CN104447529B - Method for extracting and purifying 3,6-matrigon - Google Patents
Method for extracting and purifying 3,6-matrigon Download PDFInfo
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- CN104447529B CN104447529B CN201410688272.5A CN201410688272A CN104447529B CN 104447529 B CN104447529 B CN 104447529B CN 201410688272 A CN201410688272 A CN 201410688272A CN 104447529 B CN104447529 B CN 104447529B
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- lontrel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical purification technologies, particularly relates to a method for extracting and purifying 3,6-matrigon, and aims to solve the technical problems that in the existing method, the yield is low, the operation is complex, the cost is high, and the industrial production is inapplicable. The scheme for solving the technical problems is that separation and purification are carried out for the 3,6-matrigon based on the fact that the solubility of 3,6-matrigon is different from that of the impurities under different temperatures and pH values. The method for extracting and purifying 3,6-matrigon, provided by the invention has the advantages that the method is easy to operate; the device is simple; no additional expensive separation reagent or material are required; the method is low in cost and suitable for industrial production.
Description
Technical field
The invention belongs to chemical industry purifying technique field, and in particular to the method for extraction and purification of 3,6- lontrel.
Background technology
3,6- lontrel are a kind of outstanding broadleaf weed herbicides, are worldwide widely used.3,
6- lontrel is mainly obtained by 3,4,5,6- 4 chloro pyridine formic acid dechlorinations.The method of dechlorination has two kinds, and one kind is chemistry
Dechlorinating process, one kind is electrolysis dechlorinating process.It is mesh because electrolysis dechlorination is in the advantage of the aspects such as safe and environment-friendly and atom economy
The main method of preceding production 3,6- lontrel.
But, electrolysis also has a problem demanding prompt solution, and exactly reaction terminates the extraction purification yield ratio of rear product
It is relatively low.At present the method that generally uses be after reaction terminates by the direct acidizing crystal of reaction solution (such as patent US4497697,
CN100500945), but due in reaction solution impurity it is more, the product purity for obtaining is not often high, in addition it is also necessary to secondary crystallization, this
Product yield can undoubtedly be reduced, increase production cost, the yield of product is only 70%~75%.
In order to overcome above mentioned problem, patent US4334074 discloses public using resin adsorption and patent CN102351788
The method that extraction purification yield is improved using UF membrane has been opened, but the operation of these methods is more complicated, and to use costliness
Resin or membrane material, therefore also constrain its application in terms of industrialization.
Additionally, contain the 25%~30% of 3,6- lontrel gross masses toward contact in waste liquid after crystallization, but
It is general directly as liquid waste processing because wherein impurity content is high, product design is low, but do so not only have lost part product
Product, while increased the difficulty and processing cost of liquid waste processing again, therefore also need the treatment for providing a kind of more economical simplicity badly
Method.
The content of the invention
The technical problem to be solved in the present invention be the yield of existing method for extraction and purification than relatively low, operate it is more complicated, into
This height, is not suitable for industrialized production.
The scheme that the present invention solves above-mentioned technical problem is to provide a kind of high income, with low cost, easy to operate, suitable work
The method for extraction and purification of 3, the 6- lontrel that industry metaplasia is produced, can be not only used for the extraction of product in reaction solution after electrolysis
Purifying, and be equally applicable to further extract product in waste liquid after crystallisation.
The method for extraction and purification of above-mentioned 3,6- lontrel, comprises the following steps：
A, the pH value of 3,6- lontrel mother liquors is adjusted to 10~12, filtering removal solid impurity；
3,6- lontrel mother liquor after b, filtering is again adjusted to 1.5~2.5 pH value at -5 DEG C~0 DEG C,
Insulated and stirred is separated out to there is no solid, again filtering removal solid impurity；
C, will again filter after 3,6- lontrel mother liquors be warming up to 20 DEG C~30 DEG C after, by pH value adjust to
0.5~1.0, synthermal lower standing to there is no solid separates out, and separates and obtains solid crude product；
D, crude product is mixed with acid solution, stirred at 10 DEG C~20 DEG C, filter out solid, after solid is dried, obtained
Obtain 3,6- lontrel.
In the method for extraction and purification of above-mentioned 3,6- lontrel, 3, the 6- lontrel mother liquors described in step a
Produced during the reaction solution or 3,6- clopyralid extraction purifications that are obtained for the electrolysis dechlorination of 3,4,5,6- 4 chloro pyridines formic acid
Waste liquid be concentrated into the solution that 3,6- dichloropyridine acid contents are 2%~10%.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the material used by step a regulation pH value is hydroxide
Any one in potassium, NaOH, sodium carbonate, potassium carbonate.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the time of insulated and stirred described in step b is 4~10h.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the material used by step b and c regulation pH value is salt
Any one in acid, sulfuric acid, glacial acetic acid.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the time stood described in step c is 8~20h.
In the method for extraction and purification of above-mentioned 3,6- lontrel, acid solution described in step d is hydrochloric acid or sulfuric acid.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the mass concentration of acid solution described in step d be 3%~
8%.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the mass ratio of crude product described in step d and acid solution
It is 1：5~20.Wherein, the quality of the crude product is with re-computation of giving money as a gift.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the time stirred described in step d is 1~4h.
The beneficial effects of the present invention are：(1) present invention does not need secondary crystallization or the auxiliary material using costliness, just
Efficiently separating for 3,6- clopyralids can be realized, up to 97.20%, purity reaches 96.11% to high income.(2) present invention behaviour
Work is easy, device is simple, low cost, is adapted to industrialized production.(3) present invention is applied to from high impurity content (impurity content 40
Extraction purification 3 in~3,6- lontrel mother liquors 60%), 6- lontrel, with obvious economic advantages, together
When extract after waste liquid in the content of organic pollution drastically decline, substantially reduce the number follow-up waste liquid cost of disposal difficult with disposal
Degree, with obvious environment-friendly advantage.
Specific embodiment
The method for extraction and purification of 3,6- lontrel, comprises the following steps：
A, the pH value of 3,6- lontrel mother liquors is adjusted to 10~12, filtering removal solid impurity；
3,6- lontrel mother liquor after b, filtering is again adjusted to 1.5~2.5 pH value at -5 DEG C~0 DEG C, is protected
Temperature 4~10h of stirring, separates out to there is no solid, again filtering removal solid impurity；
C, will again filter after 3,6- lontrel mother liquors be warming up to 20 DEG C~30 DEG C after, by pH value adjust to
0.5~1.0,8~20h of synthermal lower standing, separate out to there is no solid, and filtering obtains solid crude product；
D, by crude product with acid solution mix, at 10 DEG C~20 DEG C stir 1~4h, filter out solid, solid is done
After dry, solid 3,6- lontrel are obtained.
In the method for extraction and purification of above-mentioned lontrel, 3, the 6- lontrel mother liquor described in step a is 3,
What is produced during the 4,5,6- 4 chloro pyridines formic acid reaction solution that obtains of electrolysis dechlorination or 3,6- clopyralid extraction purifications is useless
Liquid is concentrated into the solution that 3,6- dichloropyridine acid contents are 2%~10%.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the material used by step a regulation pH value is hydroxide
Any one in potassium, NaOH, sodium carbonate, potassium carbonate.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the material used by step b and c regulation pH value is salt
Any one in acid, sulfuric acid, glacial acetic acid.
In the method for extraction and purification of above-mentioned 3,6- lontrel, acid solution described in step d is hydrochloric acid or sulfuric acid.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the mass concentration of acid solution described in step d be 3%~
8%.
In the method for extraction and purification of above-mentioned 3,6- lontrel, the mass ratio of crude product described in step d and acid solution
It is 1：5~20.Wherein, the quality of the crude product is with re-computation of giving money as a gift.
The present invention goes the removal of impurity as much as possible creatively by the regulation and the control of temperature to pH value.If pH
Value do not occur within the above range, then Impurity removal not thoroughly, separate out impurity contain for product it is more, need product to separate out when but
The problems such as dissolving excessively causes yield to decline, regulation pH value wastes more soda acids；If temperature is not within the above range, can
There is impurity and the problems such as excessive, material freezes, energy consumption increases but is dissolved when cannot separate out, need product to separate out；In regulation pH value
Material selection on, ensure that new impurity will not be introduced as far as possible, it is smaller with yield influence on the purity of finished product.
Embodiment 1
3, the 6- lontrel mother liquors that electrolysis is directly synthesized, 3, the 6- lontrel absolute contents in mother liquor
5.10%, total amount 100kg, it is 10.0 to add sodium carbonate regulation pH, and filtering removal solid impurity, carries out being cooled to 0 DEG C, sulfuric acid afterwards
Regulation pH be 1.5, stirring insulation crystallization 10h, filtering removal solid impurity, after feed liquid is warming up to 20 DEG C, sulphur acid for adjusting pH is
0.5, quiescent crystallization 8h, filtering obtain crude product, and weight is 10.52kg, and it is 52% that crude product is determined into moisture, adds folding
The 3%wt hydrochloric acid of 5 times of quality after dry weight, it is 10 DEG C to control temperature, agitator treating 4h, after filtering, in 150 DEG C of drying, is obtained
3,6- lontrel, purity is 96.11%, and weight is 4.52kg, and yield is 85.16%.
Embodiment 2
Evaporation concentration method is by 3,6- lontrel crystal waste concentrates, 3,6- dichloropyridines first in the liquid after concentrate
Sour absolute content 8.98%, total amount 100kg, it is 10.0 to add potassium hydroxide solution regulation pH, and filtering removal solid impurity, is carried out afterwards
Be cooled to -5 DEG C, salt acid for adjusting pH is 2.5, stirring insulation crystallization 4h, filtering removal solid impurity, after feed liquid is warming up to 30
DEG C, salt acid for adjusting pH is 1.0, quiescent crystallization 20h, and filtering obtains crude product, and weight is 26.56kg, and crude product is determined into moisture
Content is 68%, adds the 8%wt hydrochloric acid of 20 times of quality after weight of giving money as a gift, and it is 20 DEG C to control temperature, agitator treating 1h, filtering,
In 150 DEG C of drying, 3,6- lontrel is obtained, purity is 95.23%, and weight is 7.83kg, and yield is 83.32%.
Embodiment 3
3, the 6- lontrel mother liquors that electrolysis is directly synthesized, 3, the 6- lontrel absolute contents in mother liquor
7.50%, total amount 150kg, it is 13.0 to add NaOH regulation pH, and the removal of impurity is gone in filtering, and rear feed liquid is cooled to 0 DEG C, and sulfuric acid is adjusted
Section pH is 2.50, stirred crystallization 8h, and the removal of impurity is gone in filtering, after mother liquor is warming up to 25 DEG C, sulphur acid for adjusting pH is 1.0, crystallization
16h, filtering obtains crude product, and remnants are crystal waste, and weight is 20.83kg, and it is 56% that crude product is determined into moisture, plus
Enter the 5%wt hydrochloric acid of 7 times of quality after weight of giving money as a gift, control temperature for 15 DEG C, agitator treating 4h is filtrated to get solid, and remnants are
Crystal waste, in 150 DEG C of drying, obtains 3,6- lontrel, and purity is 95.89%, and weight is 9.99kg.
Through embrane method by above-mentioned 3,6- lontrel crystal waste concentrate, 3,6- dichloropyridines first in the liquid after concentrate
Sour absolute content 5.98%, total amount 27.49kg, it is 10.0 to add potassium carbonate liquid regulation pH, and filtering removal solid impurity, is carried out afterwards
Be cooled to -3 DEG C, ice glacial acetic acid regulation pH is 1.5, stirring insulation crystallization 8h, filtering removal solid impurity, after feed liquid is warming up to
20 DEG C, salt acid for adjusting pH is 0.5, quiescent crystallization 12h, and filtering obtains crude product, and weight is 2.74kg, and crude product is determined into moisture
Content is 57%, adds the hydrochloric acid of 15 times the 5% of quality after weight of giving money as a gift, and it is 15 DEG C to control temperature, agitator treating 4h, filtering,
In 150 DEG C of drying, 3,6- lontrel is obtained, purity is 95.11%, and weight is 1.41kg.
Above-mentioned two parts operation obtains the product 11.40kg of purity ＞ 95.10% altogether, and the total recovery of purifying is 97.08%.
The method for providing of the invention is easy to operate, device is simple, low cost, is adapted to industrialized production.
Claims (7)
- The method for extraction and purification of 1.3,6- lontrel, comprises the following steps：A, the pH value of 3,6- lontrel mother liquors is adjusted to 10~12, filtering removal solid impurity；Described 3,6- bis- Chloropyridine formic acid mother liquor is that the reaction solution that the electrolysis dechlorination of 3,4,5,6- 4 chloro pyridines formic acid is obtained or 3,6- lontrel are carried Take the waste liquid produced in purge process and be concentrated into the solution that 3,6- lontrel contents are 2%~10%；3,6- lontrel mother liquor after b, filtering is again adjusted to 1.5~2.5, insulation pH value at -5 DEG C~0 DEG C Stirring is separated out to there is no solid, again filtering removal solid impurity；C, will filter again after 3,6- lontrel mother liquors be warming up to 20 DEG C~30 DEG C after, pH value is adjusted to 0.5~ 1.0, synthermal lower standing to there is no solid separates out, and separates and obtains solid crude product；D, crude product is mixed with acid solution, is stirred at 10 DEG C~20 DEG C, filter out solid, after solid is dried, obtain 3, 6- lontrel.
- 2. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Step a is adjusted Material used by pH value is any one in potassium hydroxide, NaOH, sodium carbonate, potassium carbonate.
- 3. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Step b and c are adjusted Material used by section pH value is any one in hydrochloric acid, sulfuric acid, glacial acetic acid.
- 4. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Described in step d Acid solution is hydrochloric acid or sulfuric acid.
- 5. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Described in step d The mass concentration of acid solution is 3%~8%.
- 6. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Described in step d Crude product is 1 with the mass ratio of acid solution：5~20；The quality of the crude product is with re-computation of giving money as a gift.
- 7. the method for extraction and purification of 3,6- lontrel according to claim 1, it is characterised in that：Described in step d The time of stirring is 1~4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410688272.5A CN104447529B (en) | 2014-11-25 | 2014-11-25 | Method for extracting and purifying 3,6-matrigon |
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| CN201410688272.5A CN104447529B (en) | 2014-11-25 | 2014-11-25 | Method for extracting and purifying 3,6-matrigon |
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| CN104447529B true CN104447529B (en) | 2017-05-24 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105801474B (en) * | 2016-05-26 | 2018-01-16 | 张玲 | A kind of method of refined 3,6 lontrel |
| CN105817149B (en) * | 2016-05-26 | 2018-03-16 | 张玲 | A kind of preparation method of the lontrel permeable membrane of concentrate 3,6 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334074A (en) * | 1981-02-02 | 1982-06-08 | The Dow Chemical Company | Method of recovering 3,6-dichloropicolinic acid from basic aqueous solutions of salts thereof |
| US6670505B1 (en) * | 2000-03-07 | 2003-12-30 | Eastman Chemical Company | Process for the recovery of organic acids from aqueous solutions |
| CN100500945C (en) * | 2007-11-16 | 2009-06-17 | 利尔化学股份有限公司 | Electrolytic synthesis method for 3,6-dichloropicolinic acid |
| CN102351788B (en) * | 2011-08-11 | 2013-08-14 | 横店集团东阳英洛华绿色电化学有限公司 | Method for extracting and refining clopyralid |
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