CN1032688C - Method for purification of hydroxy-acetic acid from organic acid-and its salt-containing water solution - Google Patents
Method for purification of hydroxy-acetic acid from organic acid-and its salt-containing water solution Download PDFInfo
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Abstract
The present invention discloses a method for purifying glycolic acid from an organic acid and salt thereof containing water solution. The method mainly comprises inorganic acid is used for acidifying organic acid salt in pretreated water phase; extraction agent TBP or TRPO containing organic phase is used for pre-extracting other organic acid in the water phase; extraction agent N235 containing organic phase selectively extracts the glycolic acid from the water phase; a pure water solution of the glycolic acid is obtained by hot water stripping.
Description
The present invention relates to a kind of from the aqueous solution that contains oxyacetic acid the method for extraction and cleaning oxyacetic acid, particularly a kind of from the reaction solution of Mono Chloro Acetic Acid highly basic hydrolysis the method for purifying hydroxy-acetic acid.
As everyone knows, oxyacetic acid is the simplest a kind of aliphatic hydroxyl carboxylic acid, and it is present in the natural plant widely, but because its content in plant is very low, and with the coexistence of other material, so be difficult to separation and Extraction.Main at present dependence chemical synthesis process is produced, and the synthetic method of comparative maturity has: the acid by electrolytic reduction of oxalic method, and formaldehyde carbon monoxide acid catalyzed reaction method, hydroxyacetonitrile acidified water solution, and Mono Chloro Acetic Acid strong lye solution etc.But all contain a large amount of impurity in the aqueous solution of the oxyacetic acid that all these method reactions obtain, as mineral acid, inorganic salt, metal ion and other organic acid and salt thereof etc.Obviously, make purified oxyacetic acid, must adopt suitable process for purification to give purifying at different hydroxyl acetic acid water solution.Because oxyacetic acid easily decomposes in the time of 100 ℃.So can not adopt common rectificating method to make with extra care the purifying oxyacetic acid.The method that is suitable for purifying hydroxy-acetic acid has: the esterification catalysis method, and ion exchange method, and extraction separation method etc., wherein,
The esterification catalysis method: be that the oxyacetic acid in the solution is at first become hydroxy methyl acetate with methyl alcohol reaction esterification, tell esterification products then and after clean again with the esterification products hydrolysis, thereby reach the purpose of purifying hydroxy-acetic acid.Obviously, there are shortcomings such as raw material consumption is big, operation is complicated, production cost height in this method, only is suitable for production SILVER REAGENT oxyacetic acid product.
Ion exchange method: du pont company has been developed ion exchange method for the production technique that cooperates " formaldehyde carbon monoxide high pressure-temperature acid catalyzed reaction synthesis of hydroxy acetate ", and is U.S. Pat 3,859, and 347 is disclosed.This method comprises four processes at least.Be activated carbon decolorizing, weak anionic exchange removes acid catalyst, and stripping removes low boiling substance, and cationic exchange removes impurity metal ion, thereby reaches the purpose of purifying hydroxy-acetic acid.Obviously, the treating process of this method also is quite complicated, adds seriously corroded, and E.I.Du Pont Company has now stopped using this method to produce.
Extraction separation method: U.S. Pat 3,980701,3,980,702,3,980,703,3,980,704, proposed respectively with the alkylphosphonic acid carboxylic acid dialkyl, the dialkyl group alkyl phosphate, dialkyl sulphoxide, tetraalkyl ureas is an extraction agent.(extract oxyacetic acid＜20g/l) the aqueous solution from rare oxyacetic acid; German patent DE 3,436,348 have proposed to be extraction agent, to be the organic extractant phase separation oxyacetic acid of promotor composition with phenol, ethyl naphthol, octyl phenol, nonylphenol etc. with tri-n-octyl amine, three n-Decylamines.But four said extraction agents of patent of the U.S. are to the distribution ratio of oxyacetic acid all smaller (＜0.5), so have that the consumption of extraction agent is big, construction investment is many and shortcoming such as the concentration process energy consumption is big; And the said extracting process of German Patent, though theoretic partition ratio is bigger, owing to need do extraction promotor with phenol type substances, facts have proved that this method not only extraction agent costs an arm and a leg, and easily emulsification, the difficulty that is separated, thereby the prospect of its industrial application is little.
The present invention is the above-mentioned shortcoming that overcomes prior art, on the basis of a large amount of practices, proposed a kind of from containing other organic acid and salt thereof, and the method for purifying hydroxy-acetic acid in the aqueous solution of mineral acid and salt thereof, have advantages such as technology is simple, production cost is low, less investment, not only can satisfy the needs of existing industrial refining oxyacetic acid, and can from the factory effluent (as producing the waste water of CMC) that contains oxyacetic acid, reclaim purifying hydroxy-acetic acid.
Design of the present invention is such:
In the aqueous solution by Mono Chloro Acetic Acid highly basic hydrolysis reaction gained, except containing the product hydroxyl acetate, also contain a large amount of inorganic salt, chloroacetate salt, dichloroacetate, impurity such as trichloroacetate and metal ion, difference according to the alkalization condition, said hydroxyl acetate can be hydroxy acid sodium, oxyacetic acid potassium, oxyacetic acid ammonium or their mixture, said inorganic salt are sodium-chlor, Repone K, ammonium chloride or their mixture, said other organic acid salt is the Monochloro Acetic Acid ammonium, Monochloro Acetic Acid sodium, Monochloro Acetic Acid potassium, the dichloro acetic acid ammonium, dichloroacetate sodium, dichloro acetic acid potassium, the trichoroacetic acid(TCA) ammonium, sodium trichloroacetate, three fluoroacetic acid potassium etc.Again in view of in the factory effluent of producing Walocel MT 20.000PV (CMC), except containing hydroxyl acetate, also contain inorganic salt such as a large amount of ammonium chloride, Repone K, sodium-chlor, and organic acid such as oxalic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA) or their ammonium salt, sodium salt, sylvite.In the face of the above-mentioned hydroxyl acetic acid water solution of enumerating, because the component complexity, prior art is powerless.
The said method of purification of the present invention mainly comprises gives processing, gives extraction, the extraction and four processes of stripping, wherein,
Give processing: in the face of the complicated aqueous solution that closes oxyacetic acid, at first this aqueous solution is given processing with mineral acid, purpose makes the organic acid salt in the aqueous solution change into corresponding organic acid and inorganic salt, (comprise sodium salt, sylvite, ammonium salt as hydroxyl acetate, down with) and mineral acid (comprise hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid etc., down together) reaction generates oxyacetic acid and inorganic salt, and and for example chloracetate and inorganic acid reaction generate corresponding Mono Chloro Acetic Acid and inorganic salt.By that analogy.Point out in passing,, then preferentially be neutralized into corresponding inorganic salt by mineral acid as there being free alkali in the aqueous solution.
Owing to give processing reaction and must under the condition of excessive mineral acid, carry out, therefore give the mineral acid that contains 0～1.0Mol/l in the aqueous solution after the processing.
Give post-treatment aqueous phase and be one and contain oxyacetic acid, other organic acid, mineral acid, inorganic salt and the little metal ionic aqueous solution.
Give extraction: the purpose of giving extraction is to remove other organic acid from give post-treatment aqueous phase, as impurity such as Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), oxalic acid.
Available is extraction agent by tributyl phosphate (TBP) or TRPO (TRPO), octanol is a promotor, kerosene is that the organic phase selective extraction that thinner is formed is removed other organic acid is regulated water again with sig water PH=1～2, makes the free mineral acid of aqueous phase be neutralized into corresponding inorganic salt simultaneously.
Extraction: will obtain the organic phase of load oxyacetic acid through giving extraction and the water of adjusting behind the PH, use optionally extracting and separating oxyacetic acid of the organic phase formed by " extraction agent N235+ promotor octanol+diluent kerosene ".
Strip: with the organic phase of load oxyacetic acid, use the hot water back extraction, obtain purified hydroxy acid solution, directly go reduction vaporization to concentrate, obtain 70% (Wt%) oxyacetic acid product.
The present invention also is achieved in that
For the ease of setting forth, be example to purify Mono Chloro Acetic Acid highly basic hydrolysis reaction solution.
Give processing: at first the hydroxyl acetate in the above-mentioned reaction solution, chloroacetate salt, dichloroacetate, trichloroacetate are become in corresponding oxyacetic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA) and corresponding inorganic salt such as the reaction solution to have free alkali with the mineral acid acidifying, then preferentially be neutralized into corresponding inorganic salt by first machine acid.Said mineral acid is hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid etc.Give the suitable excessive 0～1.0Mol/l of mineral acid when handling.Said inorganic salt are sodium-chlor, Repone K, ammonium chloride, sodium sulfate, vitriolate of tartar, ammonium sulfate, S-WAT, potassium sulfite, ammonium sulphite, sodium phosphate, potassiumphosphate, ammonium phosphate etc.
Metal ion in the reaction solution mainly comes from the corrosion product of material in the reaction process, is generally metal ions such as Fe, Cu, and content is less than 1g/l.
Give extraction: with the above-mentioned post-treatment aqueous phase (A that gives
1) use the organic phase (O that forms by " extraction agent TBP (or TRPO)+promotor octanol+diluent kerosene "
1).Wherein,
Extraction agent: TBP, suitable concentration is 30～50% (volume ratios, down together),
Or TRPO, suitable concentration is: 10～20%.
Promotor: octanol, suitable concentration are 5～15%.
Thinner: kerosene, suitable concentration are 35～85%, carry out the two phase countercurrent flow contact by the following extraction process condition of giving, and other organic acid is removed in extraction, as Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA).Processing condition when giving extraction are:
Compare: O
1/ A
1=0.5～3.0 (volume ratios, down together), suitable scope is
1.0～1.5。
Give extraction temperature: T
1=10～35 ℃, suitable scope is 15～25 ℃,
Duration of contact: t
1＞5 minutes, be preferably 10 minutes,
Theoretical stage: n
1=5～12 grades.Because selected organic phase is very little to the partition ratio of oxyacetic acid when giving extraction, and it is all bigger to other organic acid partition ratio, therefore oxyacetic acid and other organic acid separation factor can reach 50～1000, therefore give extraction by multi-stage countercurrent, can remove other organic acid of aqueous phase effectively, other organic acid total amount of aqueous phase remnants can be reduced to below 0.01%, separates purpose thereby reach oxyacetic acid with other organic acid.
Other organic acid organic phase water of load or sig water back extraction separate negative after, return and give collection workshop section and recycle; Water after the back extraction (containing other organic acid, as Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA) etc.) can return Mono Chloro Acetic Acid highly basic hydrolysis workshop section and recycle.
Extraction: the water after giving extraction is used earlier from the sig water of alkali lye storage tank and is regulated water
PH=1～2, the inorganic acid alkali of aqueous phase changes into corresponding inorganic salt, again
Ratio of components (depending on the extraction process requirement) with deionized water allotment water.
Said sig water can be NH
4OH, NaOH, KOH or their mixture, suitable concentration are 1～2Mol/l, and it can add deionized water with high alkali liquid and prepare; Can also add the raffinate water that contains a large amount of inorganic salt with high alkali liquid prepares.
Said inorganic salt can be sodium-chlor, Repone K, ammonium chloride, sodium sulfate, vitriolate of tartar ammonium sulfate, S-WAT, potassium sulfite, ammonium sulphite, sodium phosphate, potassiumphosphate, ammonium phosphate etc.
Water (A after allotment
2) being the water that enters extraction workshop section, its suitable concentration range is (mainly regulating and control the concentration of oxyacetic acid):
The concentration of oxyacetic acid is 10～150g/l,
The concentration of inorganic salt is unrestricted below their saturation ratio,
Other organic acid concentration＜0.01g/l,
Concentration＜the 1.0g/l of other metal ion.
Extract used organic phase (O
2) form by extraction agent+promotor+thinner.Wherein, said extraction agent is trialkylamine (as N235), the carbonatoms on its alkyl
Be preferably 6～10, the suitable consumption of extraction agent is 50～70% in the organic phase
(volume ratio, down together);
Said promotor is octanol, and the suitable consumption of promotor is 5～15% in the organic phase;
Said thinner is a kerosene, and the suitable consumption of thinner is 15～45% in the organic phase.
With above-mentioned organic phase (O
2) pass through an extractor from water (A
2) in optionally extract oxyacetic acid, obtain the organic phase of load oxyacetic acid.Processing condition are during extraction:
Compare: O
2/ A
2=0.5～3.0 (volume ratios, down together).Suitable scope
Be 1.0～1.5.
Extraction temperature: T=10～35 ℃, suitable scope is 15～25 ℃.
Duration of contact: t＞5 minute are preferably 10 minutes
Theoretical stage: n=3～10 grade.
Because extraction agent of the present invention is to impurity such as the inorganic salt of aqueous phase, metal ions, extracting power is very little, and therefore extraction hardly can obtain the high oxyacetic acid solution that purifies.
The raffinate water that contains a large amount of inorganic salt can return the usefulness that the alkali lye storage tank is made the allotment sig water.Raffinate water after repeatedly recycling during near saturation ratio, can return the alkali lye storage tank as wherein inorganic salt again after the part inorganic salt are removed in evaporation, cooling, crystallization.The purpose that makes inorganic salt enter water is to bring into play its " saltouing " effect when extraction, improves the partition ratio of oxyacetic acid in organic phase.
Back extraction: with the organic phase (O of load oxyacetic acid
3) usefulness deionized water (A
3) carry out back extraction as reverse-extraction agent, the processing condition during back extraction are:
Compare: A
3/ O
3=0.5～2.0 (volume ratios, down together),
Suitable scope is 0.75～1.25
Back extraction temperature: T=70～100 ℃, suitable scope is 85～95 ℃
Duration of contact: t＞5 minute are preferably 10 minutes
Theoretical stage: n=6～15 grade.
Load organic phases through back extraction separate negative after, return extraction workshop section and recycle; Water after the back extraction is one to contain the solution of pure oxyacetic acid, directly goes reduction vaporization to concentrate, and can obtain the oxyacetic acid product of 70% (Wt%).
Further illustrate content of the present invention below in conjunction with embodiment.
Embodiment 1
For to come from the reaction solution of making the Mono Chloro Acetic Acid highly basic hydrolysis gained of basifier with sodium hydroxide, aqueous phase contains hydroxy acid sodium, Monochloro Acetic Acid sodium, dichloroacetate sodium, sodium trichloroacetate, free sodium hydroxide, sodium-chlor and a spot of impurity metal ion to water (A).(1) at first above-mentioned water is given processing, make the organic acid salt acidifying of aqueous phase with mineral acid
Become corresponding organic acid and inorganic salt, make the free alkali NaOH of water be neutralized into phase simultaneously
The inorganic salt of answering.The excessive 0.1Mol/l of mineral acid.Because said mineral acid can be hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid or their mixture, therefore said inorganic salt are sodium-chlor, sodium sulfate, S-WAT, sodium phosphate.Give post-treatment aqueous phase (A
1) for containing oxyacetic acid, other organic acid, as Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), mineral acid, example hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, and the inorganic salt and the little metal ionic aqueous solution.
(2) will give post-treatment aqueous phase (A
1) use the organic phase (O that forms by 50%TBP+10% octanol+40% kerosene
1) give extraction, remove other organic acid of aqueous phase with separation.The processing condition of pre-extraction are:
Compare: O
1/ A
1=1 (volume ratio)
Temperature: T=25 ℃ of pre-collection
Duration of contact: t=10 minute
Theoretical stage: the water after the pre-collection of n=8 level, wherein oxyacetic acid, inorganicly change, inorganic salt, metal ion equal size remain unchanged, and other organic acid total concn is reduced to below the 0.01g/l.
(3) water after the pre-extraction is the PH=1 of the sig water adjusting water of 1Mol/l with concentration earlier, and the mineral acid of water is neutralized into corresponding inorganic salt, and said sig water can be NH
4The aqueous solution of OH, NaOH, KOH or their mixture; Be deployed into the water (A that is suitable for the extraction process requirement with deionized water again
2):
Oxyacetic acid: 123.5g/l,
Inorganic salt: 0.6Mol/l,
Other organic acid: 0.005g/l,
Metal ion: (0.5g/l,
PH＝1。
With above-mentioned water (A
2) use the organic phase (O that forms by " 50%N235+10% octanol+40% kerosene "
2) carry out one-level balance extraction.Processing condition during its extraction are:
Compare: O
2/ A
2=1 (volume ratio).
Extraction temperature: T=25 ℃.
Duration of contact: t=10 minute.
After static phase-splitting in 5 minutes, getting equilibrated water and organic phase respectively, to carry out the assay determination extraction results as follows:
The concentration of oxyacetic acid: 80.62g/l in the load organic phases,
The concentration of raffinate aqueous phase oxyacetic acid: 42.88g/l,
Oxyacetic acid in the partition ratio of organic phase and aqueous phase is: 1.88
The one-level percentage extraction of oxyacetic acid is: 65%.
Embodiment 2
Except entering the water (A of extractor
2) to be deployed into the hydroxyl acetic acid concentration be outside the 75.9g/l, all the other conditions are all with embodiment 1.Extraction results is as follows:
The concentration of oxyacetic acid is in the load organic phases: 53.25g/l,
The concentration of raffinate aqueous phase oxyacetic acid is: 22.65g/l,
Oxyacetic acid in the partition ratio of organic phase and aqueous phase is: 2.35,
The one-level percentage extraction of oxyacetic acid is: 70%.
Embodiment 3
Except entering the water (A of extractor
3) to be deployed into the hydroxyl acetic acid concentration be outside the 58.43g/l, all with embodiment 1, extraction results is as follows for all the other conditions:
The concentration of oxyacetic acid is in the load organic phases: 46.43g/l,
The concentration of raffinate aqueous phase oxyacetic acid is: 12.0g/l,
Oxyacetic acid in the partition ratio of organic phase and aqueous phase is: 3.87
The one-level percentage extraction of oxyacetic acid is: 79.4%.
By embodiment 1～3 as seen: along with water (A
3) in the reduction of concentration of oxyacetic acid.The one-level percentage extraction of oxyacetic acid is significantly improved (being increased to 70%79% respectively by 65%), helps industrial realization multi-stage solvent extraction.
Embodiment 4
Except water (A
3) in inorganic salt concentration be outside the 2.1Mol/l, all the other conditions are all with embodiment 1.Extraction results is as follows:
The concentration of oxyacetic acid is in the load organic phases: 115.68g/l,
The concentration of raffinate aqueous phase oxyacetic acid is: 7.82g/l,
Oxyacetic acid in the partition ratio of organic phase and aqueous phase is: 14.8,
The one-level percentage extraction of oxyacetic acid is: 93.6%.
Comparative Examples
Preparation one only contains the water (A that oxyacetic acid concentration is 123.5g/l
2), with embodiment 1 described organic phase (O
2) carry out the extraction of one-level balance, its extraction process condition is as follows with embodiment 1, extraction results:
The concentration of oxyacetic acid is in the load organic phases: 67.g/l,
The concentration of raffinate aqueous phase oxyacetic acid is: 55.6g/l,
Oxyacetic acid in the partition ratio of organic phase and aqueous phase is: 1.22,
The one-level percentage extraction of oxyacetic acid is: 55%.
By embodiment 1,4 and Comparative Examples as seen: the inorganic salt of aqueous phase have the effect of " saltouing " significantly, can promote the oxyacetic acid of aqueous phase to shift to organic phase, when the concentration of the inorganic salt of aqueous phase was increased to 0.6Mol/l, 2.1Mol/l respectively by 0, the one-level percentage extraction of oxyacetic acid was increased to 65%, 93.6% respectively by 55%.This shows that the raffinate water that the present invention will contain a large amount of inorganic salt returns the technical scheme that the alkali lye storage tank is used for allocating diluted alkaline, not only can avoid the discharging of waste water, and have positive technique effect.
Embodiment 5
Water (A
2) composition and organic phase (O
2) composition all with embodiment 1, with above-mentioned water (A
2) and organic phase (O
2), by comparing O
2/ A
2=1, by one 6 grades mixer-settler extractor.Carry out the two phase countercurrent flow extraction, extraction temperature is 20 ℃, and be 10 minutes duration of contact.Extraction results is as follows:
The concentration of the oxyacetic acid in the outlet water (raffinate water) can be reduced to 0.3g/l, and the concentration of inorganic salt remains on 0.6Mol/l;
The concentration of the oxyacetic acid in the outlet organic phase (load organic phases) can reach 203.8g/l;
The stage efficiency of extractor can reach more than 95%, and total percentage extraction of oxyacetic acid can reach more than 99%.
With the mixer-settler extractor of load organic phases (being above-mentioned outlet organic phase) by one 12 grades, use the deionized water back extraction, be in a ratio of 1 during back extraction, temperature during back extraction is 90 ± 2 ℃, be 10 minutes duration of contact, the concentration of the oxyacetic acid in the back extraction back loading organic phase can be reduced to below the 2.2g/l, and the concentration of oxyacetic acid can reach 216.5g/l in the strip liquor, and back extraction ratio can reach more than 98.Separating organic phase after negative through back extraction returns extraction workshop section and recycles.Water after the back extraction (being strip liquor) can directly carry out reduction vaporization and concentrate the oxyacetic acid product that obtains 70% (Wt%).
Embodiment 6
Water (A) wherein contains: hydroxy acid sodium 15g/l, sodium oxalate 14.5g/l, Monochloro Acetic Acid sodium 12.2g/l for coming from the trade effluent of producing Walocel MT 20.000PV (CMC).Dichloroacetate sodium 10.8g/l.Sodium trichloroacetate 11.6g/l.Sodium-chlor 30g/l, Repone K 10g/l, and metal ion 1g/l such as a spot of Fe, Cu.
By embodiment 1 identical method above-mentioned water (A) is carried out pre-treatment, pre-extraction,
Water after the pre-extraction is used the NH of 2Mol/l again
4OH solution is regulated the PH=2 of water, makes the mineral acid (excess acid of bringing into during pre-treatment) of aqueous phase be neutralized into corresponding salt simultaneously.Water after regulating PH is the water (A that enters extractor
2), it consists of: oxyacetic acid: 11.6g/l, inorganic salt: 1.15Mol/l, and a spot of other organic acid 0.005g/l, metal ion 0.5g/l such as Fe, Cu.
With above-mentioned water (A
2) with the organic phase (O that forms by " 50%N235+10% octanol+40% kerosene "
2), by comparing O
2/ A
2=1, by one 4 grades of mixer-settler extractors, carry out the two phase countercurrent flow extraction, extraction results is as follows:
The concentration of the oxyacetic acid in the outlet water (raffinate water) can be reduced to 0.05g/l, and the concentration of inorganic salt remains unchanged, and still is 1.15Mol/l;
The concentration of oxyacetic acid can reach 21.8g/l in the outlet organic phase (load organic phases).The stage efficiency of extractor can reach more than 95%.The percentage extraction of oxyacetic acid can reach more than 99.5%.
Above-mentioned load organic phases (being above-mentioned outlet organic phase) is used the deionized water back extraction, be in a ratio of 1 during back extraction, temperature during back extraction is 90 ± 2 ℃, be 10 minutes duration of contact, after 10 stage countercurrent back extractions, oxyacetic acid concentration in the load organic phases can be reduced to below the 1g/l, and the oxyacetic acid concentration in the strip aqueous can reach 22.2g/l, and back extraction ratio is more than 95%.Water after the back extraction can directly go reduction vaporization to concentrate, and obtains the oxyacetic acid product of 70% (Wt%).
In sum, method of the present invention not only can satisfy the needs of purifying hydroxy-acetic acid from the reaction solution of producing oxyacetic acid, and can reclaim purifying hydroxy-acetic acid from industrial waste water.The embodiment that is provided only can industrializedly give an example as method of the present invention, and it does not limit protection scope of the present invention.Obviously, in Mono Chloro Acetic Acid highly basic hydrolytic process.As adopt KOH, NH
4When OH and their mixture etc. were made basifier, the reaction solution of its gained, or other similar hydroxyl acetic acid water solution all can adopt method of the present invention to realize industrialization.
Claims (9)
1. the method for a purifying hydroxy-acetic acid from the aqueous solution that contains organic acid and salt thereof is characterized in that said method of purification comprises:
(1) at first water is carried out the acidifying pre-treatment, the organic acid salt acidifying of aqueous phase is become with mineral acid
Corresponding organic acid and inorganic salt, the suitable excessive 0～1.0mol/l of mineral acid;
(2) remove water with the pre-collection of the organic phase that contains extraction agent tributyl phosphate or TRPO then
In other organic acid, the processing condition when it comes together in advance are:
Compare: organic phase/water=0.5～3.0 (volume ratio),
Extraction temperature: T=10～35 ℃,
Duration of contact: t＞5 minute,
Theoretical stage: n=2～12 grade;
(3) with sig water the PH of water is transferred to 1～2, make the mineral acid of aqueous phase be neutralized into corresponding nothing
Machine salt, and the concentration of the oxyacetic acid of aqueous phase is regulated and control to 10～150g/l;
(4) use by organic phase that the extraction agent trialkylamine+promotor octanol+diluent kerosene is formed from water
In optionally extract oxyacetic acid, the processing condition in its when extraction are:
Compare: water/organic phase=0.5～3.0 (volume ratio),
Back extraction temperature: T=10～35 ℃,
Duration of contact: t＞5 minute,
Theoretical stage: n=2～10 grade.
(5) strip with deionized water, the processing condition during back extraction are:
Compare: organic phase/water=0.5～2 (volume ratio),
Pre-collection temperature: T=70～100 ℃,
Duration of contact: t＞5 minute,
Theoretical stage: n=6～15 grade;
2. the method for claim 1 is characterized in that said organic acid salt is ammonium salt, sodium salt, the sylvite of oxyacetic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), oxalic acid formation.
3. the method for claim 1 is characterized in that said other organic acid is Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), oxalic acid.
4. the method for claim 1, used mineral acid is hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid or their mixture when it is characterized in that the acidifying pre-treatment.
5. the method for claim 1, the organic phase when it is characterized in that extracting in advance have a suitable ratio of components to be:
The extraction agent tributyl phosphate: 30～50% (volume ratios, down together),
Or TRPO: 10～20%,
The promotor octanol: 5～15%,
Diluent kerosene: 85～35%.
6. as claim 1,5 described methods, the processing condition when it is characterized in that extracting in advance are:
Compare: organic phase/water=1.0～1.5 (volume ratio),
Pre-collection temperature: T=15～25 ℃,
Duration of contact: t=10 minute,
Theoretical stage: n=2～12 grade.
7. the method for claim 1, the organic phase when it is characterized in that extracting have a suitable ratio of components:
The extraction agent trialkylamine: 50～70% (volume ratios, down together),
The promotor octanol: 5～15%,
Diluent kerosene: 45～15%.
8. as claim 1,7 described methods, the processing condition when it is characterized in that extracting are:
Compare: organic phase/water=1.0～1.5 (volume ratio),
Extraction temperature: T=15～25 ℃,
Duration of contact: t=10 minute,
Theoretical stage: n=2～10 grade.
9. the method for claim 1, the processing condition when it is characterized in that back extraction are:
Compare: water/organic phase=0.75～1.5 (volume ratio),
Back extraction temperature: T=85～95 ℃,
Duration of contact: t=10 minute,
Theoretical stage: n=6～15 grade.
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|---|---|---|---|---|
| US9227896B2 (en) | 2010-08-18 | 2016-01-05 | Eastman Chemical Company | Process for the separation and purification of a mixed diol stream |
| US8709376B2 (en) * | 2010-09-23 | 2014-04-29 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| CN102633399B (en) * | 2012-04-19 | 2013-09-04 | 中蓝连海设计研究院 | Comprehensive treatment and resource utilization technology of 2-naphthol production wastewater |
| CN105503592B (en) * | 2016-01-20 | 2017-10-31 | 宁波永顺精细化工有限公司 | The method that ester-interchange method handles the waste water containing isobutyrate |
| CN108640093B (en) * | 2018-06-22 | 2021-11-09 | 湖北永绍科技股份有限公司 | Separation and purification process of mixed waste acid solution |
| CN109503352A (en) * | 2018-12-04 | 2019-03-22 | 桂林理工大学 | A method of recycling acetic acid and separation other elements from acetate solution |
| CN112961044A (en) * | 2021-03-01 | 2021-06-15 | 恒达亲水胶体泰州有限公司 | Method for extracting, separating and purifying glycollic acid from CMC industrial production wastewater |
-
1993
- 1993-06-26 CN CN 93112467 patent/CN1032688C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1084503A (en) | 1994-03-30 |
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