CN103304398B - A kind of method of purification of carboxylic acid aqueous solution - Google Patents
A kind of method of purification of carboxylic acid aqueous solution Download PDFInfo
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- CN103304398B CN103304398B CN201310187269.0A CN201310187269A CN103304398B CN 103304398 B CN103304398 B CN 103304398B CN 201310187269 A CN201310187269 A CN 201310187269A CN 103304398 B CN103304398 B CN 103304398B
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Abstract
The present invention relates to a kind of method of purification of carboxylic acid aqueous solution, after the aqueous solution of the purificant containing ionic liquid and carboxylic acid, carboxylic acid is combined by hydrogen bond with the ionic liquid in purificant, except anhydrating after layering, pass through the control of processing condition again by hydrogen bond rupture, be reduced to purificant and carboxylic acid, then crystallization and purification is carried out, obtain high purity target product, this purificant is applicable to multiple separating device, purifying technique is environmentally friendly pollution-free, and purificant loss is little and separation efficiency is high, has very high economic benefit and competitive power in the industrial production.
Description
Technical field
The present invention relates to a kind of method of purification of carboxylic acid aqueous solution, specifically mixed with carboxylic acid by the purificant containing ionic liquid, both pass through hydrogen bonded, except anhydrating, and then hydrogen bond rupture is reduced into carboxylic acid and purificant, then carboxylic acid is separated with purificant, obtain highly purified carboxylic acid.
Background technology
Carboxylic acid is the important Organic chemical products of a class, and its kind is a lot of, and for methacrylic acid, it can prepare the product such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate with alcohols esterification.At present Separation of Water the processes well known of purifying methyl acrylic mainly extracts methacrylic acid by making extraction agent of organic solvent from methacrylic aqueous acid from methacrylic aqueous acid, and by method that extraction agent is separated with methacrylic acid.If European patent EP 710643A is by 5-9 fat of carbon atom hydrocarbon, aromatic hydrocarbons, ester or its mixture, from aqueous solution, extract the moisture methacrylic acid solution obtained by cooling and condensation reaction gas.EP345083B describes the stable hydrocarbon extraction methacrylic acid with 6-9 carbon atom.Above-mentioned extraction agent, when methacrylic acid extraction, is not desirable especially to Methacrylic acid selectivity, often extracts all the other impurity simultaneously, as water, acetic acid, acetone etc., these foreign matter contents often have about 10wt%, and therefore Solvent quantity is large, and follow-up methacrylic acid purification energy consumption is high; Above-mentioned extraction agent high volatility simultaneously, in use procedure, loss is serious, and consider from security standpoint, above-mentioned extraction agent is inflammable, explosive, and thus many investigators are looking for the extraction agent or assistant agent that can substitute volatile organic solvent.
With traditional extraction solvent phase ratio, ionic liquid is more and more paid attention to for extracting research in recent years.Ionic liquid is room temperature or close to presenting salt that is liquid, that be made up of zwitterion completely under room temperature condition, low temperature molten salt (low temperature molten salts), organic ion liquid (organic ionicliquids), ionic liquid at room temperature (Room temperature ionic liquids) etc. can be referred to as, generally be made up of organic cation and inorganic anion.Ionic liquid mainly contains in extracting metals ion, biomolecules, organic compound, desulfurization, denitrogenation and gas delivery etc. in extraction application, and ionic liquid is more for organic compound extraction limitation, such as, when extracting for carboxylic acid, because each organic acid solvability in ionic liquid affects larger by temperature, pH value, concentration etc., adjusting and optimizing need be carried out to critical process, ionic liquid just can be made to possess good solvability to target compound.In addition, with ionic liquid and carboxylic acid by inverse decomposition again after hydrogen bonded, the method for Crystallization Separation carboxylic acid yet there are no bibliographical information.
Summary of the invention
The shortcoming such as the object of the invention is to overcome that energy consumption in prior art is high, organic solvent loss is serious and provide a kind of and use purificant containing ionic liquid to the method for carboxylic acid of purifying, it is few and can the advantage such as recycle, pollution-free, good separating effect that the method has purificant consumption.
In order to reach above object, the present invention adopts following technical scheme:
A method of purification for carboxylic acid, the method comprises following process: 1) mixed with purificant by carboxylic acid aqueous solution, and carboxylic acid and ionic liquid form hydrogen bond, are removed by aqueous phase after layering; 2) then hydrogen bond rupture is reduced to purificant and carboxylic acid, then purificant and carboxylic acid are carried out crystallization and purification.
In the present invention, described purificant can be the mixed solution of ionic liquid or ionic liquid and organic solvent, and wherein the negatively charged ion of ionic liquid is Tf
2n
-(two fluoroform sulfimide foundation group), PF
6 -(phosphofluoric acid group), HSO
4 -(bisulfate ion group), OH
-, HCO
3 -(bicarbonate group), BF
4 -(Tetrafluoroboric acid group) and Tf
2o
-one or two or more in (trifluoro sulphur anhydride group), positively charged ion can be [C
6mIm]
+(1-hexyl-3-Methylimidazole group), [C
8mIm]
+(1-octyl group-3-Methylimidazole group), [Hnmp]
+(METHYLPYRROLIDONE group), [Hmim]
+(1-Methylimidazole group), [BMIm]
+(1-butyl-3-Methylimidazole group) and [DMIm]
+one or two or more in (1,3-methylimidazole group); Wherein it should be noted that, in ionic liquid, can cause when acidic-group and basic group coexist occurring unnecessary salts substances in purification process, affect the refining effect of target compound, occur when therefore two kinds of groups are different; When purificant is the mixed solution of ionic liquid and organic solvent, described organic solvent is the one or two or more in normal hexane, octane, benzene,toluene,xylene and normal heptane, the one or two or more in preferred normal heptane, toluene and normal hexane.
In the present invention, purificant can be write as following form, XA:YB, and wherein A represents ionic liquid, and B represents organic solvent, and X, Y represent both shared massfractions in purificant respectively, and wherein the scope of X+Y=1, X is 0.5 ~ 1, and preferably 0.6 ~ 1.
In the present invention, in carboxylic acid aqueous solution, the concentration of carboxylic acid is 5 ~ 40wt%, preferably 20 ~ 38wt%, and usually containing partial impurities, the mainly light constituent such as aldehyde, ketone material in carboxylic acid aqueous solution, foreign matter content often accounts for carboxylic acid quality 5 ~ 10%.The quality of purificant is 0.3 ~ 2.1 times of carboxylic acid aqueous solution quality, preferably 0.35 ~ 1.5 times.
In the present invention, described carboxylic acid is the one of the one in acetic acid, propionic acid, butyric acid, valeric acid, vinylformic acid, methacrylic acid, maleic acid and 3 Methylbutanoic acid, preferred propionic acid, vinylformic acid and methacrylic acid.
In the present invention, mainly pass through temperature, pH, pressure, the control of the processing condition such as reflux ratio carrys out high efficiency separation carboxylic acid, wherein process 1) carry out in reaction, extraction tower, extraction tower temperature is 20 ~ 100 DEG C, preferably 35 ~ 70 DEG C, pressure range (relative pressure, as follows) 10 ~ 70kPa, preferably 25 ~ 50kPa, wherein ionic liquid is the ionic liquid possessing functionalization group, its principal character is negatively charged ion or positively charged ion is hydric group, under these processing condition, carboxylic acid and ionic liquid form hydrogen bond, by after hydrogen bonded by ion liquid abstraction and and aqueous phase separation.Process 2) carry out in rectifying crystal system, rectifying crystal system is made up of rectifying tower and crystallizer, process 1) in formed hydrogen bond rupture in rectifying tower, reduce become carboxylic acid and purificant, wherein tower bottom of rectifying tower temperature range is 50 ~ 180 DEG C, preferably 70 ~ 150 DEG C, tower reactor pH value range 1 ~ 6, preferably 4 ~ 5.5, tower reactor pressure range (relative pressure) 5 ~ 50kPa, preferably 10 ~ 40kPa, in rectifying tower, light constituent reflux ratio is 0.3 ~ 2, preferably 0.5 ~ 1.5; Rectifying tower heavy constituent enters crystallizer, and carboxylic acid is Crystallization Separation in a crystallizer, and mould temperature scope is-30 ~ 50 DEG C, preferably-25 DEG C ~ 30 DEG C, pressure range (relative pressure) 5 ~ 30kPa, preferably 7 ~ 20kPa; The material such as aldehyde, ketone that wherein said light constituent refers to atmospheric boiling point less than 70 DEG C, C atomicity is less than 5, heavy constituent refers to the material such as purificant, carboxylic acid.
In the present invention, described reaction, extraction tower can have broad variety, comprises single-stage or multi-stage column, specifically can adopt mixing clarification tower or continuous countercurrent tower.Carboxylic acid adopts rectifying crystallization method with being separated of purificant: rectifying tower can have one, two or more separation phase, separation phase number refers to have regular or without the theoretical tray number of regular packed tower or the stage number of tray column, rectifying tower type can be tray column or packing tower, the example of tray column column plate is as sieve column plate, bubble cap plate, valve tray, slot sieve column plate, jet tray, centrifugal column plate, tunnel-cover column plate etc., packing tower is Raschig ring without regular examples of fillers, Pall ring, Lessing rings, square saddle etc., structured packing example is Rombo-pak type, Montz-pak type etc., crystallizer can have various ways, can be continuous crystallizer or periodic crystallisation device, also can be Recycling Mother Solution crystallizer or magma (mother liquor and crystals coexist) circulation crystallization device etc.
Positively effect of the present invention is:
1. purificant used in the present invention has high percentage extraction, the highlyest can reach 99%, and purificant regenerative process is simple, can recycle, environmentally safe.Whole sepn process is simple, and energy consumption is low, and operational path possesses very strong competitive power.
2. having purified in rear aqueous phase, survivor ion strength of fluid is lower than 0.01wt%, and the loss amount of ionic liquid is very little.
3. the ionic liquid that the present invention adopts has extraordinary chemical stability, nontoxic, also nonflammable; And ionic liquid has very large solubleness to separated component, simultaneously less to other components dissolved degree except separated component, its selectivity for target compound is the highest can reach more than 99%.
Accompanying drawing illustrates:
Fig. 1 meets a kind of process flow sheet in all Alternatives of the present invention.
The explanation of Fig. 1 symbol:
A: reaction, extraction tower;
B: rectifying tower;
C: crystallizer;
1: carboxylic acid aqueous solution feeding line;
2: purificant feeding line;
3: purificant reflux pipeline;
4: after extraction, organic phase enters rectifying tower pipeline;
5: aqueous phase outlet line after extraction;
6: rectifying tower tower top material outlet pipe line;
7: rectifying tower light constituent reflux pipeline;
8: rectifying tower light fraction outlet pipeline;
9: tower bottom of rectifying tower taphole pipeline;
10: carboxylic acid outlet line.
Embodiment
Further describe the method for purification of carboxylic acid provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Fig. 1 is a kind of technical process provided by the invention, but do not limit to so, its process description is as follows: carboxylic acid aqueous solution, purificant is respectively through pipeline 1, pipeline 2 enters reaction, extraction tower A and fully contacts, purificant and carboxylic acid form hydrogen bond, with aqueous phase separation, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower B through pipeline 4, in rectifying tower B, tower bottom of rectifying tower temperature 50 ~ 180 DEG C can be passed through, pH value range 1 ~ 6, hydrogen bond rupture is impelled under the condition of pressure range (relative pressure) 5 ~ 50kPa, light constituent is through pipeline 6, 8 separate, part light constituent refluxes through pipeline 7, reflux ratio is 0.3 ~ 2, after separation completes, heavy constituent enters crystallizer by pipeline 9, temperature-30 ~ 50 DEG C in crystallization control device, under the condition of pressure (relative pressure) 5 ~ 30kPa, purificant is separated with carboxylic acid, after purificant has been separated with carboxylic acid, purificant loops back purificant raw material storage tank through pipeline 3, high density carboxylic acid is from pipeline 10 extraction.
Now by specific embodiment, the present invention will be further described.
Percentage extraction is defined as:
Selectivity is defined as:
In the present invention, liquid-phase chromatographic analysis condition is as follows:
Chromatogram model: Agilent1200,
Chromatographic detector: UV-detector and differential refraction detector,
Chromatogram flow phase: methyl alcohol, acetonitrile are chromatographically pure,
Stratographic analysis standard model: selected carboxylic acid sample purity is 99.99%.1-butyl-3-Methylimidazole hexafluorophosphate, 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-octyl group-3-Methylimidazole hexafluorophosphate, METHYLPYRROLIDONE hydrosulfate, hydroxide 1-butyl, 3-Methylimidazole, hydrogen-carbonate 1-butyl-3-Methylimidazole standard substance (source Aladdin reagent).
Chromatographiccondition:
Chromatographic column selects Zorbax Eclipse plus C18 (4.6x250.5um),
Determined wavelength scope 200 ~ 300nm,
Flow velocity selects 0.8ml/min,
Sample size 10 microlitre.
Main raw material source in the present invention:
Carboxylic acid aqueous solution: Yantai Wanhua Polyurethane Co., Ltd's oxidizing reaction pilot plant.
Embodiment 1
As shown in Figure 1, reaction, extraction tower adopts counter current contact, its theoretical plate number is 6, relative pressure is 30kPa, temperature 50 C, drop into 4kg/h ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate continuously successively, 0.5kg/h ionic liquid N-N-methyl-2-2-pyrrolidone N-hydrosulfate and 9kg/h30wt% methacrylic aqueous acid, extract rear aqueous phase to discharge from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts packing tower, filler is Pall ring, its theoretical plate number is 20, tower bottom of rectifying tower temperature controls at 100 DEG C, pH value is 4.2, relative pressure 40kPa, tower top temperature 60 DEG C, light constituent acetaldehyde, acetone etc. are through pipeline 6, 8 extraction, reflux ratio is 0.5, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, temperature 30 DEG C in crystallizer, relative pressure 15kPa, crystallizer purificant is out back to purificant raw material storage tank through pipeline 3, methacrylic acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of remaining purificant in the percentage extraction of methacrylic acid, selectivity and water, the results are shown in table 1.Analyze pipeline 10 methacrylic acid purity after rectifying crystallization, purity is 99.9%.
Embodiment 2
As shown in Figure 1, reaction, extraction tower adopts counter current contact, its theoretical plate number is 6, relative pressure is 50kPa, temperature 90 DEG C, continuous mixing drops into 3.2kg/h ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate, 0.8kg/h ionic liquid N-N-methyl-2-2-pyrrolidone N-hydrosulfate and 9kg/h5wt% methacrylic aqueous acid, after having extracted, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts packing tower, filler is Raschig ring, its theoretical plate number is 20, tower bottom of rectifying tower temperature controls at 150 DEG C, pH value is 2, relative pressure 20kPa, tower top temperature 70 DEG C, light constituent acetaldehyde, acetone etc. are through pipeline 6, 8 extraction, reflux ratio is 1.5, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, temperature-5 DEG C in crystallizer, pressure 20kPa, crystallizer purificant is out back to purificant raw material storage tank through pipeline 3, methacrylic acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of survivor ion liquid in the percentage extraction of methacrylic acid, selectivity and water, the results are shown in table 1.Analyze pipeline 10 methacrylic acid purity after rectifying crystallization, purity is 98.9%.
Table 1
| 。 | embodiment 1 | embodiment 2 |
| percentage extraction (%) | 99 | 97 |
| selectivity (%) | 99.5 | 98.5 |
| aqueous phase intermediate ion strength of fluid (wt%) | 0.01 | 0.01 |
Embodiment 3
As shown in Figure 1, reaction, extraction tower adopts counter current contact, and its theoretical plate number is 5, and its relative pressure is 45kPa, temperature 60 C, drops into 3.6kg/h ionic liquid 1-hexyl-3-methyl imidazolium tetrafluoroborate, 0.3kg/h ionic liquid [Bmim] HCO continuously successively
3with 4kg/h15wt% acrylic acid aqueous solution, after having extracted, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts packing tower, filler is Pall ring, its theoretical plate number is 25, tower bottom of rectifying tower temperature controls at 88 DEG C, pH value is 3, relative pressure 20kPa, tower top temperature 77 DEG C, light constituent formaldehyde, acetaldehyde etc. are through pipeline 6, 8 extraction, reflux ratio is 1.1, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, temperature-5 DEG C in crystallizer, relative pressure 20kPa, crystallizer purificant ionic liquid is out back to purificant raw material storage tank through pipeline 3, vinylformic acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of survivor ion liquid in acrylic acid percentage extraction, selectivity and water, the results are shown in table 2.Analyze pipeline 10 vinylformic acid purity after rectifying crystallization, purity is 99.2%.
Embodiment 4
As shown in Figure 1, reaction, extraction tower adopts counter current contact, its theoretical plate number is 4, its relative pressure is 40kPa, temperature 40 DEG C, drop into 3.5kg/h ionic liquid 1-octyl group-3-Methylimidazole hexafluorophosphate continuously successively, 0.2kg/h ionic liquid [Bmim] OH, 1kg/h normal heptane and the 6kg/h24wt% maleic acid aqueous solution, after having extracted, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts tray column, column plate type selecting sieve column plate, its theoretical plate number is 25, bottom temperature controls 80 DEG C, pH value is 5.2, relative pressure 20kPa, tower top temperature 70 DEG C, light constituent acetone, formaldehyde etc. are through pipeline 6, 8 extraction, reflux ratio is 1.5, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, temperature-30 DEG C in crystallizer, relative pressure 10kPa, crystallizer purificant is out back to purificant raw material storage tank through pipeline 3, maleic acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of survivor ion liquid in the percentage extraction of maleic acid, selectivity and water, the results are shown in table 2.Analyze pipeline 10 maleic acid purity after rectifying crystallization, purity is 98.7%.
Table 2
| Embodiment 3 | Embodiment 4 | |
| Percentage extraction (%) | 95 | 93 |
| Selectivity (%) | 99.5 | 98.5 |
| Aqueous phase intermediate ion strength of fluid (wt%) | 0.008 | 0.01 |
Embodiment 5
As shown in Figure 1, reaction, extraction tower adopts counter current contact, its theoretical plate number is 6, relative pressure is 70kPa, temperature 25 DEG C, continuous mixing drops into 8kg/h ionic liquid 1-hexyl-3-methyl imidazolium tetrafluoroborate, 0.6kg/h ionic liquid N-N-methyl-2-2-pyrrolidone N-hydrosulfate, 0.5kg/h toluene and the 5.5kg/h40wt% valeric acid aqueous solution, after having extracted, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts packing tower, filler adopts Raschig ring, its theoretical plate number is 20, tower bottom of rectifying tower temperature controls at 170 DEG C, pH value is 1.2, relative pressure 50kPa, tower top temperature 70 DEG C, light constituent acetaldehyde, acetone etc. are through pipeline 6, 8 extraction, reflux ratio is 2, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, mould temperature-28 DEG C, relative pressure 30kPa, crystallizer purificant is out back to purificant raw material storage tank through pipeline 3, valeric acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of survivor ion liquid in the percentage extraction of valeric acid, selectivity and water, the results are shown in table 3.Analyze pipeline 10 valeric acid purity after rectifying crystallization, purity is 99.5%.
Embodiment 6
As shown in Figure 1, reaction, extraction tower adopts counter current contact, its theoretical plate number is 8, relative pressure is 10kPa, temperature 100 DEG C, continuous mixing drops into 2kg/h ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate, 0.2kg/h ionic liquid N-N-methyl-2-2-pyrrolidone N-hydrosulfate, 0.4kg/h normal hexane and the 1.7kg/h10wt% propionic acid aqueous solution, after having extracted, aqueous phase is discharged from pipeline 5, organic phase enters rectifying tower through pipeline 4, rectifying tower adopts packing tower, filler adopts Pall ring, its theoretical plate number is 22, tower bottom of rectifying tower temperature 60 C, pH value is 3.2, relative pressure 9kPa, tower top temperature 50 DEG C, light constituent acetaldehyde, formaldehyde etc. are through pipeline 6, 8 extraction, reflux ratio is 1.7, tower reactor feed liquid enters magma circulation crystallization device through pipeline 9, the temperature of crystallizer is 45 DEG C, relative pressure 5kPa, crystallizer purificant is out back to purificant raw material storage tank through pipeline 3, propionic acid is from pipeline 10 extraction.Wherein, after extraction tower has extracted, pipeline 4 mixing solutions and pipeline 5 aqueous solution are sampled, adopt liquid chromatography analysis, measure the concentration of survivor ion liquid in the percentage extraction of propionic acid, selectivity and water, the results are shown in table 3.Analyze pipeline 10 propionic acid purity after rectifying crystallization, purity is 99.7%.
Table 3
| Embodiment 5 | Embodiment 6 | |
| Percentage extraction (%) | 96.5 | 97 |
| Selectivity (%) | 99.5 | 99.6 |
| Aqueous phase intermediate ion strength of fluid (wt%) | 0.009 | 0.01 |
Comparative example 1
Equally with embodiment 1 object extract methacrylic acid, purificant changes 4kg/h normal heptane into.And, analyze pipeline 4 extraction agent and pipeline 5 aqueous solution similarly to Example 1, measure the concentration of remaining extraction agent in the percentage extraction of methacrylic acid, selectivity and water, the results are shown in table 4.Analyze pipeline 10 methacrylic acid purity after rectifying crystallization, purity is 98.5%.
Comparative example 2
Equally with embodiment 1 object extract methacrylic acid, purificant changes 4kg/h normal hexane into.And, analyze pipeline 4 extraction agent and pipeline 5 aqueous solution similarly to Example 1, measure the concentration of remaining extraction agent in the percentage extraction of methacrylic acid, selectivity and water, the results are shown in table 4.Analyze pipeline 10 methacrylic acid purity after rectifying crystallization, purity is 97.6%.
Table 4
| Comparative example 1 | Comparative example 2 | |
| MAA percentage extraction (%) | 85 | 90 |
| MAA extraction selectivity (%) | 98.5 | 97.5 |
| Remaining extractant concentration (wt%) in aqueous phase | 0.1 | 0.1 |
Claims (11)
1. a method of purification for carboxylic acid aqueous solution, is characterized in that, the method comprises following process:
1) mixed with the purificant containing ionic liquid by carboxylic acid aqueous solution, carboxylic acid and ionic liquid form hydrogen bond, are removed by aqueous phase after layering;
2) then hydrogen bond rupture is reduced to ionic liquid and carboxylic acid, then purificant and carboxylic acid are carried out crystallization and purification;
Described carboxylic acid is selected from the one in acetic acid, propionic acid, butyric acid, valeric acid, vinylformic acid, methacrylic acid, maleic acid and 3 Methylbutanoic acid;
Process 2) carry out in rectifying crystal system, rectifying crystal system is made up of rectifying tower and crystallizer;
Described purificant is ionic liquid or ionic liquid and organic solvent mixed solution, purificant can be described as following general formula: X A:Y B, wherein A represents ionic liquid, B represents organic solvent, X, Y represent both shared massfractions in purificant respectively, wherein X+Y=1, X scope is 0.5 ~ 1;
The quality of described purificant is 0.3 ~ 2.1 times of carboxylic acid aqueous solution quality;
The negatively charged ion of described ionic liquid is selected from two fluoroform sulfimide foundation group, phosphofluoric acid group, HSO
4 -, OH
-, HCO
3 -, one or two or more in Tetrafluoroboric acid group and trifluoro sulphur anhydride group; Positively charged ion is selected from one or two or more in 1-hexyl-3-Methylimidazole group, 1-octyl group-3-Methylimidazole group, METHYLPYRROLIDONE group, 1-Methylimidazole group, 1-butyl-3-Methylimidazole group and 1,3-methylimidazole group; And occur when in ionic liquid, acidic-group is different from basic group;
Described tower bottom of rectifying tower temperature is 50 ~ 180 DEG C, and tower reactor pH value is 1 ~ 6, and tower reactor relative pressure is 5 ~ 50kPa, and in rectifying tower, light constituent reflux ratio is 0.3 ~ 2; Rectifying tower heavy constituent enters crystallizer and is separated, and mould temperature is-30 ~ 50 DEG C, and relative pressure is 5 ~ 30kPa.
2. method according to claim 1, is characterized in that, described X scope is 0.6 ~ 1.
3. method according to claim 1, is characterized in that, described purificant be ionic liquid and organic solvent mixed solution time, organic solvent is the one or two or more in normal hexane, octane, benzene,toluene,xylene and normal heptane.
4. method according to claim 3, is characterized in that, described organic solvent is the one or two or more in normal heptane, toluene and normal hexane.
5. method according to claim 1, is characterized in that, described carboxylic acid is selected from the one in propionic acid, vinylformic acid and methacrylic acid.
6. method according to claim 1, is characterized in that, the concentration of carboxylic acid aqueous solution is 5 ~ 40wt%.
7. method according to claim 6, is characterized in that, the concentration of carboxylic acid aqueous solution is 20 ~ 38wt%.
8. method according to claim 1, is characterized in that, the quality of described purificant is 0.35 ~ 1.5 times of carboxylic acid aqueous solution quality.
9. method according to claim 1, is characterized in that, process 1) carry out in reaction, extraction tower, wherein temperature 20 ~ 100 DEG C, relative pressure 10 ~ 70kPa.
10. method according to claim 9, is characterized in that, process 1) temperature be 35 ~ 70 DEG C, relative pressure is 25 ~ 50kPa.
11. methods according to claim 1, is characterized in that, process 2) tower bottom of rectifying tower temperature is 70 ~ 150 DEG C, tower reactor pH value is 4 ~ 5.5, and tower reactor relative pressure is 10 ~ 40kPa, and in rectifying tower, light constituent reflux ratio is 0.5 ~ 1.5; Mould temperature is-25 DEG C ~ 30 DEG C, and relative pressure is 7 ~ 20kPa.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102428066A (en) * | 2009-05-20 | 2012-04-25 | 巴斯夫欧洲公司 | Method for purifying carboxylic acids containing halogen compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
| Title |
|---|
| 张玮.疏水性离子液体萃取分离中草药中阿魏酸和咖啡酸的研究.《中国优秀硕士学位论文全文数据库,工程科技I辑》.2008,B016-65页. * |
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