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CN-122006618-A - Continuous reaction equipment for N-N-butyl thiophosphoric triamide and preparation method

CN122006618ACN 122006618 ACN122006618 ACN 122006618ACN-122006618-A

Abstract

A continuous reaction device of N-N-butyl thiophosphoric triamide and a preparation method. The invention discloses a continuous preparation method and reaction equipment of N-N-butyl thiophosphoryl triamide, belonging to the technical field of fine chemical engineering. The preparation method comprises the steps of taking phosphorus trichloride as an initial raw material, uniformly mixing the initial raw material with a solvent in a batching kettle to prepare phosphorus trichloride solution, respectively adding the phosphorus trichloride solution, N-butylamine and inert gas into a microchannel reactor through a flow pump to carry out substitution reaction, separating hydrogen chloride gas and N-N-butyldichlorophosphoryl amide solution through a gas-liquid separator, then adding the N-N-butyldichlorophosphoryl amide solution and liquid ammonia into a tubular reactor through the flow pump to obtain N-N-butylthiophosphoryl triamide solution, finally concentrating an organic phase, crystallizing, separating and drying to obtain the high-purity N-N-butylthiophosphoryl triamide. The method is safe and efficient, simple and convenient to operate, good in reaction selectivity, high in yield, less in pollutant emission, low in production cost and suitable for industrial production.

Inventors

  • SHI YUHUA
  • YU YIZHONG
  • Gu Xuanyu
  • SHEN WENCHAO
  • WANG XIAOHONG
  • Yu Penghai
  • ZHANG JUNLIN
  • PENG YULING
  • CHEN JUNAN
  • YU YAJIE
  • LIU JIAHUAN
  • GAO YU

Assignees

  • 武威金仓生物科技有限公司
  • 金仓(上海)医药生物科技有限公司

Dates

Publication Date
20260512
Application Date
20260306

Claims (10)

  1. 1. A continuous reaction device for N-N-butyl thiophosphoryl triamide is characterized by comprising a batching kettle (2) with a top fixedly connected with a feeding pipe (1), a microchannel reactor (6) communicated with a discharge port of the batching kettle (2) through a first communication pipe (201), a gas-liquid separator (7) communicated with the discharge port of the microchannel reactor (6) through a third communication pipe (601), a liquid outlet pipe (9) fixedly connected to the bottom of the gas-liquid separator (7), a second flow pump (11) fixedly connected to one end, far away from the gas-liquid separator (7), of the liquid outlet pipe (9), a tubular reactor (12) connected with the second flow pump (11) through a fourth communication pipe (1101), a liquid ammonia feeding pipeline (10) fixedly connected to the second flow pump (11), a first flow pump (5) fixedly connected to the tail end of the first communication pipe (201), a normal butylamine pipeline (3) and a nitrogen pipeline (4) respectively fixedly connected to the first flow pump (5), and a second flow pump (501) fixedly connected to the second communication pipe (501) and the second flow pump (6).
  2. 2. The continuous reaction device of N-N-butyl thiophosphoryl triamide according to claim 1, wherein an air outlet pipe (8) is fixedly connected to the side wall of the top of the gas-liquid separator (7).
  3. 3. A continuous production method of N-butyl thiophosphoric triamide by using the production apparatus according to claim 1 or 2, characterized by comprising the steps of: Firstly, mixing phosphorus oxychloride serving as a starting material with a solvent in a batching kettle (2) uniformly to prepare a phosphorus oxychloride solution, respectively adding the phosphorus oxychloride solution, N-butylamine and inert gas into a microchannel reactor (6) through a first communication pipe (201), an N-butylamine feeding pipeline (3) and a nitrogen feeding pipeline (4) through a first flow pump (5) for substitution reaction, and separating hydrogen chloride gas through a gas-liquid separator (7) to obtain an N-N-butyl dichloro thiophosphamide solution; (2) Adding liquid ammonia into a tubular reactor (12) through a second flow pump (11) by using an N-N-butyl dichloro thiophosphamide solution and a liquid ammonia feeding pipeline (10) through a liquid outlet pipe (9) to obtain an N-N-butyl thiophosphoryl triamide solution; (3) The N-N-butyl thiophosphoric triamide solution is extracted and washed, and the organic phase is concentrated, crystallized, separated and dried to obtain the high-purity N-N-butyl thiophosphoric triamide.
  4. 4. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (1), the concentration of the phosphorus oxychloride solution is 5% -50%, and the reaction temperature is 0-60 ℃.
  5. 5. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (1), the molar ratio of the phosphorus oxychloride, the N-butylamine and the inert gas is 1:0.8-1.2:0.5-1.5.
  6. 6. A continuous production method of N-N-butylthiophosphoric triamide according to claim 3, wherein in the step (1), the solvent is selected from toluene, methylene chloride, dichloroethane, chlorobenzene, anisole, isopropyl acetate and 2-methyltetrahydrofuran, and the inert gas is selected from nitrogen or argon.
  7. 7. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (1), the flow rate of a phosphorus oxychloride solution is 20-500 g/min, the flow rate of N-butylamine is 2-50 g/min, the flow rate of nitrogen is 0.5-50 g/min, and the reaction residence time of a micro-channel is 20-600 seconds.
  8. 8. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (2), the mol ratio of N-N-butyl dichloro thiophosphoryl amide to liquid ammonia is 1:2-100, the reaction temperature is 0-50 ℃, the flow rate of the N-N-butyl dichloro thiophosphoryl amide solution is 20-600 g/min, and the flow rate of the liquid ammonia is 2-60 g/min.
  9. 9. The continuous production method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (2), the inner diameter of the pipe reactor is 5-200 mm, the reaction residence time is 5-60 minutes, and the length of the pipe reactor is 1-500 m.
  10. 10. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 3, wherein in the step (2), the post-treatment is that water quenching is added after the reaction is finished, the extraction and layering are carried out, the organic phase is concentrated, crystallized and refined to obtain the product of N-butyl thiophosphoryl triamide, and the byproduct ammonium chloride is recovered after the water phase is treated.

Description

Continuous reaction equipment for N-N-butyl thiophosphoric triamide and preparation method Technical Field The invention relates to a method for preparing N-N-butyl thiophosphoryl triamide by combining a micro-channel and pipelining and reaction equipment, belonging to the technical field of fine chemical engineering. Background N-N-butyl thiophosphoric triamide is one of the most effective soil urease inhibitors at present, has the outstanding advantages of high efficiency, no toxicity, no side effect and the like, and is usually used as an active ingredient of compound fertilizer. In CN101337976a, a method for N-butyl thiophosphoryl triamide is reported, which adopts trichlorothiophosphoryl to react with N-butylamine and separates intermediate N-butyl dichloro thiophosphoryl amide, and the purified N-butyl dichloro thiophosphoryl amide is treated after reaction with ammonia gas to obtain N-butyl thiophosphoryl triamide. The process is complicated, relates to the requirements of high-temperature and low-temperature reaction, has poor reaction selectivity, long production period and higher cost, and does not have commercial advantages. CN101412733a reports a synthesis method for preparing N-butyl thiophosphoryl triamide by a one-pot method, triethylamine is used as alkali in the reaction, and the reaction time for introducing ammonia gas at last is long (usually 2 hours), so that the production cost is increased, and great environmental protection hidden trouble exists in the use of triethylamine and a large excess of ammonia gas. CN102030775B reports a synthesis method for producing N-butyl thiophosphoryl triamide in a pipelining manner, but the tubular reaction is only applied to the first step reaction, the second step reaction still adopts a traditional intermittent reaction kettle, and the reaction time for introducing ammonia gas (usually 2.5-3 hours) is longer, so that the production cost is higher, and the problems of control of the production cost and potential environmental protection hidden trouble are not solved. CN102746333B reports a method for preparing N-butyl thiophosphoric triamide by using inorganic base as acid binding agent, but the method requires to drop N-butylamine and inorganic alkaline aqueous solution at the same time, has extremely high operation requirement on drop acceleration control, and is not suitable for industrial production. CN110950904B reports a continuous preparation method for preparing N-butyl thiophosphoryl triamide by using a microchannel and tubular reaction device, although a continuous mode is adopted, hydrogen chloride generated by the reaction in the first key step always accompanies the continuous reaction process, and the removal of a large amount of gas depends on an ion resin device, so that the efficiency is low. Therefore, if the heat and mass transfer and separation effects can be further improved through engineering and technical means on the basis of the original mature process route, the selectivity problem caused by high reaction activity is overcome, the continuous production of N-N-butyl thiophosphoryl triamide is realized, and the method has great benefits for improving the raw material conversion efficiency and the comprehensive competitiveness of the product. In order to solve the problems of the traditional process, the technology takes a continuous flow method as a technical basis, takes phosphorus oxychloride, N-butylamine and ammonia gas as raw materials, and realizes the continuous production of the production process of N-N-butyl thiophosphoryl triamide through a microchannel reaction and a tubular reaction device in solution, thereby overcoming the defects of the prior art, further simplifying the process, improving the reaction selectivity and the yield result, and achieving the purposes of clean production, improving the efficiency, shortening the production period and reducing the production cost. Disclosure of Invention In order to overcome the technical defects, the invention provides a continuous flow technology and equipment for fusing a micro-channel reaction and a tubular reaction, and a method for continuously preparing N-N-butyl thiophosphoric triamide in a micro-reactor and a tubular reactor. The method is safe and efficient, simple and convenient to operate, good in reaction selectivity, high in yield, less in pollutant emission, low in production cost and suitable for industrial production. The invention provides continuous preparation equipment of N-N-butyl thiophosphoryl triamide, which comprises a batching kettle, a micro-channel reactor, a gas-liquid separator, a metering pump, a flow pump and a tubular reactor. The top of the batching kettle is fixedly connected with a charging pipe; the microchannel reactor is communicated with the discharge port of the batching kettle through a first communication pipe; the gas-liquid separator is communicated with the discharge port of the microchannel reactor through a third comm