CN101899016A - New technology for recycling metribuzin methylate mother liquor - Google Patents
New technology for recycling metribuzin methylate mother liquor Download PDFInfo
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- CN101899016A CN101899016A CN2009100859103A CN200910085910A CN101899016A CN 101899016 A CN101899016 A CN 101899016A CN 2009100859103 A CN2009100859103 A CN 2009100859103A CN 200910085910 A CN200910085910 A CN 200910085910A CN 101899016 A CN101899016 A CN 101899016A
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- mother liquor
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Abstract
The invention provides a new technology for recycling metribuzin methylated mother liquor. The technology uses bromomethane as methylating agent to react with triazone under alkaline condition and obtain metribuzin; and methylated mother and bromine are recycled for cyclic utilization, thus achieving the aim of the reutilization of wastewater. The inorganic salt content and discharge amount of waste water in methylating working section can be effectively reduced, and the difficulty and cost of treating waste water are largely reduced. The invention has good environmental benefit, social benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of to being that triazone is a raw material with the cyclization product, under alkaline condition, carry out methylation reaction and generate the process for cleanly preparing that piperazine humulone mother liquor that workshop section produces is applied mechanically processing and bromine carries out recycle, belong to technical field of chemistry and chemical engineering with monobromethane.
Background technology
The piperazine humulone, English popular name: metribuzin, other titles; Sencorex, Sai Ke (Sencor), Garrick remove (Lexone), Beyer94337.Be interior suction selective herbicide, mainly by root absorption, stem, leaf also can absorb.1 year living broadleaf weeds and part gramineous weeds there is good preventive effect.The piperazine humulone is a kind of efficient, low toxicity dry land herbicide that soybean, tomato, potato, clover, orchard and other crops are prevented and kill off multiple broadleaf weeds and some gramineous weeds that can be used for, and is one of main weedicide kind of China.
Piperazine humulone production workshop section mainly comprises: chlorination, alkaline hydrolysis, oxidation, cyclization, five main workshop sections such as methylate.1), cyclization waste water the waste water main source has two parts in the piperazine humulone production process:; 2), methylated wastewater.This waste water flavor is big, mainly contain heterocyclic, ketone, alcohols organic compound and halogen, wherein in the methylated wastewater methanol content up to 5%, salt content is up to 6%, contain organism such as a large amount of ketones and triazines, belong to high salt, the difficult organic waste water of high pollution, difficulty in treatment such as having can not be biochemical, oxidisability difference and interfering substance serious interference.Indivedual manufacturers are under the pressure of environmental protection pressure even be in the state that stops production or partly stop production.
The synthetic method commonly used of bibliographical information adopts in methanol solution mostly, sodium hydroxide exists down makes 4-amino-6-tertiary butyl-3-coloured glaze base-1 with methylating reagents such as monobromethane, methyl chloride, 2,4-triazine-5 (4H)-ketone (abbreviation triazone) is carried out S-and is methylated and make product, and its reaction formula is as follows:
The piperazine humulone of the methylation reaction preparation of under these processing condition, carrying out, separate out from system with the solid form, methylate mother liquor is the trade effluent of one supersalinity, high COD, it is one of difficult problem of piperazine humulone industry, seek a cleaning, cheaply, recycling treatment process is extremely urgent, also meet simultaneously the general requirement of cleaner production and recycling economy, have good social benefit, economic benefit and environmental benefit.
Summary of the invention
The present invention is directed to the defective that existing technology exists, invented the process for cleanly preparing of a comprehensive treating process methylate mother liquor and resource utilization.
Solution of the present invention is to be that raw material and monobromethane carry out methylation reaction and generate the piperazine humulone under alkaline condition with the triazone that generates in traditional piperazine humulone production process, the piperazine humulone is separated out from system with the solid form, after the solid-liquid separation, contain a spot of unreacted methylate by product, sodium hydroxide, methyl alcohol and Sodium Bromide of triazone, N-completely in the mother liquor; Mother liquor is added after adding amount of methanol and sodium hydroxide and is dissolved a certain amount of triazone, carries out methylation reaction again in the presence of monobromethane, thereby reaches the purpose of methylate mother liquor recycled, reduces discharging methylated wastewater from the source; Along with the concentration of Sodium Bromide in the increase mother liquor of applying mechanically number of times increases gradually, viscosity increases, can't overlap the time spent, suitably concentrate the back and add amount of methanol, slowly drip the vitriol oil at a certain temperature, bromizate sodium and methyl alcohol and under the catalysis of the vitriol oil, react and generate methyl bromide gas and can directly overlap and be used for methylation reaction.This technology has not only reduced the consumption of water, greatly reduces the cost of handling waste water, has realized the use of bromine resource circulation simultaneously, meets the requirement of cleaner production and recycling economy, has good economic benefit, social benefit and environmental benefit.
The inventive method comprises the steps:
1, methylate mother liquor pre-treatment: the normal sodium hydroxide of triazone 1-1.4 before methylate mother liquor replenishes and applies mechanically, add the normal methyl alcohol of 1-5.0, thorough mixing is even.
2, applying mechanically of methylate mother liquor: with the methylate mother liquor in the step 1 and apply mechanically before normal triazone device join in the methylation reaction, after thorough mixing and the dissolving, feed the normal methyl bromide gas of 1-2.0 under 0-20 ℃ of temperature condition, reaction 3-5h afterreaction finishes substantially.
Reaction finishes back repetitive operation step 1 and 2 and carries out mother liquid recycle, and applying mechanically number of times is 1-20, is preferably 3-8 time.
3, methylate mother liquor prepares monobromethane: after methylate mother liquor is applied mechanically certain number of times, can utilize following reaction principle to prepare monobromethane, thereby reach the purpose of bromine resource utilization:
CH
3OH+NaBr+H
2SO
4→CH
3Br+NaHSO
4+H
2O
Apply mechanically and again it is carried out suitable concentrating after methylate mother liquor behind certain number of times reclaims methyl alcohol, the concentration that concentrates back system Sodium Bromide is 10-60%, be preferably 20-50%, add 0.8～2.0 normal methyl alcohol, be preferably the 1-1.6 equivalent, heating controlled temperature then is 40～80 ℃, is preferably 50-70 ℃, the 1-2.5 that slowly drips the Sodium Bromide amount of substance when temperature reaches works as the vitriol oil, is preferably the 1.5-2 equivalent; Temperature of reaction is controlled at 40-90 ℃, is preferably 60-80 ℃, and the dropping time is 1-4h, is preferably 2-4h.The methyl bromide gas of gained can directly overlap and be used for methylation reaction.
The inventive method has following characteristics
The present invention applies mechanically by the methylate mother liquor that piperazine humulone production process is produced, reduced discharging trade effluent from the source, the mother liquor that to repeatedly apply mechanically enrichment simultaneously, concentrate Sodium Bromide is by adding the methyl alcohol and vitriol oil production monobromethane, and recycling for the bromine resource utilization provides novel method.
This novel process has been captured methylate mother liquor processing difficulty, cost is high, and Sodium Bromide is difficult to difficult problems such as recycling treatment.Be a cleaning, cheaply, recycling treatment process, meet the general requirement of cleaner production and recycling economy, have good social benefit, economic benefit and environmental benefit.
Embodiment
Present embodiment is example with the laboratory operation:
Comparative examples 1
Methanol mixed with process water and the 7.8g of 46.0g, sodium hydroxide with 2.8g joins in the alcohol-water mixture then, add triazone 23.9g (42%) again, in system, feed monobromethane 7.8g after dissolving fully at ambient temperature and make system keep the state of comparatively sealing to react 5h down, solid-liquid separation gets product 9.7g after the washing and drying, measuring product content is 96.0%, the solid yield is 87%, methylate mother liquor 65.8g.
Embodiment 1
1.1, the applying mechanically of methylate mother liquor
Get methylate mother liquor 65.8g in the above-mentioned comparative examples 1, add methyl alcohol 3.8g and sodium hydroxide 2.7g, with (42%) reaction process of triazone 23.2g with comparative examples 1.Getting quality product after the washing and drying is 9.7g, and content is 95.8%, and the solid yield is 87.5%.Methylate mother liquor 72.6g.
Methylate mother liquor is applied mechanically operation with 1.1, applies mechanically data and sees the following form:
| Apply mechanically | 0 | 1 | 2 | 3 |
| The solid yield | 87.5％ | 88.7％ | 88.1％ | 87.9％ |
| Product content | 96.0％ | 95.8％ | 95.9％ | 95.8 |
| The amount of mother liquor | 65.8g | 72.6g | 78.9g | 85.6g |
1.2, methylate and apply mechanically mother liquor and prepare monobromethane
Get the methylate mother liquor 85.6g after applying mechanically, reclaim methyl alcohol and suitably concentrated, add methyl alcohol 9.17g, when rising to 60 ℃, temperature drips vitriol oil 35.7g, be controlled at about 2h and dropwise, maintain the temperature between 60～80 ℃, the recovery after cold-trap liquefies of the gas of generation through washing and drying, monobromethane 13.4g must liquefy.
1.3, the self-control monobromethane carry out methylation reaction
By the operation of comparative examples 1, carry out methylation reaction with the monobromethane for preparing among the embodiment 1.2 as methylating reagent and triazone, reaction finishes the back solid-liquid separation, get product 9.8g after the washing and drying, measuring product content is 95.8%, and the solid yield is 87%, methylate mother liquor 66g.
Claims (9)
1. the invention provides the process for cleanly preparing that a comprehensive treating process methylate mother liquor and bromine resource circulation are used, it comprises the steps:
1), methylate mother liquor is applied mechanically: mother liquor adds after adding amount of methanol and sodium hydroxide and an amount of triazone, feeds an amount of monobromethane in the certain temperature condition then and carries out methylation reaction, and after the solid-liquid separation, mother liquor continues recycled;
2), bromine recycling: the methyl alcohol behind the mother liquid recycle in the recovery system also suitably concentrates, add amount of methanol then, slowly drip the vitriol oil at a certain temperature, bromizate sodium and methyl alcohol and under the catalysis of the vitriol oil, react and generate methyl bromide gas, can directly overlap and be used for methylation reaction.
2. method according to claim 1, wherein in the step 1), adding methanol usage is the 1.0-5.0 equivalent of triazone.
3. method according to claim 1, wherein in the step 1), the amount of adding sodium hydroxide is the 1.0-1.4 equivalent of triazone.
4. method according to claim 1, wherein in the step 1), it is 1-10 time that Recycling Mother Solution is applied mechanically number of times.
5. method according to claim 1, wherein step 2) in, the concentration that is concentrated into Sodium Bromide after the Methanol Recovery is 10-60%.
6. method according to claim 1, wherein step 2) in, the addition of methyl alcohol is the 0.8-2.0 equivalent of system Sodium Bromide.
7. method according to claim 1, wherein step 2) in, the consumption of the vitriol oil is the 1-2.5 equivalent of Sodium Bromide amount of substance.
8. method according to claim 1, wherein step 2) in, the temperature when dripping the vitriol oil is 40-80 ℃, temperature of reaction is 40-90 ℃.
9. method according to claim 1, wherein step 2) in, the vitriol oil dropping time is 1-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910085910A CN101899016B (en) | 2009-05-27 | 2009-05-27 | New technology for recycling metribuzin methylate mother liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910085910A CN101899016B (en) | 2009-05-27 | 2009-05-27 | New technology for recycling metribuzin methylate mother liquor |
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| CN101899016A true CN101899016A (en) | 2010-12-01 |
| CN101899016B CN101899016B (en) | 2012-08-29 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319424A (en) * | 2013-07-03 | 2013-09-25 | 苏州诚和医药化学有限公司 | Synthesis method of 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine-5(4H)-one |
| CN103319425A (en) * | 2013-07-03 | 2013-09-25 | 苏州诚和医药化学有限公司 | Method for synthesizing 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine-5(4H)-one |
| CN103333130A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Preparation method of 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine 5 (4H)-ketone |
| CN103333129A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Method for preparing 4-amino-6-tertiary butyl-3-methylmercapto-1,2,4-triazine-5(4H)-ketone |
| CN107118169A (en) * | 2017-05-05 | 2017-09-01 | 江苏剑牌农化股份有限公司 | The synthetic method of 4 amino, 6 tertiary butyl, 3 methyl mercapto 1,2,4 triazine 5 (4H) ketone |
| CN109320470A (en) * | 2018-10-31 | 2019-02-12 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of metribuzin and the processing method of waste liquid |
| CN109503504A (en) * | 2018-12-29 | 2019-03-22 | 江苏瑞邦农药厂有限公司 | The preparation method of metribuzin |
-
2009
- 2009-05-27 CN CN200910085910A patent/CN101899016B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103333130B (en) * | 2013-07-03 | 2016-04-06 | 苏州诚和医药化学有限公司 | The preparation method of the 4-amino-6-tertiary butyl-3-methylthio group-1,2,4-triazine-5 (4H)-one |
| CN103319425A (en) * | 2013-07-03 | 2013-09-25 | 苏州诚和医药化学有限公司 | Method for synthesizing 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine-5(4H)-one |
| CN103333130A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Preparation method of 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine 5 (4H)-ketone |
| CN103333129A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Method for preparing 4-amino-6-tertiary butyl-3-methylmercapto-1,2,4-triazine-5(4H)-ketone |
| CN103319425B (en) * | 2013-07-03 | 2015-10-07 | 苏州诚和医药化学有限公司 | The method of the synthesis 4-amino-6-tertiary butyl-3-methylthio group-1,2,4-triazine-5 (4H)-one |
| CN103319424B (en) * | 2013-07-03 | 2016-01-20 | 苏州诚和医药化学有限公司 | A kind of synthetic method of the 4-amino-6-tertiary butyl-3-methylthio group-1,2,4-triazine-5 (4H)-one |
| CN103319424A (en) * | 2013-07-03 | 2013-09-25 | 苏州诚和医药化学有限公司 | Synthesis method of 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazine-5(4H)-one |
| CN103333129B (en) * | 2013-07-03 | 2016-04-06 | 苏州诚和医药化学有限公司 | One prepares the method for the 4-amino-6-tertiary butyl-3-methylthio group-1,2,4-triazine-5 (4H)-one |
| CN107118169A (en) * | 2017-05-05 | 2017-09-01 | 江苏剑牌农化股份有限公司 | The synthetic method of 4 amino, 6 tertiary butyl, 3 methyl mercapto 1,2,4 triazine 5 (4H) ketone |
| CN107118169B (en) * | 2017-05-05 | 2020-06-09 | 江苏剑牌农化股份有限公司 | Synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone |
| CN109320470A (en) * | 2018-10-31 | 2019-02-12 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of metribuzin and the processing method of waste liquid |
| CN109503504A (en) * | 2018-12-29 | 2019-03-22 | 江苏瑞邦农药厂有限公司 | The preparation method of metribuzin |
| CN109503504B (en) * | 2018-12-29 | 2022-01-07 | 江苏瑞邦农化股份有限公司 | Preparation method of metribuzin |
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| CN101899016B (en) | 2012-08-29 |
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