CN106167481B - A kind of production method of imidacloprid synthesis technology wastewater zero discharge - Google Patents
A kind of production method of imidacloprid synthesis technology wastewater zero discharge Download PDFInfo
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- CN106167481B CN106167481B CN201610540318.8A CN201610540318A CN106167481B CN 106167481 B CN106167481 B CN 106167481B CN 201610540318 A CN201610540318 A CN 201610540318A CN 106167481 B CN106167481 B CN 106167481B
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- C07—ORGANIC CHEMISTRY
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The present invention provides a kind of production methods of imidacloprid synthesis technology wastewater zero discharge, in the technique of imidazolidine and 2-vhloro-5-chloromethylpyridine imidacloprid synthesis, technique waste water to be applied, reaches by-product salt, does not generate sewage effect using butanone as solvent.Generate technique waste water recycled 11 times of imidacloprid synthesis technology, sodium chloride salt content is i.e. full closes in waste water after applying three times, then and has applied 8 times, it is believed that can be with recycled.Technique waste water, which is applied, reduces environmental pollution, reduces cost for wastewater treatment, while by applying technique waste water, because recycling to water-soluble product, makes after batch applying, folding reaction yield improves 1 ~ 1.5%.
Description
Technical field
The present invention relates to agricultural chemicals waste water processing technology fields, and in particular to a kind of imidacloprid synthesis technology wastewater zero discharge
Production method.
Background technique
Imidacloprid is the novel nicotinamide insecticide developed by Bayer A.G the 1980s, have high activity,
Less toxic and environmentally safe feature, correlative study get more and more people's extensive concerning all the time.Its present production technology phase
To maturation, having reached kiloton production capacity realizes big chemical industry, but following three wastes problem, as environmental protection pressure increases, solution
Certainly imidacloprid three wastes problem is extremely urgent.Imidacloprid wastewater complicated component, organic concentration high (COD is up to tens of thousands of mg/L) are difficult
Degradation belongs to high-salt wastewater, and processing difficulty is big, and costly.It is studied long-standing, common wastewater treatment method is such as
Under:
1, physical-chemical process
Physico-chemical process frequently as a kind of Wastewater Pretreatment means, pretreated purpose be by recycling waste water in it is useful at
Point, or some difficult for biological degradation objects are handled, to reach removal organic matter, biochemical feasibility is improved, is reduced at biochemistry
Load is managed, the purpose for the treatment of effeciency is improved.Common physico-chemical process has extraction, absorption method, coagulant sedimentation etc..Physico-chemical process technique letter
It is single, it spends human and material resources, increase production cost, and treatment effect is limited.
2, chemical method
Method of chemical treatment is directed to that chemical agent is added in waste water, makes it that chemical reaction occur with pollutant and generate harmless
The process of object, this method are also used often as the preprocess method of biochemical treatment.It to be adjusted before the biochemical treatment as useless
The acid-base property of water uses neutralisation.In the improvement of agricultural chemicals waste water, through frequently with chemical method can be summarized as aoxidize or restore
Method, and based on oxidation.Such as: CN102010318A, Jiang Weiqun etc. change imidacloprid pesticide wastewater treatment method
Into then carrying out Fenton oxidation and catalysis oxidation respectively using chemical dephosphorization, Fe-C light electrolysis；It is resistance to by biochemical treatment
Aerobic biochemical in the presence of aerobic.CN104150567A, Wang Yuqin, Li Yetao etc. are useless using electrochemical method processing imidacloprid
Water.
3, biochemical treatment process
Biochemical method is the method using the metabolism conversion degradation of organic substances of biology.According to micro- life in participation wastewater treatment
The type of object metabolism, the biologic treating technique of waste water can be divided into Aerobic biological process and anaerobic bio-treated two major classes.Wherein, exist
In aerobic biological treatment process, it is desirable to provide enough air are to meet microorganism to organic matter degradation in the process to the need of oxygen
It asks.And during anaerobic bio-treated, the microorganism because participating in organic matter degradation answers strict control waste water due to carrying out anaerobic respiration
The content of middle oxygen.Since Aerobic biological process has, high-efficient, adaptation is wide, thus becomes a kind of leading wastewater processing technology,
It is widely used in the processing of chemical industry waste water.
Biochemical treatment is one of current wastewater treatment common method, but biochemical treatment process is for handling containing for pesticide imidacloprid
Effect is undesirable when salt organic waste water.Because containing a large amount of NaC1, the alkali metal salts such as Na2S04, salt in the waste water of imidacloprid
Excessive concentration can generate inhibition to the growth of microorganism, while the toxic component in waste water has killing effect to microorganism, directly
It connects and affects using effect.
4, incineration technology
It is that the waste liquid for containing high-enriched organics is carried out to oxygenolysis at high temperature to turn organic matter that incineration method, which disposes waste liquid,
Turn to the innocuous substances such as water, carbon dioxide.In general, high-concentration chemical industry organic liquid waste is handled frequently with this method.Waste liquid
The mass fraction of middle organic matter generally when 10% or more or COD is 300g/L, is considered as incineration method processing.Foreign countries use
Incineration method is more, domestic because incineration method processing cost is higher, using also not universal.
Summary of the invention
Present invention aims to overcome that above-mentioned the deficiencies in the prior art, provide a kind of imidacloprid synthesis technology waste water zero-emission
The production method put, so that using butanone as solvent, it is only secondary with the technique of imidazolidine and 2-vhloro-5-chloromethylpyridine imidacloprid synthesis
Salt is produced, waste water is not generated, reduces environmental protection pressure.
The present invention adopts the following technical scheme:
A kind of production method of imidacloprid synthesis technology wastewater zero discharge the steps include: to react in imidacloprid synthesis technology
After, process water is added into reaction solution and carries out first wash, stands, liquid separation, adds again into the organic phase that upper layer separates
Enter process water and carry out second wash, then stand, liquid separation, the water phase merging washed twice is applied to second batch imidacloprid reaction solution
Post-processing in be used as first wash process water, insufficient water supplemented with fresh water, repeats above-mentioned washing, standing, liquid separation, conjunction
And the step of water phase, the water phase washed twice merge in the post-processing for being applied to third batch imidacloprid reaction solution as first time water
Process water is washed, and so on, circulate operation.
Preferably, the temperature of first wash is 20-80 DEG C, and amount of water is 1/4 ~ 2 times of reaction solution quality, second of water
The temperature washed is 20~80 DEG C, and amount of water is the 1/20 ~ 1/2 of reaction solution quality.
Preferably, the water phase washed twice is down to room temperature after merging, and has the precipitation of solid imidacloprid, filtering, filtered water
The mutually first wash process water as next group reaction solution.
Preferably, when being salted out in first wash process water, heat filtering is carried out at 20~80 DEG C, will filter out
Salt collection send to there is the processing of qualification producer to use, filtrate merges with the water phase of second wash again.
Imidacloprid synthesis technology of the present invention are as follows: using butanone as solvent, closed with imidazolidine and 2-vhloro-5-chloromethylpyridine
At imidacloprid.
The beneficial effect that the present invention obtains is: the present invention realizes imidacloprid synthesis technology wastewater zero discharge, does not influence to produce
Quality reduces environmental pollution, reduces cost for wastewater treatment, while by applying technique waste water, because to water-soluble product
It is recycled, is made after batch applying, folding reaction yield improves 1 ~ 1.5%.
Specific embodiment
Technical solution of the present invention is described in detail with specific embodiment below.
Embodiment 1: imidacloprid synthetic reaction qualification post-processes to obtain a waste water
1000g imidacloprid synthesis reaction solution after reaction is directly taken, (60 DEG C or so) stirring 0.5h of 500g hot water are added,
Liquid separation is stood, organic water progress for being added to 60 DEG C of 100g is secondary to wash material, stands liquid separation, organic phase concentration crystallizes to obtain product pyrrole
Worm quinoline, content 98.0%.It aqueous phase extracted (about 480g) will merge twice, and have solid precipitation after being down to room temperature, filter, solid is dried
After dry, 1.5 grams must be expected, be 91.4% through HPLC detection imidacloprid content, filtrate is a waste water, and imidacloprid content is
0.15%, an above-mentioned waste water is directly applied.
Embodiment 2: imidacloprid synthetic wastewater is once applied
A waste water polishing for taking above-described embodiment 1 to obtain is heated to 60 DEG C and is applied to the synthesis of 1000g imidacloprid to 500g
Qualified reaction solution stirs 0.5h, stands liquid separation, and organic water progress for being added to 60 DEG C of 100g is secondary to wash material, stands liquid separation, has
Machine is mutually concentrated, and crystallizes to obtain product, content 98.3%.It aqueous phase extracted will merge twice, and have solid precipitation after being down to room temperature, filter, it is right
Solid drying after, must expect 1.3 grams, through HPLC detection imidacloprid content be 88.7%, filtrate as next group a washing water,
It is 0.17% through HPLC detection imidacloprid content, directly preheating carries out secondary apply.
Embodiment 3: imidacloprid synthetic wastewater carries out secondary apply
The filtrate polishing that Example 2 obtains is heated to 60 DEG C to 500g and is applied to the qualified reaction of 1000g imidacloprid synthesis
In liquid.0.5h is stirred, there is insoluble white sodium chloride in lower layer.It stands, lower layer's salt and water phase is separated, salt is filtered to obtain at 60 DEG C
It 20 grams, collects dress polybag and seals up for safekeeping.By upper organic phase be added 100g water carry out it is secondary wash material, stand liquid separation, organic phase is concentrated,
Crystallize to obtain product, content 98.6%.Waste water is merged, has solid precipitation after being down to room temperature, is filtered, after solid drying, must be expected
1.8 grams, be 90.4% through HPLC detection imidacloprid content, and imidacloprid content is 0.185% in filtrate, and directly preheating is covered three times
With.
Embodiment 4: imidacloprid synthetic wastewater is applied three times
The filtrate polishing that Example 3 obtains is heated to 60 DEG C to 500g and is applied to the qualified reaction of 1000g imidacloprid synthesis
In liquid.0.5h is stirred, standing separates lower layer's salt and water phase, and 60 DEG C are filtered to obtain 52 grams of salt, collects dress polybag and seals up for safekeeping.It is organic
Be added to 100g water carry out it is secondary wash material, stand liquid separation, organic phase is concentrated, and crystallizes to obtain product, content 98.2%.Waste water is merged,
It is 0.2% through HPLC detection imidacloprid aqueous phase content, by water phase and solid is precipitated, directly preheating apply for four times.It (is precipitated solid
Body with embodiment 1-3's as a result, be 90% or so imidacloprid product, apply middle precipitation solid below and be identical with this.It is preceding right three times
Be precipitated solid be filtered, dry, weighing operation, be for the amount of imidacloprid in verifying water, convenient for calculating using right after the method
The influence of yield does not need directly to be applied to next group to solid filtering is precipitated in actual operation.)
Embodiment 5: imidacloprid synthetic wastewater apply for four times
The last gained waste water polishing of Example 4 is heated to 60 DEG C to 500g and is applied to 1000g imidacloprid synthesis qualification instead
It answers in liquid.0.5h is stirred, standing separates lower layer's salt and water phase, 49.5 grams of salt is filtered to obtain at 60 DEG C, collection is sealed up for safekeeping.Organic addition
Enter 100g water carry out it is secondary wash material, stand liquid separation, organic phase is concentrated, and crystallizes to obtain product, content 98.4%.Waste water is merged, is passed through
It is 0.195% that HPLC, which detects imidacloprid aqueous phase content, and water phase and precipitation solid are directly preheated progress the 5th time and applied.
Embodiment 6: imidacloprid synthetic wastewater apply for five times
It takes above-mentioned five waste water polishings to be heated to 60 DEG C to 500g to be applied in the qualified reaction solution of 1000g imidacloprid synthesis.
0.5h is stirred, standing separates lower layer's salt and water phase, 51.1 grams of salt is filtered to obtain at 60 DEG C, collection is sealed up for safekeeping.It is organic to be added to 100g
Water progress is secondary to wash material, stands liquid separation, and organic phase concentration crystallizes to obtain product, content 98.0%.Waste water is merged, is detected through HPLC
Imidacloprid aqueous phase content is 0.201%, and water phase and precipitation solid are directly preheated progress six times and applied.
Embodiment 7: imidacloprid synthetic wastewater recycled
Circulation has carried out 11 times and has applied experiment according to the above method, and imidacloprid product content is >=98.0%.
Finally, taking aggregate sample to the by-product salt of collection, sodium chloride 96.3%, moisture content 3.5% are detected.
In conclusion 1) can be obtained by being down to room temperature containing imidacloprid in every batch of water phase by about 1.5 grams of imidacloprid, deduct content factor and
Other uncertain factors fold rate and improve 1 ~ 1.5%.2) imidacloprid synthetic wastewater after applying three times, and salt content reaches in water phase
Saturation, applies through 11 times and does not impact to product quality, it is believed that can apply infinitely.
Embodiment 8
The method for repeating embodiment 1-7, the difference is that: first wash temperature is 20 DEG C, and amount of water is feed liquid matter
2 times of amount, the temperature of second wash are 20 DEG C, and amount of water is the 1/2 of feed liquid quality, when having salt in first wash process water
When precipitation, it is filtered at 20 DEG C.Experimental result shows suitable with embodiment 1-7.
Embodiment 9
The method for repeating embodiment 1-7, the difference is that: first wash temperature is 80 DEG C, and amount of water is feed liquid matter
The 1/4 of amount, the temperature of second wash are 80 DEG C, and amount of water is the 1/20 of feed liquid quality, is had when in first wash process water
When salting out, it is filtered at 80 DEG C.Experimental result shows suitable with embodiment 1-7.
Above-described embodiment is only better embodiment of the invention, but protection scope of the present invention is not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made under spiritual essence and principle of the invention should all
For equivalent substitute mode, it is included within the scope of the present invention.
Claims (4)
1. a kind of production method of imidacloprid synthesis technology wastewater zero discharge, it is characterised in that: reacted in imidacloprid synthesis technology
After, process water is added into reaction solution and carries out first wash, stands, liquid separation, adds again into the organic phase that upper layer separates
Enter process water and carry out second wash, then stand, liquid separation, the water phase merging washed twice is applied to second batch imidacloprid reaction solution
Post-processing in be used as first wash process water, insufficient water supplemented with fresh water, repeats above-mentioned washing, standing, liquid separation, conjunction
And the step of water phase, the water phase washed twice merge in the post-processing for being applied to third batch imidacloprid reaction solution as first time water
Process water is washed, and so on, circulate operation；
The imidacloprid synthesis technology are as follows: using butanone as solvent, with imidazolidine and 2-vhloro-5-chloromethylpyridine imidacloprid synthesis.
2. production method according to claim 1, it is characterised in that: the temperature of first wash is 20 ~ 80 DEG C, amount of water
It is 1/4 ~ 2 times of reaction solution quality, the temperature of second wash is 20 ~ 80 DEG C, and amount of water is the 1/20~1/ of reaction solution quality
2。
3. production method according to claim 2, it is characterised in that: the water phase washed twice is down to room temperature after merging, and has
Solid imidacloprid is precipitated, filtering, first wash process water of the filtered water phase as next group reaction solution.
4. production method according to claim 3, it is characterised in that: when being salted out in first wash process water,
Be filtered at 20 ~ 80 DEG C, the collection of the salt that will filter out is sent to there is the processing of qualification producer to use, filtrate again with second wash
Water phase merge.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935704A (en) * | 2006-10-17 | 2007-03-28 | 盐城师范学院 | Method for treating condensation waste water for producing imidacloprid and resourcized recovering its imidazolidine |
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN103145302A (en) * | 2013-03-27 | 2013-06-12 | 南京工业大学 | Pre-treatment process of imidacloprid wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935704A (en) * | 2006-10-17 | 2007-03-28 | 盐城师范学院 | Method for treating condensation waste water for producing imidacloprid and resourcized recovering its imidazolidine |
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN103145302A (en) * | 2013-03-27 | 2013-06-12 | 南京工业大学 | Pre-treatment process of imidacloprid wastewater |
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