CN102001970A - Method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping - Google Patents
Method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping Download PDFInfo
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- CN102001970A CN102001970A CN2009100906513A CN200910090651A CN102001970A CN 102001970 A CN102001970 A CN 102001970A CN 2009100906513 A CN2009100906513 A CN 2009100906513A CN 200910090651 A CN200910090651 A CN 200910090651A CN 102001970 A CN102001970 A CN 102001970A
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Abstract
The invention relates to a method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping, which comprises the steps of: adding urea and phenylamine in an agitated reactor according to the mol proportion of 1:3.5-8, stirring, introducing nitrogen and gas-stripping for 2-6h to obtain a reaction by-product of ammonia, heating and raising the temperature to 145-180 DEG C, and reacting under normal pressure, wherein the nitrogen flow is 3-8 times reactor volume per hour; and after the reaction is ended, stopping stirring, naturally reducing the temperature and crystallizing, and leaching a reaction crystallized product to obtain a crystal diphenylsulfourea product. The method is easy to control the reaction process; the product is separated out in a crystal manner, simple in separation and high in product yield; the diphenylsulfourea yield is 90-95 percent, and the nitrogen consumption is 60-200L/kg DPU.
Description
Technical field
The present invention relates to a kind of is the raw material direct reaction by urea and aniline, shifts out the method that the by product ammonia prepares diphenyl urea with nitrogen.
Background technology
Diphenyl urea (N, N '-Diphenyluea), have another name called N, N '-diphenyl urea; 1, the 3-diphenyl urea is called for short DPU.Diphenyl urea can be made plant-growth regulator, has the cell fission of promotion, growth, improves quality, the effect that increases output and gather in the crops in advance; Along with carrying out in a deep going way of diphenyl urea research, diphenyl urea will be brought into play more and more significant effect in agriculture production.In addition, diphenyl urea through alcoholysis or and dimethyl carbonate, but synthesizing Amino-methye-formate is the important intermediate of non-phosgene synthesizing diphenyl methane vulcabond (MDI).
Synthesizing of diphenyl urea, Chinese scholars has been carried out a lot of trials.Usefulness primary isoamyl alcohol such as Xie Rongchun are solvent, with aniline and the urea mol ratio mixed with 2: 1, stir 20h under 140-148 ℃ of condition, and productive rate (in aniline) is 88%.Wang Bin etc. are solvent with dimethylbenzene, and aniline mixes with 2.05: 1 with urea mol ratio, at 130 ℃ of backflow 6h, and cooling, filtration, solid washs with dimethylbenzene, and productive rate is 93%.These two kinds of methods have increased the cost of solvent recuperation owing to added solvent.Other has Fan Nengting to mix with aqueous solution of urea with aniline hydrochloride, 100 ℃ of backflow 1h, and insulation 1h, productive rate (in aniline hydrochloride) is 36%-38%.Problems such as equally there is equipment corrosion in the commercial run that this method simultaneous interpretation controlling is equipped with diphenyl urea, produces a large amount of waste water, and productive rate is lower.
Development in recent years be the synthetic diphenyl urea of raw material reducing carbonyl method with oil of mirbane, though raw material is easy to get, need precious metal (ruthenium, rhodium, palladium) complex compound catalyst, reaction pressure higher (greater than 5MPa), and will use the bigger oil of mirbane of toxicity.
Problems such as CN1189452C uses aniline hydrochloride salt and urea to be raw material, is reaction medium with water, generates phenylurea and diphenyl urea, has equipment corrosion, and reaction needs pressurization, and the diphenyl urea yield is lower.
Urea and aniline direct reaction prepare diphenyl urea, have the productive rate height, do not have the characteristics of equipment corrosion.Ammonia is shifted out the direction that helps reacting to generating diphenyl urea carry out from system, vacuumizing under the situation that shifts out ammonia, reaction is violent, the difficult control of speed of response, and part aniline easily is drawn out of reactive system, and the loss of aniline is bigger.In addition, vacuumize the seal request of conversion unit sternlyer, seal badly, outside air enters reaction system, easily causes the aniline oxidation, also can increase the loss of aniline.
Summary of the invention
The purpose of this invention is to provide a kind of urea and aniline direct reaction, shift out the method that the by product ammonia prepares diphenyl urea with nitrogen, reaction process is easy to control, and the aniline loss is few.
The concrete preparation method of the present invention comprises the steps:
The ratio of urea and aniline in molar ratio 1: 3.5-8 adds in the reactor, stir, logical nitrogen gas proposes the byproduct of reaction ammonia, nitrogen flow be 3-8 times of reactor volume/hour, heat temperature raising is to 145-180 ℃ temperature of reaction, synthesis under normal pressure, in the logical 2-6 hour nitrogen reaction times, reaction stops stirring the nature decrease temperature crystalline after finishing, the reactive crystallization product is carried out suction filtration, obtain crystalloid diphenyl urea product.
Aforesaid temperature of reaction optimum is 155-175 ℃.
The optimum mol ratio of aforesaid urea and aniline is 1: 5-8.
The nitrogen consumption calculating formula of per kilogram diphenyl urea product:
The nitrogen consumption (rise/kgDPU)=nitrogen flow (rise/hour) * the logical nitrogen time of reaction (hour)/(urea mole number * 0.0021225 * diphenyl urea productive rate (%))
The present invention has following advantage:
Reaction process is easy to control, and the aniline loss is few, and product is separated out with crystalline form, separate simply product yield height, diphenyl urea productive rate 90-95%, the nitrogen consumption is at 60-200 liter/kgDPU, and the diphenyl urea purity that obtains is 93-95%, can be directly as the raw material of synthesizing phenyl carbamate.
Embodiment
Embodiment 1:
In 3 liters of reactors that have stirring and reflux exchanger, add 3mol urea and 12mol aniline, open stirring, logical nitrogen, heating up begins reaction, nitrogen flow remain on 3 times of reactor volumes/hour, temperature of reaction 150-160 ℃, synthesis under normal pressure, the logical 6 hours nitrogen time of reaction.Reaction stops stirring the nature decrease temperature crystalline after finishing, and under the vacuum tightness of 400mmHg the reactive crystallization product is carried out suction filtration, obtains crystalloid diphenyl urea product, purity 93.4%, and the nitrogen consumption is 93.0 liters/kgDPU, diphenyl urea productive rate 91.2%.
Embodiment 2:
In 3 liters of reactors that have stirring and reflux exchanger, add 3mol urea and 21mol aniline, open stirring, logical nitrogen, heating up begins reaction, nitrogen flow remain on 6 times of reactor volumes/hour, temperature of reaction 160-170 ℃, synthesis under normal pressure, the logical 4 hours nitrogen time of reaction.Reaction stops stirring the nature decrease temperature crystalline after finishing, and under the vacuum tightness of 700mmHg the reactive crystallization product is carried out suction filtration, obtains crystalloid diphenyl urea product, purity 94.7%, and the nitrogen consumption is 119.3 liters/kgDPU, diphenyl urea productive rate 94.8%.
Embodiment 3:
In the 1 liter of reactor that has stirring and reflux exchanger, add 1mol urea and 8mol aniline, open stirring, logical nitrogen, heating up begins reaction, nitrogen flow remain on 8 times of reactor volumes/hour, temperature of reaction 160-170 ℃, synthesis under normal pressure, the logical 2 hours nitrogen time of reaction.Reaction stops stirring the nature decrease temperature crystalline after finishing, and under the vacuum tightness of 660mmHg the reactive crystallization product is carried out suction filtration, obtains crystalloid diphenyl urea product, purity 94.1%, and the nitrogen consumption is 83.3 liters/kgDPU, diphenyl urea productive rate 90.5%.
Claims (3)
1. urea and aniline direct reaction nitrogen gas are obtained through refining the method for diphenyl urea fully, it is characterized in that: comprise the steps:
The ratio of urea and aniline in molar ratio 1: 3.5-8 adds in the reactor, stir, logical nitrogen gas proposes the byproduct of reaction ammonia, nitrogen flow be 3-8 times of reactor volume/hour, heat temperature raising is to 145-180 ℃ temperature of reaction, synthesis under normal pressure, the logical 2-6 hour nitrogen time of reaction, reaction stops stirring the nature decrease temperature crystalline after finishing, the reactive crystallization product is carried out suction filtration, obtain crystalloid diphenyl urea product.
2. a kind of urea according to claim 1 and aniline direct reaction nitrogen gas are obtained through refining the method for diphenyl urea fully, and it is characterized in that: described temperature of reaction is 155-175 ℃.
3. a kind of urea according to claim 1 and aniline direct reaction nitrogen gas are obtained through refining the method for diphenyl urea fully, and it is characterized in that: the mol ratio of described urea and aniline is 1: 5-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100906513A CN102001970A (en) | 2009-09-02 | 2009-09-02 | Method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100906513A CN102001970A (en) | 2009-09-02 | 2009-09-02 | Method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping |
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| CN102001970A true CN102001970A (en) | 2011-04-06 |
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| CN2009100906513A Pending CN102001970A (en) | 2009-09-02 | 2009-09-02 | Method for preparing diphenylsulfourea by directly reacting urea with phenylamine through nitrogen gas stripping |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748891A (en) * | 2016-12-30 | 2017-05-31 | 陕西煤业化工技术开发中心有限责任公司 | A kind of method that aniline prepares diphenyl urea with urea |
-
2009
- 2009-09-02 CN CN2009100906513A patent/CN102001970A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748891A (en) * | 2016-12-30 | 2017-05-31 | 陕西煤业化工技术开发中心有限责任公司 | A kind of method that aniline prepares diphenyl urea with urea |
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Application publication date: 20110406 |