CN110950904B - Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide - Google Patents
Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide Download PDFInfo
- Publication number
- CN110950904B CN110950904B CN201911101948.5A CN201911101948A CN110950904B CN 110950904 B CN110950904 B CN 110950904B CN 201911101948 A CN201911101948 A CN 201911101948A CN 110950904 B CN110950904 B CN 110950904B
- Authority
- CN
- China
- Prior art keywords
- reactor
- butyl
- reaction
- toluene solution
- phosphorus oxychloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a continuous preparation method and a preparation device of N-N-butyl thiophosphoryl triamide, wherein the preparation method comprises the following steps: (1) Adding a phosphorus oxychloride toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichloro phosphoroamid toluene solution, treating the toluene solution by anion exchange resin, and then entering a storage tank; (2) Adding the solution in the storage tank and ammonia gas into a tubular reactor for reaction to obtain N-N-butyl thiophosphoryl triamide toluene solution; (3) And (3) extracting and washing the obtained solution, concentrating and recrystallizing the organic phase, separating and drying to obtain the high-purity N-N-butyl thiophosphoric triamide. The continuous preparation method and the preparation device realize the continuity of the production process of the N-N-butyl thiophosphoryl triamide, overcome the defect of intermittent operation of a kettle type reactor, simplify the process, improve the reaction selectivity and achieve the aims of clean production, shortened production period and reduced production cost.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a continuous preparation method and a preparation device of N-N-butyl thiophosphoric triamide.
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.
CN101337976a reports a method for N-butyl thiophosphoryl triamide, 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. However, 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, in which triethylamine is used as a base in the reaction, but the reaction time for introducing ammonia gas at last is long (usually 2 hours), so that the production cost is increased, and the use of triethylamine and a large amount of excess ammonia gas has a great environmental protection hidden trouble. CN102030775B reports a synthesis method for producing N-butyl thiophosphoryl triamide by a pipelining manner, but the tubular reaction is only applied to the first step reaction, the second step reaction still adopts a traditional batch reaction kettle, and the problems of longer reaction time (usually 2.5-3 hours), higher production cost and potential environmental protection hidden trouble exist. CN102746333B reports a method for preparing N-butyl thiophosphoryl triamide by using inorganic base as acid-binding agent, but the method requires to drop N-butylamine and inorganic base aqueous solution at the same time, has extremely high operation requirement on drop acceleration control, and is not suitable for industrial production.
The continuous flow reaction technology is an emerging organic synthesis technology, and compared with the traditional kettle type intermittent reaction, the continuous flow reaction technology has the following steps: generally has no amplification effect, can improve the selectivity of the reaction, has low energy consumption and has the advantages of stronger heat and mass transfer effects through optimizing the retention time.
Therefore, the design of the synthesis method can overcome the selectivity problem caused by high reaction activity, and realize continuous production of N-N-butyl thiophosphoryl triamide while obtaining products with better quality in a large scale, thus being a problem which needs to be solved by the technicians in the field.
Disclosure of Invention
The invention provides a continuous preparation method and a preparation device of N-N-butyl thiophosphoryl triamide, which are used for solving the problems of long reaction time, higher production cost, inapplicability to industrial production, potential environmental protection hidden trouble and the like in the existing N-N-butyl thiophosphoryl triamide synthesis technology.
The method takes phosphorus oxychloride, N-butylamine and ammonia gas as raw materials, and continuously reacts in a microchannel reactor and a tubular reaction device, thereby realizing the continuity of the production process of N-N-butyl thiophosphoryl triamide, overcoming the defect of intermittent operation of a kettle type reactor, simplifying the process, improving the reaction selectivity and achieving the aims of clean production, shortening the production period and reducing the production cost.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aspect of the invention provides a continuous preparation method of N-N-butyl thiophosphoric triamide, which comprises the following steps:
(1) Mixing phosphorus oxychloride with toluene to form a phosphorus oxychloride toluene solution, adding the phosphorus oxychloride toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichloro phosphoroamidetoluene solution, and treating the solution by anion exchange resin and then entering a storage tank;
(2) Respectively adding the N-N-butyl dichloro thiophosphoryl amide toluene solution and ammonia gas in the storage tank into a tubular reactor for reaction to obtain N-N-butyl thiophosphoryl triamide toluene solution;
(3) And (3) extracting and washing the obtained N-N-butyl thiophosphoric triamide toluene solution, concentrating and recrystallizing an organic phase, separating and drying to obtain the high-purity N-N-butyl thiophosphoric triamide.
Further, in the step (1), the concentration of the phosphorus oxychloride toluene solution is 5-50%, and the mass ratio of the phosphorus oxychloride to the n-butylamine is 1:0.8-1.2, wherein the temperature of the substitution reaction is 0-60 ℃, and the reaction residence time is 30-180s.
Further preferably, in the step (1), the concentration of the toluene solution of the phosphorus oxychloride is 10-15%, and the mass ratio of the phosphorus oxychloride to the n-butylamine is 1:0.9-1.1, wherein the temperature of the substitution reaction is 15-35 ℃, and the reaction residence time is 60-80s.
Further, in the step (1), the inner diameter of the microchannel reactor is 0.4-60mm, and the length is 0.5-10m; the flow rate of the reaction liquid in the micro-channel reactor is 0.5-6m/min.
Further preferably, in the step (1), the micro-channel reactor has an inner diameter of 3-10mm and a length of 1.5-5m; the flow rate of the reaction liquid in the micro-channel reactor is 1.5-2.5m/min.
Further, in the step (2), the mass ratio of the N-N-butyl dichloro thiophosphamide to the ammonia gas is 1:4-5000, wherein the reaction temperature is 0-50 ℃ and the reaction residence time is 120-300s.
Further preferably, in the step (2), the mass ratio of the N-butyldichlorophosphorous amide to ammonia gas is 1:10-60, wherein the temperature of the reaction is 15-30 ℃, and the reaction residence time is 180-240s.
Further, in the step (2), the inner diameter of the pipeline reactor is 5-200mm, and the length of the pipeline reactor is 0.5-20m; the flow rate of the reaction liquid in the pipeline reactor is 0.2-1.0m/min.
Further preferably, in the step (2), the inner diameter of the pipeline reactor is 10-50mm and the length is 2-5m; the flow rate of the reaction liquid in the pipeline reactor is 0.3-0.6m/min.
Further, in the step (3), the organic solvent used for concentrating and recrystallizing the organic phase is toluene, methanol, ethanol, propanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, methyl tertiary butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, etc., preferably one or a mixture of several of toluene, ethyl acetate and methyl tertiary butyl ether.
Further, in step (1), the anion exchange resin is a DOWEX ion exchange resin.
The second aspect of the invention provides a continuous preparation device for N-N-butyl thiophosphoryl triamide, which comprises a batching kettle, a micro-channel reactor, anion resin, a storage tank and a pipeline reactor which are connected in sequence.
Further, a first liquid metering pump is arranged between the batching kettle and the microchannel reactor, and an inlet of the first liquid metering pump is respectively connected with a phosphorus sulfur trichloride toluene solution outlet of the batching kettle, a n-butylamine feeding pipeline and an outlet of the first liquid metering pump are connected with the microchannel reactor.
Further, a second liquid metering pump and a gas flow valve are arranged between the storage tank and the pipeline reactor.
Further, one end of the second liquid metering device is connected with the storage tank, and the other end of the second liquid metering device is connected with the pipeline reactor; one end of the gas flow valve is connected with the pipeline reactor, and the other end of the gas flow valve is connected with an ammonia gas feeding pipeline.
Further, the anion resin is divided into a main path and a bypass, the main path and the bypass are both provided with valves, and if the anion exchange resin needs to be activated or the pipeline needs to be overhauled, the bypass pipeline can be utilized by switching the valves.
Further, the materials of the micro-channel reactor and the tubular reactor are one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Further, the materials of the micro-channel reactor and the tubular reactor are one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Compared with the prior art, the invention has the following technical effects:
(1) The preparation method adopts the microchannel reactor and the tubular reactor to be connected in series, the single toluene solvent is adopted in the synthesis process, and the key intermediate N-N-butyl dichloro thiophosphamide directly enters the tubular reactor to generate ammonia after being treated by the action of anion exchange resin, thereby greatly simplifying the production process, shortening the production period and improving the production efficiency.
(2) The preparation method has the advantages that the two reaction steps are both violent in heat release, the rapid heat exchange can be realized through the micro-channel and the tubular reactor, the back mixing condition is obviously improved, the reaction selectivity is improved, the production of the main byproduct di-n-butylamine chlorophosphamide is reduced, the reaction yield is improved, the product quality is improved, the total reaction yield reaches 85%, and the product purity is more than 98%.
(3) The preparation device of the invention is simple, has low investment cost, obviously improves the process safety and is more beneficial to industrialized production.
(4) The preparation method adopts the toluene single solvent, can greatly reduce the solvent consumption after adopting the microchannel reactor and the tubular reactor, is convenient for recycling and reusing the toluene solvent, reduces the generation of wastewater and reduces the influence on the environment.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing N-N-butylthiophosphoric triamide according to the present invention;
wherein the reference numerals are as follows:
a batching kettle 1; a phosphorus sulfur trichloride charging port 2; n-butylamine feed pipe 3; a first liquid metering pump 4; a microchannel reactor 5; a valve 6; an anionic resin 7; a storage tank 8; an ammonia gas feed line 9; a second liquid metering pump 10; a gas flow valve 11; a pipeline reactor 12.
Detailed Description
The present invention will be described in detail and in detail by way of the following examples, which are not intended to limit the scope of the invention, for better understanding of the invention.
Example 1
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 25 ℃ and the reaction residence time is controlled to be 100s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 by the calibrated second liquid metering pump 10, and at the same time, ammonia gas was also injected into the tubular reactor 12 by the calibrated gas flow valve 11, and the reactor temperature was controlled at 20 ℃ and the reaction residence time at 168s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing for layering, recovering about 80% of the organic phase (toluene) by reduced pressure distillation, slowly cooling the remainder to-10-0 ℃, insulating and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoric triamide solid, drying to obtain 102kg of white solid, and obtaining 86.1% of yield and 98.4% of purity.
As a preferred embodiment, the anion resin is divided into a main path and a bypass path, the main path and the bypass path are respectively provided with a valve, and if the anion exchange resin needs to be activated or the pipeline needs to be overhauled, a bypass pipeline can be utilized by switching the valves; the materials of the micro-channel reactor and the tubular reactor are one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Example 2
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 25 ℃ and the reaction residence time is controlled to be 120s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 through the calibrated second liquid metering pump 10, and at the same time, the ammonia gas was also injected into the tubular reactor 12 through the calibrated gas flow valve 11, and the reactor temperature was controlled at 20 ℃ and the reaction residence time at 130s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing for layering, recovering about 80% of the organic phase (toluene) by reduced pressure distillation, slowly cooling the remainder to-10-0 ℃, insulating and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoric triamide solid, drying to obtain 102kg of white solid, and obtaining 86.5% of yield and 98.2% of purity.
Example 3
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 20 ℃ and the reaction residence time is controlled to be 100s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 through the calibrated second liquid metering pump 10, and at the same time, the ammonia gas was also injected into the tubular reactor 12 through the calibrated gas flow valve 11, and the reactor temperature was controlled at 20 ℃ and the reaction residence time at 200s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing for layering, recovering about 80% of the organic phase (toluene) by reduced pressure distillation, slowly cooling the remainder to-10-0 ℃, insulating and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoric triamide solid, drying to obtain 102kg of white solid, and obtaining the product with the yield of 82.2% and the purity of 98.8%.
Example 4
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 20 ℃ and the reaction residence time is controlled to be 100s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 by the calibrated second liquid metering pump 10, and at the same time, ammonia gas was also injected into the tubular reactor 12 by the calibrated gas flow valve 11, and the reactor temperature was controlled at 20 ℃ and the reaction residence time at 250s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing for layering, recovering about 80% of the organic phase (toluene) by reduced pressure distillation, slowly cooling the remainder to-10-0 ℃, insulating and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoric triamide solid, drying to obtain 102kg of white solid, and obtaining the product with the yield of 82.2% and the purity of 98.8%.
Example 5
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 10 ℃ and the reaction residence time is controlled to be 100s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 by the calibrated second liquid metering pump 10, and at the same time, ammonia gas was also injected into the tubular reactor 12 by the calibrated gas flow valve 11, and the reactor temperature was controlled at 25℃and the reaction residence time at 160s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing and layering, concentrating the organic phase toluene to dryness to obtain about 800kg of recovered toluene, then adding 250kg of dichloromethane, slowly cooling the remainder to-10-0 ℃, carrying out heat preservation and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoryl triamide solid, and drying to obtain 102kg of white solid with the yield of 77.4% and the purity of 99.3%.
Example 6
120kg (708.3 mol,1 eq) of phosphorus oxychloride and 1000kg of toluene are added into a batching kettle 1 under the protection of nitrogen, and uniformly mixed to obtain a toluene solution of phosphorus oxychloride. Separately, a toluene solution of phosphorus oxychloride and 57kg (779 mol,1.1 eq) of n-butylamine were injected into the microchannel reactor 5 using two calibrated first liquid metering pumps 4, wherein the injection rate of the toluene solution of phosphorus oxychloride was 37ml/min and the injection rate of the n-butylamine was 2.56ml/min. The mixed reaction solution enters a micro-channel reactor 5 with an inner diameter of 5mm and a total length of 3m at a speed of 1.8m/min, and the temperature of the micro-channel reactor is controlled to be 20 ℃ and the reaction residence time is controlled to be 100s. The obtained N-N-butyl dichloro thiophosphoramide toluene solution is treated by anion exchange resin 7 and then enters a storage tank 8 for direct use in the next reaction.
The N-butyldichlorophosphoryl sulfide toluene solution in the tank 8 was injected into the tubular reactor 12 through the calibrated second liquid metering pump 10, and at the same time, the ammonia gas was also injected into the tubular reactor 12 through the calibrated gas flow valve 11, and the reactor temperature was controlled at 30℃and the reaction residence time at 200s. Wherein the sample injection speed of the N-N-butyl dichloro phosphorothioate toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6ml/min; the tubular reactor 12 has an inner diameter of 20mm and an overall length of 30m.
After the reaction is finished, directly adding water, stirring, standing and layering, concentrating the organic phase toluene to dryness to obtain about 800kg of recovered toluene, then adding 210kg of ethyl acetate, slowly cooling the remainder to-10-0 ℃, carrying out heat preservation and stirring for 1-2 hours, separating to obtain N-N-butyl thiophosphoryl triamide solid, and drying to obtain 102kg of white solid with the yield of 81.3% and the purity of 98.9%.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (4)
1. The continuous preparation method of the N-N-butyl thiophosphoric triamide is characterized by comprising the following steps of:
(1) Mixing phosphorus oxychloride with toluene to form a phosphorus oxychloride toluene solution, adding the phosphorus oxychloride toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichloro phosphoroamidetoluene solution, and treating the solution by anion exchange resin and then entering a storage tank;
the concentration of the phosphorus oxychloride toluene solution is 10-15%, and the mass ratio of the phosphorus oxychloride to the n-butylamine is 1:0.9-1.1, wherein the temperature of the substitution reaction is 15-35 ℃, and the reaction residence time is 60-80s; the inner diameter of the micro-channel reactor is 3-10mm, and the length is 1.5-5m; the flow rate of the reaction liquid in the micro-channel reactor is 1.5-2.5m/min;
(2) Respectively adding the N-N-butyl dichloro thiophosphoryl amide toluene solution and ammonia gas in the storage tank into a tubular reactor for reaction to obtain N-N-butyl thiophosphoryl triamide toluene solution;
the mass ratio of the N-N-butyl dichloro thiophosphamide to ammonia gas is 1:10-60, wherein the reaction temperature is 15-30 ℃ and the reaction residence time is 180-240s; the inner diameter of the tubular reactor is 10-50mm, and the length is 2-5m; the flow rate of the reaction liquid in the tubular reactor is 0.3-0.6m/min;
(3) Extracting and washing the obtained N-N-butyl thiophosphoric triamide toluene solution, concentrating and recrystallizing an organic phase, separating and drying to obtain high-purity N-N-butyl thiophosphoric triamide;
the device adopted by the preparation method comprises a batching kettle, a micro-channel reactor, anion resin, a storage tank and a tubular reactor which are connected in sequence; a first liquid metering pump is arranged between the batching kettle and the microchannel reactor, and an inlet of the first liquid metering pump is respectively connected with a phosphorus oxychloride toluene solution outlet of the batching kettle, an n-butylamine feeding pipeline and an outlet of the first liquid metering pump is connected with the microchannel reactor; a second liquid metering pump and a gas flow valve are arranged between the storage tank and the tubular reactor; one end of the second liquid metering device is connected with the storage tank, and the other end of the second liquid metering device is connected with the pipeline reactor; one end of the gas flow valve is connected with the pipeline reactor, and the other end of the gas flow valve is connected with an ammonia gas feeding pipeline; the anion resin is divided into a main path and a bypass, the main path and the bypass are both provided with valves, and if the anion resin needs to be activated or the pipeline needs to be overhauled, the bypass pipeline can be utilized by switching the valves.
2. The continuous preparation method of N-butyl thiophosphoric triamide according to claim 1, wherein in the step (3), the organic solvent used for concentration and recrystallization of the organic phase is one or more of toluene, methanol, ethanol, propanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, methyl tertiary butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1, 4-dioxane.
3. The continuous production method of N-butylthiophosphoric triamide according to claim 1, wherein in the step (1), the anion exchange resin is a DOWEX ion exchange resin.
4. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 1, wherein the materials of the micro-channel reactor and the tubular reactor are one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911101948.5A CN110950904B (en) | 2019-11-12 | 2019-11-12 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911101948.5A CN110950904B (en) | 2019-11-12 | 2019-11-12 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110950904A CN110950904A (en) | 2020-04-03 |
| CN110950904B true CN110950904B (en) | 2023-05-05 |
Family
ID=69977486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911101948.5A Active CN110950904B (en) | 2019-11-12 | 2019-11-12 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110950904B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560036B (en) * | 2020-05-14 | 2022-11-01 | 浙江今晖新材料股份有限公司 | NBPT production facility |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337976A (en) * | 2008-08-15 | 2009-01-07 | 张九治 | Method for producing N-alkyl substituted phosphoric triamide |
| CN101412733A (en) * | 2008-11-20 | 2009-04-22 | 大连理工大学 | Preparation of N-alkyl thiophosphoryl triamide by one-pot method |
| CN101503424A (en) * | 2009-03-20 | 2009-08-12 | 辽宁华锦化工（集团）有限责任公司 | Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide |
| CN101525348A (en) * | 2009-04-07 | 2009-09-09 | 林文斌 | Method for industrialized production of N-alkyl substituted phosphoric triamide |
| CN102030775A (en) * | 2010-09-14 | 2011-04-27 | 浙江工业大学 | Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment |
| CN102746333A (en) * | 2012-06-12 | 2012-10-24 | 上虞盛晖化工有限公司 | Synthetic method of N-(n-butyl) thiophosphoric triamide |
| CN103524551A (en) * | 2013-10-31 | 2014-01-22 | 江西吉翔医药化工有限公司 | Continuous production process of N-normal-butyl thiophosphoryl triamide |
| CN103755739A (en) * | 2014-02-25 | 2014-04-30 | 沧州金仓精细化工有限公司 | Continuous production method for N-NBPT |
| CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
| CN105131031A (en) * | 2015-07-03 | 2015-12-09 | 上虞盛晖化工股份有限公司 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
| CN105399768A (en) * | 2015-11-20 | 2016-03-16 | 江西吉翔医药化工有限公司 | Clean production process for preparing N-(N-butyl)thiophosphoric triamide |
| CN108084224A (en) * | 2017-12-12 | 2018-05-29 | 北方华锦化学工业股份有限公司 | A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7396519B2 (en) * | 2004-01-26 | 2008-07-08 | San Fu Chemical Company, Ltd. | Preparation of a high purity and high concentration hydroxylamine free base |
-
2019
- 2019-11-12 CN CN201911101948.5A patent/CN110950904B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337976A (en) * | 2008-08-15 | 2009-01-07 | 张九治 | Method for producing N-alkyl substituted phosphoric triamide |
| CN101412733A (en) * | 2008-11-20 | 2009-04-22 | 大连理工大学 | Preparation of N-alkyl thiophosphoryl triamide by one-pot method |
| CN101503424A (en) * | 2009-03-20 | 2009-08-12 | 辽宁华锦化工（集团）有限责任公司 | Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide |
| CN101525348A (en) * | 2009-04-07 | 2009-09-09 | 林文斌 | Method for industrialized production of N-alkyl substituted phosphoric triamide |
| CN102030775A (en) * | 2010-09-14 | 2011-04-27 | 浙江工业大学 | Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment |
| CN102746333A (en) * | 2012-06-12 | 2012-10-24 | 上虞盛晖化工有限公司 | Synthetic method of N-(n-butyl) thiophosphoric triamide |
| CN103524551A (en) * | 2013-10-31 | 2014-01-22 | 江西吉翔医药化工有限公司 | Continuous production process of N-normal-butyl thiophosphoryl triamide |
| CN103755739A (en) * | 2014-02-25 | 2014-04-30 | 沧州金仓精细化工有限公司 | Continuous production method for N-NBPT |
| CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
| CN105131031A (en) * | 2015-07-03 | 2015-12-09 | 上虞盛晖化工股份有限公司 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
| CN105399768A (en) * | 2015-11-20 | 2016-03-16 | 江西吉翔医药化工有限公司 | Clean production process for preparing N-(N-butyl)thiophosphoric triamide |
| CN108084224A (en) * | 2017-12-12 | 2018-05-29 | 北方华锦化学工业股份有限公司 | A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110950904A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102030775B (en) | Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment | |
| CN102875493B (en) | The method of epoxy aliphatic acid methyl ester is prepared in Continuous Flow micro passage reaction | |
| CN112225642B (en) | Method for preparing resorcinol by micro-channel reaction | |
| CN110950904B (en) | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide | |
| CN103755739A (en) | Continuous production method for N-NBPT | |
| CN109678727A (en) | A kind of method of microchannel nitration reaction synthesis 2- ethyl -5- nitroaniline | |
| CN110511157A (en) | A method of trifluoroacetamide is prepared using microchannel reaction technology | |
| JP7441863B2 (en) | Continuous synthesis method and apparatus for cyclopropane compounds | |
| CN108084224A (en) | A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines | |
| CN111004126A (en) | Preparation method of p-nitrophenol sodium salt | |
| CN111995640A (en) | Method for synthesizing (3-amino-3-cyano) propyl methyl butyl phosphite based on microchannel reactor | |
| CN101544682B (en) | 11-keto-16,17-epoxyprogesterone and industrial production method | |
| CN104610087A (en) | Device and method for purifying yellow phosphorus tail gas and continuously synthesizing oxamide | |
| CN110922409A (en) | Method for preparing BTK inhibitor zebritinib | |
| CN106636241B (en) | Method for preparing esmollin intermediate by enzyme method | |
| WO2021204095A1 (en) | Method and equipment of phenethylamine production | |
| CN105131031B (en) | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction | |
| CN108033914A (en) | A kind of preparation method of Ai Qu pools pa | |
| CN214088354U (en) | Preparation system containing 3-amino-2-formamide pyridine structure compound | |
| CN108033983B (en) | Synthetic method of 2- (3,3, 3-trifluoropropyl) thioadenosine | |
| CN110343056A (en) | A kind of preparation method of N- tertbutyloxycarbonyl-N- methyl-2-amino -4,4- dimethyl valeric acid | |
| CN103626667B (en) | A kind of method that catalytic hydrogenation prepares 3,3', 4,4'-tetramino diphenyl ether hydrochlorate | |
| CN109053797A (en) | A kind of improvement synthetic method of oxygen phosphoric acid-l-tyrosine | |
| CN112724089B (en) | Synthesis process of 2-amino-3-bromo-6-chloropyrazine | |
| CN114276355B (en) | Preparation method of ibrutinib |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |