Chloroamine continuous synthesis equipment and process thereof

Abstract

This invention discloses a continuous synthesis apparatus and process for chloroamines, belonging to the field of organic synthesis technology. The continuous synthesis apparatus for chloroamines includes, in series, an acetamide sodium salt reactor, an allylamide reactor, a chloroamine synthesis reactor, and an automatic phase separator. The lower liquid outlet of the automatic phase separator is connected to a solvent removal tower, and the upper liquid outlet is connected to a dealcoholization tower. A condenser and an alcohol receiving tank are connected in series at the top of the dealcoholization tower, and the bottom of the dealcoholization tower is connected to an alkalization reactor, an automatic phase separator, and a product distillation tower. This invention also discloses a continuous synthesis process for chloroamines. The equipment of this invention can accurately monitor the reaction, shorten the reaction time, significantly improve product yield and output, and ensure stable product quality.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a continuous synthesis equipment and process for chloroamines. Background Technology

[0002] Trans-3-chloro-2-propenylhydroxylamine (hereinafter referred to as chloroamine) is a colorless liquid and is a very important intermediate in the pesticide and pharmaceutical industries. It is widely used in cyclohexenone herbicides.

[0003] Most existing publicly available processes are batch reactions. For example, patent CN113773224A discloses a process for producing chloroamine by first recovering methanol; patent CN114105810A discloses a microchannel continuous flow process for synthesizing chloroamine. Each of these technologies has its advantages and disadvantages. Batch reactors offer higher yields, and microchannel continuous flow offers a high safety factor. However, batch reactor production does not provide guidance on overcoming safety issues such as heat accumulation and over-reaction; it also cannot guarantee zero accidents by handling additional reactant equipment and addressing leakage problems during loading and unloading. Microchannel continuous flow production has lower yields, requires larger equipment investments, and increases production costs.

[0004] Batch reactor operation is difficult and expensive to automate; due to the high concentration of reactants, it is difficult to quickly remove the heat of reaction, and the high concentration of raw materials makes side reactions more likely, reducing production efficiency; batch reactor operation requires a long preparation time before the next stage, which is not energy-efficient. Microchannel reaction has a lower generation efficiency than batch reactor reaction, and the equipment investment cost is much higher than that of batch reactor production for the same output. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned technical deficiencies and provide a continuous synthesis equipment and process for chloroamines, solving the technical problems of difficult temperature control, high production cost, long production time, and low product yield in the prior art.

[0006] To achieve the above-mentioned technical objectives, the present invention provides a continuous synthesis apparatus and process for chloroamines. A continuous synthesis apparatus for chloroamines includes, in series, an acetamide sodium salt reactor, an allylamide reactor, a chloroamine synthesis reactor, and an automatic phase separator. The automatic phase separator has an upper liquid outlet and a lower liquid outlet. The lower liquid outlet is connected to a solvent removal tower. The solvent removal tower is in series with a condenser and a solvent receiving tank. The upper liquid outlet is connected to a dealcoholization tower. The top of the dealcoholization tower is in series with a condenser and an alcohol receiving tank. The bottom of the dealcoholization tower is connected to an alkalization reactor. The alkalization reactor is connected to the automatic phase separator, which is also connected to a product distillation tower.

[0007] Preferably, the automatic phase separator II is provided with an aqueous phase outlet and an organic phase outlet, and the organic phase outlet is connected to the product distillation column.

[0008] Preferably, one output end of the product distillation column is connected to a chloroamine collector, and the other output end is connected to a solvent receiving tank.

[0009] Preferably, a transfer pump is installed between the dealcoholization tower and the alkalization reactor.

[0010] Preferably, a condenser is provided between the product distillation column and the chloroamine collector and / or solvent receiving tank 2.

[0011] A continuous synthesis process for chloroamines, based on the equipment described above, includes the following steps;

[0012] S1. The raw materials methyl acetate, hydroxylamine hydrochloride, and liquid alkali are pumped into the sodium acetamide salt reactor to carry out reaction 1, and sodium acetamide salt is obtained.

[0013] S2. Sodium acetamide is pumped into the allylamide reactor, and trans-1,3-dichloropropene is added at the same time to carry out reaction 2 to obtain allylamide.

[0014] S3. Allylamide is pumped into the chloroamine synthesis reactor, and hydrochloric acid and dichloromethane are added at the same time to carry out reaction 3 and obtain reaction 3 solution;

[0015] S4. The solution of reaction 3 is overflowed into the automatic phase separator one. The acid hydrolysate from the upper liquid outlet of the automatic phase separator one enters the alcohol removal tower, and the organic phase from the lower liquid outlet enters the solvent removal tower.

[0016] S5. The desolventizing tower is automatically fed and continuously distilled and condensed to obtain dichloromethane, which can be reused in the reaction system.

[0017] S6. The dealcoholization tower is automatically fed and continuously distilled to remove low-boiling-point alcohols. The bottom of the dealcoholization tower is discharged into the alkalization kettle.

[0018] S7. Pump liquid alkali and dichloromethane into the alkalization reactor to carry out reaction 4 and obtain reaction 4 solution;

[0019] S8. The solution from reaction 4 overflows into the automatic phase separator II. The upper aqueous phase enters the wastewater treatment, and the lower organic phase enters the product distillation column to obtain the product chloroamine.

[0020] Preferably, the reaction temperature of reaction 1 is 26-30℃.

[0021] Preferably, the reaction temperature of reactions 2 and 3 is 78-82℃.

[0022] Preferably, the reaction temperature of reaction 4 is 48-52℃.

[0023] Preferably, the flow rate of methyl acetate is 77-78 kg / h, the flow rate of hydroxylamine hydrochloride aqueous solution is 130-159.2 kg / h, and the flow rate of liquid alkali is 60-80 kg / h.

[0024] The continuous reactor equipment and process employed in this invention, through the control of material flow rate, reaction temperature, and residence time, enables more precise monitoring of the reaction, timely transfer of fully reacted materials to the next stage, shortening reaction time, significantly improving product yield and output, and ensuring stable product quality. The continuous flow of materials through the series of reactors effectively avoids leakage during material transfer, greatly reduces the workload of production personnel, improves production efficiency, and significantly increases product output; it also better meets the national standards for automation, environmental protection, and safety. Attached Figure Description

[0025] Figure 1 This is a structural diagram of a continuous chloroamine synthesis device provided in a specific embodiment of the present invention.

[0026] Among them: 1-acetamide sodium salt reactor; 2-allylamide reactor; 3-chloroamine synthesis reactor; 4-automatic phase separator one; 41-upper liquid outlet, 42-lower liquid outlet; 5-desolventizing tower; 6-condenser one; 7-solvent receiving tank one; 8-de-alcoholizing tower; 9-condenser two; 10-alcohol receiving tank; 11-transfer pump; 12-alkalization reactor; 13-automatic phase separator two; 14-product distillation tower; 15-condenser three; 16-solvent receiving tank two; 17-chloroamine collector. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0028] Example 1

[0029] Please see Figure 1A continuous synthesis apparatus for chloroamine includes an acetamide sodium salt reactor 1, an allylamide reactor 2, a chloroamine synthesis reactor 3, and an automatic phase separator 4 connected in series. The automatic phase separator 4 has an upper liquid outlet 41 and a lower liquid outlet 42. The lower liquid outlet 42 is connected to a solvent removal tower 5. The solvent removal tower 5 is connected in series with a condenser 6 and a solvent receiving tank 7. The upper liquid outlet 41 is connected to a dealcoholization tower 8. The top of the dealcoholization tower 8 is connected in series with a condenser 9 and an alcohol receiving tank 10. The bottom of the dealcoholization tower 8 is connected to an alkalization reactor 12. A transfer pump 11 is installed between the dealcoholization tower 8 and the alkalization reactor 12. The alkalization reactor 12 is connected to an automatic phase separator 13. The automatic phase separator 13 is connected to a product distillation tower 14. The automatic phase separator 13 has an aqueous phase outlet and an organic phase outlet. The organic phase outlet is connected to the product distillation tower 14. One output end of the product distillation column 14 is connected to the chloroamine collector 17, and the other output end is connected to the solvent receiving tank 16. A condenser 15 is provided between the product distillation column 14 and the chloroamine collector 17 and / or the solvent receiving tank 16.

[0030] All the reactors are 3000L, 5000L, and 6300L in size, with overflow and feed ports on the side, and are made of stainless steel or enamel. The specific number of reactors is determined by the reaction time and flow rate. An automatic phase separator automatically separates the phases, and the continuous desolvation tower and distillation tower fundamentally solve the problem of having many personnel in the workshop.

[0031] A continuous synthesis process for chloroamines, based on the equipment described above, includes the following steps;

[0032] The raw materials are pumped into sodium acetamide reactor 1 at a flow rate of 77 kg / h for methyl acetate, 159.2 kg / h for hydroxylamine hydrochloride aqueous solution, and 78 kg / h for liquid alkali (30% sodium hydroxide), with the reactor temperature controlled at 26°C. The material in sodium acetamide reactor 1 is increased until it overflows through the overflow port into allyl amide reactor 2, where trans-1,3-dichloropropene is pumped in at a flow rate of 58.8 kg / h, and the reaction temperature is controlled at 78°C via the reactor jacket. The material in allyl amide reactor 2 is increased until it overflows through the overflow port into chloroamine synthesis reactor 3, where hydrochloric acid and dichloromethane water are pumped in at flow rates of 98 kg / h and 55 kg / h, respectively, with the reaction temperature controlled at 78°C via the reactor jacket. The material is then transferred from the chloroamine reactor... The overflow from amine synthesis reactor 3 is sent to automatic phase separator 4. The upper acid hydrolysate enters dealcoholization tower 8, and the lower organic phase enters desolventization tower 5. Desolventization tower 5 is automatically fed and continuously distilled and condensed to obtain dichloromethane, which is recycled back into the system. Dealcoholization tower 8 is automatically fed and continuously distilled to remove low-boiling alcohols. The bottom product enters alkalization reactor 12. Liquid alkali and dichloromethane are pumped into alkalization reactor 12 at flow rates of 89.9 kg / h and 60 kg / h, respectively. The reaction temperature is controlled at 48°C by the reactor jacket. The material overflows from alkalization reactor 12 to automatic phase separator 13. The upper water enters wastewater treatment, and the lower organic phase enters product distillation tower 14 to obtain a product with a chloroamine content of 98.1% and a comprehensive yield of 89%.

[0033] Example 2

[0034] The equipment in this embodiment is the same as that in Embodiment 1. The continuous synthesis process of chloroamine in this embodiment includes the following steps: Raw materials are pumped into sodium acetamide reactor 1 at a flow rate of 77 kg / h methyl acetate, 130 kg / h hydroxylamine hydrochloride aqueous solution, and 60 kg / h liquid alkali, with the reactor temperature controlled at 30°C; the material in sodium acetamide reactor 1 is increased until it overflows through the overflow port into allyl amide reactor 2, and trans-1,3-dichloropropene is pumped in at a flow rate of 58.8 kg / h; the material in allyl amide reactor 2 is increased until it overflows through the overflow port into chloroamine synthesis reactor 3, and hydrochloric acid and dichloromethane water are pumped in at flow rates of 98 kg / h and 55 kg / h respectively, with the reaction temperature controlled at 82°C by the reactor jacket; the reaction... The material overflows from the chloroamine synthesis reactor 3 to the automatic phase separator 4. The upper acid hydrolysate enters the dealcoholization tower 8, and the lower organic phase enters the solvent removal tower 5. The solvent removal tower 5 is automatically fed and continuously distilled and condensed to obtain dichloromethane, which is recycled back into the system. The dealcoholization tower 8 is automatically fed and continuously distilled to remove low-boiling alcohols. The bottom product enters the alkalization reactor 12. Liquid alkali and dichloromethane are pumped into the alkalization reactor 12 at flow rates of 89.9 kg / h and 60 kg / h, respectively. The reaction temperature is controlled at 52°C by the reactor jacket. The material overflows from the alkalization reactor 12 to the automatic phase separator 13. The upper water enters the wastewater treatment, and the lower organic phase enters the product distillation tower 14 to obtain a product with a chloroamine content of 99.1% and a comprehensive yield of 87%.

[0035] Example 3

[0036] The equipment in this embodiment is the same as that in Embodiment 1. The continuous synthesis process of chloroamine in this embodiment includes the following steps: Raw materials are pumped into sodium acetamide reactor 1 at a flow rate of 78 kg / h for methyl acetate, 150 kg / h for hydroxylamine hydrochloride aqueous solution, and 80 kg / h for liquid alkali, while controlling the reactor temperature at 30°C; the material in sodium acetamide reactor 1 is increased until it overflows through the overflow port into allyl amide reactor 2, and trans-1,3-dichloropropene is pumped in at a flow rate of 60 kg / h, while controlling the reaction temperature at 80°C through the reactor jacket; the material in allyl amide reactor 2 is increased until it overflows through the overflow port into chloroamine synthesis reactor 3, and hydrochloric acid and dichloromethane water are pumped in at flow rates of 90 kg / h and 55 kg / h, respectively. The material overflowing from the chloroamine synthesis reactor C is transferred to an automatic phase separator. The upper acid hydrolysate enters the dealcoholization tower 8, and the lower organic phase enters the solvent removal tower 5. The solvent removal tower 5 is automatically fed and continuously distilled and condensed to obtain dichloromethane, which is recycled back into the system. The dealcoholization tower 8 is automatically fed and continuously distilled to remove low-boiling alcohols. The bottom product enters the alkalization reactor 12. Liquid alkali and dichloromethane are pumped into the alkalization reactor 12 at flow rates of 90 kg / h and 60 kg / h, respectively. The reaction temperature is controlled at 50°C by the reactor jacket. The material overflowing from the alkalization reactor 12 is transferred to an automatic phase separator. The upper water enters the wastewater treatment plant, and the lower organic phase enters the product distillation tower 14 to obtain a product with a chloroamine content of 98.0% and a comprehensive yield of 90%.

[0037] Compared with the prior art, the present invention has significant advantages in the following aspects:

[0038] 1) Precise reaction control. Due to the characteristics of series reactors, continuous reactor processes can more accurately monitor the reaction by controlling material flow, reaction temperature, and residence time. This allows for timely transfer of fully reacted materials to the next stage, shortening reaction time, significantly improving product yield and output, and ensuring stable product quality. Compared to instantaneous reaction volumes, constant temperature minimizes reaction risks.

[0039] 2) Reduced workload for personnel. The continuous flow of materials through series reaction vessels effectively avoids leakage problems during material transfer, greatly reduces the workload of production personnel, improves production efficiency, and significantly increases product output.

[0040] 3) Low investment. Compared to microchannel reactors, continuous batch reactors achieve far higher efficiency with the same investment, but require only 1 / 3 or even less investment.

[0041] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A continuous synthesis process for chloroamines, based on a continuous synthesis equipment for chloroamines, characterized in that, The equipment includes an acetamide sodium salt reactor, an allylamide reactor, a chloroamine synthesis reactor, and an automatic phase separator connected in series. The automatic phase separator has an upper liquid outlet and a lower liquid outlet. The lower liquid outlet is connected to a solvent removal tower. The solvent removal tower is connected in series with a condenser and a solvent receiving tank. The upper liquid outlet is connected to a dealcoholization tower. The top of the dealcoholization tower is connected in series with a condenser and an alcohol receiving tank. The bottom of the dealcoholization tower is connected to an alkalization reactor. The alkalization reactor is connected to the automatic phase separator. The automatic phase separator is connected to a product distillation tower. The continuous synthesis process of the chloroamine includes the following steps: S1. The raw materials methyl acetate, hydroxylamine hydrochloride, and liquid alkali are pumped into the sodium acetamide salt reactor to carry out reaction 1, and sodium acetamide salt is obtained; S2. Sodium acetamide is pumped into the allylamide reactor, and trans-1,3-dichloropropene is added at the same time to carry out reaction 2 to obtain allylamide. S3. Allylamide is pumped into the chloroamine synthesis reactor, and hydrochloric acid and dichloromethane are added at the same time to carry out reaction 3 and obtain reaction 3 solution; S4. The solution of reaction 3 is overflowed into the automatic phase separator one. The acid hydrolysate from the upper liquid outlet of the automatic phase separator one enters the alcohol removal tower, and the organic phase from the lower liquid outlet enters the solvent removal tower. S5. The desolventizing tower is automatically fed, and distillation and condensation are performed to obtain dichloromethane. S6. The dealcoholization tower is automatically fed and continuously distilled to remove low-boiling-point alcohols. The bottom of the dealcoholization tower is discharged into the alkalization kettle. S7. Pump liquid alkali and dichloromethane into the alkalization reactor to carry out reaction 4 and obtain reaction 4 solution; S8. The solution from reaction 4 overflows into the automatic phase separator II. The upper aqueous phase enters the wastewater treatment, and the lower organic phase enters the product distillation column to obtain the product chloroamine.

2. The continuous synthesis process of chloroamines according to claim 1, characterized in that, The automatic phase separator is equipped with an aqueous phase outlet and an organic phase outlet, and the organic phase outlet is connected to the product distillation column.

3. The continuous synthesis process of chloroamines according to claim 2, characterized in that, One output end of the product distillation column is connected to a chloroamine collector, and the other output end is connected to a solvent receiving tank.

4. The continuous synthesis process of chloroamines according to claim 3, characterized in that, A transfer pump is installed between the alcohol removal tower and the alkalization reactor.

5. The continuous synthesis process of chloroamines according to claim 4, characterized in that, A condenser is provided between the product distillation column and the chloroamine collector or solvent receiving tank 2.

6. The continuous synthesis process of chloroamines according to claim 1, characterized in that, The reaction temperature of reaction 1 is 26-30℃.

7. The continuous synthesis process of chloroamines according to claim 6, characterized in that, The reaction temperatures for reactions 2 and 3 are 78-82℃.

8. The continuous synthesis process of chloroamines according to claim 1, characterized in that, The reaction temperature of reaction 4 is 48-52℃.

9. The continuous synthesis process of chloroamines according to claim 1, characterized in that, The flow rate of methyl acetate is 77-78 kg / h, the flow rate of hydroxylamine hydrochloride aqueous solution is 130-159.2 kg / h, and the flow rate of liquid alkali is 60-80 kg / h.

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