Device for preparing 2-chloro-5-chloromethylthiazole through gas-liquid countercurrent continuous flow

Abstract

The utility model relates to a device for preparing 2-chloro-5-chloromethylthiazole by gas-liquid countercurrent continuous flow, which comprises a feeding device, a tower reactor, a discharging device and a recovery device which are sequentially connected through pipelines, and the feeding device comprises a liquid feeding device and a gas feeding device. According to the utility model, a traditional intermittent kettle type process is converted into a gas-liquid countercurrent continuous flow type process, so that the operation efficiency is improved, the liquid holdup of a reaction system is reduced, the raw material cost is reduced, the energy utilization rate is improved, the quality and yield of 2-chloro-5-chloromethylthiazole are improved, the generation of three wastes is reduced, and the safety of personnel is further improved.

Description

TECHNICAL FIELD

[0001] The utility model belongs to chemical equipment technical field, concretely relates to a kind of 2-chloro-5-chloromethylthiazole device of gas-liquid countercurrent continuous flow preparation. BACKGROUND

[0002] 2-chloro-5-chloromethylthiazole is the key intermediate of second generation nicotine insecticide clothianidin, flubendiamide and medicine ritonavir synthesis, has gradually caused the extensive attention of pesticide, medicine researchers in recent years, and the market trend of this intermediate is generally good. Its preparation principle is mainly that 2-chloropropenyl isothiocyanate is reacted with chlorinating reagent, and then deaeration is converted into 2-chloro-5-chloromethylthiazole.

[0003] The preparation method reported in the current domestic and foreign public patent literature is mainly to use 2-chloropropenyl isothiocyanate as raw material, dichloroethane as solvent, and complete the reaction by chlorination of chlorinating reagent. The manufacturers of this intermediate all use tank type batch reaction for production, and in order to achieve a certain production capacity, multiple production lines need to be installed, which has the problem of large production workshop area. At the same time, because the chlorination process is one of the 18 dangerous processes, and the mass transfer and heat transfer problems affect the production capacity and product quality obviously, therefore, the continuous research of this intermediate product is imminent. SUMMARY

[0004] In view of the above problems, the utility model provides a kind of 2-chloro-5-chloromethylthiazole device of gas-liquid countercurrent continuous flow preparation, chlorination process realizes automatic control, reduces the number of field operators, at the same time, reduce the floor space, more important is to reduce the liquid holdup of reaction system, intrinsic safety is promoted, at the same time, the quality and yield of 2-chloro-5-chloromethylthiazole are improved, and the income is increased.

[0005] The utility model provides a kind of 2-chloro-5-chloromethylthiazole device of gas-liquid countercurrent continuous flow preparation, including feeding device, tower type reactor, discharging device and recovery device, each device is sequentially connected by pipeline;

[0006] The feeding device includes liquid feeding device and gas feeding device;The liquid feeding device includes 2-chloropropenyl isothiocyanate storage tank, dichloroethane storage tank, mixed precooling tank and weighing module, the 2-chloropropenyl isothiocyanate storage tank and dichloroethane storage tank are connected with mixed precooling tank by material pipeline;The lower pipeline of mixed precooling tank is connected with weighing module;The gas feeding device includes liquid chlorine tank area, vaporizer, chlorinating reagent buffer tank and nitrogen trichloride receiving tank, liquid chlorine tank area, vaporizer and chlorinating reagent buffer tank are sequentially connected, and nitrogen trichloride receiving tank is connected with the lower pipeline of chlorinating reagent buffer tank;

[0007] The mixing pre-cooling tank is connected with the upper distributor of the tower reactor; the chlorinating agent buffer tank is connected with the lower part of the tower reactor through a material pipeline;

[0008] The discharging device comprises a degassing kettle, a condenser A and a tail gas absorption device A; the condenser A is connected with the upper pipeline of the degassing kettle and then connected with the tail gas absorption device A;

[0009] The recycling device comprises a condenser B, a falling film absorption device, a by-product hydrochloric acid receiving tank and a hydrochloric acid tank, which are sequentially connected; the other end of the condenser B is connected with the upper part of the dichloroethane receiving tank; the falling film absorption device is further provided with a tail gas absorption device B on the side;

[0010] Further, the mixing pre-cooling tank and the outer part of the tower reactor are respectively provided with a jacket A and a jacket B;

[0011] Further, the jacket A is provided with a cooling medium inlet a, a cooling medium outlet a and a cooling medium flow rate adjusting valve a; the jacket B is provided with a cooling medium inlet b, a cooling medium outlet b and a cooling medium flow rate adjusting valve b;

[0012] Further, the vaporizer comprises a primary vaporizer and a secondary vaporizer;

[0013] Further, the vaporizer is externally provided with a heat preservation jacket, and the heat preservation jacket is provided with a medium inlet and a medium outlet;

[0014] Further, the chlorinating agent buffer tank and the material pipeline in front of the mixing pre-cooling tank are both provided with a mass flow meter;

[0015] Further, the mixing pre-cooling tank and the material pipeline in front of the by-product hydrochloric acid receiving tank are provided with a centrifugal rotary pump;

[0016] Further, the upper part of the tower reactor is provided with a temperature control system and a pressure gauge;

[0017] Further, the tower reactor is internally provided with an electrically-driven stirring mixer;

[0018] Further, a check valve is arranged on the material pipeline connecting the tower reactor with the chlorinating agent buffer tank

[0019] Compared with the prior art, the utility model has the following remarkable advantages:

[0020] The utility model converts the traditional batch kettle process into a gas-liquid countercurrent continuous flow type, improves the operation efficiency, reduces the liquid holdup of the reaction system, reduces the raw material cost, improves the energy utilization rate, improves the quality and yield of 2-chloro-5-chloromethylthiazole, reduces the generation of three wastes, and further improves the safety of personnel.BRIEF DESCRIPTION OF DRAWINGS BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a kind of gas-liquid countercurrent continuous flow preparation 2-chloro-5-chloromethylthiazole device structure schematic diagram of the utility model;

[0022] In the figure:

[0023] 1-2-chloropropenyl isothiocyanate storage tank, 2-dichloroethane storage tank, 3-mixed pre-cooling tank, 31-jacket A, 311-cooling medium inlet a, 312-cooling medium outlet a, 313-cooling medium flow rate regulating valve a, 32-centrifugal transfer pump A, 33-mass flow meter A, 4-liquid chlorine tank area, 5-vaporizer, 51-first-stage vaporizer, 52-second-stage vaporizer, 53-heat preservation jacket, 531-medium inlet, 532-medium outlet, 6-chlorinated reagent buffer tank, 61-mass flow meter B, 62-check valve, 7-nitrogen trichloride receiving tank, 8-tower reactor, 81-jacket B, 811-cooling medium inlet b, 812-cooling medium outlet b, 813-cooling medium flow rate regulating valve b, 82-temperature control system, 83-distributing device, 84-electric stirring mixer, 85-pressure gauge, 9-deaerating kettle, 10-condenser A, 11-tail gas absorption device A, 12-condenser B, 13-dichloroethane receiving tank, 14-falling film absorption device, 15-by-product hydrochloric acid receiving tank, 151-centrifugal transfer pump B, 16-hydrochloric acid tank, 17-tail gas absorption device B, 18-weighing module. DETAILED DESCRIPTION

[0024] The preferred embodiments of the utility model are described below in conjunction with the drawings, and it should be understood that the specific embodiments described herein are only used to illustrate and explain the utility model, and are not used to limit the utility model.

[0025] Example 1:

[0026] A kind of gas-liquid countercurrent continuous flow preparation 2-chloro-5-chloromethylthiazole device, chlorination process realizes automation control, reduces the number of field operators, while reducing the floor space, more importantly, reduce the liquid holdup of reaction system, intrinsic safety is promoted, while improving 2-chloro-5-chloromethylthiazole quality and yield, increase the income.

[0027] The utility model provides a kind of gas-liquid countercurrent continuous flow preparation 2-chloro-5-chloromethylthiazole device, including feeding device, tower reactor (8), discharging device and recovery device, each device is sequentially connected by pipeline;

[0028] The feeding device includes a liquid feeding device and a gas feeding device; the liquid feeding device includes a 2-chloropropenyl isothiocyanate storage tank (1), a dichloroethane storage tank (2), a mixing pre-cooling tank (3), and a weighing module (18), the 2-chloropropenyl isothiocyanate storage tank (1) and the dichloroethane storage tank (2) are connected with the mixing pre-cooling tank (3) through material pipelines; the lower pipeline of the mixing pre-cooling tank (3) is connected with the weighing module (18); a centrifugal material pump A (32) is arranged on the other end of the pipeline to pump the liquid material into a tower reactor (8).

[0029] The gas feeding device includes a liquid chlorine tank area (4), a vaporizer (5), a chlorinating agent buffer tank, and a nitrogen trichloride receiving tank (7), the liquid chlorine tank area (4), the vaporizer (5), and the chlorinating agent buffer tank (6) are sequentially connected, a check valve (62) is further arranged on the material pipeline connected with the chlorinating agent buffer tank (6) to prevent backflow.

[0030] The nitrogen trichloride receiving tank (7) is connected with the lower pipeline of the chlorinating agent buffer tank (6), in order to ensure safety, the chlorinating agent buffer tank (6) needs to be cleaned regularly, and impurities such as nitrogen trichloride are quenched and treated in the nitrogen trichloride receiving tank (7).

[0031] The vaporizer (5) includes a first-stage vaporizer (51) and a second-stage vaporizer (52); the liquefied reagent in the liquid chlorine tank area (4) passes through the first-stage vaporizer (51) and the second-stage vaporizer (52) and is then introduced into the tower reactor (8) after secondary vaporization.

[0032] The chlorinating agent can be sulfuryl chloride, liquid chlorine, or the like, and is preferably liquid chlorine. The vaporizer (5) is externally provided with a heat preservation jacket (53), the heat preservation jacket is provided with a medium inlet (531) and a medium outlet (532); the medium is hot water or reduced pressure and temperature steam, and the temperature is controlled to be 10-70°C.

[0033] The mixing pre-cooling tank (3) is connected with an upper distributor (83) of the tower reactor (8); the chlorinating agent buffer tank (6) is connected with the lower part of the tower reactor (8) through a material pipeline; a mass flow meter is arranged on the front end material pipeline of the chlorinating agent buffer tank (6) and the mixing pre-cooling tank (3); the liquid and the gas are respectively metered by a mass flow meter A (33) and a mass flow meter B (61) and are introduced into the tower reactor (8) in a quantitative manner, the tower kettle is sampled and detected to detect the reaction condition, and the system is kept in balance. An electric stirring mixer (84) is further arranged in the tower reactor (8) to strengthen the gas-liquid mixing effect and improve the conversion rate.

[0034] The discharge device comprises a degassing kettle (9), a condenser A (10), and a tail gas absorption device A (11); the condenser A (10) is connected with the upper pipeline of the degassing kettle (9) and then connected with the tail gas absorption device A (11);

[0035] The recovery device comprises a condenser B (12), a falling film absorption device (14), a by-product hydrochloric acid receiving tank (15), and a hydrochloric acid tank (16), which are sequentially connected; a centrifugal pump B (151) is arranged on the front end material pipeline of the by-product hydrochloric acid receiving tank (15), that is, after the by-product hydrogen chloride gas is absorbed by the condenser B (12) and the falling film absorption device (14) and then enters the by-product hydrochloric acid receiving tank (15), the hydrogen chloride gas enters the hydrochloric acid tank (16) through the centrifugal pump B. The other end of the condenser B (12) is connected with the upper part of a dichloroethane receiving tank (13); the falling film absorption device (14) is further provided with a tail gas absorption device B (17).

[0036] Further, the mixing pre-cooling tank (3) is externally provided with a jacket A (31), the jacket A (31) is provided with a cooling medium inlet a (311), a cooling medium outlet a (312), and a cooling medium flow rate adjusting valve a (313); the tower reactor (8) is externally provided with a jacket B (81), the jacket B is provided with a cooling medium inlet b (811), a cooling medium outlet b (812), and a cooling medium flow rate adjusting valve b (813); the cooling medium is -15℃ salt water or ethylene glycol, and the control temperature is -7-35℃. The tower reactor (8) is further provided with a temperature control system (82) and a pressure gauge (85) at the upper part; the cooling medium flow rate adjusting valve a (313) and the cooling medium flow rate adjusting valve b (813) are temperature interlocked with the mixing pre-cooling tank (3) and the tower reactor (8), and are controlled by the temperature control system according to the process temperature requirement.

[0037] Specifically, 2-chloropropenyl isothiocyanate and dichloroethane are taken in a certain molar ratio, pre-cooled by the mixing pre-cooling tank (3), and subjected to a ring closure reaction with a chlorinating reagent under the low-temperature condition of the tower reactor (8) in a molar ratio; then the reaction product is controlled by an adjusting valve to control the production amount, quantitatively transferred to the degassing kettle (9) to perform degassing, and the reaction temperature is controlled at -5-90℃ to complete the reaction, enter the subsequent crystallization and distillation processes, and obtain 2-chloro-5-chloromethylthiazole finished products, with a yield of 93% or more.

[0038] The above embodiment is only a preferred technical solution of the present application, and should not be regarded as a limitation of the present application. The protection scope of the present application should be based on the technical solution recorded in the claims, including the equivalent replacement solution of the technical features recorded in the claims, that is, the equivalent replacement improvement within the scope is also within the protection scope of the present application.

Claims

1. A device for the continuous flow preparation of 2-chloro-5-chloromethylthiazole by gas-liquid counter-current flow, characterized in that, It comprises a feeding device, a tower reactor, a discharging device and a recovery device, which are connected in sequence through pipelines. The feeding device comprises a liquid feeding device and a gas feeding device; the liquid feeding device comprises a 2-chloropropenyl isothiocyanate storage tank, a dichloroethane storage tank, a mixing pre-cooling tank and a weighing module; the 2-chloropropenyl isothiocyanate storage tank and the dichloroethane storage tank are connected with the mixing pre-cooling tank through material pipelines; the lower pipeline of the mixing pre-cooling tank is connected with the weighing module; the gas feeding device comprises a liquid chlorine tank area, a vaporizer, a chlorinating agent buffer tank and a nitrogen chloride receiving tank; the liquid chlorine tank area, the vaporizer and the chlorinating agent buffer tank are connected in sequence; the nitrogen chloride receiving tank is connected with the lower pipeline of the chlorinating agent buffer tank. The mixing pre-cooling tank is connected with an upper distributor of the tower reactor; the chlorinating agent buffer tank is connected with the lower part of the tower reactor through a material pipeline. The discharging device comprises a degassing kettle, a condenser A and a tail gas absorption device A. The condenser A is connected with the upper pipeline of the degassing kettle and then connected with the tail gas absorption device A. The recovery device comprises a condenser B, a falling film absorption device, a by-product hydrochloric acid receiving tank and a hydrochloric acid tank, which are connected in sequence; the other end of the condenser B is connected with the upper part of the dichloroethane receiving tank; the falling film absorption device is additionally provided with a tail gas absorption device B.

2. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The mixing pre-cooling tank and the tower reactor are respectively provided with a jacket A and a jacket B.

3. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 2, characterized in that, The jacket A is provided with a cooling medium inlet a, a cooling medium outlet a and a cooling medium flow rate adjusting valve a; the jacket B is provided with a cooling medium inlet b, a cooling medium outlet b and a cooling medium flow rate adjusting valve b.

4. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The vaporizer comprises a primary vaporizer and a secondary vaporizer.

5. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 4, characterized in that, The vaporizer is externally provided with a heat preservation jacket, which is provided with a medium inlet and a medium outlet.

6. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The chlorinating agent buffer tank and the mixing pre-cooling tank are respectively provided with a mass flow meter on the front end material pipeline.

7. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The mixing pre-cooling tank and the by-product hydrochloric acid receiving tank are respectively provided with a centrifugal transfer pump on the front end material pipeline.

8. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The tower reactor is provided with a temperature control system and a pressure gauge on the upper part.

9. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The tower reactor is internally provided with an electric stirring mixer.

10. The apparatus for the gas-liquid countercurrent continuous flow production of 2-chloro-5-chloromethylthiazole according to claim 1, characterized in that, The tower reactor and the chlorinating agent buffer tank are respectively provided with a check valve on the material pipeline.

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