CN110950904A - Continuous preparation method and device of N-N-butyl thiophosphoryl triamide - Google Patents
Continuous preparation method and device of N-N-butyl thiophosphoryl triamide Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 trichlorothiophosphoryl toluene Chemical compound 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003860 storage Methods 0.000 claims abstract description 25
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- FNGLQNMQHOAIJQ-UHFFFAOYSA-N Cl[S](Cl)Cl Chemical compound Cl[S](Cl)Cl FNGLQNMQHOAIJQ-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical compound NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 238000002347 injection Methods 0.000 description 24
- 239000007924 injection Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- BMDVPRGEZHHGLJ-UHFFFAOYSA-N [S](Cl)(Cl)Cl.[P] Chemical compound [S](Cl)(Cl)Cl.[P] BMDVPRGEZHHGLJ-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229960001952 metrifonate Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 239000002601 urease inhibitor Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
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- 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 continuous preparation device of N-N-butyl thiophosphoric triamide, wherein the preparation method comprises the following steps: (1) adding the trichlorothiophosphoryl toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichlorothiophosphoryl amide toluene solution, treating by anion exchange resin, and then feeding into a storage tank; (2) adding the solution in the storage tank and ammonia gas into a tubular reactor for reaction to obtain a N-N-butyl thiophosphoric triamide toluene solution; (3) and (3) extracting and washing the obtained solution, concentrating and recrystallizing an organic phase, separating and drying to obtain the high-purity N-N-butyl thiophosphoric triamide. The continuous preparation method and the preparation device of the invention realize the continuity of the production process of the N-N-butyl thiophosphoric triamide, overcome the defect of intermittent operation of the kettle type reactor, simplify the process, improve the reaction selectivity and achieve the aims of clean production, shortening the production period and reducing the production cost.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a continuous preparation method and a continuous 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 effective component of a compound fertilizer.
CN101337976A reports a method for preparing N-N-butyl thiophosphoryl triamide, which comprises the steps of reacting thiophosphoryl trichloride with N-butylamine, separating an intermediate N-N-butyl dichlorothiophosphoryl amide, reacting purified N-N-butyl dichlorothiophosphoryl amide with ammonia gas, and then treating to obtain the N-N-butyl thiophosphoryl triamide. However, the process is complicated, involves the requirements of high-temperature and low-temperature reactions, has poor reaction selectivity, long production period and high cost, and does not have commercial advantages. CN101412733A reports a synthesis method for preparing N-N-butyl thiophosphoryl triamide by a one-pot method, wherein triethylamine is used as an alkali in the reaction, but the reaction time for introducing ammonia gas is long (usually 2 hours), the production cost is increased, and the use of triethylamine and a large excess amount of ammonia gas has great environmental protection hidden trouble. CN102030775B reports a synthetic method for producing N-N-butyl thiophosphoric triamide in a pipelining mode, 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) for introducing ammonia gas, higher production cost and potential environmental protection hidden trouble exist. CN102746333B reports a method for preparing N-N-butyl thiophosphoryl triamide by using inorganic base as an acid-binding agent, but the method requires to simultaneously dropwise add N-butylamine and an inorganic base aqueous solution, has extremely high operation requirement on dropwise adding speed control, and is not suitable for industrial production.
As an emerging organic synthesis technology, the continuous flow reaction technology has the following advantages compared with the traditional kettle type intermittent reaction: generally, the method has no amplification effect, can improve the selectivity of the reaction by optimizing the retention time, has low energy consumption and has the advantages of stronger heat transfer and mass transfer effects.
Therefore, designing a synthetic method can overcome the selectivity problem caused by high reaction activity, and realize continuous production of N-N-butyl thiophosphoric triamide while obtaining products with better quality in large batch, which is a problem to be solved by technicians in the field urgently.
Disclosure of Invention
The invention provides a continuous preparation method and a continuous preparation device of N-N-butyl thiophosphoric triamide, aiming at solving the problems of long reaction time, higher production cost, unsuitability for industrial production, potential environmental protection hidden trouble and the like in the existing N-N-butyl thiophosphoric triamide synthesis technology.
The method takes the trichlorothion, the N-butylamine and the 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 the N-N-butyl thiophosphoric triamide, overcoming the defect of intermittent operation of a kettle type reactor, simplifying the process, improving the reaction selectivity, and achieving the purposes of clean production, shortening the production period and reducing the production cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a continuous preparation method of N-N-butyl thiophosphoryl triamide, which comprises the following steps:
(1) mixing trichloro-sulfur and toluene to form a trichloro-sulfur toluene solution, adding the trichloro-sulfur toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichlorothiophosphoryl amide toluene solution, and treating the N-N-butyl dichlorothiophosphoryl amide toluene solution by anion exchange resin and then feeding the N-N-butyl dichlorothiophosphoryl amide toluene solution into a storage tank;
(2) respectively adding the N-N-butyl dichlorothiophosphoryl triamide toluene solution and ammonia gas in the storage tank into a tubular reactor for reaction to obtain an 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 toluene solution of trichlorfon is 5-50%, and the mass ratio of the trichlorfon to the n-butylamine is 1: 0.8-1.2, the temperature of the substitution reaction is 0-60 ℃, and the reaction residence time is 30-180 s.
Further preferably, in the step (1), the concentration of the toluene solution of trichloro-sulfur and phosphorus is 10-15%, and the mass ratio of the trichloro-sulfur and the n-butylamine is 1: 0.9-1.1, the temperature of the substitution reaction is 15-35 ℃, and the reaction residence time is 60-80 s.
Further, in the step (1), the inner diameter of the microchannel reactor is 0.4-60mm, and the length of the microchannel reactor is 0.5-10 m; the flow speed of the reaction liquid in the microchannel reactor is 0.5-6 m/min.
Further preferably, in the step (1), the inner diameter of the microchannel reactor is 3-10mm, and the length of the microchannel reactor is 1.5-5 m; the flow speed of the reaction liquid in the microchannel reactor is 1.5-2.5 m/min.
Further, in the step (2), the mass ratio of the N-N-butyl dichlorothiophosphoryl amide to the ammonia gas is 1: 4-5000, the reaction temperature is 0-50 ℃, and the reaction residence time is 120-300 s.
Further preferably, in the step (2), the mass ratio of the N-N-butyl dichlorothiophosphoryl amide to the ammonia gas is 1: 10-60, the reaction temperature is 15-30 ℃, and the reaction residence time is 180-240 s.
Further, in the step (2), the inner diameter of the pipeline reactor is 5-200mm, and the length of the pipeline reactor is 0.5-20 m; the flow speed of the reaction liquid in the pipeline reactor is 0.2-1.0 m/min.
Further preferably, in the step (2), the inner diameter of the pipeline reactor is 10-50mm, and the length is 2-5 m; the flow speed of the reaction liquid in the pipeline reactor is 0.3-0.6 m/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 tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, etc., preferably one or more of toluene, ethyl acetate, and methyl tert-butyl ether.
Further, in the step (1), the anion exchange resin is DOWEX ion exchange resin.
The invention provides a continuous preparation device of N-N-butyl thiophosphoryl triamide, which comprises a batching kettle, a microchannel reactor, anion resin, a storage tank and a pipeline reactor which are connected in sequence.
Furthermore, a first liquid metering pump is arranged between the batching kettle and the microchannel reactor, an inlet of the first liquid metering pump is respectively connected with a trichlorothiophosphoryl toluene solution outlet and a n-butylamine feeding pipeline of the batching kettle, and an outlet of the first liquid metering pump is 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.
Furthermore, one end of the second liquid metering is connected with the storage tank, and the other end of the second liquid metering is connected with the pipeline reactor; and 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 path, the main path and the bypass path are both provided with valves, 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.
Furthermore, the microchannel reactor and the tubular reactor are made of one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Furthermore, the microchannel reactor and the tubular reactor are made of one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) the preparation method adopts the series connection of the microchannel reactor and the tubular reactor, adopts a single toluene solvent in the synthesis process, directly enters the tubular reactor after the key intermediate N-N-butyldichlorothiophosphoryl amide is treated by the action of anion exchange resin and generates ammonia gas, greatly simplifies the production process, shortens the production period and improves the production efficiency.
(2) In the preparation method, the two reaction steps are both violent in heat release, rapid heat exchange can be realized through the microchannel and the tubular reactor, the back mixing condition is obviously improved, the reaction selectivity is improved, the production of a main byproduct of di-n-butylamine chlorophosphoramide is reduced, the reaction yield is improved, the product quality is improved, the total reaction yield reaches 85 percent, and the product purity is over 98 percent.
(3) The preparation device is simple, the investment cost is low, the process safety is obviously improved, and the industrial production is more facilitated.
(4) The preparation method of the invention adopts a single toluene solvent, can greatly reduce the solvent consumption after adopting the microchannel reactor and the tubular reactor, is convenient for recycling the toluene solvent, reduces the generation of waste water and reduces the influence on the environment.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing N-N-butyl thiophosphoric triamide according to the present invention;
wherein the reference numerals are:
a batching kettle 1; a trichloro sulfur phosphorus feed inlet 2; a n-butylamine charging 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 specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
Example 1
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 25 ℃, and the reaction residence time is 100 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 20 ℃, and controlling the reaction residence time to be 168 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then is kept stand for layering, after about 80% of organic phase (toluene) is distilled under reduced pressure, the temperature of the remainder is slowly reduced to-10-0 ℃, the mixture is kept at the temperature and stirred for 1-2 hours, then N-N-butyl thiophosphoric triamide solid is obtained through separation, and after drying, 102kg of white solid is obtained, the yield is 86.1%, and the purity is 98.4%.
As a preferred embodiment, the anion resin is divided into a main path and a bypass path, both of which are provided with valves, if the anion exchange resin needs activation treatment or the pipeline needs maintenance, the bypass pipeline can be utilized by switching the valves; the microchannel reactor and the tubular reactor are made of one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic and silicon carbide.
Example 2
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 25 ℃, and the reaction residence time is 120 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 20 ℃, and controlling the reaction residence time to be 130 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then is kept stand for layering, after about 80% of organic phase (toluene) is distilled under reduced pressure, the temperature of the remainder is slowly reduced to-10-0 ℃, the mixture is kept at the temperature and stirred for 1-2 hours, then N-N-butyl thiophosphoric triamide solid is obtained through separation, and after drying, 102kg of white solid is obtained, the yield is 86.5%, and the purity is 98.2%.
Example 3
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 20 ℃, and the reaction residence time is 100 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 20 ℃ and the reaction residence time to be 200 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then is kept stand for layering, after about 80% of organic phase (toluene) is distilled under reduced pressure, the temperature of the remainder is slowly reduced to-10-0 ℃, the mixture is kept at the temperature and stirred for 1-2 hours, then N-N-butyl thiophosphoric triamide solid is obtained through separation, and after drying, 102kg of white solid is obtained, the yield is 82.2%, and the purity is 98.8%.
Example 4
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 20 ℃, and the reaction residence time is 100 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 20 ℃, and controlling the reaction residence time to be 250 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then is kept stand for layering, after about 80% of organic phase (toluene) is distilled under reduced pressure, the temperature of the remainder is slowly reduced to-10-0 ℃, the mixture is kept at the temperature and stirred for 1-2 hours, then N-N-butyl thiophosphoric triamide solid is obtained through separation, and after drying, 102kg of white solid is obtained, the yield is 82.2%, and the purity is 98.8%.
Example 5
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 10 ℃, and the reaction residence time is 100 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 25 ℃ and the reaction residence time to be 160 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then stands for layering, organic phase toluene is concentrated to be dry, about 800kg of recovered toluene is obtained, 250kg of dichloromethane is added, the temperature of the remainder is slowly reduced to-10-0 ℃, the mixture is kept for stirring for 1-2 hours and then is separated to obtain N-N-butyl thiophosphoryl triamide solid, and the white solid is obtained after drying, wherein the yield is 77.4%, and the purity is 99.3%.
Example 6
Under the protection of nitrogen, 120kg (708.3mol, 1eq) of trichloro sulfur phosphorus and 1000kg of toluene are added into a batching kettle 1 and mixed evenly to obtain trichloro sulfur phosphorus toluene solution. Two calibrated first liquid metering pumps 4 are respectively used for injecting trichloro-sulfur-phosphorus toluene solution and 57kg (779mol, 1.1eq) of n-butylamine into a microchannel reactor 5, wherein the injection speed of the trichloro-sulfur-phosphorus toluene solution is 37ml/min, and the injection speed of the n-butylamine is 2.56 ml/min. The mixed reaction solution enters a microchannel reactor 5 with the inner diameter of 5mm and the total length of 3m at the speed of 1.8m/min, the temperature of the microchannel reactor is controlled to be 20 ℃, and the reaction residence time is 100 s. The obtained N-N-butyl dichlorothiophosphoryl amide toluene solution enters a storage tank 8 after being treated by anion exchange resin 7 and is directly used for the next reaction.
Injecting the N-N-butyl dichlorothiophosphoryl toluene solution in the storage tank 8 into the tubular reactor 12 through the calibrated second liquid metering pump 10, simultaneously injecting ammonia gas into the tubular reactor 12 through the calibrated gas flow valve 11, controlling the temperature of the reactor to be 30 ℃ and the reaction residence time to be 200 s. Wherein the sample injection speed of the N-N-butyl dichlorothiophosphoryl toluene solution is 50ml/min, and the sample injection speed of ammonia gas is 6 ml/min; the tubular reactor 12 had an internal diameter of 20mm and a total length of 30 m.
After the reaction is finished, water is directly added, the mixture is stirred and then stands for layering, organic phase toluene is concentrated to be dry, about 800kg of recovered toluene is obtained, 210kg of ethyl acetate is added, the remainder is slowly cooled to minus 10-0 ℃, the mixture is stirred for 1-2 hours under heat preservation, N-N-butyl thiophosphoric triamide solid is obtained through separation, and white solid 102kg is obtained after drying, the yield is 81.3%, and the purity is 98.9%.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (17)
1. A continuous preparation method of N-N-butyl thiophosphoric triamide is characterized by comprising the following steps:
(1) mixing trichloro-sulfur and toluene to form a trichloro-sulfur toluene solution, adding the trichloro-sulfur toluene solution and N-butylamine into a microchannel reactor for substitution reaction to obtain an N-N-butyl dichlorothiophosphoryl amide toluene solution, and treating the N-N-butyl dichlorothiophosphoryl amide toluene solution by anion exchange resin and then feeding the N-N-butyl dichlorothiophosphoryl amide toluene solution into a storage tank;
(2) respectively adding the N-N-butyl dichlorothiophosphoryl triamide toluene solution and ammonia gas in the storage tank into a tubular reactor for reaction to obtain an 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.
2. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (1), the concentration of the toluene solution of trichloro-sulfur and phosphorus is 5-50%, and the mass ratio of the trichloro-sulfur to the N-butylamine is 1: 0.8-1.2, the temperature of the substitution reaction is 0-60 ℃, and the reaction residence time is 30-180 s.
3. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 2, wherein in the step (1), the concentration of the toluene solution of trichloro-sulfur and phosphorus is 10-15%, and the mass ratio of the trichloro-sulfur and N-butylamine charge is 1: 0.9-1.1, the temperature of the substitution reaction is 15-35 ℃, and the reaction residence time is 60-80 s.
4. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (1), the inner diameter of the microchannel reactor is 0.4-60mm, and the length is 0.5-10 m; the flow speed of the reaction liquid in the microchannel reactor is 0.5-6 m/min.
5. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 4, wherein in the step (1), the inner diameter of the microchannel reactor is 3-10mm, and the length is 1.5-5 m; the flow speed of the reaction liquid in the microchannel reactor is 1.5-2.5 m/min.
6. The continuous production method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (2), the mass ratio of the N-N-butyl dichlorothiophosphoryl amine to the ammonia gas is 1: 4-5000, the reaction temperature is 0-50 ℃, and the reaction residence time is 120-300 s.
7. The continuous preparation method of N-N-butyl thiophosphoryl triamide according to claim 6, wherein in the step (2), the mass ratio of the N-N-butyl dichlorothiophosphoryl amine to the ammonia gas is 1: 10-60, the reaction temperature is 15-30 ℃, and the reaction residence time is 180-240 s.
8. The continuous production method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (2), the pipe reactor has an inner diameter of 5 to 200mm and a length of 0.5 to 20 m; the flow speed of the reaction liquid in the pipeline reactor is 0.2-1.0 m/min.
9. The continuous production method of N-N-butyl thiophosphoric triamide according to claim 8, wherein in the step (2), the pipe reactor has an inner diameter of 10 to 50mm and a length of 2 to 5 m; the flow speed of the reaction liquid in the pipeline reactor is 0.3-0.6 m/min.
10. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (3), the organic solvent used for the concentration and recrystallization of the organic phase is toluene, methanol, ethanol, propanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, 1, 4-dioxane, etc., preferably one or more of toluene, ethyl acetate, and methyl tert-butyl ether.
11. The continuous preparation method of N-N-butyl thiophosphoric triamide according to claim 1, wherein in the step (1), the anion exchange resin is DOWEX ion exchange resin.
12. An apparatus for preparing N-N-butyl thiophosphoric triamide according to the preparation method of any one of claims 1 to 11, which comprises a batch kettle, a microchannel reactor, an anion resin, a storage tank and a pipeline reactor which are connected in sequence.
13. The preparation device of claim 12, wherein a first liquid metering pump is arranged between the batching kettle and the microchannel reactor, an inlet of the first liquid metering pump is respectively connected with a trichlorothiophosphorus toluene solution outlet of the batching kettle, a n-butylamine feeding pipeline and an outlet of the first liquid metering pump are respectively connected with the microchannel reactor.
14. The apparatus of claim 12, wherein a second liquid metering pump and a gas flow valve are disposed between the storage tank and the pipeline reactor.
15. The apparatus as set forth in claim 14, wherein said second liquid meter is connected at one end to said storage tank and at the other end to said pipeline reactor; and 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.
16. The apparatus according to claim 12, wherein the anion exchange resin is divided into a main path and a bypass path, and both the main path and the bypass path are provided with valves, and if the anion exchange resin requires activation treatment or the piping requires maintenance, a bypass line can be used by switching the valves.
17. The apparatus of claim 12, wherein the microchannel reactor and the tubular reactor are made of one of hastelloy, polytetrafluoroethylene, polyethylene, glass, ceramic, and silicon carbide.
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