a continuous gas-liquid reactor, a coil reactor and a micro-channel reactor.

[0025] Further, the second continuous chlorination reaction unit further comprises a liquid chlorine gas inlet, and the second continuous chlorination reactor is any one of a coil reactor and a micro-channel reactor.

[0026] The technical scheme of the utility model discloses, the continuous synthesis device can realize the continuous production of 2-chloro-1-(1-chlorocyclopropyl)ethanone, and the artificial cost is reduced;The continuous reactor has a large heat exchange area, can quickly remove the reaction heat, realizes accurate temperature control, and the reaction selectivity is high;The contact interface of the gas-liquid two-phase in the continuous reactor is large, the reaction rate is fast, and the process amplification is easy. BRIEF DESCRIPTION OF DRAWINGS

[0027] The drawings accompanying the specification integrated in part of the utility model are used to provide further understanding of the utility model, and the illustrative embodiment of the utility model and its explanation are used to explain the utility model, and do not constitute improper limitation to the utility model.

[0028] Figure 1 The structure schematic diagram of the continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl)ethanone according to the utility model is shown;

[0029] Figure 2 The structure schematic diagram of the first continuous purification device according to one embodiment of the utility model is shown;

[0030] Figure 3 The continuous chloro-reaction device schematic diagram of α-acetyl-α-chloro-γ-butyrolactone according to embodiment 1 of the utility model is shown;

[0031] Figure 4 The continuous ring-opening reaction device schematic diagram of 3,5-dichloro-2-pentanone according to embodiment 1 of the utility model is shown;

[0032] Figure 5 The continuous ring-closing reaction device schematic diagram of 1-(1-chlorocyclopropyl)ethanone according to embodiment 1 of the utility model is shown;

[0033] Figure 6 The continuous reaction system schematic diagram of 2-chloro-1-(1-chlorocyclopropyl)ethanone according to embodiment 1 of the utility model is shown.

[0034] Figure 7 The continuous liquid chlorine reaction system schematic diagram of 2-chloro-1-(1-chlorocyclopropyl)ethanone according to embodiment 2 of the utility model is shown.

[0035] Figure 8 The continuous reaction device schematic diagram of α-acetyl-α-chloro-γ-butyrolactone according to embodiment 3 of the utility model is shown.

[0036] Figure 9A continuous chlorination reaction device schematic diagram of alpha-acetyl-alpha-chloro-gamma-butyrolactone according to the embodiment of the utility model is shown.

[0037] Wherein, the above-mentioned drawing includes the following reference signs: 1, alpha-acetyl-gamma-butyrolactone storage tank; 2, liquid chlorine storage tank; 3, alpha-acetyl-gamma-butyrolactone pre-cooler; 4, liquid chlorine pre-cooler; 5, first continuous chlorination reaction device; 6, continuous degassing device; 7, alpha-chloro-alpha-acetyl-gamma-butyrolactone storage tank;

[0038] 001, third continuous gas-liquid separation device; 002, falling film evaporator; 003, falling film gas-liquid separator; 004, condenser; 005, first light phase tank; 006, first heavy phase tank; 007, rectification column; 008, reboiler; 009, second heavy component tank; 010, light component tank; 011, second light phase tank;

[0039] 101, first gas buffer tank; 102, second gas buffer tank;

[0040] 301, first continuous chlorination reactor; 302, first gas-liquid separator; 303, second continuous chlorination reactor; 304, second gas-liquid separation device; 305, water washing device; 306, liquid-liquid extraction module; 307, second continuous reaction module; 308, first extraction device; 310, third continuous reaction module; 311, pH adjusting device; 312, second extraction device; 313, second liquid separation device; 314, first plate microchannel reactor; 315, third gas-liquid separator; 316, fourth liquid-liquid separator; 317, second plate microchannel reactor; 318, third gas-liquid separator;

[0041] 501, first rectification column; 502, second rectification column; 503, first concentration device;

[0042] 605, alpha-acetyl-alpha-chloro-gamma-butyrolactone receiving bottle; 606, concentrated hydrochloric acid storage tank; 610, second chlorine liquefaction tank; 611, first chlorine liquefaction tank;

[0043] 801, first pre-cooler; 802, second pre-cooler; 803, first pre-heater; 804, second pre-heater; 805, fifth temperature control module; 806, sixth temperature control module; 807, seventh temperature control module; 808, eighth temperature control device; 809, ninth temperature control module. DETAILED DESCRIPTION

[0044] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The utility model will be described in detail below with reference to the drawings and in combination with the embodiments.

[0045] As analyzed in the background of the present application, the prior art has the problems of high cost and poor safety in the synthesis of 2-chloro-1-(1-chlorocyclopropyl) ethanone. In order to solve this problem, the present application provides a continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone. As shown in Figure 1 The continuous device includes a raw material continuous supply unit 10, a first continuous chlorination reaction unit 20, an opening ring reaction unit 30, a ring closing reaction unit 40 and a second continuous chlorination reaction unit 50. The first continuous chlorination reaction unit 20 has a raw material inlet, a first continuous chlorination reactor, a first continuous gas-liquid separation device and a first product outlet. The raw material inlet is in communication with the raw material continuous supply unit 10. The opening ring reaction unit 30 includes a second continuous feeding module, a second continuous reaction module and a second product outlet. The second continuous feeding module includes a first product continuous feeding module and a concentrated hydrochloric acid continuous feeding module. The first product continuous feeding module is in communication with the first product outlet. The ring closing reaction unit 40 includes a third continuous feeding module and a third continuous reaction module and a third product outlet. The third continuous feeding module includes a second product continuous feeding module, a sodium hydroxide continuous feeding module and a tetrabutylammonium bromide continuous feeding module. The second product continuous feeding module is in communication with the second product outlet. The second continuous chlorination reaction unit 50 has a 1-(1-chlorocyclopropyl) ethanone inlet, a second continuous chlorination reactor, a continuous purification device and a 2-chloro-1-(1-chlorocyclopropyl) ethanone product outlet. The 1-(1-chlorocyclopropyl) ethanone inlet is in communication with the product outlet.

[0046] The continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone of the present application can use chlorine gas as the chlorinating agent for the synthesis of 2-chloro-1-(1-chlorocyclopropyl) ethanone. Compared with sulfuryl chloride, the atomic utilization rate is higher, the raw material is cleaner, and no excess impurities are generated, reducing the cost of the post-processing process, especially the labor cost, improving the safety of the reaction process, and the continuous device of the present application can make the two-step chlorination reaction for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone use chlorine gas as the raw material, and can realize precise control of the process parameters, thereby significantly improving the selectivity of the chlorination reaction and the conversion rate of the raw material, improving the reaction rate, and significantly reducing the preparation cost of 2-chloro-1-(1-chlorocyclopropyl) ethanone.

[0047] On the other hand, the continuous device described above can realize the continuous production of 2-chloro-1-(1-chlorocyclopropyl) ethanone, reduce the labor cost; the continuous reactor has a large heat exchange area, which can quickly remove the reaction heat, realize precise temperature control, and has high reaction selectivity; the contact interface between the gas and liquid phases in the continuous reactor is large, the reaction rate is fast, and the process can be easily scaled up.

[0048] The continuous device for synthesizing 2-chloro-1-(1-chlorocyclopropyl)ethanone of the present application can continuously prepare α-acetyl-γ-butyrolactone according to the following synthesis route.

[0049]

[0050] In some embodiments of the present application, as shown in Figure 9 The raw material continuous supply unit 10 includes an α-acetyl-γ-butyrolactone supply device and a chlorine gas supply device; the α-acetyl-γ-butyrolactone supply device includes an α-acetyl-γ-butyrolactone storage tank 1 and an α-acetyl-γ-butyrolactone pre-cooler 3; the chlorine gas supply device includes a chlorine gas storage tank 2 and a chlorine gas pre-cooler 4. The α-acetyl-γ-butyrolactone and chlorine gas are introduced into the first continuous chlorination reaction device 5 through the above-mentioned α-acetyl-γ-butyrolactone supply device and chlorine gas supply device, and the reaction product is subjected to gas-liquid separation treatment through the continuous degassing device 6 (i.e. the first continuous gas-liquid separation device), and then the obtained product enters the α-chloro-α-acetyl-γ-butyrolactone storage tank for standby.

[0051] In some embodiments of the present application, the above-mentioned raw material continuous supply unit includes a chlorine gas supply device, which includes a gas flow meter and a gas buffer device connected with the gas flow meter, which is arranged to protect the flow meter from being damaged by liquid materials, wherein the gas buffer device works in the following way: when the gas passage is blocked or negative pressure is generated, the sucked liquid will flow into the buffer device and will not enter the flow meter, so as to prevent the flow meter from being stuck or damaged.

[0052] In the first continuous chlorination reaction unit 20, the chlorine gas can be introduced into the first continuous chlorination reactor in a gaseous state or a liquid state.

[0053] In some typical embodiments of the present application, the chlorine gas is introduced into the first continuous chlorination reactor in a gaseous state, i.e. the chlorine gas supply device is a gaseous raw material supply device, and the first continuous chlorination reactor is any one of a continuous gas-liquid reactor, a coil and a micro-channel reactor; preferably, the pressure of the first chlorination reaction is 0-0.5 MPa, more preferably 0.05-0.25 MPa, and when the chlorine gas is introduced into the first continuous chlorination reactor in a gaseous state, by providing a certain reaction pressure, the contact between the chlorine gas and the liquid raw material can be promoted, and the selectivity of the first chlorination reaction can be further improved, thereby improving the yield of α-chloro-α-acetyl-γ-butyrolactone.

[0054] In some typical embodiments of the present application, in the first continuous chlorination reaction process, the chlorine gas supply device is a liquid feed supply device, the chlorine gas is supplied in liquid state into the first continuous chlorination reactor, and the first continuous chlorination reactor is any one of a dynamic tubular reactor, a coil reactor and a microchannel reactor. Preferably, the pressure of the first chlorination reaction is 0.5-2.0 MPa, and more preferably 0.7-1.0 MPa. The chlorine gas supplied in liquid state is beneficial to further improve the yield of α-chloro-α-acetyl-γ-butyrolactone at the reaction pressure.

[0055] In some embodiments of the present application, in order to accurately adjust the pressure of the first chlorination reaction, the first continuous chlorination reactor is provided with a first back pressure valve. The pressure in the first continuous chlorination reactor is accurately controlled by adjusting the flow rate of the reaction system, which is beneficial to improve the selectivity of the first chlorination reaction.

[0056] In some embodiments of the present application, the first continuous chlorination reaction unit comprises a first temperature control device, which comprises a heating element, a cooling element, a temperature sensor, a temperature controller and a software control system. The first temperature control device is configured to pre-cool the first continuous chlorination reactor to -5-0℃ or control the temperature to 0-10℃, which is beneficial to improve the selectivity of the first chlorination reaction and reduce the generation of by-products.

[0057] In some embodiments of the present application, the reaction time of the first chlorination reaction is 5-30 min, i.e. the residence time of the chlorine gas and α-acetyl-γ-butyrolactone in the first continuous chlorination reactor is 5-30 min. The raw material has high selectivity and conversion rate. Preferably, the reaction time is 5-15 min.

[0058] In some embodiments of the present application, in the first chlorination reaction, the molar ratio of the chlorine gas and α-acetyl-γ-butyrolactone is 1-1.5:1, and preferably 1-1.2:1. Since the first chlorination reaction of the present application is carried out in a continuous chlorination reactor, the gas-liquid mixing effect is good, and the reaction rate is easy to control. Therefore, the selectivity of the chlorination reaction is good, and the utilization rate of chlorine gas is high. A small amount of chlorine gas not involved in the reaction can be treated by acid-base neutralization, and the post-treatment is simple. Preferably, the molar ratio of the chlorine gas and α-acetyl-γ-butyrolactone is 1:1, which realizes the maximum utilization of chlorine atoms and takes into account the selectivity of the reaction and the yield of the product.

[0059] The first chlorination reaction system obtained after the above reaction is separated by a first continuous gas-liquid separation device to separate the by-product HCl generated after the chlorination reaction, and obtain α-chloro-α-acetyl-γ-butyrolactone. Preferably, the temperature of the first continuous gas-liquid separation is -10-10℃, and the separation effect is good.

[0060] In some typical embodiments of the present application, in order to improve the safety of the above chlorination reaction, the reactor is subjected to air tightness detection before the material is fed in. The method of air tightness detection can refer to the prior art, and the present application has no limitation in this regard. As an example, the air tightness detection is carried out as follows: 0-0.5 MPa air tightness test is carried out with nitrogen, and if the pressure decreases by less than 0.01 MPa after 2 hours, it is qualified.

[0061] In order to further improve the selectivity of the first chlorination reaction, in some embodiments of the present application, nitrogen and chlorine are used to replace the gas in the first continuous chlorination reactor before the α-acetyl-γ-butyrolactone and chlorine are fed in, so that the first chlorination reaction is carried out in a chlorine atmosphere. Preferably, the first continuous chlorination reactor is pre-cooled to -20-0°C before the α-acetyl-γ-butyrolactone and chlorine are fed in.

[0062] In some typical embodiments of the present application, the process steps carried out in the above first continuous chlorination reaction unit 20 include: (1) reaction device air tightness detection: 0-0.5 MPa air tightness test is carried out with nitrogen, and if the pressure decreases by less than 0.01 MPa after 2 hours, it is qualified. (2) Reaction device gas replacement: open the nitrogen inlet valve, replace the air in the reaction device, the nitrogen pressure in the first continuous chlorination reactor is 0-0.5 MPa, and the replacement frequency is 1-5 times; (3) open the chlorine inlet valve, replace the nitrogen in the first continuous chlorination reactor, the chlorine pressure in the reaction device is 0-0.5 MPa, and the replacement frequency is 1-5 times; (4) temperature control: after the replacement of nitrogen and chlorine is completed, the first continuous chlorination reactor is pre-cooled to -20-0°C; (5) feeding: open the chlorine feed flowmeter and the reaction solution feeding plunger pump; (6) continuous chlorination reaction: α-acetyl-γ-butyrolactone and chlorine are reacted in the first continuous chlorination reactor; (7) separation: the gas-liquid mixture is separated in the first continuous gas-liquid separation device, wherein the separated liquid is collected in the product storage tank for the next process.

[0063] In some typical embodiments of the present application, the first continuous chlorination reaction procedure includes: (1) reaction device airtightness detection: 0-1.0 MPa airtightness test is carried out by using nitrogen, and after 2 hours, the pressure is reduced by less than 0.01 MPa, which is qualified. (2) Reaction device gas replacement: open the nitrogen inlet valve, replace the air in the reaction device, the nitrogen pressure in the reactor is 0-0.5 MPa, and the replacement frequency is 1-5 times; open the chlorine inlet valve, replace the nitrogen in the first continuous chlorination reactor, the chlorine pressure in the reaction device is 0-0.5 MPa, and the replacement frequency is 1-5 times; (3) Chlorine liquefaction: after the liquefaction of chlorine is completed in the -15-0℃ external bath of the liquefaction tank, the liquefaction tank is pressurized to 0.7-1.0 MPa by using nitrogen; (4) Temperature control: after the replacement of nitrogen and chlorine is completed, the first continuous chlorination reactor is pre-cooled to -20-0℃; (5) Pressure control: the internal pressure of the reactor is controlled to 0.7-1 MPa; (6) Feeding: open the chlorine and reaction solution feeding plunger pump; (7) Continuous chlorination reaction: α-acetyl-γ-butyrolactone and chlorine are reacted in the first continuous chlorination reactor (such as a micro-channel reactor); (8) Separation: the gas-liquid mixture is separated in the first continuous gas-liquid separation device, wherein the separated liquid enters the product storage tank for collection, which is used for the next process.

[0064] The ring-opening reaction unit 30 includes a second continuous feeding module, a second continuous reaction module, and a second product outlet, and the second continuous feeding module includes a first product continuous feeding module and a concentrated hydrochloric acid continuous feeding module, wherein the first product continuous feeding module and the first product outlet are in communication.

[0065] In some embodiments of the present application, in the continuous ring-opening reaction step, the mass ratio of α-acetyl-α-chloro-γ-butyrolactone to concentrated hydrochloric acid is 1:(1.5-2.0). Further, the reaction temperature of the ring-opening reaction is 80-100℃, and the residence time is 1-4h; preferably, the ring-opening reaction is carried out under a nitrogen atmosphere.

[0066] In some embodiments of the present application, the ring-opening reaction unit 30 further includes a second purification device, which is configured to separate and purify the reaction liquid output from the second continuous reaction module to obtain the target product of the ring-opening reaction and output from the second product outlet; the second purification device includes a first extraction device, a first liquid separation device, and a first concentration device arranged in sequence.

[0067] In some typical embodiments of the present application, the process carried out in the ring-opening reaction unit 30 includes: (1) reaction device airtightness detection: 0-0.5 MPa airtightness test is carried out with nitrogen, and after 2 hours, the pressure is reduced by less than 0.01 MPa, which is qualified. (2) Reaction device gas replacement: open the nitrogen inlet valve, replace the air in the reaction device, and the nitrogen pressure in the reactor is 0-0.5 MPa, and the replacement frequency is 1-5 times; (3) Temperature control: control the temperature to 80-100°C, and set the retention time to 1-4h; (4) Feeding: the first chlorinated product α-acetyl-α-chloro-γ-butyrolactone and concentrated hydrochloric acid are respectively fed into the mixing module through the α-acetyl-α-chloro-γ-butyrolactone continuous feeding module and the concentrated hydrochloric acid continuous feeding module, and then sent into the second continuous reaction module after being uniformly mixed, while nitrogen is supplied through the nitrogen protection module; (5) Reaction: ring-opening reaction is carried out to obtain the ring-opening product 3,5-dichloro-2-pentanone crude product; (6) Purification: sent into the first extraction device, the first liquid separation device and the first concentration device connected in sequence to obtain the ring-opening product 3,5-dichloro-2-pentanone pure product.

[0068] The ring-closing reaction unit 40 includes a third continuous feeding module and a third continuous reaction module and a third product outlet; the third continuous feeding module includes a second product continuous feeding module, a sodium hydroxide continuous feeding module and a tetrabutylammonium bromide continuous feeding module, and the second product continuous feeding module is in communication with the second product outlet.

[0069] In some preferred embodiments of the present application, in the above-mentioned continuous ring-closing reaction process, the mass ratio of 3,5-dichloro-2-pentanone, alkali solution and phase transfer catalyst is 1:(1-2):(0.01-0.22). The alkali solution and the phase transfer catalyst can be selected in the prior art, for example, the alkali solution can be sodium hydroxide solution, and the phase transfer catalyst can be tetrabutylammonium bromide.

[0070] Further, the reaction temperature of the ring-closing reaction is 80-100°C, and the residence time is 5-20 min;

[0071] In some embodiments of the present application, the above-mentioned ring-closing reaction unit 40 further includes a second purification device, which is configured to separate and purify the reaction liquid output from the third continuous reaction module to obtain the target product of the ring-closing reaction and output from the third product outlet; the third purification device includes a pH adjusting device, a second liquid separation device and a second concentration device arranged in sequence.

[0072] In some typical embodiments of the present application, the continuous closed-loop reaction process comprises: (1) reaction device airtightness detection: 0-0.5 MPa airtightness test is carried out with nitrogen, and after 2 hours, if the pressure decreases by less than 0.01 MPa, it is qualified. (2) Reaction device gas replacement: open the nitrogen inlet valve, replace the air in the reaction device, the nitrogen pressure in the reactor is 0-0.5 MPa, and the replacement frequency is 1-5 times; (3) Temperature control: control the temperature at 80-100℃, and set the retention time to 5-10 min; (4) Feeding: the open-loop product 3,5-dichloro-2-pentanone, sodium hydroxide and tetrabutylammonium bromide are respectively fed into the third continuous reaction module through the 3,5-dichloro-2-pentanone continuous feeding module, the sodium hydroxide continuous feeding module and the tetrabutylammonium bromide continuous feeding module; (5) Reaction: closed-loop reaction is carried out to obtain the crude closed-loop product 1-acetyl-1-chlorocyclopropane; (6) Purification: sent to the sequentially connected pH adjusting device, second extraction device and second liquid separation device to obtain the pure 1-acetyl-1-chlorocyclopropane product solution.

[0073] The second continuous chlorination reaction unit 50 has a 1-(1-chlorocyclopropyl)ethanone inlet, a second continuous chlorination reactor, a first continuous purification device and a 2-chloro-1-(1-chlorocyclopropyl)ethanone product outlet, and the 1-(1-chlorocyclopropyl)ethanone inlet communicates with the product outlet.

[0074] The solvent and catalyst used in the second continuous chlorination reaction process can be selected in the prior art. For example, the solvent includes but is not limited to C2-C12 aliphatic hydrocarbon solvents, C6-C12 aromatic hydrocarbon solvents, C1-C5 alcohol solvents, C2-C12 carboxylic acid ester solvents, C2-C12 amide solvents, C4-C12 heterocyclic solvents and C1-C5 halogenated hydrocarbon solvents. The catalyst includes but is not limited to any one or more of methanol, ethanol, propanol, isopropanol and n-butanol. Preferably, the molar ratio of the catalyst to 1-(1-chlorocyclopropyl)ethanone is 1:1-0.2:1.

[0075] In some embodiments of the present application, in the second chlorination reaction, the molar ratio of the chlorine gas introduced to 1-(1-chlorocyclopropyl)ethanone is 1-2.5:1, which is beneficial to further improve the selectivity of the second chlorination reaction. Preferably, in the second chlorination reaction, the molar ratio of the chlorine gas introduced to 1-(1-chlorocyclopropyl)ethanone is 1-1.2:1. Preferably, the weight ratio of the solvent introduced to 1-(1-chlorocyclopropyl)ethanone is 1:0.1-1:5; preferably, the feeding flow rate of 1-(1-chlorocyclopropyl)ethanone is 0.1-10 g / min.

[0076] In some embodiments of the present application, the reaction temperature of the second chlorination reaction is 20-35°C, and the reaction time is 5 min-60 min, which can further improve the yield and selectivity of the reaction. In some preferred embodiments of the present application, in order to better control the reaction temperature and reduce temperature fluctuation, the second continuous chlorination reactor is pre-cooled to 10-25°C before the 1-(1-chlorocyclopropyl)ethanone, solvent, catalyst and chlorine gas are introduced.

[0077] In some other embodiments of the present application, the second continuous chlorination reaction unit comprises a second temperature control device, which comprises a heating element, a cooling element, a temperature sensor, a temperature controller and a software control system, and is configured to pre-cool the second continuous chlorination reactor to 10-25°C or control the temperature to 20-35°C.

[0078] The specific temperature control method of the first temperature control device or the second temperature control device can be selected from the prior art. For example, a jacket is arranged outside the reactor, and a coolant is introduced into the jacket for temperature adjustment.

[0079] In some typical embodiments of the present application, in the second continuous chlorination reaction process, chlorine gas is introduced into the second continuous chlorination reactor in a gaseous state, i.e., the second continuous chlorination reaction unit 50 further comprises a gaseous chlorine gas inlet, and the second continuous chlorination reactor is any one of a continuous gas-liquid reactor, a coil reactor and a micro-channel reactor. Preferably, the pressure of the second chlorination reaction is 0-0.5 MPa, preferably 0.02-0.20 MPa, and more preferably 0.03-0.1 MPa. Under this pressure, the contact between chlorine gas and liquid raw material is more sufficient, and it is easy to control, which can significantly improve the selectivity of the second chlorination reaction and the yield of the target product.

[0080] In some typical embodiments of the present application, in the second continuous chlorination reaction process, chlorine gas is introduced into the second continuous chlorination reactor in a liquid state, i.e., the second continuous chlorination reaction unit 50 comprises a liquid chlorine gas inlet, and the second continuous chlorination reactor is any one of a dynamic tube reactor, a coil reactor and a micro-channel reactor. Preferably, the pressure of the second chlorination reaction is 0.5-2.0 MPa, and more preferably 0.7-1.0 MPa.

[0081] In some embodiments of the present application, the second continuous chlorination reactor is provided with a second back pressure valve, which can accurately adjust the reaction pressure in the second continuous chlorination reactor, which is beneficial to improve the selectivity of the second chlorination reaction and the yield of the target product, and further reduce the preparation cost of 1-(1-chlorocyclopropyl)ethanone.

[0082] In some embodiments of the present application, the first continuous purification device comprises a second continuous gas-liquid separation device, a water washing device, a liquid-liquid separation device and a first rectification device, which can sequentially separate, wash, separate and rectify the second chlorination reaction product. Preferably, the separation is carried out at 0-10°C. The first continuous purification device can separate the gas-liquid mixture prepared by the second chlorination reactor in a gas-liquid separator, wherein the separated liquid enters the water washing device for water washing, the water washing product enters the liquid-liquid separator, the separated heavy component enters the first rectification device, and the 2-chloro-1-(1-chlorocyclopropyl) ethanone product is obtained. In some embodiments of the present application, the first rectification device comprises a first rectification column and a second rectification column, and the heavy component separated by the liquid-liquid separator sequentially enters the first rectification column and the second rectification column, the solvent is removed in the first rectification column, and the light component is separated in the second rectification column to obtain the product.

[0083] In some embodiments of the present application, as shown in Figure 2 The first continuous purification device comprises a third continuous gas-liquid separation device 001, a falling film evaporator 002 and a second continuous rectification device arranged in sequence. Specifically, the reaction liquid enters the third continuous gas-liquid separation device 001 for gas-liquid separation, and the obtained liquid phase component enters the falling film evaporator 002 to separate the solvent in the reaction liquid. The vaporized system in the falling film evaporator 002 enters a falling film gas-liquid separator 003, wherein the light component is cooled by a condenser 004, and the cooling liquid enters a first light phase tank 005; the heavy component enters a first heavy phase tank 006, and the concentrated liquid in the heavy phase tank continuously enters a rectification column 007 of the second continuous rectification device for rectification; the process parameters such as the temperature and the reflux ratio of rectification are adjusted by a reboiler 008, a condenser and a light component tank 010, the obtained heavy phase enters a second heavy component tank 009, and the light component enters a second light phase tank to obtain the rectification product.

[0084] Preferably, the second continuous gas-liquid separation device or the third continuous gas-liquid separation device and the first continuous gas-liquid separation device described above are provided with a temperature control module, which can control the temperature of the gas-liquid separator to 0-10°C.

[0085] In some typical embodiments of the present application, chlorine is fed in a gaseous state, and the second continuous chlorination reaction process comprises: (1) opening the chlorine inlet valve to make the chlorine pressure in the reaction device 0.01-0.5 MPa; (2) pre-cooling the second continuous chlorination reactor to 10-25°C; (3) opening the chlorine feed flowmeter and the reaction solution feed plunger pump for feeding; (4) 1-(1-chlorocyclopropyl) ethanone and chlorine are subjected to the second chlorination reaction in the continuous gas-liquid reactor to obtain a gas-liquid mixture; (5) the gas-liquid mixture is subjected to purification and separation in the first continuous purification device to obtain the product.

[0086] In some typical embodiments of this application, chlorine is fed in liquid form. The second continuous chlorination reaction process includes: (1) Preparation: Dissolve 1-(1-chlorocyclopropyl)ethyl ketone in dichloromethane in a mixing bottle to prepare a 12% to 60% (w / w) dichloromethane solution of 1-(1-chlorocyclopropyl)ethyl ketone. Add 1.0 equivalent of methanol and place the prepared solution in a raw material storage tank. (2) Air tightness test of the reaction device: Perform an air tightness test at 0-1.0 MPa with nitrogen. If the pressure drop is less than 0.01 MPa after 2 hours, it is considered qualified. (3) Gas replacement of the reaction device: Open the nitrogen inlet valve to replace the air in the reaction device. The nitrogen pressure in the reactor is 0-0.5 MPa, and the replacement is performed 1-5 times. (4) Chlorine liquefaction: After liquefying chlorine in a liquefaction tank with an external bath at -15-0℃, pressurize the liquefaction tank to 0.7-1.0 MPa with nitrogen. (5) Temperature control: After the nitrogen and chlorine are replaced, the temperature of the second continuous chlorination reactor is controlled. (6) Pressure control: The internal pressure of the reactor is controlled to 0.7-1 MPa. (7) Feeding: The chlorine and reaction solution feed plunger pumps are turned on. (8) Continuous chlorination reaction: 1-(1-chlorocyclopropyl)acetone solution and chlorine react in a microchannel reactor to obtain a gas-liquid mixture. (9) The gas-liquid mixture is purified and separated into products in the first continuous purification unit.

[0087] In some embodiments of this application, the continuous purification apparatus includes a second continuous gas-liquid separation device, a water washing device, a liquid-liquid separation device, and a continuous distillation device arranged sequentially. Preferably, the second continuous gas-liquid separation device and the aforementioned first continuous gas-liquid separation device are equipped with a temperature control module, which can control the temperature of the gas-liquid separator to 0-10°C.

[0088] In some preferred embodiments of this application, the first continuous chlorination reaction unit and the second continuous chlorination reaction unit further include a tail gas absorption device, which is capable of absorbing the HCl gas produced in the chlorination reaction.

[0089] The beneficial effects that this application can achieve will be further illustrated below with reference to embodiments and comparative examples.

[0090] Example 1

[0091] First continuous chlorination reaction process

[0092] The continuous reaction apparatus for preparing α-acetyl-α-chloro-γ-butyrolactone in this process is as follows: Figure 3 As shown, the first continuous chlorination reactor 301 is a cylindrical gas-liquid reactor made of Hastelloy alloy. The reaction equation for this process is as follows:

[0093]

[0094] The α-acetyl-α-chloro-γ-butyrolactone is prepared by using the above reaction system according to the following method:

[0095] (1) The raw material α-acetyl-γ-butyrolactone is placed in the α-acetyl-γ-butyrolactone storage tank.

[0096] (2) Temperature control: After the reaction system is qualified for the gas tightness test, nitrogen replacement is performed, and after completion, the first continuous chlorination reactor 301 and the receiving bottle are subjected to temperature control treatment, and the temperature is set to -5°C and 0°C, respectively.

[0097] (3) Reaction solution delivery: When the temperatures in the first continuous chlorination reactor 301 and the receiving bottle are stabilized at -5°C and 0°C, respectively, the chlorine gas is made to flow through the first gas buffer tank 101 at a flow rate controlled by the flow meter, and the chlorine gas flow rate is set to 1.4 L / min, and the pressure in the first continuous chlorination reactor 301 is controlled to be 0.18-0.2 Mpa. After the gas flow rate is stabilized, the raw material α-acetyl-γ-butyrolactone feeding pump is started to make it enter the first continuous chlorination reactor 301 after being pre-cooled by the first pre-cooler 801, and the feeding flow rate is set to 8.7 g / min.

[0098] (4) Continuous chlorination reaction: The α-acetyl-γ-butyrolactone is fully mixed with chlorine gas at the bottom of the first continuous chlorination reactor 301, and the gas-liquid mixture enters the first continuous chlorination reactor 301 for reaction, and the temperature of the reaction liquid is controlled to be 0°C, and the retention time is 10 min.

[0099] (5) Product purification: After the reaction is completed, the reaction liquid flows out from the upper part of the first continuous chlorination reactor 301, and is subjected to temperature control in the receiving bottle, and is subjected to gas-liquid separation in the first gas-liquid separator 302, and the liquid phase enters the α-acetyl-α-chloro-γ-butyrolactone receiving bottle 605 as the raw material for the subsequent reaction step. The product purity is 98.1%, and the yield is 98.2%.

[0100] The continuous ring-opening reaction process, and the continuous device of the process is shown in Figure 4

[0101] (1) System inerting: The entire reaction system is subjected to nitrogen replacement by the nitrogen protection module, and the replacement is performed 1-5 times, and nitrogen protection is simultaneously performed during the reaction;

[0102] (2) Temperature control: The second continuous reaction module 307 is controlled to have a temperature of 100°C.

[0103] ​(3) Reaction solution delivery: The first chlorination product α-acetyl-α-chloro-γ-butyrolactone of the α-acetyl-α-chloro-γ-butyrolactone receiving bottle 605 and the concentrated hydrochloric acid of the concentrated hydrochloric acid storage tank 606 are respectively fed into the first preheater 803 and the second preheater 804 by the α-acetyl-α-chloro-γ-butyrolactone continuous feeding module at a mass flow rate of 1.18 kg / h and 1.90 kg / h, respectively, preheated, mixed uniformly, and then fed into the second continuous reaction module 307, while nitrogen is supplied by the nitrogen protection module;

[0104] (4) Open ring reaction: The retention time is controlled for 1 h to obtain the open ring product 3,5-dichloro-2-pentanone crude product;

[0105] (5) Purification: The 3,5-dichloro-2-pentanone crude product is fed into the first extraction device 308, the first liquid separation device (not shown in the figure), and the first concentration device 503 connected in sequence, the solvent is fed into the receiving tank after concentration, and the product is fed into the 3,5-dichloro-2-pentanone receiving tank to obtain the open ring product 3,5-dichloro-2-pentanone pure product with a yield of 85.7%.

[0106] Continuous closed ring reaction process, the continuous device of the process is shown in Figure 5 , and the specific implementation method is as follows:

[0107] (1) Temperature control: The third continuous reaction module is controlled at 90°C;

[0108] (2) Feeding: The open ring product 3,5-dichloro-2-pentanone pure product, sodium hydroxide, and tetrabutylammonium bromide are respectively fed into the fifth temperature control module 805, the sixth temperature control module 806, and the seventh temperature control module 807 at a mass flow rate of 0.98 kg / h, 1.88 kg / h, and 0.02 kg / h, respectively, preheated, and then fed into the third continuous reaction module 310;

[0109] (3) Reaction: The closed ring reaction is performed, the retention time is 5-10 min, and the closed ring product 1-acetyl-1-chlorocyclopropane crude product is obtained;

[0110] (4) Purification: fed into the pH adjusting device 311, the second extraction device 312, and the second liquid separation device 313 connected in sequence to obtain the closed ring product 1-acetyl-1-chlorocyclopropane with a yield of 85.4%.

[0111] Second continuous chlorination reaction process:

[0112] The 2-chloro-1-(1-chlorocyclopropyl) ethanone continuous reaction system of the process is shown in Figure 6 , wherein the second continuous chlorination reactor 303 is a glass column reactor with packing (Pall ring), the solvent used is dichloromethane, and the catalyst used is anhydrous methanol. The reaction equation of the process is as follows:

[0113]

[0114] 2-chloro-1-(1-chlorocyclopropyl)ethanone was prepared by using the above reaction system according to the following method:

[0115] (1) Preparation of a solution of 1-(1-chlorocyclopropyl)ethanone: In a charging bottle, the raw material 1-(1-chlorocyclopropyl)ethanone was dissolved in dichloromethane to prepare a 12% by mass dichloromethane solution of 1-(1-chlorocyclopropyl)ethanone, 0.3 equivalents of methanol were added, and the prepared solution was placed in a raw material storage tank.

[0116] (2) Temperature control: After the airtightness of the second continuous chlorination reactor 303 was qualified, nitrogen replacement was performed, and after completion, the second continuous chlorination reactor 303 and the receiving bottle were subjected to temperature control treatment, and the temperatures were set to 25°C and 0°C, respectively.

[0117] (3) Reaction solution delivery: When the temperatures in the reactor and the receiving bottle were stabilized at 10°C and 0°C, respectively, the chlorine gas was made to flow through the flowmeter to control the flow rate through the second gas buffer tank 102, the equivalent of chlorine gas was 1.1 eq (i.e., the molar ratio to 1-(1-chlorocyclopropyl)ethanone was 1.1:1), the flow rate of chlorine gas was set to 0.16 L / min, and the pressure of the second continuous chlorination reactor 303 was controlled to 0.06 MPa; after the flow rate was stabilized, the feed pump of the dichloromethane solution of 1-(1-chlorocyclopropyl)ethanone was opened, and the feed flow rate was set to 2.71 g / min, and after being pre-cooled by the second pre-cooler 802, it was sent to the second continuous chlorination reactor 303.

[0118] (4) Continuous chlorination reaction: The dichloromethane solution of 1-(1-chlorocyclopropyl)ethanone was thoroughly mixed with chlorine gas at the bottom of the second continuous chlorination reactor 303, the gas-liquid mixture entered the chlorination reactor to react, the temperature of the reaction solution was controlled to 30°C, and the retention time was 45 min.

[0119] (5) Product washing: After the reaction was completed, the reaction solution flowed out from the upper part of the reactor, was cooled in the receiving bottle, was subjected to gas-liquid separation in the second gas-liquid separation device 304, the liquid phase entered the receiving bottle, was thoroughly stirred and washed with water in the water washing device 305, was subjected to liquid-liquid separation in the liquid-liquid separation module 306, and the heavy component entered the product receiving bottle.

[0120] (6) Product purification: After the product solution was concentrated and desolvated by the first rectifying column 501, and was purified by the second rectifying column 502, a light yellow liquid was obtained, the yield was 96.2%, and the purity was 96.9%.

[0121] (7) Material circulation: The solvent distilled under reduced pressure was recharged into the charging bottle for charging.

[0122] Example 2

[0123] The difference from Example 1 is the second continuous chlorination reaction process, which is as follows:

[0124] The continuous reaction system of 2-chloro-1-(1-chlorocyclopropyl)ethanone in this process is shown in FIG. 2, wherein the second continuous chlorination reactor is a first plate micro-channel reactor 314 made of silicon carbide, the solvent used is dichloromethane, and the catalyst used is anhydrous methanol. The reaction equation of this process is as follows: Figure 7

[0125] 2-chloro-1-(1-chlorocyclopropyl)ethanone is prepared by using the above reaction system according to the following method:

[0126] (1) Preparation of 1-(1-chlorocyclopropyl)ethanone solution: Dissolve the raw material 1-(1-chlorocyclopropyl)ethanone in dichloromethane in a batching bottle to prepare a 13% by mass 1-(1-chlorocyclopropyl)ethanone dichloromethane solution, add 1.0 equivalent of methanol, and place the prepared solution in a raw material storage tank.

[0127] (2) Reaction device airtightness test: Perform a 0-1.0 MPa airtightness test with nitrogen, and after 2 hours, if the pressure decreases by less than 0.01 MPa, it is qualified.

[0128] (3) Reaction device gas replacement: Open the nitrogen inlet valve to replace the air in the reaction device, and the nitrogen pressure in the reactor is 0-0.5 MPa, and the replacement frequency is 1-5 times;

[0129] (4) Chlorine liquefaction: After the chlorine is liquefied in the first chlorine liquefaction tank 611 with an external bath at -15-0°C, nitrogen is used to pressurize the first chlorine liquefaction tank 611 to 0.8-1.0 MPa;

[0130] (5) Temperature control: After the airtightness test of the second continuous chlorination reactor is qualified, nitrogen replacement is performed, and after completion, the first plate micro-channel reactor 314 and the receiving bottle are subjected to temperature control treatment, and the temperature is set to 10°C and 0°C, respectively;

[0131] (6) Pressure control: The internal pressure of the reactor is controlled to 0.8-0.9 MPa;

[0132]

[0133] ​(7) Reaction solution delivery: When the temperature of the reactor and receiving bottle is stabilized at 10°C and 0°C, the liquid chlorine is controlled by the feed pump to control the pressure in the first plate micro-channel reactor 314 at 0.85-0.95 MPa. After the liquid chlorine flow is stabilized, the feed pump of the 1-(1-chlorocyclopropyl) ethanone dichloromethane solution is opened, and the feed flow is set at 2.71 g / min. After temperature control by the ninth temperature control module 809, the solution is sent to the first plate micro-channel reactor 314;

[0134] (8) Continuous chlorination reaction: The 1-(1-chlorocyclopropyl) ethanone dichloromethane solution is mixed with liquid chlorine in the first plate micro-channel reactor 314 and reacts. The temperature of the reaction solution is controlled at 30°C, and the residence time is 45 min.

[0135] (9) Product washing: After the reaction is completed, the reaction solution flows out from the upper part of the reactor, and gas-liquid separation is performed in the third gas-liquid separator 315. The heavy component liquid phase enters the receiving bottle, and the light component liquid phase is subjected to liquid-liquid separation in the fourth liquid-liquid separator 316 to obtain dichloromethane for recycling.

[0136] (10) Product purification: After the product solution is concentrated and desolventized in the product receiving bottle and subjected to rectification purification, a light yellow liquid is obtained, with a yield of 96.2% and a purity of 96.9%.

[0137] (11) Material circulation: The solvent subjected to vacuum distillation is added to the batching bottle for batching.

[0138] Example 3

[0139] The difference from Example 1 is only in the first continuous chlorination reaction process, which is as follows:

[0140] The continuous reaction device for preparing α-acetyl-α-chloro-γ-butyrolactone in this process is shown in Figure 8 , wherein the first continuous chlorination reactor is a second plate micro-channel reactor 317 made of silicon carbide. The reaction equation of this process is as follows:

[0141]

[0142] α-acetyl-α-chloro-γ-butyrolactone is prepared by using the above reaction system according to the following method:

[0143] (1) Preparation: The raw material α-acetyl-γ-butyrolactone is placed in the α-acetyl-γ-butyrolactone storage tank.

[0144] (2) Reaction device airtightness test: The airtightness test is performed at 0-1.0 MPa with nitrogen. After 2 hours, the pressure is reduced by less than 0.01 MPa, which is qualified.

[0145] (3) Chlorine liquefaction: The temperature and pressure of the chlorine liquefaction tank were controlled, and after passing the test, the chlorine was introduced into the second chlorine liquefaction tank 610 for liquefaction. After the liquefaction was completed, the liquefaction tank was pressurized to 0.9-1.0 MPa using nitrogen.

[0146] (4) Temperature control: After the reaction system passed the gas tightness test, nitrogen replacement was performed, and after completion, the second plate-type microchannel reactor 317 and the receiving bottle were subjected to temperature control treatment, with the temperature set to -5°C and 0°C, respectively.

[0147] (5) Reaction solution delivery: When the temperatures in the second plate-type microchannel reactor 317 and the receiving bottle were stabilized at -5°C and 0°C, respectively, the flow rate of liquid chlorine was controlled by the feed pump, and the pressure in the second plate-type microchannel reactor 317 was controlled at (0.90±0.05) MPa. After the flow rate of liquid chlorine was stabilized, the feed pump of the raw material α-acetyl-γ-butyrolactone was opened to make it enter the second plate-type microchannel reactor 317 after being pre-cooled by the eighth temperature control device 808. The feed flow rate was set to 8.7 g / min.

[0148] (6) Continuous chlorination reaction: α-acetyl-γ-butyrolactone was mixed with liquid chlorine in the first continuous chlorination reactor, and the temperature of the reactor was controlled at -15°C with a residence time of 10 min.

[0149] (7) Product purification: After the reaction was completed, the reaction liquid flowed out from the upper part of the first continuous chlorination reactor, and the temperature was controlled in the receiving bottle. The gas-liquid separation was performed in the third gas-liquid separator 318, and the liquid phase entered the receiving bottle as the raw material for the subsequent reaction step. The product purity was 97.14%, and the yield was 98.79%.

[0150] Example 4

[0151] The difference between Example 1 and Example 4 is that in the first continuous chlorination process, the pressure of chlorine is not controlled in step (3) and the subsequent reaction process, i.e., the pressure of chlorine is not adjusted in the second chlorination process.

[0152] In this process, the yield of α-chloro-α-acetyl-γ-butyrolactone was 82.47%, and the purity was 86.65%.

[0153] From the above description, it can be seen that the above-mentioned embodiments of the utility model realize the following technical effects: by using the technical scheme of the utility model, using chlorine as the chlorinating agent for synthesizing 2-chloro-1-(1-chlorocyclopropyl) ethanone, compared with sulfuryl chloride, the atomic utilization rate is higher, the raw material is cleaner, no extra impurities are generated, the separation cost of post-processing is reduced, the safety of reaction processing is improved, especially in the synthesis method of the application, liquid chlorine is used for chlorination reaction, which can significantly improve the selectivity of chlorination reaction and the conversion rate of raw materials, improve the reaction rate, and can reduce the amount of chlorination reagent, thereby reducing the preparation cost. On the other hand, by using the above continuous synthesis method, the continuous production of 2-chloro-1-(1-chlorocyclopropyl) ethanone can be realized, the labor cost is reduced; the continuous reactor has a large heat exchange area, the reaction heat can be quickly removed, precise temperature control can be realized, the reaction selectivity is high; the contact interface of gas-liquid two phases in the continuous reactor is large, the reaction rate is fast, and the process amplification is easy.

[0154] The above only describes the preferred embodiments of the utility model and is not used to limit the utility model. For those skilled in the art, the utility model can have various changes and variations. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the utility model should be included in the protection scope of the utility model.

Claims

1. A continuous apparatus for synthesizing 2-chloro-l-(l-chlorocyclopropyl)ethanone, characterized by, The application relates to a continuous production device for 2-chloro-1-(1-chlorocyclopropyl)ethanone, which comprises the following parts: a raw material continuous supply unit (10); a first continuous chlorination reaction unit (20) having a raw material inlet, a first continuous chlorination reactor, a first continuous gas-liquid separation device and a first product outlet, wherein the raw material inlet is communicated with the raw material continuous supply unit (10); an opening ring reaction unit (30) comprising a second continuous feeding module, a second continuous reaction module and a second product outlet, wherein the second continuous feeding module comprises a first product continuous feeding module and a concentrated hydrochloric acid continuous feeding module, and the first product continuous feeding module is communicated with the first product outlet; a ring closure reaction unit (40) comprising a third continuous feeding module and a third continuous reaction module and a third product outlet, wherein the third continuous feeding module comprises a second product continuous feeding module, a sodium hydroxide continuous feeding module and a tetrabutylammonium bromide continuous feeding module, and the second product continuous feeding module is communicated with the second product outlet; a second continuous chlorination reaction unit (50) having a 1-(1-chlorocyclopropyl)ethanone inlet, a second continuous chlorination reactor, a first continuous purification device and a 2-chloro-1-(1-chlorocyclopropyl)ethanone product outlet, wherein the 1-(1-chlorocyclopropyl)ethanone inlet is communicated with the product outlet.

2. The continuous apparatus of claim 1, wherein, The first continuous chlorination reaction unit (20) comprises a first temperature control device, which comprises a heating element, a cooling element, a temperature sensor, a temperature controller and a software control system, and is arranged to precool the first continuous chlorination reactor to-5-0 DEG C or control the first continuous chlorination reactor to 0-10 DEG C. The first continuous chlorination reaction unit (20) comprises a second temperature control device, which comprises a heating element, a cooling element, a temperature sensor, a temperature controller and a software control system, and is arranged to precool the second continuous chlorination reactor to 10-25 DEG C or control the second continuous chlorination reactor to 20-35 DEG C. The first continuous purification device comprises a second continuous gas-liquid separation device, a water washing device, a liquid-liquid separation device and a first continuous rectification device arranged in sequence.

3. The continuous apparatus according to claim 1 or 2, characterized in that, The raw material continuous supply unit (10) comprises an alpha-acetyl-gamma-butyrolactone supply device and a chlorine gas supply device. The alpha-acetyl-gamma-butyrolactone supply device comprises an alpha-acetyl-gamma-butyrolactone storage tank and an alpha-acetyl-gamma-butyrolactone pre-cooler. The chlorine gas supply device comprises a chlorine gas storage tank and a chlorine gas pre-cooler.

4. The continuous apparatus of claim 3, wherein, The chlorine gas supply device is a gaseous raw material supply device, and the first continuous chlorination reactor is any one of a continuous gas-liquid reactor, a coil reactor and a micro-channel reactor.

5. The continuous apparatus of claim 3, wherein, The chlorine gas supply device is a liquid raw material supply device, and the first continuous chlorination reactor is any one of a dynamic tubular reactor, a coil reactor and a micro-channel reactor.

6. The continuous apparatus of claim 1 or 2, wherein, The first continuous chlorination reaction unit (20) further comprises a first mixing device, which comprises a material inlet communicated with the raw material inlet and a material outlet communicated with the first continuous chlorination reactor.

7. The continuous apparatus of claim 1, wherein, The first continuous purification device comprises a third continuous gas-liquid separation device, a falling film evaporator and a third continuous rectification device arranged in sequence.

8. The continuous apparatus of claim 1, wherein, The second continuous chlorination reaction unit (50) further comprises a second mixing device which is in communication with the second continuous chlorination reactor, and is configured to mix 1-(1-chlorocyclopropyl) ethanone and other raw materials uniformly and pass them into the second continuous chlorination reactor.

9. The continuous apparatus of claim 1, wherein, The second continuous chlorination reaction unit (50) further comprises a gaseous chlorine inlet, and the second continuous chlorination reactor is any one of a continuous gas-liquid reactor, a continuous gas-liquid reactor, a coil reactor and a micro-channel reactor.

10. The continuous apparatus of claim 1, wherein, The second continuous chlorination reaction unit (50) further comprises a liquid chlorine inlet, and the second continuous chlorination reactor is any one of a coil reactor and a micro-channel reactor.

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