CN108084224A - A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines - Google Patents
A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines Download PDFInfo
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- CN108084224A CN108084224A CN201711323251.3A CN201711323251A CN108084224A CN 108084224 A CN108084224 A CN 108084224A CN 201711323251 A CN201711323251 A CN 201711323251A CN 108084224 A CN108084224 A CN 108084224A
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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Abstract
The invention discloses the methods that successive reaction in a kind of microreactor prepares normal-butyl thiophosphoryl triamine, n-butylamine and phosphorus thiochloride are uniformly mixed respectively with solvent first, then film is added to by feed pump to disperse in microreactor, n-butylamine is distributed in the form of microlayer model in the mixed liquor of phosphorus thiochloride, normal-butyl phosphorothioic dichlorides are obtained by the reaction at a certain temperature, while are passed through the acid binding agent that ammonia is hydrogen chloride；Reactant is then delivered to tubular microreactors, ammonia is continuously passed through to reactor by gas distributor, obtains normal-butyl thiophosphoryl triamine and ammonium chloride；Product is collected finally by kettle is collected, by operations such as crystallization, filtering, dryings, obtains product.The present invention method work flow it is short, reaction condition is mild, technological operation is simple, by-product is few, low energy consumption, high income, it is at low cost the advantages that, be suitble to scale industrial production.
Description
Technical field
The invention belongs to chemical process method fields, and in particular to a kind of to be continuously synthesizing to N- normal-butyls using microreactor
The method of thiophosphoryl triamide.
Background technology
N- normal-butyl thiophosphoryl triamines (NBPT) are a kind of efficient soil urease inhibitor, it has excellent urase
Inhibitory action can significantly reduce the decomposition of urea in the soil, increase utilization rate of the crop to nitrogen.Its inhibiting mechanism is to strive
To take ligand by force, reduce urease activity, the nickle atom in nitrogen-atoms and urase in NBPT molecules forms (N-Ni) ligand, point
Amino-compound in son can also form terdentate ligand with the oxygen atom in carbamic acid bridge, terdentate ligand than urea with
The monodentate ligand that urase is formed is secured, so as to reduce contact of the urea with urase, slows down the hydrolysis rate of urea, improves
The utilization rate of urea.
Synthesis technology on NBPT can be divided into there are many document report according to the difference of reactor:Pipe reaction and
Two kinds of techniques of still reaction.Pipe reaction is usually, by reaction mass by it is a kind of in a tubular form, the very big tubular reactor of draw ratio
The continuous operation technology that device is reacted has been widely studied and has gradually been applied to industrialized production at present, and the technique is with two
Chloromethanes or toluene are that solvent, phosphorus thiochloride and n-butylamine are raw material, and n-butylamine is acid binding agent, in being made using tubular reactor
Thio two phosphoryl chloride phosphorus oxychloride of mesosome normal-butyl, then reaction solution carry out aminating reaction again after filtering and NBPT be made, the process is total
Yield is relatively low.And using raw material n-butylamine as acid binding agent, the organic hydrochloride generated after reaction is recycled, and waste liquid is more
And production cost is high.Autoclave method is broadly divided into according to the difference of operating procedure:" two-step method " and " one kettle way "." two-step method " route
The substance is synthesized using chloroform as solvent, triethylamine has synthesized normal-butyl phosphorothioic dichlorides as acid binding agent, and reaction solution is filtered
Triethylamine hydrochloride is removed, then ammonia is passed through reaction solution to prepare NBPT, this method uses organic acid binding agent triethylamine, reaction
Solvent toxicity is higher." one kettle way " prepares N- normal-butyl thiophosphoryl triamines method using tetrahydrofuran as reaction dissolvent, triethylamine
As acid binding agent, ammonia to reaction is directly passed through into reaction solution after the completion of reaction and is finished, filters and removes ammonium chloride, filtrate decompression
Be distilled to recover solvent and triethylamine, remaining light yellow thick liquid vacuum drying obtains solid crude product, yield can reach 95% with
On.The process advantage is triethylamine hydrochloride without separation, be passed through in second step after ammonia can separate out generate three second
Amine and ammonium chloride, then by filtering and vacuum distillation is separately recovered.But above two method using triethylamine or excess
For n-butylamine as acid binding agent, by-product is more, and separation and purification acquire a certain degree of difficulty, and the most intermediate demand separation of these techniques,
Reaction time is long, and material back-mixing is serious, and impurity is more, and high energy consumption, yield is low, and environmental pollution is more serious.
The content of the invention
In order to overcome the shortcomings of the prior art, the present invention provides a kind of microreactors to be continuously synthesizing to N- normal-butyls
The method of thiophosphoryl triamide.Specific technical solution is as follows：
A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines, includes the following steps：
(1) n-butylamine and solvent are sufficiently mixed uniformly, as the first component；Phosphorus thiochloride is sufficiently mixed with solvent
It is even, as the second component, the first component and the second component are disperseed into microreactor by film and reacted, and is passed through ammonia simultaneously
It is reacted as acid binding agent, obtains N- phosphorothioic dichlorides ammonium chlorides；
(2) above-mentioned product is passed through in tubular microreactors, while is continuously passed through ammonia conduct through gas distributor and ties up acid
Agent is reacted, and obtains normal-butyl thiophosphoryl triamine reaction solution, the caliber of the tubular microreactors is 5-20mm, and pipe range is
10-20m.
(3) after reaction, reaction solution is crystallized, filtered, it is dry, obtain normal-butyl thiophosphoryl triamine product.
Preferably, the film average pore size that the film disperses microreactor is 5-50 μm；
Preferably, the reaction temperature is 10-30 DEG C, residence time 10-45s.
The solvent is：Dichloromethane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, ethyl acetate, one of benzene or pentane
Or its mixture；
The mass ratio of solvent and n-butylamine is 0:1~0.5, the mass ratio of solvent and phosphorus thiochloride is 0:1~0.3；First
The velocity ratio of component and the second component is 0.5~2.0.
The present invention has the following advantages that than the prior art：
(1) present invention proposes the method using micro disperse reactor synthesis normal-butyl thiophosphoryl triamine, compared to tradition
Stirred tank or tubular reactor can realize that n-butylamine drop is quick equal in the mixed liquor containing phosphorus thiochloride in the short time
It is even to be dispersed into droplet, the dissolving and reaction of n-butylamine are enhanced significantly, it is not necessary to deliberately be maintained low temperature in initial reaction phase, be made
The restricted problem of low temperature slow reaction is subject to be addressed when mixing heterogeneity；
(2) microreactor is compared with traditional reaction kettle, and microreactor has that work flow is short, continuous metaplasia can be achieved
Production, reaction condition is mild, technological operation is simple, by-product is few, low energy consumption, high income, it is at low cost, it is entire reaction without reflow treatment
The advantages that.
(3) using ammonia as acid binding agent, can by depressurize filter it is quick realize separation of solid and liquid, saving production cost,
And the by-product of two-step reaction is ammonium chloride, reduces the species of by-product in building-up process, shortens the production cycle；
(4) the normal-butyl thiophosphoryl triamine product yield that the technique obtains is up to more than 90%, and product purity is up to 98%.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of microreactor method is continuously synthesizing to the device of normal-butyl thiophosphoryl triamine, comprises the following steps：
(1) n-butylamine and dichloromethane are sufficiently mixed uniformly, as the first component, phosphorus thiochloride and dichloromethane is filled
Divide and be uniformly mixed, as the second component, the first component and the second component are disperseed into microreactor by feeding constant-flux pump input film
In reacted, while ammonia is passed through by gas distributor, film disperses the metal sintering membrane aperture of microreactor for 5 μm, instead
It should be 20s the residence times, reaction temperature is 23 DEG C, obtains N- phosphorothioic dichlorides ammonium chlorides；
(2) above-mentioned product is passed through in tubular microreactors, while is continuously passed through ammonia through gas distributor and is reacted,
Tubular microreactors caliber is 10mm, pipe range 5m, residence time 30s, and reaction temperature is 25 DEG C, obtains the thio phosphorus of normal-butyl
Acyl triamine；
(3) after reaction, reaction solution is crystallized, filtered, it is dry, obtain normal-butyl thiophosphoryl triamine product.Product
Yield 87%, purity 95%.
Embodiment 2
A kind of microreactor method is continuously synthesizing to the device of normal-butyl thiophosphoryl triamine, comprises the following steps：
(1) n-butylamine and dichloromethane are sufficiently mixed uniformly, as the first component, phosphorus thiochloride and dichloromethane is filled
Divide and be uniformly mixed, as the second component, the first component and the second component are disperseed into microreactor by feeding constant-flux pump input film
In reacted, while ammonia is passed through by gas distributor, film disperses the metal sintering membrane aperture of microreactor for 8 μm, instead
It should be 18s the residence times, reaction temperature is 23 DEG C, obtains N- phosphorothioic dichlorides ammonium chlorides；
(2) above-mentioned product is passed through in tubular microreactors, while is continuously passed through ammonia through gas distributor and is reacted,
Tubular microreactors caliber is 10mm, pipe range 5m, residence time 30s, and reaction temperature is 25 DEG C, obtains the thio phosphorus of normal-butyl
Acyl triamine；
(3) after reaction, reaction solution is crystallized, filtered, it is dry, obtain normal-butyl thiophosphoryl triamine product.Product
Yield 85%, purity 92%.
Embodiment 3
A kind of microreactor method is continuously synthesizing to the device of normal-butyl thiophosphoryl triamine, comprises the following steps：
(1) n-butylamine and chloroform are sufficiently mixed uniformly, as the first component, phosphorus thiochloride and chloroform is sufficiently mixed
It is even, as the second component, the first component and the second component are disperseed in microreactor to carry out instead by feeding constant-flux pump input film
Should, while ammonia is passed through by gas distributor, film disperses the metal sintering membrane aperture of microreactor for 8 μm, when reaction stops
Between for 18s, reaction temperature is 23 DEG C, obtains N- phosphorothioic dichlorides ammonium chlorides；
(2) above-mentioned product is passed through in tubular microreactors, while is continuously passed through ammonia through gas distributor and is reacted,
Tubular microreactors caliber is 10mm, pipe range 5m, residence time 30s, and reaction temperature is 25 DEG C, obtains the thio phosphorus of normal-butyl
Acyl triamine；
(3) after reaction, reaction solution is crystallized, filtered, it is dry, obtain normal-butyl thiophosphoryl triamine product.Product
Yield 80%, purity 89%.
Claims (7)
1. a kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines, which is characterized in that including walking as follows
Suddenly：
(1) n-butylamine and solvent are sufficiently mixed uniformly, as the first component；Phosphorus thiochloride is sufficiently mixed uniformly with solvent, is made
For the second component, the first component and the second component are disperseed into microreactor by film and reacted, and is passed through ammonia conduct simultaneously
Acid binding agent is reacted, and obtains N- phosphorothioic dichlorides ammonium chlorides；
(2) above-mentioned product is passed through in tubular microreactors, at the same be continuously passed through through gas distributor ammonia as acid binding agent into
Row reaction, obtains normal-butyl thiophosphoryl triamine reaction solution；
(3) after reaction, reaction solution is crystallized, filtered, it is dry, obtain normal-butyl thiophosphoryl triamine product.
2. according to the method described in claim 1, it is characterized in that, the solvent described in step (1) is：Dichloromethane, tetrahydrochysene furan
It mutters, Isosorbide-5-Nitrae-dioxane, ethyl acetate, one of benzene or pentane or its mixture.
3. according to the method described in claim 1, it is characterized in that, the mass ratio of the solvent and n-butylamine described in step (1) is
0:1~0.5, the mass ratio of solvent and phosphorus thiochloride is 0:1~0.3.
4. according to the method described in claim 1, it is characterized in that, the film that the film described in step (1) disperses microreactor is averaged
Aperture is 5-50 μm.
5. according to the method described in claim 1, it is characterized in that, reaction temperature described in step (1) is 10-30 DEG C, stop
Time is 10-45s.
6. the according to the method described in claim 1, it is characterized in that, flow velocity of step (1) first component and the second component
Than for 0.5~2.0.
7. according to the method described in claim 1, it is characterized in that, the caliber of step (2) described tubular microreactors is 5-
20mm, pipe range 10-20m.
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Cited By (4)
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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 |
| CN110294769A (en) * | 2019-08-07 | 2019-10-01 | 清华大学 | A method of Piperacillin is synthesized using microreactor |
| 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 |
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| CN110294769A (en) * | 2019-08-07 | 2019-10-01 | 清华大学 | A method of Piperacillin is synthesized using microreactor |
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