CN109384714A - The recovery method and production method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid - Google Patents
The recovery method and production method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid Download PDFInfo
- Publication number
- CN109384714A CN109384714A CN201710653039.7A CN201710653039A CN109384714A CN 109384714 A CN109384714 A CN 109384714A CN 201710653039 A CN201710653039 A CN 201710653039A CN 109384714 A CN109384714 A CN 109384714A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- acid
- solution
- pyridinedicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07D213/80—Acids; Esters in position 3
-
- 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
Abstract
The present invention relates to pyridinedicarboxylic acid fields, disclose the recovery method and production method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid.Recovery method includes the following steps: that extract liquor is added in the solution for substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid that (1) Xiang Hanyou formula (I) indicates to be extracted, and raffinate phase and extraction phase are obtained；(2) lye is added in Xiang Suoshu extraction phase and is adjusted to alkalinity, then carry out water-oil separating and obtain organic phase and contain the water phase of substituted or unsubstituted 2,3- dipicolinates；(3) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of formula (I) expression is obtained by filtration, wherein in formula (1), R1、R2、R3It is each independently H, C1‑C4Alkyl, C1‑C4Alkoxy, halogen, hydroxyl, nitro or amino.Recovery method of the invention can increase substantially the rate of recovery, and effect of extracting is preferable, and method is simple, be conducive to industrialized production.
Description
Technical field
The present invention relates to pyridinedicarboxylic acid fields, and in particular to the recycling side of substituted or unsubstituted 2,3- pyridinedicarboxylic acid
Method and production method.
Background technique
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid class intermediate is the important intermediate for synthesizing imidazolone type pesticide,
Imidazolone type pesticide is a kind of imidazolidinone weedicide containing pyridine ring, and mechanism of action mainly inhibits the synthesis of acetic acid hydroxy acid
The activity of enzyme (AHAs) influences three kinds of branched-chain amino acid-valines, leucine, the biosynthesis with isoleucine, final broken
The synthesis of bad egg's white matter, interference DNA synthesis and cell division and growth.Such herbicide can effectively prevent most of annual standing grain
Undergraduate course and broadleaf weeds, such as wild avena sativa, barnyard grass, herba setariae viridis, setaria glauca, amur foxtail.
The compound of substituted or unsubstituted 2,3- pyridinedicarboxylic acid structure is the key that in synthesis imidazolone type pesticide
Mesosome, such as 2,3- pyridinedicarboxylic acid, 5- methyl -2,3- pyridinedicarboxylic acid, 5- ethyl -2,3- pyridinedicarboxylic acid, 5- methoxy first
Base -2,3- pyridinedicarboxylic acid, general formula of molecular structure are as follows:
Wherein, in formula (I), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitre
Base or amino.
Currently, the synthetic method of 2,3- pyridinedicarboxylic acids is mainly using quinoline or 8-hydroxyquinoline as raw material, using oxidant
Such as: potassium permanganate, hydrogen peroxide, ozone, sodium chlorate and oxygen are aoxidized, or with 2,3- dialdehyde yl pyridines or 2- methyl -3-
Carboxyl pyridine is the oxidizing process of raw material, and the product obtained after oxidation is the copper complex or sodium salt of pyridinedicarboxylic acid, rear copper complexing
Object obtains product through alkaline hydrolysis, acidification.
The synthetic method of 5- methyl -2,3- pyridinedicarboxylic acid is mainly as follows:
It uses 5- methyl -8-hydroxyquinoline quinoline for raw material, is aoxidized using the method for being similar to 2,3- pyridinedicarboxylic acid,
Obtain 5- methyl -2,3- pyridinedicarboxylic acid.
US5227491, which discloses to be condensed with 2- methyl-propen aldoxime with or mixtures thereof amino maleate, is made 5- first
Base-pyridine diester arrives 5- methyl -2,3- pyridinedicarboxylic acid by alkaline hydrolysis acidification.
US4723011 and EP0965589 is disclosed to be deposited with the chloro- 3- oxo succinate of 2- in ammonium salt with ethyl acrylic aldehyde
5- EthylPyridine diester is synthesized in lower closed loop, arrives 5- methyl -2,3- pyridinedicarboxylic acid by alkaline hydrolysis acidification.
US4723011 and EP0965589 discloses the synthetic method of 5- ethyl -2,3- pyridinedicarboxylic acid, with metering system
With the chloro- 3- oxo succinate of 2-, closed loop in the presence of ammonium salt synthesizes 5- EthylPyridine diester to aldehyde, by arriving for alkaline hydrolysis acidification
Product.
The synthetic method of 5- methoxyl methyl -2,3- pyridinedicarboxylic acid is mainly as follows:
US5760239A and EP0548532A1 is disclosed with 5- methyl -2,3- pyridine dicarboxylate as raw material, through halogenated,
At salt, hydrolysis obtains 5- methoxyl methyl -2,3- pyridinedicarboxylic acid after methoxylation, after acidification.
US5281713A, which is disclosed, uses 5- methoxyl methyl -8-hydroxyquinoline quinoline for raw material, using similar to 2,3- pyridine
The method of dicarboxylic acids is aoxidized, and 5- methoxyl methyl -2,3- pyridinedicarboxylic acid is obtained after acidification.
Industrially prepared 2, the method for Niacin Nicitinic Acid class compound is all the carboxylic acid sodium salt for first obtaining product, by acidification,
Target product is obtained by filtration, according to the difference of substituent group, the yield after product hydrolysis acidification is between 70-85%.After filtering
Filtrate in still remain 2,3- pyridinedicarboxylic acid, if but the processing mode is not using filtrate as the direct outlet of waste liquid
Only not environmentally and cause a large amount of waste.
Currently, industrial use a large amount of highly polar organic solvent such as n-butanol, n-octyl alcohol to 2, the 3- pyrrole in filtrate
Pyridine carboxylic acid carries out extraction and recovery, using this method, needs using a large amount of alcohols as extractant, while used alcohols
It is miscible with water to have part, while increased costs, increases the processing difficulty of waste water, cinchomeronic acid is carried out using this method
Extraction and recovery, the rate of recovery is less desirable, only 40% or so.Moreover, often occurring extracting in industrial processes not doing
Net problem still contains a large amount of organic matter in waste water, i.e. 2,3- pyridinedicarboxylic acid content is still higher, and content is up to 7%.
JP03101661, which is disclosed, to carry out catalyzing and synthesizing 2,3- pyridinedicarboxylic acid using anhydrous cupric sulfate, using copper sulphate with
The method for the metal complex that picolinic acid is formed recycles pyridinedicarboxylic acid class compound remaining in filtrate.Using this
Method total yield of products is only 76%, and used copper sulphate is completely converted into copper oxide, can not be reused, cause recycling at
This is higher, and operating procedure is complex.
In conclusion there are the rate of recovery in the recovery method of existing substituted or unsubstituted 2,3- pyridinedicarboxylic acid
It is low, cost recovery is high, operating procedure is complicated, effect of extracting is bad, introduces heavy metal copper the problem of increasing wastewater treatment difficulty.
Moreover, not having the industrial production of substituted or unsubstituted 2,3- pyridinedicarboxylic acid and inexpensive, easy recovery method yet
The process blended.
Summary of the invention
The purpose of the invention is to overcome, the rate of recovery of substituted or unsubstituted 2,3- pyridinedicarboxylic acid is low, cost recovery
High, operating procedure complexity, effect of extracting are bad, introducing heavy metal copper increases wastewater treatment difficulty, in commercial process
In, the problem of not combining reasonable, inexpensive recovery method, provide substituted or unsubstituted 2,3- pyridinedicarboxylic acid
Recovery method and production method, the recovery method is high, easily operated with the rate of recovery, heavy metal ion is avoided to enter water body, drops
The advantages of low wastewater treatment difficulty.Production method through the invention, can fully, recycle in filtrate remain at low cost
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid.
To achieve the goals above, the present invention provides a kind of recycling sides of substituted or unsubstituted 2,3- pyridinedicarboxylic acid
Method, wherein this method comprises the following steps:
(1) Xiang Hanyou formula (I) indicate substituted or unsubstituted 2,3- pyridinedicarboxylic acid solution in be added extract liquor into
Row extraction, obtains raffinate phase and extraction phase；
(2) lye is added in Xiang Suoshu extraction phase and is adjusted to alkalinity, then carry out water-oil separating and obtain organic phase and contain
The water phase of substituted or unsubstituted 2,3- dipicolinates；
(3) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and formula (I) expression is obtained by filtration
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitre
Base or amino.
Preferably, this method further include: before lye is added into extraction phase in step (3), be added into extraction phase
Solution containing substituted or unsubstituted 2,3- dipicolinates.
Second aspect of the present invention provides a kind of method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid of production, this method packet
Include following steps:
(A) it to containing lye is added in substituted or unsubstituted 2,3- pyridinedicarboxylic acid ethyl ester solution, is formed containing substituted
Or the solution of unsubstituted 2,3- dipicolinates；
(B) acid solution is added into the obtained solution containing substituted or unsubstituted 2,3- dipicolinates, and carries out
Filtering, obtains product cake and filtrate, wherein filtrate contains substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of formula (I) expression；
(C) extract liquor is added into obtained filtrate to be extracted, obtains raffinate phase and extraction phase；
(D) lye is added in Xiang Suoshu extraction phase and is adjusted to alkalinity, then carry out water-oil separating and obtain organic phase and contain
The water phase of substituted or unsubstituted 2,3- dipicolinates；
(E) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and formula (I) expression is obtained by filtration
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (I), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitre
Base or amino.
Preferably, this method further include: before lye is added into extraction phase in step (D), be added into extraction phase
Solution containing substituted or unsubstituted 2,3- dipicolinates.
The recovery method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid through the invention, can increase substantially recycling
Rate, effect of extracting is preferable, can effectively reduce the content of organic matter in waste water.Recovery method is simple and easy to do, and waste water extracted can
With the direct emission without biochemical treatment.
Production method through the invention, substituted or unsubstituted 2,3- pyridine dicarboxyl that can sufficiently in Recycling of waste liquid
Acid, process is easy, low in cost, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the schematic diagram of the recovery method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid of the invention；
Fig. 2 is the schematic diagram of the method for the substituted or unsubstituted 2,3- pyridinedicarboxylic acid of production of the invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of recovery methods of substituted or unsubstituted 2,3- pyridinedicarboxylic acid, as shown in Figure 1, its
In, this method comprises the following steps:
(1) Xiang Hanyou formula (I) indicate substituted or unsubstituted 2,3- pyridinedicarboxylic acid solution in be added extract liquor into
Row extraction, obtains raffinate phase and extraction phase；
(2) lye is added in Xiang Suoshu extraction phase and is adjusted to alkalinity, then carry out water-oil separating and obtain organic phase and contain
The water phase of substituted or unsubstituted 2,3- dipicolinates；
(3) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and formula (I) expression is obtained by filtration
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitre
Base or amino.
In the present invention, containing formula (I) indicate substituted or unsubstituted 2,3- pyridinedicarboxylic acid solution can for containing
The waste water of substituted or unsubstituted 2,3- pyridinedicarboxylic acid.
In the present invention, extract liquor is used for from substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid indicated containing formula (I)
Substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid that extraction formula (I) indicates in solution (waste water), by will be substituted or unsubstituted
2,3- pyridinedicarboxylic acids are complexed with extractant, and substituted or unsubstituted 2,3- pyridinedicarboxylic acid is separated with solution.
Extract liquor includes extractant and retarder thinner.
In the present invention, with extract liquor total weight, the weight percent containing the extractant is 5%-35%, preferably
For 15%-20%.
In the present invention, in step (1), substituted or unsubstituted 2, the 3- pyridine dicarboxyl indicated containing formula (I)
The solution of acid and the molar ratio of the extractant are 1:(0.5-10).
In the present invention, the extractant can be with are as follows: trialkylamine and/or trialkylphosphine oxide.
In the present invention, the trialkylamine can be but be not limited to: three n-octylamines, tri-tert amine, three hexyl amines,
In three n-pentyl amine, three positive heptyl amice tri-n-nonylamines, three (undecyl) amine, tridodecylamine and three (myristyl) amine
It is at least one.
In the present invention, the trialkylphosphine oxide can be but be not limited to: trihexylphosphine oxide, trioctylphosphine oxide (TOPO), three heptyl
Phosphine oxide, dihexyl octylphosphine oxide, dioctyl hexyl phosphine oxide, diamyl hexyl phosphine oxide, dioctyl heptyl phosphine oxide, diheptyl hexyl oxygen
At least one of phosphine and diheptyl nonyl phosphine oxide.
In the present invention, the retarder thinner can be at least one in ether, alkane, chlorinated solvents and solvent containing phenyl ring
Kind.
In the present invention, the ether is selected from ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, 1,2- diformazan
At least one of oxygroup ethane, dioxane and methyl phenyl ethers anisole.
In the present invention, the alkane be selected from kerosene, petroleum ether, pentane, n-hexane, hexamethylene, octane, heptane and 1,2,
At least one of 3,4- tetrahydronaphthalene.
In the present invention, the chlorinated solvents are selected from chloromethanes, methylene chloride, chloroform, carbon tetrachloride, 1,2- bis-
At least one of chloroethanes, 1,1- dichloroethanes and chlorobenzene.
In the present invention, the solvent containing phenyl ring be selected from benzene, toluene, monochloro-benzene, dichloro-benzenes, trichloro-benzenes, fluorobenzene, phenol and
At least one of methylphenol.
In the present invention, in step (1), raffinate phase is waste water up to standard, can be with direct emission.
In the present invention, in step (2), the lye and substituted or unsubstituted 2,3- pyridinedicarboxylic acid form and replace
Or unsubstituted 2,3- dipicolinates, for by substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid in extraction phase from extraction
It is transferred in water phase in phase (i.e. organic phase).The lye can be the lye of this field routine, such as can be sodium hydroxide
In solution, potassium hydroxide solution, lithium hydroxide solution, calcium hydroxide solution, sodium carbonate liquor, calcium carbonate soln and ammonium hydroxide extremely
Few one kind.
In the present invention, in step (2), the pH value of the alkalinity is 8-14, preferably 10-14.
In the present invention, in step (3), the acid solution and substituted or unsubstituted 2,3- pyridinedicarboxylic acid reactant salt,
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid is generated, acid solution herein forms substituted or unsubstituted 2,3- pyridine for being acidified
Dicarboxylic acids, i.e. target product.The acid solution can be hydrochloric acid, sulfuric acid, phosphoric acid or the hydrobromic acid etc. of this field routine.
In the present invention, in step (3), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
In the preferred embodiments of the present invention, shown in dotted line frame as shown in figure 1, this method further include: in step (3)
Be added before lye into extraction phase, be added into extraction phase molten containing substituted or unsubstituted 2,3- dipicolinates
Liquid.Wherein, the solution containing substituted or unsubstituted 2,3- dipicolinates can by lye with it is substituted or unsubstituted
2,3- pyridinedicarboxylic acid ethyl ester solution reacted to obtain, can for next batch production raw material it is (substituted or unsubstituted
2,3- dipicolinates).For example, the raw material produced every time using next batch, thus substituted by the residual of this batch
Or the solution of unsubstituted 2,3- pyridinedicarboxylic acid is combined with the raw material of next batch, can be recycled fully, at low cost
Remaining substituted or unsubstituted 2,3- pyridinedicarboxylic acid in filtrate.In situations where it is preferred, described containing substituted or unsubstituted
2,3- dipicolinates solution concentration be 10-60%, preferably 10-40%, more preferably 30-40%.
In the present invention, acid solution is added in step (3), in Xiang Suoshu water phase and is adjusted to acidity, then carries out standing and divide
Layer and substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid (product cake namely target product) that formula (I) expression is obtained by filtration, with
And the solution (waste water) containing formula (I) the substituted or unsubstituted 2,3- pyridinedicarboxylic acid indicated.
In situations where it is preferred, substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid that formula (I) indicates is 2,3- pyridine dicarboxyl
Acid, 5- methyl -2,3- pyridinedicarboxylic acid, 5- ethyl -2,3- pyridinedicarboxylic acid, 5- methoxyl methyl -2,3- pyridinedicarboxylic acid,
Second aspect of the present invention provides a kind of method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid of production, such as Fig. 2 institute
Show, this method comprises the following steps:
(A) it to containing lye is added in substituted or unsubstituted 2,3- pyridinedicarboxylic acid ethyl ester solution, is formed containing substituted
Or the solution of unsubstituted 2,3- dipicolinates；
(B) acid solution is added into the obtained solution containing substituted or unsubstituted 2,3- dipicolinates, and carries out
Filtering, obtains product cake and filtrate, wherein filtrate contains substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of formula (I) expression；
(C) extract liquor is added into obtained filtrate to be extracted, obtains raffinate phase and extraction phase；
(D) lye is added in Xiang Suoshu extraction phase and is adjusted to alkalinity, then carry out water-oil separating and obtain organic phase and contain
The water phase of substituted or unsubstituted 2,3- dipicolinates；
(E) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and formula (I) expression is obtained by filtration
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitre
Base or amino.
In the present invention, product cake contains substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of formula (I) expression, i.e. target
Product.
In the present invention, filtrate refer to after the production of this batch caused by containing substituted or unsubstituted 2,3- pyridine two
The solution (waste water) of carboxylic acid.
In the present invention, in step (C), raffinate phase is waste water up to standard, can be with direct emission.
In the present invention, in the preferred embodiments of the present invention, as shown in the upper left dotted line frame in Fig. 2, this method
Further include: before lye is added into extraction phase in step (D), it is added into extraction phase and contains substituted or unsubstituted 2,3-
The solution of dipicolinates.Wherein, the solution containing substituted or unsubstituted 2,3- dipicolinates can be by alkali
Liquid and substituted or unsubstituted 2,3- pyridinedicarboxylic acid ethyl ester solution are reacted to obtain, and can be the raw material of next batch production
(substituted or unsubstituted 2,3- dipicolinates).For example, the raw material produced every time using next batch, thus by this batch
The secondary solution for remaining substituted or unsubstituted 2,3- pyridinedicarboxylic acid is combined with the raw material of next batch, can be abundant
Ground recycles remaining substituted or unsubstituted 2,3- pyridinedicarboxylic acid in filtrate at low cost.In situations where it is preferred, described contain
The concentration of the solution of substituted or unsubstituted 2,3- dipicolinates be 10-60%, preferably 10-40%, more preferably
30-40%.
In situations where it is preferred, substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid that formula (I) indicates is 2,3- pyridine dicarboxyl
Acid, 5- methyl -2,3- pyridinedicarboxylic acid, 5- ethyl -2,3- pyridinedicarboxylic acid, 5- methoxyl methyl -2,3- pyridinedicarboxylic acid,
In the present invention, as shown in the dotted line frame of bottom right in Fig. 2, containing formula (I) indicate substituted or unsubstituted 2,3-
The solution (waste water) of pyridinedicarboxylic acid can carry out step C, D, E again, i.e. addition extractant, plus-minus, acid adding step, realize work
Industryization circulation production.
In the present invention, in step (A), contain substituted or unsubstituted 2,3- pyridinedicarboxylic acid ethyl ester solution and lye
Additional amount, for the purpose of it can obtain substituted or unsubstituted 2,3- dipicolinates.
In the present invention, in step (B), the acid solution and substituted or unsubstituted 2,3- pyridinedicarboxylic acid reactant salt,
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid is generated, acid herein forms substituted or unsubstituted 2,3- pyridine two for being acidified
Carboxylic acid, i.e. target product.The acid solution can be hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid etc..
In the present invention, in step (B), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
In the present invention, in step (B), it is preferable that product cake is purified, such as: water elution, drying obtain
To substituted or unsubstituted 2,3- pyridinedicarboxylic acid, target product.
In the present invention, in step (C), extract liquor is used for from substituted or unsubstituted 2,3- indicated containing formula (I)
Substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid that formula (I) is indicated is extracted in the filtrate of pyridinedicarboxylic acid, by indicating formula (I)
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid be complexed with extractant, by formula (I) indicate substituted or unsubstituted 2,
3- pyridinedicarboxylic acid is separated with filtrate.Extract liquor includes extractant and retarder thinner.
In the present invention, in step (C), with extract liquor total weight, the weight percent containing the extractant is
5%-35%, preferably 15%-20%.
In the present invention, in step (C), substituted or unsubstituted 2, the 3- pyridine dicarboxyl indicated containing formula (I)
The solution of acid and the molar ratio of the extractant are 1:(0.5-10).
In the present invention, in step (C), the extractant can be with are as follows: trialkylamine and/or trialkylphosphine oxide.
In the present invention, the trialkylamine can be but be not limited to: three n-octylamines, tri-tert amine, three hexyl amines,
In three n-pentyl amine, three positive heptyl amice tri-n-nonylamines, three (undecyl) amine, tridodecylamine and three (myristyl) amine
It is at least one.
In the present invention, the trialkylphosphine oxide can be but be not limited to: trihexylphosphine oxide, trioctylphosphine oxide (TOPO), three heptyl
Phosphine oxide, dihexyl octylphosphine oxide, dioctyl hexyl phosphine oxide, diamyl hexyl phosphine oxide, dioctyl heptyl phosphine oxide, diheptyl hexyl oxygen
At least one of phosphine and diheptyl nonyl phosphine oxide.
In the present invention, in step (C), the retarder thinner can be ether, alkane, chlorinated solvents and solvent containing phenyl ring
At least one of.
In the present invention, the ether is selected from ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, 1,2- diformazan
At least one of oxygroup ethane, dioxane and methyl phenyl ethers anisole.
In the present invention, the alkane be selected from kerosene, petroleum ether, pentane, n-hexane, hexamethylene, octane, heptane and 1,2,
At least one of 3,4- tetrahydronaphthalene.
In the present invention, the chlorinated solvents are selected from chloromethanes, methylene chloride, chloroform, carbon tetrachloride, 1,2- bis-
At least one of chloroethanes, 1,1- dichloroethanes and chlorobenzene.
In the present invention, the solvent containing phenyl ring be selected from benzene, toluene, monochloro-benzene, dichloro-benzenes, trichloro-benzenes, fluorobenzene, phenol and
At least one of methylphenol.
In the present invention, in step (D), the lye and substituted or unsubstituted 2,3- pyridinedicarboxylic acid form and replace
Or unsubstituted 2,3- dipicolinates, for by substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid in extraction phase from extraction
It is transferred in water phase in phase (i.e. organic phase).The lye can be the lye of this field routine, such as can be sodium hydroxide
In solution, potassium hydroxide solution, lithium hydroxide solution, calcium hydroxide solution, sodium carbonate liquor, calcium carbonate soln and ammonium hydroxide extremely
Few one kind.
In the present invention, in step (D), the pH value of the alkalinity is 8-14, preferably 10-14.
In the present invention, in step (E), the acid solution and substituted or unsubstituted 2,3- pyridinedicarboxylic acid reactant salt,
Substituted or unsubstituted 2,3- pyridinedicarboxylic acid is generated, acid solution herein forms substituted or unsubstituted 2,3- pyridine for being acidified
Dicarboxylic acids, i.e. target product.The acid solution can be the acid solution of this field routine, such as can be hydrochloric acid, sulfuric acid, phosphoric acid or hydrogen
Bromic acid etc..
In the present invention, in step (E), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
In the present invention, acid solution is added in step (E), in Xiang Suoshu water phase and is adjusted to acidity, then carries out standing and divide
Layer and substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid (product cake namely target product) that formula (I) expression is obtained by filtration, with
And the solution (waste water) containing formula (I) the substituted or unsubstituted 2,3- pyridinedicarboxylic acid indicated.
A kind of specific embodiment according to the present invention, the producer of substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid
Method includes the following steps:
(a) extractant is diluted, obtains extract liquor, substituted or unsubstituted 2, the 3- pyrrole that Xiang Hanyou formula (I) indicates
Extract liquor is added in the solution of diphosphoglyceric acid, temperature is controlled at 20-100 DEG C, is warming up to 40-100 DEG C, and stirring is cooled to room temperature,
Raffinate phase and the extraction phase containing complex compound are obtained, raffinate phase can be with direct emission；
(b) next batch is added into the extraction phase containing complex compound contains substituted or unsubstituted 2,3- pyridine
Then the reaction solution of dicarboxylate is added lye and pH to 8-14 is adjusted, stirs 0.5-3h at 10-60 DEG C, obtain organic
Phase and the water phase for containing substituted or unsubstituted 2,3- dipicolinates.
(c) it is warming up to 30-40 DEG C, acid solution is added into the water phase containing substituted or unsubstituted 2,3- dipicolinates
It carries out second of pH value adjusting, adjusts pH value to 0.5-2.4, be cooled to 20-30 DEG C, the solids that is precipitated and contain formula
(I) solution of substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid indicated, filtering, collects the solids of precipitation, the precipitation
Solids obtains substituted or unsubstituted 2,3- pyridinedicarboxylic acid (product cake namely the target production of formula (I) expression by purifying
Object),
The purifying includes water elution, drying.
Preferably, organic phase step (b) obtained is as in next batch production process, the extract liquor of step (a), into
Row is recycled.
Preferably, by step (c) obtain containing formula (I) indicate substituted or unsubstituted 2,3- pyridinedicarboxylic acid it is molten
Liquid repeats step (a), (b) and (c), that is, realizes industrialization circulation production.
In situations where it is preferred, in the reaction solution containing substituted or unsubstituted 2,3- dipicolinates of next batch
In, the content of substituted or unsubstituted 2,3- dipicolinates is 10-60%, preferably 10-40%, more preferably 30-
40%.
By the present invention in that with extractant of the invention by substituted or unsubstituted 2,3- pyridinedicarboxylic acid from waste water into
Row extraction, obtains complex compound, and alkali is then added, adds acid.So that the recycling of substituted or unsubstituted 2,3- pyridinedicarboxylic acid
Rate is high, easily operated, the advantages of avoiding heavy metal ion from entering water body, reducing wastewater treatment difficulty.
The method achieve the recyclings of extractant, reduce the processing difficulty of waste water, are suitable for consecutive production, have
Conducive to industrialized production.
Below will by embodiment, present invention is further described in detail, but protection scope of the present invention is not limited in
This.
Preparation example 1
Prepare the solution containing 5- methyl -2,3- pyridinedicarboxylic acid sodium salt of next batch
At room temperature, by 30% sodium hydrate aqueous solution 147g (1.1mol), it is added dropwise to 5- methyl -2,3- pyridinedicarboxylic acid
In the mixed solution of ethyl ester 122g (0.5mol) and 50g water, 2h is finished, and is warming up to 80 DEG C, insulated and stirred 3h.It is down to room temperature, is obtained
To 5- methyl -2,3- pyridinedicarboxylic acid sodium salt of 220ml, external standard method measures 5- methyl -2,3- pyridinedicarboxylic acid in the reaction solution
The concentration of sodium salt is 35%.
Preparation example 2
Prepare the solution containing 5- ethyl -2,3- pyridinedicarboxylic acid sodium salt of next batch
At room temperature, by 30% sodium hydrate aqueous solution 147g (1.1mol), it is added dropwise to 5- ethyl -2,3- pyridinedicarboxylic acid
In the mixed solution of ethyl ester 128.1g (0.5mol) and 60g water, 2h is finished, and is warming up to 50 DEG C, insulated and stirred 3h.Room temperature is down to,
5- ethyl -2,3- pyridinedicarboxylic acid sodium salt of 248ml is obtained, external standard method measures 5- ethyl -2,3- pyridine dicarboxyl in the reaction solution
Acid sodium-salt concentration is 32%.
Embodiment 1-4 is for illustrating recovery method of the invention.
Embodiment 1
(1) content of 5- methyl -2,3- pyridinedicarboxylic acid in solution (waste water) is measured
Prepare the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml, external standard method measures 5- methyl-in the solution
2,3- pyridinedicarboxylic acid content is 7.0%.
(2) 2,3- pyridinedicarboxylic acid in solution is recycled
At room temperature, by trioctylphosphine oxide (TOPO) 40g, dihexyl octylphosphine oxide 15g, trihexylphosphine oxide 30g are dissolved in 550ml kerosene
Obtain 570ml extract liquor (with extract liquor total weight, the weight percent containing the extractant be 16.2%).To
550ml extract liquor (the molar ratio of waste water and extractant is added in the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml
For 1:0.6), mix stirring, be warming up to 50 DEG C, stir 2h, be cooled to room temperature, stratification, obtain 336ml raffinate phase and
The extraction phase containing 5- methyl -2,3- pyridinedicarboxylic acid trialkylphosphine oxide complex compound of 580ml.Use liquid chromatogram (Agilent
Company model is LC1200) raffinate phase to be analyzed, the content for measuring 5- methyl -2,3- pyridinedicarboxylic acid is 30ppm, 5- first
Base -2,3- pyridinedicarboxylic acid recovery of extraction is 99%, and water phase can direct emission.
At room temperature, 5- methyl -2,3- pyridinedicarboxylic acid sodium salt reaction solution of next batch is added into 580ml extraction phase
320g (concentration 35%, preparation example 1), finishes, and is added dropwise sodium hydroxide (concentration 30%), and adjusting pH is 14, stirs at 20 DEG C
2h is mixed, water-oil separating, obtains 550ml organic phase and 356g contains 5- methyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution.Recycling
550ml extract liquor is produced as extract liquor set for lower batch.356g is contained into 5- methyl -2,3- pyridinedicarboxylic acid sodium
Saline solution is warming up to 40 DEG C, and sulfuric acid (concentration 30%) is added and adjusts pH to 0.5, stratification simultaneously filters, filter cake 50g water
Elution, obtains 5- methyl -2,3- pyridinedicarboxylic acid 90.05g, and the purity of external standard method measurement 5- methyl -2,3- pyridinedicarboxylic acid is
98%, yield 98%.The solution for obtaining the 2,3- pyridinedicarboxylic acid containing 5- methyl -2,3- pyridinedicarboxylic acid of 352ml is (useless
Water), the content that external standard method measures 5- methyl -2,3- pyridinedicarboxylic acid is 6.9%.
Embodiment 2
(1) content of 5- ethyl -2,3- pyridinedicarboxylic acid in solution (waste water) is measured
Prepare the solution containing 5- ethyl -2,3- pyridinedicarboxylic acid of 390ml, external standard method measures 5- ethyl-in the waste water
2,3- pyridinedicarboxylic acid content is 8.6%.
(2) 2,3- pyridinedicarboxylic acid in waste water is recycled
At room temperature, it by trioctylamine 160g, is dissolved in 600ml chlorobenzene and obtains the extract liquor of 750ml.Contain 5- to 390ml
750ml extract liquor is added in the solution of ethyl -2,3- pyridinedicarboxylic acid, mixes stirring, is warming up to 80 DEG C, stirs 2h, is cooled to
Room temperature, stratification obtain the chlorobenzene solution 780ml of 5- ethylpyridine -2,3- dicarboxylic acids trioctylamine complex compound, use liquid chromatogram
Water phase is analyzed, the content for measuring 5- ethyl -2,3- pyridinedicarboxylic acid is 45ppm, 5- ethyl -2,3- pyridinedicarboxylic acid extraction
Fetching yield is 99%, and water phase can direct emission.
At room temperature, 5- ethyl -2,3- pyridinedicarboxylic acid sodium salt solution 335g of next batch is added into 780ml extraction phase
(concentration 32%, preparation example 2), finishes, and 30% sodium hydroxide is added dropwise, and adjusting pH is 10, and 2h, grease point are stirred at 30 DEG C
From obtaining 750ml organic phase and 375g contain 5- ethyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution.750ml extract liquor is recycled,
It is produced as extract liquor set for lower batch.375g is contained into the heating of 5- ethyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution
To 30 DEG C, hydrochloric acid (concentration 30%) is added and adjusts pH to 1.1, stratification simultaneously filters, and filter cake is eluted with 50g water, obtains 5-
Ethyl -2,3- pyridinedicarboxylic acid 96.5g, the purity that external standard method measures 5- ethyl -2,3- pyridinedicarboxylic acid is 99%, and yield is
98.3%.The solution (waste water) containing 5- ethyl -2,3- pyridinedicarboxylic acid of 390ml is obtained, external standard method measures 5- ethyl -2,3- pyrrole
The content of diphosphoglyceric acid is 8.4%.
Embodiment 3
According to the method for embodiment 1, unlike,
By trioctylamine 160g, it is dissolved in and obtains the extract liquor of 750ml in 600ml chlorobenzene and replace with trihexylphosphine oxide 7g and two
Octyl heptyl phosphine oxide 8g, which is dissolved in, to be obtained the extract liquor of 260ml and (with extract liquor total weight, contains the extraction in 240ml toluene
5%) weight percent of agent is.
550ml extract liquor (solution and extraction are added into the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml
The molar ratio of agent is 1:0.6) replace with into 350ml solution be added 250ml extract liquor (molar ratio of solution and extractant be 1:
0.5)。
It is added dropwise sodium hydroxide (concentration 30%), adjusts pH as 14 and replace with dropwise addition sodium hydroxide (concentration 40%), adjust
Saving pH is 8.
Sulfuric acid (concentration 30%) adjusting pH to 0.5 is added and replaces with addition sulfuric acid (concentration 20%) adjusting pH to 0.9.
5- methyl -2,3- pyridinedicarboxylic acid 17g is obtained, the purity of external standard method measurement 5- methyl -2,3- pyridinedicarboxylic acid is
98%, yield 92%.The solution (waste water) of 5- methyl -2,3- pyridinedicarboxylic acid of 330ml is obtained, external standard method measures secondary wastewater
The content of middle 5- methyl -2,3- pyridinedicarboxylic acid is 4.5%.
Embodiment 4
According to the method for embodiment 1, unlike,
By trioctylamine 160g, be dissolved in obtained in 600ml chlorobenzene 750ml extract liquor replace with three n-pentyl amine 150g and
Three (myristyl) amine 46g, which are dissolved in, to be obtained the extract liquor of 580ml and (with extract liquor total weight, contains the extraction in 455ml kerosene
35%) weight percent for taking agent is.
550ml extract liquor (solution and extraction are added into the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml
The molar ratio of agent is 1:0.6) replace with into 350ml solution be added 560ml extract liquor (molar ratio of solution and extractant be 1:
10)。
It is added dropwise sodium hydroxide (concentration 30%), adjusts pH as 14 and replace with dropwise addition sodium hydroxide (concentration 30%), adjust
Saving pH is 10.
Sulfuric acid (concentration 30%) adjusting pH to 0.5 is added and replaces with addition sulfuric acid (concentration 30%) adjusting pH to 2.4.
5- methyl -2,3- pyridinedicarboxylic acid 87g is obtained, the purity of external standard method measurement 5- methyl -2,3- pyridinedicarboxylic acid is
98%, yield 96.5%.The solution (waste water) of 5- methyl -2,3- pyridinedicarboxylic acid of 317ml is obtained, external standard method measurement is secondary useless
The content of 5- methyl -2,3- pyridinedicarboxylic acid is 4.7% in water.
Embodiment 5
(1) content of 5- methyl -2,3- pyridinedicarboxylic acid in solution (waste water) is measured
Prepare the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml, external standard method measures 5- methyl-in the solution
2,3- pyridinedicarboxylic acid content is 7.0%.
(2) 2,3- pyridinedicarboxylic acid in solution is recycled
At room temperature, by trioctylphosphine oxide (TOPO) 40g, dihexyl octylphosphine oxide 15g, trihexylphosphine oxide 30g are dissolved in 550ml kerosene
Obtain 570ml extract liquor (with extract liquor total weight, the weight percent containing the extractant be 16.2%).To
550ml extract liquor (the molar ratio of waste water and extractant is added in the solution containing 5- methyl -2,3- pyridinedicarboxylic acid of 350ml
For 1:0.6), mix stirring, be warming up to 50 DEG C, stir 2h, be cooled to room temperature, stratification, obtain 336ml raffinate phase and
The extraction phase containing 5- methyl -2,3- pyridinedicarboxylic acid trialkylphosphine oxide complex compound of 580ml.Use liquid chromatogram (Agilent
Company model is LC1200) raffinate phase to be analyzed, the content for measuring 5- methyl -2,3- pyridinedicarboxylic acid is 30ppm, 5- first
Base -2,3- pyridinedicarboxylic acid recovery of extraction is 99%, and water phase can direct emission.
At room temperature, sodium hydroxide (concentration 30%) is added dropwise into 580ml extraction phase, adjusting pH is 14, is stirred at 20 DEG C
2h is mixed, water-oil separating, obtains 550ml organic phase and 130g contains 5- methyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution.Recycling
550ml extract liquor.130g is contained into 5- methyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution and is warming up to 40 DEG C, sulfuric acid (concentration is added
30%) to adjust pH to 0.5, stratification is simultaneously filtered, and filter cake is eluted with 50g water, obtains 5- methyl -2,3- pyridinedicarboxylic acid
21.0g, the purity that external standard method measures 5- methyl -2,3- pyridinedicarboxylic acid is 98%, yield 71.1%.110ml waste water is obtained, outside
The content that mark method measures 5- methyl -2,3- pyridinedicarboxylic acid is 6.6%.
Comparative example 1
According to the method for embodiment 1, unlike, use 85g n-butanol as extractant, three in alternative embodiment 1
Octylphosphine oxide 40g, dihexyl octylphosphine oxide 15g, trihexylphosphine oxide 30g.
The content for measuring 5- methyl -2,3- pyridinedicarboxylic acid is 1.5%, 5- methyl -2,3- pyridinedicarboxylic acid extraction and recovery
Rate is 74%.
Comparative example 2
According to the method for embodiment 1, unlike, sodium hydroxide is not added dropwise after addition extract liquor, sulfuric acid is not also added dropwise.
Using this method, it is unable to get 5- methyl -2,3- pyridinedicarboxylic acid.
By the result of comparative example 1 and 2, it can be seen that if not using extractant of the invention, 5- methyl -2,3- pyridine
The content and yield of dicarboxylic acids are significantly lower than extractant of the invention.Moreover, if extractant of the invention is used only, but not
The step of adding alkali, acid adding is carried out, target product is unable to get.The present invention is exactly based on using specific extractant, and add and subtract,
The step of acid adding, so that target product is fully recycled.
Production Example 1
1) preparation of 5- methyl -2,3- pyridinedicarboxylic acid
At room temperature, by 30% sodium hydrate aqueous solution 147g (1.1mol), it is added dropwise to 5- picoline -2,3- dicarboxylic acids
In the mixed solution of ethyl ester 122g (0.5mol) and 50g water, 2h is finished, and is warming up to 80 DEG C, and insulated and stirred 3h, reaction terminates, this
When reaction solution 5- picoline -2,3- Sodium Dicarboxylic Acid salinity be 35%, be cooled to 40 DEG C, be slowly added dropwise 30% to reaction solution
Sulfuric acid, 3h are finished, and adjust pH value to 1.5, filtering, filter cake is eluted with 50g water, and filter cake dries to obtain 5- methyl -2,3- pyridine dicarboxyl
Sour 75.0g, content 98.5%, yield 82%.Filtrate 418g is obtained, wherein 5- methyl -2,3- pyridinedicarboxylic acid content is 7.0%,
Filtrate volume 350ml.
2) preparation of 5- methyl -2,3- pyridinedicarboxylic acid trialkylphosphine oxide complex compound
At room temperature, by trioctylphosphine oxide (TOPO) 40g, dihexyl octylphosphine oxide 15g, trihexylphosphine oxide 30g are dissolved in 550ml kerosene
Obtain 570ml extract liquor (with extract liquor total weight, the weight percent containing the extractant be 16.2%), will
The extract liquor of 550ml and resulting 350ml filtrate, which mix, stirs, and is warming up to 50 DEG C, stirs 2h, is cooled to room temperature, stratification,
The kerosin 580ml of 5- picoline -2,3- dicarboxylic acids trialkylphosphine oxide complex compound is obtained, wherein water phase analyzes 5- methyl pyrrole
The content of pyridine -2,3- dicarboxylic acids is i.e. 30ppm, and 5- methyl -2,3- pyridinedicarboxylic acid recovery of extraction is 99% or more.
3) dissociation of 5- methyl -2,3- pyridinedicarboxylic acid trialkylphosphine oxide complex compound, recycling
At room temperature, the kerosin 580ml of 5- methyl -2,3- pyridinedicarboxylic acid trialkylphosphine oxide complex compound is added next
5- picoline -2,3- Sodium Dicarboxylic Acid salting liquid 320g (concentration 35%) of batch, finishes, and 30% sodium hydroxide is added dropwise, and adjusts
Saving pH is 14, stirs 2h, water-oil separating, recycling extraction agent solution 550ml, complexing extraction of the set for next batch acidified filtrate again
It takes.5- methyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution 356g is obtained, is warming up to 40 DEG C, it is 1.5 that acidification, which adjusts pH, stratification
And filter, filter cake is eluted with 50g water, 5- methyl -2,3- pyridinedicarboxylic acid 90.05g, content 98%, yield 98%.Obtain filtrate
422g, wherein 5- methyl -2,3- pyridinedicarboxylic acid content is 6.9%, filtrate volume 352ml.
Production Example 2
1) preparation of 5- ethyl -2,3- pyridinedicarboxylic acid
At room temperature, by 30% sodium hydrate aqueous solution 147g (1.1mol), it is added dropwise to 5- ethylpyridine -2,3- dicarboxylic acids
In the mixed solution of ethyl ester 128.1g (0.5mol) and 60g water, 2h is finished, and is warming up to 50 DEG C, and insulated and stirred 3h, reaction terminates,
Reaction solution 5- ethylpyridine -2,3- Sodium Dicarboxylic Acid salinity is 32% at this time, is cooled to 20 DEG C, is slowly added dropwise 30% to reaction solution
Sulfuric acid, 2h finishes, and adjusts pH value to 1.1, filtering, filter cake is eluted with 50g water, and filter cake dries to obtain 5- ethylpyridine -2,3- bis-
Carboxylic acid 77.8g, content 99%, yield 79%.Filtrate 453g is obtained, wherein 5- ethyl -2,3- pyridinedicarboxylic acid content is 8.6%,
Filtrate volume 390ml.
2) preparation of 5- ethyl -2,3- pyridinedicarboxylic acid trioctylamine complex compound
At room temperature, by trioctylamine 160g, it is dissolved in the extraction agent solution for obtaining 750ml in 600ml chlorobenzene, agent solution will be extracted
It mixing and stirs with 390ml filtrate obtained by upper step, be warming up to 80 DEG C, stir 2h, be cooled to room temperature, stratification obtains ethyl -2 5-,
The chlorobenzene solution 780ml of 3- pyridinedicarboxylic acid trioctylamine complex compound, wherein water phase analyzes containing for 5- ethyl -2,3- pyridinedicarboxylic acid
Amount is 45ppm, and 5- ethyl -2,3- pyridinedicarboxylic acid recovery of extraction is 99% or more.
3) dissociation of 5- ethyl -2,3- pyridinedicarboxylic acid trioctylamine complex compound, recycling
At room temperature, next batch is added in the chlorobenzene solution 780ml of 5- ethyl -2,3- pyridinedicarboxylic acid trioctylamine complex compound
5- ethyl -2,3- pyridinedicarboxylic acid sodium salt solution 335g (concentration 32%), finish, be added dropwise 30% sodium hydroxide, adjust pH
It is 12, stirs 2h, water-oil separating, recycling extraction agent solution 750ml, complexometric extraction of the set for next batch acidified filtrate again.
5- ethyl -2,3- pyridinedicarboxylic acid sodium-salt aqueous solution 375g is obtained, is warming up to 20 DEG C, it is 1.1 that acidification, which adjusts pH, stratification and mistake
Filter, filter cake are eluted with 50g water, 5- ethyl -2,3- pyridinedicarboxylic acid 96.5g, content 99%, yield 98.3%.Filtrate 455g is obtained,
Wherein 5- ethyl -2,3- pyridinedicarboxylic acid content is 8.4%, filtrate volume 390ml.
It can be seen that by comparative example and comparative example using method of the invention, the recycling of 2,3- pyridinedicarboxylic acids
Rate is greater than 99%, and purity is greater than 98.5%.Organic matter in waste water extracted, i.e. the content of 2,3- pyridinedicarboxylic acid <
50ppm.Using method of the invention, heavy metal ion is not introduced, recycling for extractant may be implemented, while of the invention
Method is simple, is suitable for consecutive production, purifying products are at low cost, are conducive to industrial production.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited thereto.At this
, can be with various simple variants of the technical solution of the present invention are made in the range of the technology design of invention, including each technical characteristic
It is combined with any other suitable method, these simple variants and combination equally should be considered as in disclosed in this invention
Hold, all belongs to the scope of protection of the present invention.
Claims (15)
1. a kind of recovery method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid, which is characterized in that this method includes following step
It is rapid:
(1) extract liquor is added in the solution for the substituted or unsubstituted 2,3- pyridinedicarboxylic acid that Xiang Hanyou formula (I) indicates to be extracted
It takes, obtains raffinate phase and extraction phase；
(2) in Xiang Suoshu extraction phase be added lye be adjusted to alkalinity, then carry out water-oil separating obtain organic phase with contain it is substituted
Or the water phase of unsubstituted 2,3- dipicolinates；
(3) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and taking for formula (I) expression is obtained by filtration
Generation or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitro or
Amino.
2. recovery method according to claim 1, wherein the extract liquor includes extractant and retarder thinner,
Preferably, with extract liquor total weight, the weight percent containing the extractant is 5%-35%, preferably 15%-
20%；
Preferably, the solution and the extractant of substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid indicated containing formula (I)
Molar ratio be 1:(0.5-10).
3. recovery method according to claim 2, wherein the extractant is trialkylamine and/or trialkylphosphine oxide；
Preferably, the trialkylamine is three n-octylamines, tri-tert amine, three hexyl amines, three n-pentyl amine, three positive heptyl amices three
At least one of positive nonyl amine, three (undecyl) amine, tridodecylamine and three (myristyl) amine；
Preferably, the trialkylphosphine oxide is trihexylphosphine oxide, trioctylphosphine oxide (TOPO), triheptylphosphine oxide, dihexyl octylphosphine oxide, two
In octyl hexyl phosphine oxide, diamyl hexyl phosphine oxide, dioctyl heptyl phosphine oxide, diheptyl hexyl phosphine oxide and diheptyl nonyl phosphine oxide
It is at least one.
4. recovery method according to claim 2, wherein the retarder thinner is ether, alkane, chlorinated solvents and contains phenyl ring
At least one of solvent；
Preferably, the ether is selected from ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, 1,2- dimethoxy second
At least one of alkane, dioxane and methyl phenyl ethers anisole；
Preferably, the alkane is selected from kerosene, petroleum ether, pentane, n-hexane, hexamethylene, octane, heptane and 1,2,3,4- tetrahydros
Change at least one of naphthalene；
Preferably, the chlorinated solvents are selected from chloromethanes, methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,
At least one of 1- dichloroethanes and chlorobenzene；
Preferably, the solvent containing phenyl ring is selected from benzene, toluene, monochloro-benzene, dichloro-benzenes, trichloro-benzenes, fluorobenzene, phenol and methylphenol
At least one of.
5. recovery method according to claim 1, wherein in step (2), the lye is sodium hydroxide solution, hydrogen
At least one of potassium oxide solution, lithium hydroxide solution, calcium hydroxide solution, sodium carbonate liquor, calcium carbonate soln and ammonium hydroxide；
Preferably, in step (2), the pH value of the alkalinity is 8-14, preferably 10-14.
6. recovery method according to claim 1, wherein in step (3), the acid solution be hydrochloric acid, sulfuric acid, phosphoric acid or
Hydrobromic acid；
Preferably, in step (3), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
7. recovery method described in any one of -6 according to claim 1, wherein this method further include: step (3) to
It is added before lye in extraction phase, the solution for containing substituted or unsubstituted 2,3- dipicolinates is added into extraction phase.
8. a kind of method of substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of production, this method comprises the following steps:
(A) to containing lye is added in substituted or unsubstituted 2,3- pyridinedicarboxylic acid ethyl ester solution, being formed containing substituted or not
The solution of substituted 2,3- dipicolinates；
(B) acid solution is added into the obtained solution containing substituted or unsubstituted 2,3- dipicolinates, and is filtered,
Obtain product cake and filtrate, wherein filtrate contains substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid of formula (I) expression；
(C) extract liquor is added into obtained filtrate to be extracted, obtains raffinate phase and extraction phase；
(D) in Xiang Suoshu extraction phase be added lye be adjusted to alkalinity, then carry out water-oil separating obtain organic phase with contain it is substituted
Or the water phase of unsubstituted 2,3- dipicolinates；
(E) acid solution is added in Xiang Suoshu water phase and is adjusted to acidity, then carry out stratification and taking for formula (I) expression is obtained by filtration
Generation or unsubstituted 2,3- pyridinedicarboxylic acid,
Wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4Alkyl, C1-C4Alkoxy, halogen, hydroxyl, nitro or
Amino.
9. according to the method described in claim 8, wherein, this method further include: lye is added into extraction phase in step (D)
Before, the solution for containing substituted or unsubstituted 2,3- dipicolinates is added into extraction phase.
10. method according to claim 8 or claim 9, wherein in step (B), the acid solution be hydrochloric acid, sulfuric acid, phosphoric acid or
Hydrobromic acid；
Preferably, in step (B), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
11. method according to claim 8 or claim 9, wherein in step (C), the extract liquor includes extractant and dilution
Solvent,
Preferably, with extract liquor total weight, the weight percent containing the extractant is 5%-35%, preferably 15%-
20%；
Preferably, the solution and the extractant of substituted or unsubstituted 2, the 3- pyridinedicarboxylic acid indicated containing formula (I)
Molar ratio be 1:(0.5-10).
12. according to the method for claim 11, wherein the extractant is trialkylamine and/or trialkylphosphine oxide；
Preferably, the trialkylamine is three n-octylamines, tri-tert amine, three hexyl amines, three n-pentyl amine, three positive heptyl amices three
At least one of positive nonyl amine, three (undecyl) amine, tridodecylamine and three (myristyl) amine；
Preferably, the trialkylphosphine oxide is trihexylphosphine oxide, trioctylphosphine oxide (TOPO), triheptylphosphine oxide, dihexyl octylphosphine oxide, two
In octyl hexyl phosphine oxide, diamyl hexyl phosphine oxide, dioctyl heptyl phosphine oxide, diheptyl hexyl phosphine oxide and diheptyl nonyl phosphine oxide
It is at least one.
13. according to the method for claim 11, wherein the retarder thinner be ether, alkane, chlorinated solvents and containing phenyl ring it is molten
At least one of agent；
Preferably, the ether is selected from ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, 1,2- dimethoxy second
At least one of alkane, dioxane and methyl phenyl ethers anisole；
Preferably, the alkane is selected from kerosene, petroleum ether, pentane, n-hexane, hexamethylene, octane, heptane and 1,2,3,4- tetrahydros
Change at least one of naphthalene；
Preferably, the chlorinated solvents are selected from chloromethanes, methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,
At least one of 1- dichloroethanes and chlorobenzene；
Preferably, the solvent containing phenyl ring is selected from benzene, toluene, monochloro-benzene, dichloro-benzenes, trichloro-benzenes, fluorobenzene, phenol and methylphenol
At least one of.
14. method according to claim 8 or claim 9, wherein in step (D), the lye is sodium hydroxide solution, hydrogen
At least one of potassium oxide solution, lithium hydroxide solution, calcium hydroxide solution, sodium carbonate liquor, calcium carbonate soln and ammonium hydroxide；
Preferably, in step (D), the pH value of the alkalinity is 8-14, preferably 10-14.
15. method according to claim 8 or claim 9, wherein in step (E), the acid solution be hydrochloric acid, sulfuric acid, phosphoric acid or
Hydrobromic acid；
Preferably, in step (E), the pH value of the acidity is 0.5-2.4, preferably 0.5-1.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710653039.7A CN109384714B (en) | 2017-08-02 | 2017-08-02 | Process for recovering and process for producing substituted or unsubstituted 2, 3-pyridinedicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710653039.7A CN109384714B (en) | 2017-08-02 | 2017-08-02 | Process for recovering and process for producing substituted or unsubstituted 2, 3-pyridinedicarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109384714A true CN109384714A (en) | 2019-02-26 |
| CN109384714B CN109384714B (en) | 2021-04-30 |
Family
ID=65412307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710653039.7A Active CN109384714B (en) | 2017-08-02 | 2017-08-02 | Process for recovering and process for producing substituted or unsubstituted 2, 3-pyridinedicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109384714B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336698A (en) * | 2021-05-29 | 2021-09-03 | 安徽金禾实业股份有限公司 | Method for recovering mother liquor in 4-trifluoromethyl nicotinic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057455A (en) * | 1990-06-15 | 1992-01-01 | 美国氰胺公司 | Prepare pyridine-2 by dichloro succinate dialkyl ester, the method for 3-dicarboxylic acid dialkyl esters and derivative thereof |
| JP2004189651A (en) * | 2002-12-10 | 2004-07-08 | Sumikin Air Water Chemical Inc | Method for producing 2,3-pyridinedicarboxylic acid |
| CN101781245A (en) * | 2009-06-26 | 2010-07-21 | 上海海事大学 | New method for synthesizing substitutional pyridine-3-carboxylic acid and analogue |
-
2017
- 2017-08-02 CN CN201710653039.7A patent/CN109384714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057455A (en) * | 1990-06-15 | 1992-01-01 | 美国氰胺公司 | Prepare pyridine-2 by dichloro succinate dialkyl ester, the method for 3-dicarboxylic acid dialkyl esters and derivative thereof |
| JP2004189651A (en) * | 2002-12-10 | 2004-07-08 | Sumikin Air Water Chemical Inc | Method for producing 2,3-pyridinedicarboxylic acid |
| CN101781245A (en) * | 2009-06-26 | 2010-07-21 | 上海海事大学 | New method for synthesizing substitutional pyridine-3-carboxylic acid and analogue |
Non-Patent Citations (5)
| Title |
|---|
| DELIANG LI ET AL.: "Reactive Extraction of iso-Nicotinic Acid with Trialkylamine in Different Diluents", 《J. CHEM. ENG. DATA》 * |
| LI DELIANG ET AL.: "Reactive Extraction of Nicotinic Acid with Trialkylamine in n-Octanol", 《CHIN.J.CHEM.ENG.》 * |
| LING ZHANG ET AL.: "Extraction Equilibria of Picolinic Acid with Trialkylamine/n-Octanol", 《J. CHEM. ENG.DATA》 * |
| SUSHIL KUMAR ET AL.: "Extraction of Pyridine-3-carboxylic Acid Using 1-Dioctylphosphoryloctane (TOPO) with Different Diluents: Equilibrium Studies", 《J. CHEM. ENG. DATA》 * |
| 于飞: "三烷基胺络合萃取吡啶甲酸的平衡研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336698A (en) * | 2021-05-29 | 2021-09-03 | 安徽金禾实业股份有限公司 | Method for recovering mother liquor in 4-trifluoromethyl nicotinic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109384714B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103906735B (en) | New aryl-quinoline | |
| CN113929622B (en) | Synthesis method of 2,5, 6-trichloro-cyanogen | |
| CN109384714A (en) | The recovery method and production method of substituted or unsubstituted 2,3- pyridinedicarboxylic acid | |
| CN102875463B (en) | Synthesis method for high-quality and low-cost bispyrithione | |
| US4581220A (en) | Process for the extraction of metal values and novel metal extractants | |
| CN106366071B (en) | The preparation method of Vonoprazan fumarate | |
| CN101175764A (en) | Process for the production of methylcobalamin | |
| CN106243027A (en) | A kind of preparation method of 3,6 dichloro 2 picolinic acids | |
| CN105153013B (en) | The synthetic method of the ketone of 6 bromine isoindoline 1 | |
| CN104803978B (en) | A kind of preparation method of esomeprazole magnesium | |
| CN106588739B (en) | A kind of trans- 3- hydroxy-L-proline preparation method | |
| CN104388685A (en) | Method for recovering tellurium, copper and bismuth from zinc oxide soot | |
| CN105017366B (en) | The ketone group cholesterol biosynthesis method of 25 hydroxyl 7 | |
| JPH107662A (en) | Production of asymmetric 4,6-bis(aryloxy)pyrimidine compound | |
| CN107759506A (en) | A kind of Buddhist nun draws the preparation method of (4 bromophenyl) piperidines of Pabuk intermediate S 3 | |
| CN106632238A (en) | Thiacalix [4] arene mono-substituted amine Schiff base derivative and synthesis method thereof | |
| WO2015135096A1 (en) | Method for synthesizing 3-ethoxy-4-ethoxycarbonyl phenylacetic acid | |
| CN104341428A (en) | Pentamethyl pentacarbonyl cucurbit[5]uril and preparation method thereof | |
| CN114539197B (en) | Synthesis method of 3-fluoroalkyl substituted chromone derivative | |
| CN107089928A (en) | The synthetic method of N Boc L propargylglycines | |
| CN104926847B (en) | A kind of synthesis boron aminated compounds technique and products application | |
| JP3486648B2 (en) | Method for producing pyrazole carboxylic acids | |
| CN103086962A (en) | Synthetic method for 5-chlorine-2,4-dyhydroxyl pyridine | |
| CN103422114B (en) | A kind of preparation method of potassium metavanadate | |
| CN105085381B (en) | A kind of separation method of chloro-pyridine mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |