CN101417933B - Continuous production method of high-purity acetylacetone - Google Patents
Continuous production method of high-purity acetylacetone Download PDFInfo
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- CN101417933B CN101417933B CN2008102034045A CN200810203404A CN101417933B CN 101417933 B CN101417933 B CN 101417933B CN 2008102034045 A CN2008102034045 A CN 2008102034045A CN 200810203404 A CN200810203404 A CN 200810203404A CN 101417933 B CN101417933 B CN 101417933B
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Abstract
The invention discloses a continuous production method of high-purity acetylacetone, carries out azeotropic distillation with salt water to separate coarse acetylacetone liquid containing acetic acid, acetic anhydride and high-boiling product, and in such a way to continuously produce high-purity acetylacetone. The steps are as follows: in a deacidifying and deanhydriding tower T1, azeotropic mixture formed by acetylacetone and water are steamed out from the tower top, are misphased in a phase splitter S1; the water layer flows back, and the oil layer flows through the deanhydriding tower T1 and a treating column T3, thus obtaining high purity acetylacetone; the water containing cyclamate at the column bottom of the deacidifying and deanhydriding tower T1 is discharged into soda solution and a reactor R1, with the pH value of the mixture solution of 5 to 8; after flowing through a salt separator S2, the salt water with low concentration is poured into the deacidifying and deanhydriding tower T1 from the tower top; after simple recrystallization, the acetate is separated from the salt separator S2, thus obtaining high purity acetate of the byproduct. The continuous production method of high-purity acetylacetone has the advantages of continuous and steady production, little consumption, good separation effect of acetic anhydride from high-boiling products; in addition, the product purity reaches to 99.9 percent, waste water discharging is beneficial for environmental protection and the invention can be used for producing acetate byproducts.
Description
Technical field
The invention belongs to technical field of chemical separation, be specifically related to a kind of method from thick methyl ethyl diketone solution continuous production high-purity acetylacetone.
Background technology
Methyl ethyl diketone is a kind of important chemical and medicine intermediate; Can be used for synthetic sulfa drugs, fodder additives and catalyzer etc.; Development along with society; Purity requirement to methyl ethyl diketone is increasingly high, and the premium grads purity requirement reaches 99.9%, and this also has higher requirement to the continuous rectificating technique of methyl ethyl diketone.The process that isomerizing isopropenyl acetate method obtains is taken off the thick methyl ethyl diketone solution behind the low-boiling-point substance; Also contain acetic acid, aceticanhydride and a small amount of high boiling material; These impurity and methyl ethyl diketone boiling point are approaching; At present, still there is not satisfied method to can be good at separating above-mentioned impurity, the high-purity acetylacetone that obtains requiring.
English Patent GB1354180 adopts fractionated method, changes vacuum tightness, extraction acetic acid, aceticanhydride and methyl ethyl diketone step by step, and this method not only can't realize serialization production, and because boiling point is approaching, and acetic acid, aceticanhydride are not easily separated, the methyl ethyl diketone product purity is not high; GB795843 adopts thick methyl ethyl diketone is fed in the 3mol/LNH3 solution; Acetic acid, aceticanhydride are removed in reaction; Because methyl ethyl diketone has certain solubleness in water; 30 ℃ of solubleness are that 15%, 80 ℃ of solubleness is 34%, so adopt a large amount of methyl ethyl diketones of present method to flow away with waste water, the product loss is big; Japanese Patent JP1056640 adopts the reaction of adding less water to remove aceticanhydride; Then with water and acetic acid as low-boiling-point substance from the cat head extraction; Because reaction is slow down for water and aceticanhydride normal temperature; Particularly a spot of water is difficult to aceticanhydride is reacted completely, and acetic acid also is difficult to separate with methyl ethyl diketone, and methyl ethyl diketone also can't reach requirement of high purity; English Patent GB838142 adopts the mode of double tower azeotropic distillation; With water is entrainer separating acetyl acetone, and this method can be converted into acetic acid fully with aceticanhydride, can effective elimination acetic acid under the lower situation of acetic acid content; But produce a large amount of waste water in the production process; The a large amount of methyl ethyl diketones of dissolving in the hot wastewater of tower still bottom cause product to run off, and do not meet environmental requirement; And under the bigger situation of acetic acid, aceticanhydride content, then removing the acetic acid decrease in efficiency, acetic acid gets into the finished product, influences the purity of the finished product methyl ethyl diketone.
Summary of the invention
The objective of the invention is: provide the high loss of a kind of compliance with environmental protection requirements, product yield less, the method for the highly purified methyl ethyl diketone of continuous production; Contain acetic acid, aceticanhydride and high boiling material from what the separating isomerism isopropenyl acetate obtained, produce highly purified methyl ethyl diketone in the thick methyl ethyl diketone liquid after removing the low component of boiling.
For achieving the above object; The technical scheme that adopts is: a kind of continuous production method of high-purity acetylacetone; Comprise that thick methyl ethyl diketone solution takes off acid anhydride tower T1 middle part from depickling and gets into, take off acid anhydride tower T1 depickling through depickling and take off acid anhydride that dehydration tower T2 dehydration and treating tower T3 are refining; It is characterized in that: utilize salt solution to carry out acetic acid, aceticanhydride and high boiling material in the azeotropic distillation crude methyl ethyl diketone liquid, continuous production high-purity acetylacetone.Said thick methyl ethyl diketone solution takes off acid anhydride tower T1 middle part from depickling and gets into; Take off acid anhydride tower T1 cat head from depickling and add normal temperature saturated acetic acid salt brine solution; Aceticanhydride and water complete reaction generation acetic acid in the acid anhydride tower T1 are taken off in depickling, contain hydrochlorate water and discharge from tower still bottom, regulate pH value to 5～8 through neutralization tank R1; After the salt separator S2 recrystallization separating acetic acid salt, the saturated brine reuse is taken off the water inlet of acid anhydride tower T1 cat head do depickling; Methyl ethyl diketone and water form azeotrope 6 from the cat head extraction, and after the phase-splitting, oil reservoir gets into dehydration tower T2 dehydration from dehydration tower T2 cat head, and treating tower T3 subsequently is refining in the phase splitter S1.
Said normal temperature saturated acetic acid salt brine solution is that temperature is 0～25 ℃ of saturated acetic acid sodium, Potassium ethanoate or ammonium acetate aqueous solution.
Advantage of the present invention: take off the acid anhydride tower and treating tower removes for twice through depickling, high boiling material in the product (boiling point greater than 240 ℃ 2,5-hexanedione, 5-alkene-2-heptanone etc.) content is lower than 0.01%; Through neutralization tank R1 neutralization, keep salt solution pH between 5～8, strengthened the ability that acid anhydride is taken off in depickling greatly; The existence of salt effect has reduced the volatility of acetic acid, helps the separation of acetic acid and improves the purity of product methyl ethyl diketone.Adopt this technology can the continuous production high-purity acetylacetone, purity can reach 99.9%; This technology is discharged waste water no longer in a large number, has reduced the loss of methyl ethyl diketone, helps environmental protection, can produce sub product acetate simultaneously.
Description of drawings
Fig. 1 is the technical process of high-purity acetylacetone quantity-produced.
The acid anhydride tower is taken off in the T1 depickling among the figure, the T2 dehydration tower, and the T3 treating tower, R1 alkali lye neutralization tank, the S1 phase splitter, the S2 salt separator, acid anhydride column overhead condensing surface is taken off in the E1 depickling, E2 dehydration column overhead condensing surface, E3 treating tower overhead condenser.
Embodiment
Below through embodiment the present invention is described further, wherein except that specifying, material is concentration expressed in percentage by weight.
Charging: after the isopropenyl acetate isomerizing, what obtain contains acidic substance methyl ethyl diketone solution such as acetic acid, aceticanhydride, through taking off the thick methyl ethyl diketone liquid that low-boiling-point substance obtains, wherein contains acetic acid 0.1～10%, aceticanhydride 0.1～10%, high boiling material 0.1～10%.
A kind of continuous production method of high-purity acetylacetone; Comprise that thick methyl ethyl diketone solution takes off acid anhydride tower T1 depickling through depickling and takes off acid anhydride; Dehydration tower T2 dehydration and treating tower T3 are refining; It is characterized in that: utilize salt solution to carry out acetic acid, aceticanhydride and high boiling material in the azeotropic distillation crude methyl ethyl diketone liquid, continuous production high-purity acetylacetone.
Concrete steps are: thick methyl ethyl diketone solution 1 takes off acid anhydride tower T1 middle part from depickling and gets into, and normal temperature saturated acetic acid salt brine solution 4 takes off acid anhydride tower T1 cat head from depickling and adds, and the interior aceticanhydride of acid anhydride tower T1 is taken off in depickling and the water complete reaction generates acetic acid; Containing hydrochlorate water 2 discharges from tower still bottom; Add the alkali neutralization through neutralization tank R1, regulate pH value to 5～8, after 0～25 ℃ of recrystallization separating acetic acid of salt separator S2 controlled temperature salt; Saturated brine 4 reuses are taken off the water inlet of acid anhydride tower T1 cat head, recycle do depickling;
Methyl ethyl diketone and water form azeotrope 6 and take off the extraction of acid anhydride tower T1 cat head from depickling; Phase-splitting in phase splitter S1; Oil reservoir 8 gets into dehydration tower T2 dehydration from dehydration tower T2 cat head; A spot of water and methyl ethyl diketone form azeotrope 9 and return in the phase splitter from dehydration tower T2 cat head, and the methyl ethyl diketone 10 after the dehydration is by the bottom extraction of dehydration tower T2 tower still.Methyl ethyl diketone 10 after the dehydration tower T2 dehydration gets into from treating tower T3 middle and lower part; Rectification under vacuum; From the highly purified methyl ethyl diketone 12 of cat head extraction, in the said high-purity acetylacetone methyl ethyl diketone content more than or equal to 99.5%, generally can reach 99.9% or more than.Said treating tower T3 operation vacuum degree control is at 5～50kPa.
The acetate that salt separator S2 separates out can obtain highly purified acetate sub product behind recrystallization.Said acetate is compounds such as sodium-acetate, Potassium ethanoate, ammonium acetate.
Comparative Examples
Charging; Thick methyl ethyl diketone 1 flow 6ml/h wherein contains acetic acid 4.2%, aceticanhydride 12.5% and high boiling material 2.0%.
99 ℃ of acid anhydride tower T1 tower top temperatures are taken off in depickling, normal pressure, the water layer 7 flow 12ml/h that reflux; Cat head make up water 4 flow 18ml/h, tower still bottom contains hydrochlorate water 2 flow 18ml/h, wherein pH=2.0; Methyl ethyl diketone content 1.6% is directly discharged, and has caused the loss of methyl ethyl diketone product.
104 ℃ of dehydration tower T2 tower top temperatures, normal pressure, treating tower T3 decompression-78kPa, 94 ℃ of tower top temperatures obtain the product methyl ethyl diketone, and purity is 99.5%, wherein contains high boiling material 0.07%, and is moisture 0.01%, contains acetic acid 0.42%.
Embodiment
Tower top temperature and pressure, the treating tower T3 decompression-78kPa of acid anhydride tower T1 and dehydration tower T2 taken off in thick methyl ethyl diketone feed composition and flow, depickling among the embodiment, and 94 ℃ of tower top temperatures are all identical with Comparative Examples.Change the pH value of the saturated acetic acid salt brine solution 4 of reuse, with the temperature of separating out that changes the different acetate of control salt separator S2, make embodiment 1～5, obtain the product methyl ethyl diketone, purity is 99.9%, and the result lists in table 1.
Table 1, the different salt solution pH values of control and temperature continuous production high-purity acetylacetone
Can find out relatively that through embodiment and Comparative Examples the loss that the sour water reuse of acid anhydride tower T1 tower still bottom has prevented methyl ethyl diketone is taken off in depickling among the embodiment, has reduced the discharging of waste water, reclaims acetic acid simultaneously and obtains sub product acetate.Through the adjustment of pH value, and the existence of salt effect, reduced the volatility of acetic acid, help the separation of acetic acid, the oil reservoir acetic acid content obviously reduces in the quantizer, thereby has finally reduced acetic acid content in the product, has improved product quality.Through azeotropic distillation, aceticanhydride takes off complete reaction generation acetic acid among the acid anhydride tower T1 in depickling, in the quantizer oil reservoir, has not contained aceticanhydride fully.High boiling material and water and methyl ethyl diketone all do not form azeotropic, have obtained among the acid anhydride tower T1 partly separating so take off in depickling, and be finally refining through treating tower T3, reaches the high purity index request of expection.
Claims (2)
1. the continuous production method of a high-purity acetylacetone; Comprise that thick methyl ethyl diketone solution takes off acid anhydride tower (T1) depickling through depickling and takes off acid anhydride, dehydration tower (T2) dehydration and treating tower (T3) are refining, it is characterized in that: said thick methyl ethyl diketone solution takes off acid anhydride tower (T1) middle part from depickling and gets into; Taking off acid anhydride tower (T1) cat head adding temperature from depickling is 0～25 ℃ of saturated acetic acid salt brine solution (4); The interior aceticanhydride of acid anhydride tower (T1) is taken off in said depickling and the water complete reaction generates acetic acid, contains hydrochlorate water (2) and discharges from tower still bottom, regulates pH value to 5～8 through neutralization tank (R1); After salt separator (S2) the recrystallization separating acetic acid salt, saturated acetic acid salt brine solution (4) reuse is taken off the water inlet of acid anhydride tower (T1) cat head do depickling; Methyl ethyl diketone and water form azeotrope (6) from the cat head extraction, and after the interior phase-splitting of phase splitter (S1), oil reservoir (8) gets into dehydration tower (T2) dehydration and get into treating tower (T3) refining from dehydration tower (T2) cat head successively.
2. according to the continuous production method of the said a kind of high-purity acetylacetone of claim 1, it is characterized in that: said saturated acetic acid salt brine solution (4) is saturated acetic acid sodium, Potassium ethanoate or ammonium acetate aqueous solution.
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| CN2008102034045A CN101417933B (en) | 2008-11-26 | 2008-11-26 | Continuous production method of high-purity acetylacetone |
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| CN2008102034045A CN101417933B (en) | 2008-11-26 | 2008-11-26 | Continuous production method of high-purity acetylacetone |
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| CN101417933B true CN101417933B (en) | 2012-04-18 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838142A (en) * | 1957-10-10 | 1960-06-22 | Courtaulds Ltd | Improvements in and relating to the production of acetyl acetone |
| CN101306989A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Process for separating acetic acid from water by salt-containing extracting, rectifying and separating |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838142A (en) * | 1957-10-10 | 1960-06-22 | Courtaulds Ltd | Improvements in and relating to the production of acetyl acetone |
| CN101306989A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Process for separating acetic acid from water by salt-containing extracting, rectifying and separating |
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Granted publication date: 20120418 Termination date: 20171126 |