CN102030775A - Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment - Google Patents
Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- HEPPIYNOUFWEPP-UHFFFAOYSA-N n-diaminophosphinothioylbutan-1-amine Chemical compound CCCCNP(N)(N)=S HEPPIYNOUFWEPP-UHFFFAOYSA-N 0.000 title claims abstract 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000005576 amination reaction Methods 0.000 claims abstract description 30
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012044 organic layer Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims 1
- 238000013517 stratification Methods 0.000 claims 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 102000003990 Urokinase-type plasminogen activator Human genes 0.000 description 1
- 108090000435 Urokinase-type plasminogen activator Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical class NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MXWAUCNVFWNWQZ-UHFFFAOYSA-N dibutyl-chloro-sulfanylidene-lambda5-phosphane Chemical compound C(CCC)P(=S)(CCCC)Cl MXWAUCNVFWNWQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000002601 urease inhibitor Substances 0.000 description 1
- 229960005356 urokinase Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种管道化方式生产正丁基硫代磷酰三胺的方法及专用设备，所述方法为：将三氯硫磷和正丁胺分别输入Y型射流混合器中快速混合均匀，然后进入管式反应器，控制管式反应器中的反应温度在10-35℃，反应时间为5-90s；所得反应液从管式反应器出口进入预先加有有机溶剂的胺化反应器中，在20～25℃、常压下连续通入氨气反应2.5～3小时，反应完全后，经分离纯化即得正丁基硫代磷酰三胺。所述专用设备如图所示。本发明所述方法工艺合理，生产成本低，收率高，适合工业化生产。
The invention discloses a method and special equipment for producing n-butyl thiophosphoric triamide in a pipelined manner. The method is as follows: respectively inputting phosphorus trichloride and n-butylamine into a Y-shaped jet mixer to quickly mix them uniformly, Then enter the tubular reactor, control the reaction temperature in the tubular reactor at 10-35°C, and the reaction time is 5-90s; the obtained reaction liquid enters the amination reactor pre-added with organic solvent from the outlet of the tubular reactor , Continuously feed ammonia gas at 20-25°C and normal pressure to react for 2.5-3 hours. After the reaction is complete, separate and purify to obtain n-butylthiophosphoric triamide. The special equipment is shown in the figure. The method of the invention has reasonable process, low production cost and high yield, and is suitable for industrialized production.
Description
(1) technical field
The present invention relates to a kind of method and apparatus of canalization mode production normal-butyl thiophosphoryl triamine.
(2) background technology
Normal-butyl thiophosphoryl triamine is a kind of effective urease inhibitors on agricultural, the N-alkyl substituted phosphoric triamide can be mixed with compound manure in certain proportion with urea, the activity that can suppress the urokinase in the soil on the one hand, the degradation speed of urea slows down, thereby improve the utilization ratio of urea, strengthen fertilizer efficiency; Can also provide elements such as S, P on the other hand, play soil improvement action preferably.
Before making the present invention, the synthetic of normal-butyl thiophosphoryl triamine mainly contains following two kinds: (1) two-step approach, CN101337976A discloses the method that " two-step approach " prepares normal-butyl thiophosphoryl triamine, at first the reaction of phosphorus thiochloride and n-Butyl Amine 99 makes N-normal-butyl phosphorothioic dichlorides, through after the separation and purification, logical ammonia react and process aftertreatment separation obtain normal-butyl thiophosphoryl triamine.This complex process relates to low-temp reaction and back flow reaction, and the reaction times is longer, and energy consumption is bigger, and side reaction is more, and reaction yield is low, and production cost is higher.(2) one kettle way, CN101412733A discloses the method that " one kettle way " prepares normal-butyl thiophosphoryl triamine, make acid binding agent with triethylamine, phosphorus thiochloride and n-Butyl Amine 99 prepared in reaction obtain the mixing solutions of N-normal-butyl phosphorothioic dichlorides and triethylamine hydrochloride, reaction solution is not purified directly under normal pressure or pressurized conditions, logical ammonia a few hours, after obtain normal-butyl thiophosphoryl triamine after the necessary separation and purification, but this technology exists the reaction times longer equally, reaction reagent is wide in variety, acid binding agent triethylamine shortcomings such as the smell is awful, and, having increased the difficulty of aftertreatment separation and purification owing to use triethylamine as acid binding agent, operation steps is loaded down with trivial details, require certain pressure when leading to ammonia, working condition requires high.
Therefore, production method and the equipment of studying a kind of new normal-butyl thiophosphoryl triamine has considerable meaning.
(3) summary of the invention
First technical problem that the present invention will solve is to provide technology reasonable, and production cost is low, yield height, the method for the normal-butyl thiophosphoryl triamine of suitable suitability for industrialized production.
For solving the problems of the technologies described above, the present invention reacts in tubular reactor after with n-Butyl Amine 99 and the quick mixing of phosphorus thiochloride, and the directly logical ammonia react of gained reaction solution obtains normal-butyl thiophosphoryl triamine, and concrete technical scheme is as follows:
A kind of method of canalization mode production normal-butyl thiophosphoryl triamine, it is characterized in that described method is: it is even that phosphorus thiochloride and n-Butyl Amine 99 are imported in the Y type jet mixer short mix continuously, enter tubular reactor then, temperature of reaction in the control tubular reactor is at 10～35 ℃, and the reaction times is 5～90s; The gained reaction solution enters the amination reaction device that is added with organic solvent in advance from tubular reactor outlet, feeds ammonia gas react 2.5～3 hours continuously under 20～25 ℃, normal pressure, after reacting completely, promptly gets normal-butyl thiophosphoryl triamine through separation and purification.
Further, described organic solvent is selected from following a kind of or several mixing by arbitrary proportion arbitrarily: ethyl acetate, methylene dichloride, 2-methyltetrahydrofuran.The quality consumption of described organic solvent is preferably 2-5 times of phosphorus thiochloride quality.
Further, the molar ratio of described phosphorus thiochloride and n-Butyl Amine 99 be preferably 1: 1.6～1.9.
Further, the preferred 10～60s of reaction times in the described tubular reactor.
Separation purification method of the present invention is: after adding water in the described amination reaction liquid and fully stirring, standing demix separates obtaining organic layer and water layer.The gained organic layer obtains normal-butyl thiophosphoryl triamine by crystallization operation; Described crystallization operation can be organic layer to be concentrated earlier remove most of solvent postcooling (preferably being cooled to-5～0 ℃) crystallization, gets normal-butyl thiophosphoryl triamine; Perhaps described crystallization operation can be: behind the gained organic layer decompression and solvent recovery, add recrystallisation solvent, cooling (preferably being cooled to-5～0 ℃) crystallization in the gained resistates, get pure product normal-butyl thiophosphoryl triamine.The gained water layer adds alkali lye and regulates pH=11～12, stirs, and standing demix is told organic layer and is n-Butyl Amine 99, can repeat to apply mechanically behind the adding anhydrous sodium sulfate drying.Described alkali lye can be sodium hydroxide, the aqueous solution that mineral alkalis such as potassium hydroxide are mixed with.
Further, described recrystallisation solvent is preferably following a kind of or several mixing by arbitrary proportion arbitrarily: methylene dichloride, 2-methyltetrahydrofuran, sherwood oil, ethyl acetate.
The present invention also provides a kind of specific equipment of method of described canalization mode production normal-butyl thiophosphoryl triamine, and described specific equipment comprises storage tank I, storage tank II, two volume pumps, Y type jet mixer, tubular reactor and amination reaction devices; Described storage tank I and storage tank II are connected with Y type jet mixer via separately volume pump respectively, described Y type jet mixer lower end is connected with the inlet of tubular reactor by pipeline, and the outlet of described tubular reactor links to each other by the inlet of pipeline with the amination reaction device.
Tubular reactor of the present invention is well-known to those skilled in the art, comprises single tube, two-tube etc., and promptly described tubular reactor can be composed in parallel by two above pipelines.The pipe range of described pipeline is 1～50m, preferred 5～35m; Pipe diameter is 3～30mm, preferred 3～15mm.The shape of tubular reactor comprises different shapes such as straight shape, U-shaped, N shape, volution.
In conjunction with above-mentioned specific equipment, method of the present invention comprises the steps:
Phosphorus thiochloride among the storage tank I is delivered to Y type jet mixer continuously by volume pump; N-Butyl Amine 99 among the storage tank II is delivered to Y type jet mixer continuously by volume pump, after Y type jet mixer short mix is even, enter tubular reactor, by the temperature of reaction and the reaction times of control tubular reactor, the generation of the minimizing side reaction of maximum possible when guaranteeing to react completely.The gained reaction solution directly enters in the amination reaction device that adds organic solvent in advance, and logical ammonia is to reacting completely, and obtains normal-butyl thiophosphoryl triamine through the separation and purification aftertreatment of necessity.
Comparatively concrete, a kind of method of canalization mode production normal-butyl thiophosphoryl triamine is carried out according to following steps: phosphorus thiochloride and n-Butyl Amine 99 are delivered to Y type jet mixer by volume pump respectively, short mix is even, enter tubular reactor then, control reaction temperature is 10～35 ℃, reaction times is 10～60s, the gained reaction solution flows directly in the amination reaction device that adds organic solvent in advance, at the logical continuously ammonia gas react 2.5～3h of 20～25 ℃ of following normal pressures, after reaction is finished, add water and stir 1h in the amination reaction device, standing demix, organic layer decompression and solvent recovery gained resistates get pure product normal-butyl thiophosphoryl triamine after crystallization, water layer adds lye pH adjustment=11～12, stir, standing demix, telling organic layer is that n-Butyl Amine 99 can repeat to apply mechanically behind anhydrous sodium sulfate drying.Described tubular reactor is made up of a pipeline, and the pipe range of described pipeline is 5～35m, and pipe diameter is 3～15mm; Described reaction mass mol ratio is: phosphorus thiochloride: n-Butyl Amine 99=1: 1.65～1.85.
Compared with prior art, the present invention has following beneficial effect:
1) the present invention compares with traditional caldron process by key intermediate normal-butyl sulfo-two phosphoryl chlorides of tubular reactor produced normal-butyl thiophosphoryl triamine, has simplified technology, and easy and simple to handle, with short production cycle, energy consumption is low.
2) this reaction is by control phosphorus thiochloride and the charge proportion of n-Butyl Amine 99 and the temperature of reaction of tubular reactor, can make is swift in response carries out (reaction times shortened into several minutes from several hours), axial no back-mixing in the reactor, overcome the uneven problem of partial concn that prior art exists, effectively reduce the generation of main by product di-n-butyl thiophosphoryl chloride, improved reaction yield, reduced manufacturing cost, overall yield of reaction reaches more than 80%, and product purity is more than 97%.
3) to have a described device simple in the present invention, required less investment, process safety is good, easy control of reaction conditions, characteristics such as constant product quality more help suitability for industrialized production, and key intermediate normal-butyl sulfo-two phosphoryl chlorides need not separation and purification and directly can carry out amination reaction, this technology has reduced the consumption of n-Butyl Amine 99 and organic solvent simultaneously, has reduced the generation of waste water.
(4) description of drawings
Fig. 1 is the device synoptic diagram of the canalization mode production normal-butyl thiophosphoryl triamine of the present invention's employing; Wherein, 1. storage tank I, 2. storage tank II, 3., 4. volume pump, 5. Y type jet mixer, 6. tubular reactor, 7. amination reaction device.
(5) embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
The device synoptic diagram of the specific equipment that the embodiment of the invention adopted is seen Fig. 1: 5. 3. 1. described storage tank I be connected with Y type jet mixer via volume pump, 5. 4. 2. storage tank II be connected with Y type jet mixer via volume pump, described Y type jet mixer 5. lower end is connected with tubular reactor inlet 6. by pipeline, and the outlet 6. of described tubular reactor links to each other with amination reaction device inlet 7. by pipeline; Described tubular reactor is a single tube, twist.
3kg (17.7mol) phosphorus thiochloride and 2.14kg (29.2mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 10 meters of pipe ranges, 8 millimeters of calibers), control reaction temperature is 10 ℃, residence time 20s, reaction finishes afterreaction liquid and directly enters in the amination reaction device that adds the 7.5kg methylene dichloride in advance, logical ammonia gas react 3h under 25 ℃ of normal pressures of control reaction temperature after reacting completely, directly adds water 4kg, stir 1h, standing demix, after wherein about 75% solvent was reclaimed in the organic layer underpressure distillation, resistates was cooled to-5～0 ℃ of crystallizations and gets the pure product 2.46kg of normal-butyl thiophosphoryl triamine, be white crystal, 57～58 ℃ of fusing points, yield 83.1%, purity 97.8%.
3kg (17.7mol) phosphorus thiochloride and 2.14kg (29.2mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 5 meters of pipe ranges, 3 millimeters of calibers), control reaction temperature is 35 ℃, residence time 10s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 6kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 4kg, stir 1h, standing demix, wherein behind the organic layer vacuum distillation recovered solvent, resistates adds mixed solvent 1.5L (methylene dichloride: sherwood oil=1: 1) be cooled to-5～0 ℃ of crystallizations and get the pure product 2.43kg of normal-butyl thiophosphoryl triamine, be white crystal, 57～58 ℃ of fusing points, yield 82.1%, purity 98.0%.
3kg (17.7mol) phosphorus thiochloride and 2.14kg (29.2mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 15 meters of pipe ranges, 5 millimeters of calibers), control reaction temperature is 15 ℃, residence time 60s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 12kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 20 ℃ of normal pressures, after stirring reaction is complete, directly add water 4kg, stir 1h, standing demix, after wherein about 75% solvent is reclaimed in the organic layer underpressure distillation, resistates is cooled to-5～0 ℃ of crystallizations and gets the pure product 2.6kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 87.8%, purity 98.2%.
15kg (88.5mol) phosphorus thiochloride and 12kg (163.5mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 20 meters of pipe ranges, 15 millimeters of calibers), control reaction temperature is 20 ℃, residence time 35s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 75kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 2.5h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 20kg, stir 1h, standing demix, after wherein about 75% solvent is reclaimed in the organic layer underpressure distillation, resistates is cooled to-5～0 ℃ of crystallizations and gets the pure product 12.0kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 81.2%, purity 98.5%.
Embodiment 5
15kg (88.5mol) phosphorus thiochloride and 12kg (163.5mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 35 meters of pipe ranges, 10 millimeters of calibers), control reaction temperature is 25 ℃, residence time 40s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 35kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 20kg, stir 1h, standing demix, after wherein about 75% solvent is reclaimed in the organic layer underpressure distillation, resistates is cooled to-5～0 ℃ of crystallizations and gets the pure product 13.1kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 88.8%, purity 97.8%.
3kg (17.7mol) phosphorus thiochloride and 2.14kg (29.2mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 10 meters of pipe ranges, 8 millimeters of calibers), control reaction temperature is 25 ℃, residence time 20s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 7.5kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 4kg, stir 1h, standing demix, after wherein about 75% solvent is reclaimed in the organic layer underpressure distillation, resistates is cooled to-5～0 ℃ of crystallizations and gets the pure product 2.66kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 89.8%, purity 98.8%.
15kg (88.5mol) phosphorus thiochloride and 12kg (163.5mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 35 meters of pipe ranges, 10 millimeters of calibers), control reaction temperature is 25 ℃, residence time 40s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 35kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 20kg, stir 1h, standing demix, after wherein about 75% solvent is reclaimed in the organic layer underpressure distillation, resistates is cooled to-5～0 ℃ of crystallizations and gets the pure product 12.9kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 87%, purity 98.1%.
Embodiment 8
15kg (88.5mol) phosphorus thiochloride and 12kg (163.5mol) n-Butyl Amine 99 are delivered to Y type jet mixer respectively, enter tubular reactor (single tube after the mixing, 20 meters of pipe ranges, 10 millimeters of calibers), control reaction temperature is 20 ℃, residence time 35s, reaction finishes the direct feeding of afterreaction liquid and adds in advance in the amination reaction device of 30kg methylene dichloride, logical heat-eliminating medium in the amination reaction device chuck, continuous and ammonia gas react 3h under 25 ℃ of normal pressures, after stirring reaction is complete, directly add water 20kg, stir 1h, standing demix, wherein the organic layer vacuum distillation recovered solvent is to doing, and (methylene dichloride: crystallization sherwood oil=1: 1) is cooled to-5～0 ℃ of crystallizations and gets the pure product 12.4kg of normal-butyl thiophosphoryl triamine to add the 6kg mixed solvent again, be white crystal, 57～58 ℃ of fusing points, yield 83.7%, purity 97.7%.
Embodiment 9
Reaction solvent is changed to ethyl acetate, and other are operated with embodiment 1, gets the pure product 2.42kg of normal-butyl thiophosphoryl triamine, is white crystal, 57～58 ℃ of fusing points, yield 81.7%, purity 97.7%.
Embodiment 10
Reaction solvent is changed to the 2-methyltetrahydrofuran, recrystallisation solvent is that (the 2-methyltetrahydrofuran: sherwood oil=2: 1) other operations get the pure product 2.52kg of normal-butyl thiophosphoryl triamine with embodiment 2 to mixed solvent, are white crystal, 57～58 ℃ of fusing points, yield 85.3%, purity 98.0%.
Claims (6)
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| CN105254664A (en) * | 2014-10-28 | 2016-01-20 | 浙江奥复托化工有限公司 | Synthesis method for urease inhibitor and application of urease inhibitor |
| CN106422994A (en) * | 2016-10-21 | 2017-02-22 | 北京沃特尔水技术股份有限公司 | Method and device for preparing ammonium carbonate extraction solution |
| 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 |
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| CN102329243B (en) * | 2011-10-12 | 2013-11-20 | 浙江工业大学 | Tubular reaction method of L-(-)-3-chloro-2-hydroxypropyl trimethyl ammonium chloride |
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| CN106422994A (en) * | 2016-10-21 | 2017-02-22 | 北京沃特尔水技术股份有限公司 | Method and device for preparing ammonium carbonate extraction solution |
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| CN108586523A (en) * | 2018-06-09 | 2018-09-28 | 石家庄市绿丰化工有限公司 | A method of synthesis normal-butyl phosphorothioic dichlorides |
| CN110950904A (en) * | 2019-11-12 | 2020-04-03 | 武威金仓生物科技有限公司 | Continuous preparation method and device of N-N-butyl thiophosphoryl triamide |
| CN110950904B (en) * | 2019-11-12 | 2023-05-05 | 武威金仓生物科技有限公司 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
| CN111560036A (en) * | 2020-05-14 | 2020-08-21 | 浙江今晖新材料股份有限公司 | NBPT production facility |
| CN111560036B (en) * | 2020-05-14 | 2022-11-01 | 浙江今晖新材料股份有限公司 | NBPT production facility |
| CN114213454A (en) * | 2021-12-24 | 2022-03-22 | 河北威远生物化工有限公司 | Method for continuously synthesizing O-ethyl-S-sec-butyl thiophosphoryl chloride |
| CN114213454B (en) * | 2021-12-24 | 2024-02-20 | 河北威远生物化工有限公司 | Method for continuously synthesizing O-ethyl-S-sec-butyl thiophosphoryl chloride |
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