CN103524389A - Method for preparing pesticide methomyl - Google Patents
Method for preparing pesticide methomyl Download PDFInfo
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- CN103524389A CN103524389A CN201310498742.7A CN201310498742A CN103524389A CN 103524389 A CN103524389 A CN 103524389A CN 201310498742 A CN201310498742 A CN 201310498742A CN 103524389 A CN103524389 A CN 103524389A
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Abstract
The invention discloses a method for preparing pesticide methomyl. The method comprises the following steps: pulping methylthio acetaldehyde oxi me with water, dripping methyl isocyanate into the pulped methylthio acetaldehyde oxi me solution for reaction according to a mass ratio of the methylthio acetaldehyde oxi me to the methyl isocyanate being 1:(1.0-1.3), controlling the reaction temperature to be 5-15 DEG C and reacting time to be 1.5-3 hours; filtering through micropores, cooling, crystallizing, re-filtering, and drying. The method is convenient to operate, safe and controllable in production, can reduce the generation of side products, improves the yield and the quality, reduces the energy consumption and the production cost, improves the production field environment, further improves the solubility and the safety of the reaction, and reduces the emission of 'the Three Wastes'.
Description
Technical field
The present invention relates to sterilant, refer to particularly a kind of preparation method of agricultural chemicals methomyl.
Background technology
Methomyl be a kind of interior absorption have tag, the broad spectrum pesticide of the amino formate of stomach poison function, be applicable to the insects such as cotton, tobacco, fruit tree and vegetables anti-ly eliminate aphis, moth, cutworm, be to prevent and treat at present the good replacement kind of resistance cotten aphid.Methomyl also can be used as the intermediate of thiodicarb, is a kind of wide spectrum, fast-acting insecticide, effective to various pests such as aphid, bollworms, can be used for the crops such as grain, cotton, vegetables, tobacco, fruit.
Domestic agricultural chemicals methomyl is that methylthio group ethylidenehydroxylamine, methyl isocyanate react directly synthetic target product at the temperature of 5 ℃, generally adopts at present tank reactor and batch process to produce.Side reaction is many, the bad control of temperature of reaction, and long reaction time, product quality can not get ensureing.Make selection and the yield of chemosynthesis reaction not high, output is not high yet.
Summary of the invention
The object of the invention is to overcome the weak point of above-mentioned existing background technology, and a kind of preparation method of agricultural chemicals methomyl is provided, take methylmercaptan ethyl aldoxime, methyl isocyanate is raw material, at the temperature of 5～10 ℃, through reaction, makes methomyl., the production method of the former medicine of a kind of sterilant 98.5% methomyl.
Technical scheme of the present invention: a kind of preparation method of agricultural chemicals methomyl, comprise the following steps: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.0～1.3, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 5～15 ℃, reaction times 1.5～3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 50～70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50～55 ℃ by 65～70 ℃ in 45～90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 40～45 ℃, crystallization is complete, enters filter progress and filter after within 15～30 seconds, being cooled to 15～25 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.
The good technical scheme of the present invention: comprise the following steps: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.1, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 5～10 ℃, reaction times 3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 65～70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50 ℃ by 65 ℃ in 45～90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 43 ℃, crystallization is complete, enters filter progress and filter after within 15～30 seconds, being cooled to 20 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.
In such scheme, described methomyl mixed solution is put into double cone dryer when dry, controls 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa.
In such scheme, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
The invention has the advantages that: easy to operate and production safety is controlled, reduced the generation of by product, improved yield and quality, reduce energy consumption, reduced production costs, improved production on-site environment simultaneously, the solubility, the security that have further improved reaction, reduced the discharge of the three wastes.
Embodiment:
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.0, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 5 ℃, reaction times 1.5h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 50 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 55 ℃ by 70 ℃ in 45 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 40 ℃, crystallization is complete, enters filter progress and filter after within 15 seconds, being cooled to 25 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Embodiment 2: methylmercaptan ethyl aldoxime is added after water making beating, is 1:1.1 according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, and control temperature of reaction is 10 ℃, reaction times 2h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50 ℃ by 65 ℃ in 60 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 43 ℃, crystallization is complete, enters filter progress and filter after within 15 seconds, being cooled to 25 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Embodiment 3: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.2, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 15 ℃, reaction times 2.5h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 55 ℃ by 68 ℃ in 60 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 45 ℃, crystallization is complete, enters filter progress and filter after within 30 seconds, being cooled to 15 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Embodiment 4: methylmercaptan ethyl aldoxime is added after water making beating, is 1:1.3 according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, and control temperature of reaction is 5 ℃, reaction times 3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 65 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 55 ℃ by 65 ℃ in 90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 45 ℃, crystallization is complete, enters filter progress and filter after within 15 seconds, being cooled to 25 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Embodiment 5: methylmercaptan ethyl aldoxime is added after water making beating, is 1:1.1 according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, and control temperature of reaction is 10 ℃, reaction times 3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50 ℃ by 65 ℃ in 90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 43 ℃, crystallization is complete, enters filter progress and filter after within 30 seconds, being cooled to 20 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Embodiment 6: methylmercaptan ethyl aldoxime is added after water making beating, is 1:1.1 according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, and control temperature of reaction is 10 ℃, reaction times 3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 65 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50 ℃ by 65 ℃ in 45 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 43 ℃, crystallization is complete, enters filter progress and filter after within 15 seconds, being cooled to 20 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, control 65 ℃ of chuck water temperatures, massfraction to moisture after the dry 3～4h of vacuum tightness 0.01MPa reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.In addition, when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, is washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
Claims (4)
1. the preparation method of an agricultural chemicals methomyl, comprise the following steps: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.0～1.3, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 5～15 ℃, reaction times 1.5～3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 50～70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50～55 ℃ by 65～70 ℃ in 45～90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 40～45 ℃, crystallization is complete, enters filter progress and filter after within 15～30 seconds, being cooled to 15～25 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.
2. the preparation method of a kind of agricultural chemicals methomyl according to claim 1, it is characterized in that: comprise the following steps: methylmercaptan ethyl aldoxime is added after water making beating, according to the mass ratio of methylmercaptan ethyl aldoxime and methyl isocyanate, be 1:1.1, to dripping methyl isocyanate in methylmercaptan ethyl aldoxime making beating liquid, react, controlling temperature of reaction is 5～10 ℃, reaction times 3h; Above-mentioned reaction completes and in backward gained methomyl mixed solution, adds gac then to start to be warming up to 65～70 ℃ all to dissolve to material, by entering crystallization kettle decrease temperature crystalline after millipore filtration, Tc was down to 50 ℃ by 65 ℃ in 45～90 seconds, entering zone of transition starts to have crystal to separate out, controlling stir speed (S.S.) and rate of temperature fall keeps every 30min to reduce by 1 ℃ of left and right, while being cooled to 43 ℃, crystallization is complete, enters filter progress and filter after within 15～30 seconds, being cooled to 20 ℃; Dry by putting into double cone dryer through the methomyl mixed solution filtering, massfraction to moisture after dry 3～4h reaches below 0.3%, the massfraction of methomyl is more than 98.5%, gained methomyl is cooled to temperature and is 40 ℃ and packs when following.
3. the preparation method of a kind of agricultural chemicals methomyl according to claim 1 and 2, is characterized in that: described methomyl mixed solution is put into double cone dryer when dry, controls 65 ℃ of chuck water temperatures, vacuum tightness 0.01MPa.
4. the preparation method of a kind of agricultural chemicals methomyl according to claim 1 and 2, it is characterized in that: when the methomyl filtrated stock of described filter progress gained reaches 4500～5000L, described methomyl filtrated stock is squeezed into and processed still stirring, to processing, in still, drop into 800～1000kg Industrial Salt and saltout and obtain methomyl, controlling salt eutectoid temperature is 25～30 ℃, the time of saltouing is 1.5～2h, then the methomyl of gained after saltouing is carried out, washed, then carry out the methomyl that recrystallization, filtration, dry massfraction are 98.5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310498742.7A CN103524389A (en) | 2013-10-22 | 2013-10-22 | Method for preparing pesticide methomyl |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310498742.7A CN103524389A (en) | 2013-10-22 | 2013-10-22 | Method for preparing pesticide methomyl |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529847A (en) * | 2014-12-25 | 2015-04-22 | 湖北沙隆达股份有限公司 | Method for producing methomyl |
| CN104529846A (en) * | 2014-12-25 | 2015-04-22 | 湖北沙隆达股份有限公司 | Method for increasing yield of produced methomyl |
| CN111187192A (en) * | 2019-12-27 | 2020-05-22 | 安道麦股份有限公司 | Method for improving yield of methomyl |
| CN111450791A (en) * | 2020-05-08 | 2020-07-28 | 河南金鹏化工有限公司 | Continuous process and device for producing methomyl from methyl isocyanate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3752841A (en) * | 1971-05-14 | 1973-08-14 | Du Pont | Process for the preparation of carbamates of alkylthiolhydroxamates and intermediates |
| US3890362A (en) * | 1972-06-19 | 1975-06-17 | Du Pont | Preparation of thiohydroximate carbamates |
| CN102924354A (en) * | 2012-10-23 | 2013-02-13 | 海利贵溪化工农药有限公司 | Synthetic method of methomyl |
-
2013
- 2013-10-22 CN CN201310498742.7A patent/CN103524389A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3752841A (en) * | 1971-05-14 | 1973-08-14 | Du Pont | Process for the preparation of carbamates of alkylthiolhydroxamates and intermediates |
| US3890362A (en) * | 1972-06-19 | 1975-06-17 | Du Pont | Preparation of thiohydroximate carbamates |
| CN102924354A (en) * | 2012-10-23 | 2013-02-13 | 海利贵溪化工农药有限公司 | Synthetic method of methomyl |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529847A (en) * | 2014-12-25 | 2015-04-22 | 湖北沙隆达股份有限公司 | Method for producing methomyl |
| CN104529846A (en) * | 2014-12-25 | 2015-04-22 | 湖北沙隆达股份有限公司 | Method for increasing yield of produced methomyl |
| CN111187192A (en) * | 2019-12-27 | 2020-05-22 | 安道麦股份有限公司 | Method for improving yield of methomyl |
| CN111450791A (en) * | 2020-05-08 | 2020-07-28 | 河南金鹏化工有限公司 | Continuous process and device for producing methomyl from methyl isocyanate |
| CN111450791B (en) * | 2020-05-08 | 2023-04-18 | 河南金鹏化工有限公司 | Continuous process and device for producing methomyl from methyl isocyanate |
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Application publication date: 20140122 |