Method for purifying (meth)acrylic acid

Abstract

A method for purifying a crude (meth)acrylic acid obtained by a vapor phase catalytic oxidation method, characterized in that the crude (meth)acrylic acid having most parts of water and acetic acid removed therefrom, is fed to and distilled in a first distillation column of a purification system comprising first to third three distillation columns, the top fraction from the first distillation column is fed to and distilled in the second distillation column, the resulting top fraction is recovered as a high purity (meth)acrylic acid product, the bottoms from the first and second distillation columns are fed to and distilled in the third distillation column, and the resulting top fraction is fed to the first distillation column.

Description

BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a method for purifying (meth)acrylic acid, particularly to a method for purifying a crude (meth)acrylic acid obtained by vapor phase catalytic oxidation, by distillation to obtain highly pure (meth)acrylic acid which is useful for the production of a highly water absorptive resin and for the production of a (meth)acrylic ester. In this specification, (meth)acrylic acid means acrylic acid or methacrylic acid. [0003] 2. Discussion of Background [0004] a. As a method for producing (meth)acrylic acid, a method of hydrolyzing the corresponding nitrile compound may, for example, be mentioned. However, at present, a vapor phase catalytic oxidation method of the corresponding hydrocarbon such as propylene or isobutylene, is mainly employed. Recently, a study has been made also on a vapor phase catalytic oxidation method using an inexpensive corresponding alkane as the starting material inste...

AI Technical Summary

Benefits of technology

[0233] a. According to the present invention, from crude (meth)acrylic acid, both (meth)acrylic acid of the purity for an ester and (meth)acrylic acid of the purity for a highly water absorptive resin can efficiently be produced. In the present invention, only (meth)acrylic acid directed to the purity for a highly water absorptive resin, is treated by an aldehyde-removing agent, whereby the removing agent can be saved, and as the amount of the liquid to be treated is small, the removal operation is easy. Further, also in a case where only (meth)acrylic acid for a highly water absorptive resin is to be produced, the amount of the liquid to be treated in the second distillation column is small as compared with in the first distillation column, whereby the merit of the present invention to supply an aldehyde-removing agent to the second distillation column will continuously be maintained. Further, in the present invention, the bottoms from the first distillation column and the second distillation column are not discharged out of the system as they are, but they are distilled in the third distillation column, so that acrylic acid in these bottoms is recovered as much as possible and recycled to the first distillation column, whereby the obtainable ratio of the purified acrylic acid from the supplied crude acrylic acid can be maintained at a high level.

[0234] b. According to the method for producing (meth)acrylic acid according to the present invention, even if impurities such as maleic acid and / or citraconic acid are contained in a relatively large amount in the crude (meth)acrylic acid obtained by vapor phase catalytic oxidation, it becomes possible to produce high purity (meth)acrylic acid having an extremely small content of impurities constantly for a long period of time by suppressing formation of sludge during the purification by continuous distillation, and thus, its industrial value is significant.

[0235] c. Impurities contained in the crude (meth)acrylic acid obtained by vapor phase catalytic oxidation can easily be removed by the distillation method. By suppressing polymerization of a (meth)acrylic acid monomer during the distillation, constant operation for a long period of time can be carried out, and thus, its industrial value is significant.

[0236] d. According to a thin film evaporator according to the present invention, it is possible to suppress formation of a polymer in the interior of the evaporator, and even if a polymer or precipitate is formed, it is possible to prevent deposition thereof, whereby constant operation for a long period of time of the thin film evaporator is possible. It is thereby possible to stabilize the production. Thus, the thin film evaporator according to the present invention can be said to be an instrument very useful for industrial purpose.

[0237] e. By using, as the starting material, acrylic acid having the specific impurities controlled to the specific concentration according to the present invention, it is possible to avoid conventional problems such as clogging of apparatus such as pipings by a polymer, deterioration of unit consumption of the starting materials, deterioration of the quality of the product, etc., and at the same time, it is possible to provide an industrially advantageous method for producing an acrylic ester, which is excellent also in the economical efficiency.

[0238] f. According to the present invention, it is possible to produce high purity (meth)acrylic acid purified to a high level by efficiently and simply removing aldehydes contained in (meth)acrylic acid, and at the same time, it is possible to recycle the waste liquid other than the high purity (meth)acrylic acid fraction, which forms by such treatment of aldehydes without any special treatment, to a process for producing a (meth)acrylic ester, in the entire amount as it is, and to effectively use it, whereby the following excellent effects can be obtained.

[0239] {circumflex over (1)} It is possible to avoid conventional problems such as a polymerization trouble in the purification step for (meth)acrylic acid caused by an aldehyde-removing agent, or contamination or coloration of the product, etc. which used to be caused by recycling of the waste liquid to the process for producing (meth)acrylic acid.

[0240] {circumflex over (2)} Treatment of the waste liquid which used to be required, will be unnecessary.

[0241] {circumflex over (3)} Useful components such as (meth)acrylic acid and a dimer of (meth)acrylic acid which used to be disposed, can be recovered and reused, whereby unit consumption of the starting material will be improved.

[0242] {circumflex over (4)} (Meth)acrylic acid in the waste liquid can be recovered without being lost, whereby it is possible to increase the concentration of (meth)acrylic acid in the bottoms in the distillation column for purification to separate high purity (meth)acrylic acid and to avoid a trouble such as clogging in the distillation system.

[0243] {circumflex over (5)} It is possible to effectively use a polymerization inhibitor in the waste liquid, which used to be disposed, whereby the amount of the polymerization inhibitor to be used in the process for producing a (meth)acrylic ester, can be reduced.

Problems solved by technology

Namely, if crude acrylic acid is used as a starting material for a polymer of acrylic acid without removing impurities, there will be a problem such as a delay in the reaction during the polymerization reaction, a decrease in the polymerization degree or coloring of the polymerized product.

However, it is not easy to remove by distillation impurities in crude acrylic acid obtained by vapor phase catalytic oxidation.

However, such a method is primarily intended to remove an aldehyde in the crude acrylic acid, whereby removal of maleic acid and / or maleic anhydride (these will be together hereinafter referred to as “maleic acids”) tends to be inadequate.

This method is effective for removal of maleic acids, but has a problem such that the added ammonia will be distilled from the top, such being not suitable for the production of highly pure acrylic acid.

Further, this application discloses batch treatment only, and discloses nothing about a method for continuously obtaining highly pure acrylic acid on a commercial scale.

Accordingly, it has been considered that with these techniques, it is not easy to continuously produce high purity acrylic acid by sufficiently removing impurities containing maleic acids from the crude acrylic acid.

However, in order to reduce the concentration of maleic acids in the starting material crude acrylic acid, it is necessary to remove maleic acids in the step of obtaining the crude acrylic acid, and such does not provide a substantial solution to the problem.

c. On the other hand, as a purification method for (meth)acrylic acid obtained by vapor phase catalytic oxidation of propylene or isobutylene, a distillation method is common, but (meth)acrylic acid is extremely susceptible to polymerization, and its handling was problematic.

However, if acrylic acid containing high boiling point impurities, is used as the starting material, there have been problems such that undesirable polymerization reactions or side reactions are likely to take place, thus leading to clogging of apparatus such as pipes by polymerized products, deterioration of unit consumption of main materials such as acrylic acid and an alcohol, and a decrease in the quality of the product.

The reason is that if an impurity, particularly furfural, is contained in the above-mentioned (meth)acrylic acid obtained by vapor phase catalytic oxidation, there will be a problem such as delay in the reaction, deterioration of the polymerization degree, coloration of the polymerized product, etc. at the time of the polymerization reaction for a water absorptive resin.

Crystallization usually requires a large initial investment, and from the economical viewpoint, a method by distillation is employed in many cases, but it is difficult to remove the above impurity, particularly furfural, by usual distillation.

This method is effective from the viewpoint of removal of the above-mentioned impurity, but has had a problem that it causes polymerization of (meth)acrylic acid during the rectification.

Formation of a polymer causes clogging in the distillation column, whereby the performance of the distillation column decreases, or it will be required to stop the operation.

In an operation for a short time, the effect of this method is confirmed, but in a continuous operation for a long time for a usual industrial operation, the effect has been still inadequate.

i. Further, in the purification of (meth)acrylic acid or its ester by distillation, if it is attempted to recover (meth)acrylic acid or its ester by means of a thin film evaporator from a heavy component containing (meth)acrylic acid or its ester discharged from the bottom of the distillation column, there is a problem such that clogging frequently occurs at a liquid-withdrawal tube or at an outlet portion of a liquid collection part of the thin film evaporator.

Accordingly, at such a portion, the liquid flowing down, has the majority of low boiling point components removed and thus essentially has bad fluidity, and besides, no stirring by stirring vanes takes place, whereby the liquid in contact with the inner wall surface tends to be hardly renewed by a fresh liquid.

Consequently, the retention time of the liquid in contact with the inner wall surface tends to be abnormally long, and (meth)acrylic acid or its ester remaining in the liquid, tends to gradually polymerize to change the liquid to be heavy, whereby the fluidity of this liquid further decreases, and a polymer tends to accumulate on the inner wall surface.

The accumulated polymer and precipitates not only hinder the flow of the liquid, but also clog the outlet portion of the liquid collection portion or the following liquid withdrawal tube, if they are peeled off from the inner wall surface.

k. Further, it is not desirable to obtain high purity acrylic acid from the top of the above-mentioned distillation column for purification while subjecting the bottom fraction of the distillation column for purification to thermal decomposition treatment to recover it for an acrylic acid purification step, because as the thermal decomposition treatment is carried out at a high temperature, many side-reactions or decomposition reactions will take place, whereby formation of undesirable by-products which cause to accelerate polymerization of acrylic acid, to contaminate an acrylic acid product or to present coloration to the product, or regeneration of aldehydes, takes place, and such compounds are likely to be recycled to the purification step of acrylic acid.

However, if the concentration of acrylic acid in the bottom fraction is lowered, the viscosity of the bottom fraction will increase, whereby precipitation of a polymer, etc. tends to readily take place, thus leading to a trouble of clogging at the withdrawal pipe.

Accordingly, the lowering of the acrylic acid concentration is limited, whereby it has been impossible to avoid a loss of acrylic acid in an amount corresponding to the one disposed as contained in the bottom fraction.

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