CN101503424A - Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide - Google Patents
Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide Download PDFInfo
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- CN101503424A CN101503424A CNA2009100107741A CN200910010774A CN101503424A CN 101503424 A CN101503424 A CN 101503424A CN A2009100107741 A CNA2009100107741 A CN A2009100107741A CN 200910010774 A CN200910010774 A CN 200910010774A CN 101503424 A CN101503424 A CN 101503424A
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- tetrahydrofuran
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Abstract
The invention relates to a production method of N-normal-butyl thiophosphoryl triamine, comprising the following steps: dehydrating raw materials to control the water content to be within a required range, mixing phosphorus thiochloride with tetrahydrofuran, stirring the mixture, lowering the temperature, adding a mixture of n-butylamine, triethylamine and tetrahydrofuran in the mixture of the phosphorus thiochloride and the tetrahydrofuran by means of slow dripping, keeping a certain reaction temperature for 1-8h to obtain a white turbid liquid; leading ammonia gas into the a reaction system under the normal atmosphere, controlling the lead-in speed of ammonia gas, and keeping the temperature of the reaction system for 1-5h; centrifugating the reaction liquid to separate solid generated in the reaction system, distilling an obtained organic liquid in a decompression mode to remove most of the solvent and obtain a crude product, recrystallizing and refining the crude product to obtain a refined product with the purity higher than 99 percent. The invention has the advantages of wide raw material source, short process, simple operation, low cost, no three waste discharge, high economical benefit, applicability for industrial production, and the like.
Description
Technical field:
The present invention relates to the production method of a kind of production method of chemical fertilizer urease inhibitor, particularly a kind of N-normal-butyl thiophosphoryl triamine.
Background technology:
At present, Chinese scholars concentrates on its aspect that influences to the inhibition of hydrolysis of urea process and nitrated-denitrification process for the research of urase/nitrification inhibitor, on the agronomy meaning, the beneficial effect of inhibitor is to guarantee that Soil Nitrogen is to the lasting supply of crop with reduce its total loss.Studies show that what the inhibition effect was best in the mineral compound is silver salt and mercury salt.Dihydric phenol and quinones in the organic compound are that the effect of inhibition is arranged most as quinhydrones (HQ), pyrocatechol and para benzoquinone.Domestic and international research shows over nearly 10 years, and N-normal-butyl thiophosphoryl triamine is a kind of urease inhibitor efficiently.N one normal-butyl thiophosphoryl triamine can join by a certain percentage produces long-acting carbamide in the urea, can suppress the activity of the urine enzyme in the soil on the one hand, the degradation speed of the urea that slows down, thus the utilization ratio of raising urea strengthens fertilizer efficiency; Can also provide elements such as S, P on the other hand, play soil improvement action preferably.
At present, existing N-normal-butyl thiophosphoryl triamine production method mainly contains two kinds, a kind of is to be raw material with phosphorus thiochloride and n-Butyl Amine 99, adopt trichloromethane as feeding ammonia again after the reaction under the condition of solvent, the gas chlorination hydrogen that is produced in the reaction process is discharged with absorption process, makes reaction be continued to carry out; Another kind is to be raw material with phosphorus thiochloride and n-Butyl Amine 99, is solvent with the trichloromethane, and triethylamine is to feed ammonia again after the reaction under the condition of acid binding agent.These two kinds of method operation easier are big, and flow process produces the three wastes than more complicated in the reaction, and product is difficult for purifying, and employed solvent does not meet environmental protection requirement yet.For example, the production method of N one normal-butyl thiophosphoryl triamine of domestic patent documentation [publication number CN1583767] report is a catalyzer with methylformamide or methylacetamide, is solvent with the trichloromethane, triethylamine is an acid binding agent, but product yield that obtains and purity are all very low.The report of [publication number CN101337976A] is an acid binding agent with excessive alkylamine, has passed through twice in the whole process and has washed with water, extraction, drying, the products obtained therefrom yield is very low, complex operation step, technical process is longer, and three wastes discharge amount is big, and has also used the solvent that does not meet environmental requirement.
Summary of the invention:
The object of the present invention is to provide that a kind of technological operation is easy, reaction conditions is gentle, cost is low, yield and purity are high and are suitable for the production method of the N-normal-butyl thiophosphoryl triamine of industrial applications.
The present invention is achieved through the following technical solutions, and this method comprises: a plurality of processing steps such as raw material processed, building-up reactions, logical ammonia, the thick product of preparation and product recrystallizing and refining, and concrete implementation step and technical essential are as follows:
(1), raw material processed, used raw material is phosphorus thiochloride, n-Butyl Amine 99, ammonia, used solvent is a tetrahydrofuran (THF), used acid binding agent is a triethylamine, at first adopt molecular sieve or Calcium Chloride Powder Anhydrous, sodium hydroxide, potassium hydroxide, calcium oxide that phosphorus thiochloride, n-Butyl Amine 99 are carried out processed, detect water-content in claimed range 0～2000ppm with water tester;
(2), phosphorus thiochloride is mixed with tetrahydrofuran (THF), stir cooling after, slowly drip n-Butyl Amine 99, triethylamine and tetrahydrofuran (THF) mixing solutions, keep temperature of reaction-15～20 ℃, dripped back constant temperature 1～8 hour, obtain white casse liquid; Wherein, the mole proportioning of tetrahydrofuran (THF) and phosphorus thiochloride is 4～12:1, and the mole proportioning of n-Butyl Amine 99 and phosphorus thiochloride is: 1～1.2:1, and the proportioning of triethylamine and phosphorus thiochloride is: 1～1.5:1, required mixing speed is 260～350 rev/mins, and alr mode is mechanical stirring or magnetic agitation;
(3), in reaction system, feed ammonia, the mole proportioning of ammonia and phosphorus thiochloride is 2～8:1, logical ammonia speed of control and the temperature of keeping reaction system be-10～25 ℃, detect to stop ammonification when qualified when temperature of reaction no longer changes or through the TLC plate, keep and react 1～5 hour;
(4), with the centrifugal ammonium chloride that produces in the reaction system of telling of reaction solution, use the tetrahydrofuran (THF) washing leaching cake, the mass ratio of tetrahydrofuran (THF) and filter cake is 1～5:1.Filtrate and centrifugate are merged, and the organic liquor of gained is removed most of solvent through underpressure distillation, obtains the thick product of N one normal-butyl thiophosphoryl triamine, and product yield can reach more than 90%, and purity can reach more than 85%; Wherein, vacuum distillation temperature is 30～100 ℃, and pressure is 0.01～0.1Mpa;
(5), thick product is carried out recrystallizing and refining, wherein, used crystallizing agent is wherein a kind of of methyl alcohol, ethanol, ethyl acetate, water or two kinds mixture wherein, the proportioning of solvent and product is 5～15:2～5 during recrystallization, Tc is-15～0 ℃, crystallization time is 4～24 hours, obtains purity greater than 99% smart product.
The production method of N-normal-butyl thiophosphoryl triamine provided by the invention has that raw material sources are wide, flow process short, simple to operate, cost is low, three-waste free discharge, economic benefit is high and advantage such as suitable suitability for industrialized production.The byproduct ammonium chloride of present method also is a kind of fertilizer, can utilize again.
Embodiment:
Below in conjunction with embodiment enforcement of the present invention is illustrated.
Embodiment 1:
The tetrahydrofuran (THF) of 1 mole phosphorus thiochloride and 4 moles is joined in the reactor, start stirring (260 rev/mins), slowly add 1 mole n-Butyl Amine 99 and 6 moles triethylamine mixture then, temperature is controlled at-15 ℃, reacted 2 hours, feed 2 moles ammonia then in reactor, temperature is controlled at 0 ℃, reacts to obtain thick product after 7 hours.Pass through centrifugation then, remove solid residue after, gained liquid carries out underpressure distillation in the time of 70 ℃, obtain finished product N one normal-butyl thiophosphoryl triamine at last.
Embodiment 2:
The tetrahydrofuran (THF) of 1 mole phosphorus thiochloride and 8 moles is joined in the reactor, start stirring (300 rev/mins), slowly add 1 mole n-Butyl Amine 99 and 2 moles triethylamine mixture then, temperature is controlled at-10 ℃, reacted 5 hours, feed 5 moles ammonia then in reactor, temperature is controlled at-15 ℃, reacts to obtain thick product after 5 hours.Pass through centrifugation then, remove solid residue after, gained liquid carries out underpressure distillation in the time of 80 ℃, obtain finished product N one normal-butyl thiophosphoryl triamine at last.
Embodiment 3:
The tetrahydrofuran (THF) of 1 mole phosphorus thiochloride and 12 moles is joined in the reactor, start stirring (350 rev/mins), slowly add 1.5 moles n-Butyl Amine 99 and 5 moles triethylamine mixture then, temperature is controlled at 0 ℃, reacted 8 hours, feed 8 moles ammonia then in reactor, temperature is controlled at 5 ℃, reacts to obtain thick product after 1 hour.Pass through centrifugation then, remove solid residue after, gained liquid carries out underpressure distillation in the time of 90 ℃, obtain finished product N one normal-butyl thiophosphoryl triamine at last.
Embodiment 4:
10 moles tetrahydrofuran (THF)s, 1.5 moles n-Butyl Amine 99 and 3 mole of triethylamine mixtures are joined in the reactor, start stirring (300 rev/mins), the phosphorus thiochloride that slowly adds 1 mole then, temperature is controlled at 15 ℃, reacted 2 hours, feed 2 moles ammonia then in reactor, temperature is controlled 10 ℃, reacts to obtain crude product after 2 hours.Pass through centrifugation then, remove solid residue after, gained liquid carries out underpressure distillation in the time of 100 ℃, obtain finished product N one normal-butyl thiophosphoryl triamine at last.
Embodiment 5:
4 moles tetrahydrofuran (THF)s, 1 mole n-Butyl Amine 99 and 3 mole of triethylamine mixtures are joined in the reactor, start stirring (260 rev/mins), the phosphorus thiochloride that slowly adds 1 mole then, temperature is controlled at 0 ℃, reacted 8 hours, feed 8 moles ammonia then in reactor, temperature is controlled 10 ℃, reacts to obtain thick product after 7 hours.Pass through centrifugation then, remove solid residue after, gained liquid carries out underpressure distillation in the time of 100 ℃, obtain finished product N one normal-butyl thiophosphoryl triamine at last.
Claims (1)
1, a kind of production method of N-normal-butyl thiophosphoryl triamine is characterized in that this method comprises: raw material processed, building-up reactions, logical ammonia, the thick product of preparation and a plurality of processing steps of product recrystallizing and refining, and concrete implementation step and technical essential are as follows:
(1), raw material processed, used raw material is phosphorus thiochloride, n-Butyl Amine 99, ammonia, used solvent is a tetrahydrofuran (THF), used acid binding agent is a triethylamine, at first adopt molecular sieve or Calcium Chloride Powder Anhydrous, sodium hydroxide, potassium hydroxide, calcium oxide that phosphorus thiochloride, n-Butyl Amine 99 are carried out processed, detect water-content in claimed range 0～2000ppm with water tester;
(2), phosphorus thiochloride is mixed with tetrahydrofuran (THF), stir cooling after, slowly drip n-Butyl Amine 99, triethylamine and tetrahydrofuran (THF) mixing solutions, keep temperature of reaction-15～20 ℃, dripped back constant temperature 1～8 hour, obtain white casse liquid; Wherein, the mole proportioning of tetrahydrofuran (THF) and phosphorus thiochloride is 4～12:1, and the proportioning of n-Butyl Amine 99 and phosphorus thiochloride is: 1～1.2:1, and the proportioning of triethylamine and phosphorus thiochloride is: 1～1.5:1, required mixing speed is 260～350 rev/mins, and alr mode is mechanical stirring or magnetic agitation;
(3), in reaction system, feed ammonia, the mole proportioning of ammonia and phosphorus thiochloride is 2～8:1, logical ammonia speed of control and the temperature of keeping reaction system be-10～25 ℃, detect to stop ammonification when qualified when temperature of reaction no longer changes or through the TLC plate, keep and react 1～5 hour;
(4), with the centrifugal ammonium chloride that produces in the reaction system of telling of reaction solution, with a certain amount of tetrahydrofuran (THF) washing leaching cake, filtrate and centrifugate are merged, the organic liquor of gained is removed most of solvent through underpressure distillation, obtain the thick product of N one normal-butyl thiophosphoryl triamine, product yield can reach more than 90%, and purity can reach more than 85%; Wherein, vacuum distillation temperature is 30～100 ℃, and pressure is 0.01～0.1MPa;
(5), thick product is carried out recrystallizing and refining, wherein, used crystallizing agent is wherein a kind of of methyl alcohol, ethanol, ethyl acetate, water or two kinds mixture wherein, the proportioning of solvent and product is 5～15:2～5 during recrystallization, Tc is-15～0 ℃, crystallization time is 4～24 hours, and being used for the tetrahydrofuran (THF) of washing leaching cake and the mass ratio of filter cake is 1～5:1, obtains purity greater than 99% smart product.
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| CN2009100107741A CN101503424B (en) | 2009-03-20 | 2009-03-20 | Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN104045465A (en) * | 2014-07-04 | 2014-09-17 | 上海艾拜克国际贸易有限公司 | Solution system containing n-butyl sulfo-phosphoric triamide and application thereof |
| 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 |
| 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 |
| 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 |
| CN111560036A (en) * | 2020-05-14 | 2020-08-21 | 浙江今晖新材料股份有限公司 | NBPT production facility |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872800A (en) * | 2006-06-09 | 2006-12-06 | 大连轻工业学院 | Long acting urea, method of preparation, and synthesizing N alkyl thiophosphoryl triamide of urease inhibitor |
| CN101337976A (en) * | 2008-08-15 | 2009-01-07 | 张九治 | Method for producing N-alkyl substituted phosphoric triamide |
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2009
- 2009-03-20 CN CN2009100107741A patent/CN101503424B/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746333B (en) * | 2012-06-12 | 2015-04-01 | 上虞盛晖化工股份有限公司 | Synthetic method of N-(n-butyl) thiophosphoric triamide |
| 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 |
| 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 |
| CN104045465B (en) * | 2014-07-04 | 2016-04-06 | 上海艾拜克国际贸易有限公司 | A kind of solution system and application thereof containing normal-butyl thiophosphoryl triamine |
| CN104045465A (en) * | 2014-07-04 | 2014-09-17 | 上海艾拜克国际贸易有限公司 | Solution system containing n-butyl sulfo-phosphoric triamide and application thereof |
| 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 |
| CN105254664B (en) * | 2014-10-28 | 2017-09-12 | 浙江奥复托化工有限公司 | A kind of synthetic method of urease inhibitor and its application |
| 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 |
| CN105399768B (en) * | 2015-11-20 | 2018-02-27 | 江西吉翔医药化工有限公司 | A kind of process for cleanly preparing for preparing N normal-butyl thiophosphoryl triamines |
| 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 |
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| CN101503424B (en) | 2011-08-17 |
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