CN101898954A

CN101898954A - Novel alkaline hydrolysis process of dichloride chloropinacoline

Info

Publication number: CN101898954A
Application number: CN2009100859090A
Authority: CN
Inventors: 杨立雯; 查正炯
Original assignee: TH-UNIS INSIGHT Co Ltd
Current assignee: TH-UNIS INSIGHT Co Ltd
Priority date: 2009-05-27
Filing date: 2009-05-27
Publication date: 2010-12-01

Abstract

The invention provides a clean production process of an alkaline hydrolysis section in the production of pesticide metribuzin. Dichloride chloropinacoline is used as a raw material which is hydrolyzed into sodium oxybate with high yield and high selectivity under the high-concentration liquid alkali condition, therefore, the invention realizes that products are effectively separated from sodium chloride by recycling mother liquor so as to avoid waste water emission and product loss and realize clean production. The invention has favorable environmental protection benefits, social benefits and economic benefits.

Description

Novel alkaline hydrolysis process of dichloride chloropinacoline

Technical field

The present invention relates to the process for cleanly preparing of alkaline hydrolysis workshop section in a kind of agricultural chemicals piperazine humulone production, this technology is raw material with which ketone of dichloro Knit-the-brows, high yield and highly selective are hydrolyzed to Sodium under high density liquid caustic soda condition, apply mechanically by Recycling Mother Solution, have realized that product and sodium-chlor are isolating.Belong to technical field of chemistry and chemical engineering.

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 also can absorb by root absorption, stem, leaf.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, 6 main workshop sections such as methylate.Most of producer of alkaline hydrolysis workshop section all adopts following processing condition: the chlorination reaction still is obtained two chloropinacolones add reactor, add water and quantitative liquid caustic soda, the quality of material mark is 25% in the reactor at this moment, concentration is controlled under 10% the diluted alkaline condition carries out heating hydrolysis, obtains Sodium, sodium-chlor and water.Reaction equation is as follows:

The lower concentration of existing technology, discharging and the processing that the one way alkaline hydrolysis is follow-up cyclization waste water bring huge environmental protection pressure.Indivedual manufacturers are under the pressure of environmental protection pressure even be in the state that stops production or partly stop production.

Summary of the invention

The present invention is directed to the existing existing defective of technology, invented with an amount of or excessive high density liquid caustic soda alkaline hydrolysis two chloropinacolone highly selectivies, high yield and obtained Sodium, apply mechanically by Recycling Mother Solution, realized that product has separated, reduced the consumption of water with sodium-chlor, avoid the discharging of cyclization waste water, realized cleaner production.

Present inventors find, with any ketone of alkaline hydrolysis dichloro Knit-the-brows under an amount of or excessive high density liquid caustic soda, can filter out Sodium more with high yield, filtrate adds the sodium hydroxide of reaction aequum, can further separate out product, after the solid-liquid separation, in filtrate, add dichloro Knit-the-brows any ketone intensification alkaline hydrolysis again, reaction finishes the back owing to common-ion effcet precipitated sodium chloride, the recycle once more of solid-liquid separation rear filtrate.In high density liquid caustic soda alkaline hydrolysis and mother liquid recycle process, by ¹The H-NMR trace analysis finds that the excessive liquid caustic soda alkaline hydrolysis of high density is suitable with original technology to the selectivity of reaction, and product content＜1% in the isolated sodium-chlor is behind once washing ¹Almost can not find the characteristic peak of product among the H-NMR, simultaneously along with mother liquor apply mechanically by product and product has good resolution, can't enrichment in product, and all be enriched in the mother liquor.

Reacting flow chart sees accompanying drawing 1 for details.The inventive method comprises following operation steps:

1, be raw material with dichloro Knit-the-brows any ketone, with liquid caustic soda alkaline hydrolysis Sodium, which ketone amount of substance of sodium hydroxide and dichloro Knit-the-brows is than being 3-9, the concentration of liquid caustic soda is 20-60%, be preferably 30-50%, the temperature of alkaline hydrolysis is 70-120 ℃, is preferably 80-110 ℃, reaction times is 1-5h, is preferably 1.5-4.5h.Reaction cools to 0-60 ℃ after finishing, and is preferably 20-40 ℃, and solid-liquid separation gets mother liquor I and solid I, and solid I is the product Sodium.

2, get mother liquor I in the step 1, add the sodium hydrate solid of reacting weight, after fully stirring, cool to 0-60 ℃, be preferably 20-40 ℃, solid-liquid separation, mother liquor II and solid II, solid II is the product Sodium, the dichloro Knit-the-brows that adds reacting weight again in the mother liquor II is ketone where, the heat temperature raising alkaline hydrolysis, reaction cools to 0-60 ℃ after finishing, be preferably 20-40 ℃, solid-liquid separation gets mother liquor III and solid III, solid III is sodium-chlor, and mother liquor III recycled is to alkaline hydrolysis.

The inventive method has following characteristics

The present invention is optimized by the alkaline hydrolysis technology that piperazine humulone production process is produced, utilize an amount of or excessive high density liquid caustic soda alkaline hydrolysis, success the convenient of Sodium, by product and sodium-chlor separated, pass through mother liquid recycle, avoided product loss, separate out byproduct sodium chloride, avoided the discharging of alkaline hydrolysis waste water from the source.This novel process has solved which ketone lower concentration liquid caustic soda of dichloro Knit-the-brows is carried out alkaline hydrolysis, and the sodium salt yield is low, and the product of a great deal of and by product sodium-chlor all are brought in the cyclization waste water, the big unmanageable difficult problem of wastewater flow rate.Start easy, the alkaline hydrolysis novel process cheaply of cleaning, met the general requirement of cleaning cleaner production and recycling economy.

Description of drawings

Figure of description 1 is a process flow sheet.

Embodiment

Comparative examples 1

With which ketone of 50kg dichloro Knit-the-brows, 250kg content is that 15% liquid caustic soda places reactor, opens and stirs, and heat temperature raising to 80 ℃ beginning alkaline hydrolysis, controlled temperature are between 80-90 ℃, and the alkaline hydrolysis reaction finishes behind the 3h, and the content 16.3% of Sodium, transformation efficiency are 98%.

Embodiment 1

1.1, dichloro Knit-the-brows any ketone alkaline hydrolysis

With 50kg dichloro Knit-the-brows any ketone, 125kg content is that 30% liquid caustic soda places reactor, open and stir, heat temperature raising to 80 ℃ beginning alkaline hydrolysis, controlled temperature is between 80-110 ℃, 2.5h back alkaline hydrolysis reaction finishes, cool 40 ℃, solid-liquid separation gets mother liquor 101kg, wherein the content of sodium-chlor is 17.12%, and the content of sodium hydroxide is 3.54%; Solid 69kg, wherein the content of product Sodium is 45.5%, and sodium chloride content is 17.12%, and the content of water is 37.38%.

1.2, the mother liquor pre-treatment

1.1 mother liquor 101kg is placed reactor, add 68kg content simultaneously and be 50% liquid caustic soda, after stirring, solid-liquid separation, mother liquor 139kg, wherein the content of sodium-chlor is 9.46%, the content of sodium hydroxide is 24%; Solid 28kg, wherein the product Sodium 38%, and sodium chloride content is 20.1%, and the content of water is 41.9%.

1.3, mother liquid recycle

1.2 mother liquor 139kg is placed reactor, adds 50kg dichloro Knit-the-brows any ketone simultaneously, carry out alkaline hydrolysis by 1.1 operation among the embodiment 1, after the solid-liquid separation mother liquor 179kg, wherein the content of sodium-chlor is 13.48%, the content of sodium hydroxide is 2.49%; Solid 16.87kg, wherein the content of sodium-chlor is 90.55%, water content is 9%.Handle mother liquor according to 1.2 method then, obtain mother liquor 161kg, wherein the content of sodium-chlor is 13.56%, and the content of sodium hydroxide is 25%; Solid 73.5kg, wherein the content of product Sodium is 50.27%, and the content of sodium-chlor is 6.99%, and the content of water is 42.74%.

Average conversion is 98.5%

Embodiment 2

2.1, dichloro Knit-the-brows any ketone alkaline hydrolysis

With 50kg dichloro Knit-the-brows any ketone, 250kg content is that 30% liquid caustic soda places reactor, open and stir, heat temperature raising to 80 ℃ beginning alkaline hydrolysis, controlled temperature is between 80-110 ℃, 2.5h back alkaline hydrolysis reaction finishes, cool 40 ℃, solid-liquid separation gets mother liquor 200kg, wherein the content of sodium-chlor is 17.12%, and the content of sodium hydroxide is 25.3%%; Solid 97kg, wherein the content of product Sodium is 55.3%, and sodium chloride content is 7.54%%, and the content of water is 37.16%, and transformation efficiency is 98%.

2.2, mother liquid recycle

2.1 mother liquor 200kg is placed reactor, adds 50kg dichloro Knit-the-brows any ketone simultaneously, carry out alkaline hydrolysis by 2.1 operation among the embodiment 2, after the solid-liquid separation mother liquor 176kg, wherein the content of sodium-chlor is 13.48%, the content of sodium hydroxide is 26.3%; Solid 16.87kg, wherein the content of sodium-chlor is 90.55%, water content is 9%.Apply mechanically mother liquor according to 2.1 method after adding 150kg content in the mother liquor and be 50% liquid caustic soda.

Average conversion is 98.2%

Embodiment 3

According to the operation of embodiment 1,1.3 mother liquors that produce among the recycled embodiment 1, average conversion is 98.2%.Concrete experimental data sees following table for details:

Claims

1. the invention provides one is raw material with which ketone of dichloro Knit-the-brows, is hydrolyzed to Sodium under high density liquid caustic soda condition, realizes product and the process for cleanly preparing that sodium-chlor is isolating, Recycling Mother Solution is applied mechanically, and it comprises the steps:

1), be raw material with dichloro Knit-the-brows any ketone, add liquid caustic soda by sodium hydroxide and dichloro Knit-the-brows any ketone of certain proportioning and concentration, the temperature control alkaline hydrolysis, reaction finishes the back solid-liquid separation, gets mother liquor I and solid I, solid I is the product Sodium;

2), get the mother liquor I in the step 1), add the sodium hydroxide of reacting weight, after fully stirring, solid-liquid separation after cooling gets mother liquor II and solid II, and solid II is the product Sodium, dichloro Knit-the-brows any ketone that adds reacting weight again in the mother liquor II, the heat temperature raising alkaline hydrolysis, reaction cools after finishing, solid-liquid separation, mother liquor III and solid III, solid III is sodium-chlor, mother liquor III repeating step 2) operation.

2. method according to claim 1, wherein in the step 1), which ketone amount of substance of sodium hydroxide and dichloro Knit-the-brows is than being 3-9.

3. method according to claim 1, wherein step 1) and 2) in, reaction cools to 0-60 ℃ after finishing.

4. method according to claim 1, wherein step 2) in, the sodium hydroxide that is added is sheet alkali, or concentration concentration 40-70% liquid caustic soda.

5. method according to claim 1, wherein step 2) in, mother liquor III is the recycled alkaline hydrolysis repeatedly.