CN104402926A - Continuously-synthesized chlorpyrifos step-by-step crystallization process - Google Patents
Continuously-synthesized chlorpyrifos step-by-step crystallization process Download PDFInfo
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- CN104402926A CN104402926A CN201410609005.4A CN201410609005A CN104402926A CN 104402926 A CN104402926 A CN 104402926A CN 201410609005 A CN201410609005 A CN 201410609005A CN 104402926 A CN104402926 A CN 104402926A
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Abstract
The invention relates to a continuously-synthesized chlorpyrifos step-by-step crystallization process, and the steps are as follows: 1, alkaline hydrolysis reaction is performed; 2, an alkali hydrolysis solution, an ethyl chloride and a composite catalyst are respectively pumped into a condensation reaction tower, the temperature of the condensation reaction tower is controlled at 40 DEG C to obtain a condensed liquid, the condensed liquid is pumped into a phase separation tower; 3, after the condensed liquid is separated in the phase separation tower, an oil phase located in the upper part of the tower is pumped into a water washing tower for water washing, the water-washed oil phase is pumped into an evaporator for vacuum dewatering and drying to obtain a crude chlorpyrifos product with the purity of 97wt%; and 4, the crude chlorpyrifos product is transferred to a crystallizer, for step-by-step crystallization. The chlorpyrifos product with high purity can be obtained by the step-by-step crystallization method of the continuously-synthesized chlorpyrifos step-by-step crystallization process, the reacted condensed liquid is separated, washed with water, and dried, then step by step crystallized, the chlorpyrifos product quality can be significantly improved, and industrial production and purification application effect is significant.
Description
Technical field
The invention belongs to fine chemistry industry synthesis field, the Steppecd crystallization of especially a kind of serialization synthesis Chlorpyrifos 94.
Background technology
Chlorpyrifos 94, chemical name is 0,0-diethyl-(3,5,6-trichloro-2-pyridyl) thiophosphatephosphorothioate, is wide spectrum, and the organic phosphorous insecticide of middle low toxicity, safety, having a extensive future, is one of a kind of potentiality product replacing riskiest pesticide.
At present, with 4 chloro pyridine be starting raw material synthesis Chlorpyrifos 94 be one of industrial conventional method.When purification Chlorpyrifos 94, common processing method is first decrease temperature crystalline, then washing and drying obtains Chlorpyrifos 94 finished product, also or without the direct washing and drying of decrease temperature crystalline step.Because washing unit is difficult to thoroughly be washed off by impurity, so the purity of the Chlorpyrifos 94 finished product causing final drying to obtain not is very desirable.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, the Steppecd crystallization of the serialization synthesis Chlorpyrifos 94 that a kind of combined coefficient is high, product purity is high is provided.
The technical scheme that the present invention realizes object is as follows:
A Steppecd crystallization for serialization synthesis Chlorpyrifos 94, step is as follows:
(1) first Basic fluxing raction tower is preheating to 100 DEG C, and 4 chloro pyridine, softening water, catalyzer, liquid caustic soda are in proportion to charging in Basic fluxing raction tower, and start and stir, temperature 135-140 DEG C in control tower, the alkali solution liquid obtained, squeezes into cooling tank by it with pump and be cooled to 45 DEG C;
(2) alkali solution liquid, diethylaluminum monochloride, composite catalyst squeeze into condensation reaction tower in proportion with pump respectively, control condensation reaction Ta Neiwen 40 DEG C, obtain condensated liquid, condensated liquid pump is squeezed into phase-splitting tower;
(3) the oil phase being positioned at tower top after phase-splitting, is squeezed into water wash column washing with pump by condensated liquid in phase-splitting tower, and it is dry that vaporizer vacuum hydro-extraction squeezed into by the oil phase pump after washing, obtains the Chlorpyrifos 94 crude product of purity 97wt% after dry;
(4) be transferred in crystallizer by the Chlorpyrifos 94 crude product of molten state, carry out fractional crystallization, the step of concrete fractional crystallization is:
The first step: first give crystallizer slow cooling, cooling rate controls, at 2-3 DEG C/h, to be cooled to 30-35 DEG C, and the mother liquor of failing to melt is disposed to mother liquor tank;
Second step: the crystal in crystallizer is heated up, the strict heat-up rate that controls is at 1-2 DEG C/h, and be warming up to 48-49 DEG C, sweating, the impurity that can melt is disposed to sweat tank;
3rd step: be rapidly heated again by remaining crystal, heat-up rate, at 10-15 DEG C/h, after all being melted by crystal, is released Chlorpyrifos 94 finished product in crystallizer and, to finished pot, is obtained Chlorpyrifos 94 finished product.
And, the weight ratio=1:2.1:3.5:0.05 of described 4 chloro pyridine, softening water, catalyzer, liquid caustic soda.
And, the weight ratio=1:0.158:0.009 of described alkali solution liquid, diethylaluminum monochloride, composite catalyst.
And described composite catalyst is N-Methylimidazole and phase-transfer catalyst, wherein phase-transfer catalyst is quaternary ammonium salt, wherein N-Methylimidazole: the mass ratio of quaternary ammonium salt is 2:1.
And described quaternary ammonium salt is benzyl trimethyl ammonium chloride.
The advantage that the present invention obtains and beneficial effect are:
The Steppecd crystallization used in the Steppecd crystallization of 1, serialization provided by the invention synthesis Chlorpyrifos 94 is purified and can be obtained the very high Chlorpyrifos 94 product of purity, through reacted condensated liquid again after phase-splitting, washing and dehydrate, fractional crystallization again, the quality of Chlorpyrifos 94 finished product can be significantly improved, Be very effective in industrial production and application of purifying.
2, method provided by the invention take 4 chloro pyridine as starting raw material, first the alkali solution liquid based on trichloro pyridyl sodium alcoholate is obtained, then alkali solution liquid directly and diethylaluminum monochloride be obtained by reacting condensated liquid based on Chlorpyrifos 94, again through phase-splitting, wash, dehydrate and obtain Chlorpyrifos 94 crude product, the production method of Chlorpyrifos 94 finished product is obtained finally by fractional crystallisation, continuity is good, and production efficiency is high.
3, method provided by the invention adopts three step crystallizations when crystallization, the first step, is cooled to 30-35 DEG C first to the Chlorpyrifos 94 crude product of molten state, is then disposed to mother liquor tank by failing the mother liquor of crystallization; Second step, is strictly warming up to 48-49 DEG C, sweating, and the sweat melted is disposed to sweat tank; 3rd step, is rapidly heated, and the crystal in crystallizer is all melted, then puts to finished pot, obtains finished product products obtained therefrom through the crystallization purifying of two steps, significantly improves the purity of product.
Embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Embodiment 1
A Steppecd crystallization for serialization synthesis Chlorpyrifos 94, step is as follows:
(1) first Basic fluxing raction tower is preheating to 100 DEG C, 4 chloro pyridine, softening water, catalyzer (PEG400), liquid caustic soda, in proportion to charging in Basic fluxing raction tower, start and stir, temperature 135-140 DEG C in control tower, the alkali solution liquid obtained, squeezes into cooling tank by it with pump and is cooled to 45 DEG C;
Weight ratio=the 1:2.1:3.5:0.05 of described 4 chloro pyridine, softening water, catalyzer, liquid caustic soda;
(2) alkali solution liquid, diethylaluminum monochloride, composite catalyst squeeze into condensation reaction tower in proportion with pump respectively, control condensation reaction Ta Neiwen 40 DEG C, obtain condensated liquid, condensated liquid pump is squeezed into phase-splitting tower;
Weight ratio=the 1:0.158:0.009 of described alkali solution liquid, diethylaluminum monochloride, composite catalyst, wherein, composite catalyst is N-Methylimidazole and phase-transfer catalyst, and wherein phase-transfer catalyst is quaternary ammonium salt, wherein N-Methylimidazole: the mass ratio of quaternary ammonium salt is 2:1; Quaternary ammonium salt is benzyl trimethyl ammonium chloride.
(3) the oil phase being positioned at tower top after phase-splitting, is squeezed into water wash column washing with pump by condensated liquid in phase-splitting tower, and it is dry that vaporizer vacuum hydro-extraction squeezed into by the oil phase pump after washing, obtains the Chlorpyrifos 94 crude product of purity 97wt% after dry;
(4) be transferred in crystallizer by the Chlorpyrifos 94 crude product of molten state, carry out fractional crystallization, the step of concrete fractional crystallization is:
The first step: first give crystallizer slow cooling, cooling rate controls, at 2-3 DEG C/h, to be cooled to 30-35 DEG C, and the mother liquor of failing to melt is disposed to mother liquor tank;
Second step: the crystal in crystallizer is heated up, the strict heat-up rate that controls is at 1-2 DEG C/h, and be warming up to 48-49 DEG C, sweating, the impurity that can melt is disposed to sweat tank;
3rd step: be rapidly heated again by remaining crystal, heat-up rate is at 10-15 DEG C/h, and after all being melted by crystal, in releasing crystallizer, Chlorpyrifos 94 finished product is to finished pot, and obtain Chlorpyrifos 94 finished product, finally obtaining purity is 99.9wt%.
Above-mentioned steps needs strict control to heat up and rate of temperature fall, the cooling rate of selection of the present invention controls at 2-3 DEG C/h, heat-up rate controls at 1-2 DEG C/h, and what this speed effectively can ensure impurity melts the generation effect and crystallization, takes into account the optimum proportion of the two.
Applicant is comparatively found by different speed ratios, when rate of temperature fall becomes large (being greater than 4 DEG C/h), its foreign matter content significantly improves, the content of finished product only has about 90%, and when heat-up rate becomes large (being greater than 3 DEG C/h), its yield obviously declines, yield only has 70%, and strictly control scope provided by the invention, the yield of 99% can be obtained, and the high purity 99.9wt% of product.
Claims (5)
1. a Steppecd crystallization for serialization synthesis Chlorpyrifos 94, step is as follows:
(1) first Basic fluxing raction tower is preheating to 100 DEG C, and 4 chloro pyridine, softening water, catalyzer, liquid caustic soda are in proportion to charging in Basic fluxing raction tower, and start and stir, temperature 135-140 DEG C in control tower, the alkali solution liquid obtained, squeezes into cooling tank by it with pump and be cooled to 45 DEG C;
(2) alkali solution liquid, diethylaluminum monochloride, composite catalyst squeeze into condensation reaction tower in proportion with pump respectively, control condensation reaction Ta Neiwen 40 DEG C, obtain condensated liquid, condensated liquid pump is squeezed into phase-splitting tower;
(3) the oil phase being positioned at tower top after phase-splitting, is squeezed into water wash column washing with pump by condensated liquid in phase-splitting tower, and it is dry that vaporizer vacuum hydro-extraction squeezed into by the oil phase pump after washing, obtains the Chlorpyrifos 94 crude product of purity 97wt% after dry;
(4) be transferred in crystallizer by the Chlorpyrifos 94 crude product of molten state, carry out fractional crystallization, the step of concrete fractional crystallization is:
The first step: first give crystallizer slow cooling, cooling rate controls, at 2-3 DEG C/h, to be cooled to 30-35 DEG C, and the mother liquor of failing to melt is disposed to mother liquor tank;
Second step: the crystal in crystallizer is heated up, the strict heat-up rate that controls is at 1-2 DEG C/h, and be warming up to 48-49 DEG C, sweating, the impurity that can melt is disposed to sweat tank;
3rd step: be rapidly heated again by remaining crystal, heat-up rate, at 10-15 DEG C/h, after all being melted by crystal, is released Chlorpyrifos 94 finished product in crystallizer and, to finished pot, is obtained Chlorpyrifos 94 finished product.
2. the Steppecd crystallization of serialization synthesis Chlorpyrifos 94 according to claim 1, is characterized in that: the weight ratio=1:2.1:3.5:0.05 of described 4 chloro pyridine, softening water, catalyzer, liquid caustic soda.
3. the Steppecd crystallization of serialization synthesis Chlorpyrifos 94 according to claim 1, is characterized in that: the weight ratio=1:0.158:0.009 of described alkali solution liquid, diethylaluminum monochloride, composite catalyst.
4. the Steppecd crystallization of serialization synthesis Chlorpyrifos 94 according to claim 1, it is characterized in that: described composite catalyst is N-Methylimidazole and phase-transfer catalyst, wherein phase-transfer catalyst is quaternary ammonium salt, wherein N-Methylimidazole: the mass ratio of quaternary ammonium salt is 2:1.
5. the Steppecd crystallization of serialization synthesis Chlorpyrifos 94 according to claim 4, is characterized in that: described quaternary ammonium salt is benzyl trimethyl ammonium chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037424A (en) * | 2015-08-15 | 2015-11-11 | 湖州旭龙生物化学有限公司 | Chlorpyrifos refining method |
| CN113549109A (en) * | 2021-07-26 | 2021-10-26 | 江苏九九久科技有限公司 | Method for preparing chlorpyrifos |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443024A (en) * | 2011-11-21 | 2012-05-09 | 湖北犇星农化有限责任公司 | Production method for synthesizing chlorpyrifos by taking tetrachloropyridine as raw material |
| CN102977140A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Multiple composite catalyst-induced chlorpyrifos preparation method |
| CN103086960A (en) * | 2011-10-27 | 2013-05-08 | 山西康得利精细化工有限公司 | Novel process for producing chlopyrifos from pyridone by using aqueous phase method |
| CN103467515A (en) * | 2012-06-07 | 2013-12-25 | 山东天成生物科技有限公司 | Aqueous phase method for synthesis of chlorpyrifos |
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- 2014-11-03 CN CN201410609005.4A patent/CN104402926B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086960A (en) * | 2011-10-27 | 2013-05-08 | 山西康得利精细化工有限公司 | Novel process for producing chlopyrifos from pyridone by using aqueous phase method |
| CN102443024A (en) * | 2011-11-21 | 2012-05-09 | 湖北犇星农化有限责任公司 | Production method for synthesizing chlorpyrifos by taking tetrachloropyridine as raw material |
| CN103467515A (en) * | 2012-06-07 | 2013-12-25 | 山东天成生物科技有限公司 | Aqueous phase method for synthesis of chlorpyrifos |
| CN102977140A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Multiple composite catalyst-induced chlorpyrifos preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037424A (en) * | 2015-08-15 | 2015-11-11 | 湖州旭龙生物化学有限公司 | Chlorpyrifos refining method |
| CN113549109A (en) * | 2021-07-26 | 2021-10-26 | 江苏九九久科技有限公司 | Method for preparing chlorpyrifos |
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