METHOD OF CONTINUOUS RECOVERY OF (METH)ACRYLIC ACID AND APPARATUS FOR THE METHOD

Abstract

The present invention relates to a continuous recovery method of (meth)acrylic acid and an apparatus for use in the recovery method. A continuous recovery method of (meth)acrylic acid according to the present invention can ensure a high recovery rate of (meth)acrylic acid through a solvent recovering process in addition to enabling the stable recovery of (meth)acrylic acid and the operation of continuous processes.

Claims

1-8. (canceled)

9. An apparatus for continuous recovery of (meth)acrylic acid, comprising a acrylic acid absorption tower equipped with a mixed gas inlet to which a mixed gas comprising (meth)acrylic acid, organic by-products, and water vapor, produced by a synthesis reaction of (meth)acrylic acid, is fed, in which a low concentration (meth)acrylic acid aqueous solution outlet, at which a low concentration (meth)acrylic acid aqueous solution obtained by contact of the mixed gas with water is discharged, is installed at any one point corresponding to 30 to 70% from the highest part, and a high concentration (meth)acrylic acid aqueous solution outlet is installed at the lowest stage; a (meth)acrylic acid extraction tower equipped with an aqueous solution inlet that is connected with the low concentration (meth)acrylic acid aqueous solution outlet of the absorption tower through an aqueous solution transfer line, an extract outlet at which a (meth)acrylic acid extract obtained by contact of the introduced (meth)acrylic acid aqueous solution with an extraction solvent is discharged, and a raffinate outlet at which the raffinate is discharged; a solvent separation tower equipped with an extract inlet that is connected with the extract outlet of the extraction tower through an extract transfer line, an upper stage outlet at which the solvent obtained by heating the introduced extract is discharged, and a lower stage outlet at which the feed excluding the solvent recovered from the extract is discharged; and a water separation tower equipped with a feed inlet that is connected with the lower stage outlet of the solvent separation tower through a transfer line, and is connected with the high concentration (meth)acrylic acid aqueous solution outlet of the (meth)acrylic acid absorption tower through a transfer line, and a (meth)acrylic acid outlet at which acrylic acid obtained by the distillation of the introduced feed is discharged, wherein the apparatus is operated such that a weight ratio of the extraction solvent to water in the low concentration (meth)acrylic acid aqueous solution fed to the (meth)acrylic acid extraction tower is 2.7 or more, wherein the low concentration (meth)acrylic acid aqueous solution has 50 wt % or less of (meth)acrylic acid, and the high concentration (meth)acrylic acid aqueous solution has 50 wt % or more of (meth)acrylic acid.

10. The apparatus according to claim 9, wherein the feed inlet that is connected with the lower stage outlet of the solvent separation tower through a transfer line, and is connected with the high concentration (meth)acrylic acid aqueous solution outlet of the (meth)acrylic acid absorption tower through a transfer line, is positioned at any one stage corresponding to 25 to 75% from the highest stage, based on the total number of stages of the water separation tower.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0106] FIG. 1 schematically shows the method and apparatus for continuous recovery of (meth)acrylic acid according to one embodiment of the present invention.

[0107] FIG. 2 schematically shows the method and apparatus for continuous recovery of (meth)acrylic acid according to another embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0108] Hereinafter, preferable examples are presented to aid in understanding of the invention. However, these examples are only to illustrate the invention, and the scope of the invention is not limited thereto.

EXAMPLES

[0109] Using the apparatus with the construction of FIG. 1, the process for continuously recovering acrylic acid was conducted as follows.

[0110] (Extraction Process)

[0111] Among the acrylic acid aqueous solution of a low concentration (103) discharged to the side part of the absorption tower (100) (composition: acrylic acid 21.06 wt %, acetic acid 4.15 wt %, and water 74.79 wt %), acrylic acid was extracted using toluene introduced through an extraction solvent transfer line (302) according to a liquid-liquid contact method. The extract (203) was discharged to the upper part of the extraction tower (200), and the raffinate was discharged to the lower part of the extraction tower and it may be recycled to the highest part of the acrylic acid absorption tower (100) through the raffinate transfer line (201).

[0112] As the acrylic acid extraction tower (200), a Karr type of reciprocating plate column having a total of 56 stages with an inner diameter of 22 mm was used. The acrylic acid aqueous solution of a low concentration (103) discharged to the side part of the absorption tower (100) was introduced through the highest stage, i.e., the first stage of the extraction tower (200), at a flow rate of 23.8 g/min. Further, a part of the reflux flow including toluene obtained as an organic layer in the upper discharge liquid of the water separation tower (300) was used as the extraction solvent (composition: acrylic acid at about 0.27 wt %, acetic acid at about 0.48 wt %, the balance being toluene) of the extraction tower (200), wherein the extraction solvent was introduced through the lowest stage, i.e., the 56th stage of the extraction tower (200), at a flow rate of 59.44 g/min.

[0113] After stable operation was conducted, under a steady state, an acrylic acid extract (composition: toluene at about 91.32 wt %, acrylic acid at about 7.42 wt %, water at about 0.62 wt %, and acetic acid at about 0.64 wt %) was obtained at the upper part of the extraction tower (200) at a flow rate of 64.59 g/min, and the remaining raffinate (composition: water at about 93.36 wt %, acrylic acid at about 2.03 wt %, and acetic acid at about 4.61 wt %) was discharged to the lower part of the extraction tower (200).

[0114] As a result of operating the acrylic acid extraction tower (200), the water removal rate for the low concentration acrylic acid aqueous solution discharged from the side part of the acrylic acid absorption tower was 97.8%, and the acrylic acid extraction rate was 92.7%. Here, the ratio of the extraction solvent introduced into the extraction tower/water was 3.3.

[0115] (Solvent Recovery Process)

[0116] As the solvent recovery tower (250), a dual flow tray column having a total of 15 stages with an inner diameter of 20 mm was used, and the operation pressure was maintained at 100 torr. The upper extract (203) of the extraction tower (200) of the extraction process was introduced into the lowest stage of the solvent recovery tower (250) at 0.98 g/min. Further, among the upper flow of the solvent recovery tower (250), a reflux flow (252) was introduced into the highest stage, i.e. the first stage of the solvent recovery tower (250), at a flow rate of 4.41 g/min. Heat was supplied through the reboiler of the lower stage of the solvent recovery tower (250) such that a flow (251) excluding the reflux among the upper flow of the solvent recovery tower became 50 mass %, based on the extract introduced into the solvent recovery tower. After stable operation was conducted for about 4 hours, under a steady state, the flow (251) excluding the reflux among the upper flow of the solvent recovery tower was discharged at a flow rate of 0.49 g/min, and the lower flow (253) of the solvent recovery tower was discharged at a flow rate of 0.49 g/min. Here, the upper temperature and the lower temperature of the solvent recovery tower (250) were maintained at 49 C. and 62 C., respectively. Among the upper flow of the solvent recovery tower, the flow (251) excluding the reflux and the reflux flow (252) exhibited the compositions of 0.32 wt % of acrylic acid, 0.51 wt % of acetic acid, and 99.17 wt % of toluene, and the lower flow of the solvent recovery tower (250) exhibited the composition of 19.765 wt % of acrylic acid, 0.49 wt % of acetic acid, and 79.75 wt % of toluene. The acrylic acid recovery rate of the solvent recovery tower (250) was 98.4%, and the toluene stripping ratio was 55.6%.

[0117] (Distillation Process)

[0118] As the water separation tower (300), a sieve tray (including a down corner) column having a total of 39 stages with an inner diameter of 70 mm was used, and the operation pressure was maintained at 110 torr. The lower flow (253) of the solvent recovery tower (250) of the solvent recovery process was introduced into the 17th stage from the upper part of the water separation tower (300) at a flow rate of 17.3 g/min, and a lower discharge liquid (102) of the acrylic acid absorption tower (100) was introduced into the 19th stage from the upper part of the water separation tower (300) at a flow rate of 55.1 g/min. Further, the flow (251) excluding the reflux flow among the upper flow of the solvent recovery tower (250) was introduced into the phase separation tank (350) at a flow rate of 22.6 g/min, and a part of the toluene reflux flow separated from the phase separation tank (350) was introduced into the highest stage, i.e., the first stage of the water separation tower (300), at a flow rate of 54.3 g/min. Here, the mass ratio of the toluene in the reflux introduced into the upper part of the water separation tower and the toluene in the flow (251) excluding the reflux among the upper flow of the solvent recovery tower introduced into the feed introduction stage of the water separation tower was 3.7:1.

[0119] Heat was supplied through the reboiler of the lower stage of the water separation tower (300) to control such that the temperature of the feed introduction stage became 68.6 C., and the temperature of the 21th stage at the lower part of the feed introduction stage became 80 C. or more. After stable operation was conducted for about 6 hours, under a steady state, the distillate consisting of an organic phase and an aqueous phase was discharged at 37.20 g/min and 11.80 g/min, respectively, and acrylic acid flow to the lower part of the water separation tower (300) was 46.00 g/min. Here, under a steady state, the upper temperature of the water separation tower (300) was maintained at 40.9 C. and the lower temperature was maintained at 94.3 C. An organic phase distillate (304) exhibited a composition of 0.23 wt % of acrylic acid, 0.48 wt % of acetic acid, and 99.29 wt % of toluene, and the lower flow (303) of the water separation tower had a composition of 98.58 wt % of acrylic acid, 2100 ppm of acetic acid, and 1.42 wt % of heavies and polymerization inhibitor. The acrylic acid recovery rate of the water separation tower (300) was 99.8%.

Comparative Example

[0120] A process for continuous recovery of acrylic acid was conducted by the same method as in the example, except that a distillation process described below was progressed immediately after the extraction process, without the solvent recovery process.

[0121] (Distillation Process)

[0122] As the water separation tower (300), a sieve tray (including a down corner) column having a total of 39 stages with an inner diameter of 70 mm was used, and the operation pressure was maintained at 110 torr. The lower discharge liquid (102) of the acrylic acid absorption tower (100) and the upper extract (203) of the extraction tower (200) of Example 1 were introduced into the 20th stage from the upper part of the water separation tower (300) at 44.99 g/min and 36.4 g/min, respectively. Further, a part of the toluene reflux flow separated from the phase separation tank (350) was introduced into the highest stage, i.e., the first stage of the water separation tower (300), at a flow rate 22.22 g/min. Here, the mass ratio of the toluene in the reflux introduced into the upper part of the water separation tower and the toluene in the upper extract (203) of the extraction tower introduced into the feed introduction stage of the water separation tower was 0.66:1.

[0123] Heat was supplied through the reboiler of the lower stage of the water separation tower (300) to control such that the temperature of the feed introduction stage became 64.6 C., and the temperature of the 15th stage did not exceed about 46 C. After stable operation was conducted for about 6 hours, under a steady state, the distillate consisting of an organic phase and an aqueous phase was discharged to the upper part of the water separation tower (300) at 33.86 g/min and 8.50 g/min, respectively, and acrylic acid flow to the lower part of the water separation tower (300) was 39.03 g/min. Here, under a steady state, the upper temperature of the water separation tower (300) was maintained at 42.4 C., and the lower temperature was maintained at 92.3 C. The organic phase distillate (304) exhibited a composition of 0.73 wt % of acrylic acid, 0.76 wt % of acetic acid, and 98.51 wt % of toluene, and the lower flow (303) of the water separation tower exhibited a composition of 98.15 wt % of acrylic acid, 3000 ppm of acetic acid, and 1.85 wt % of acrylic acid polymer and polymerization inhibitor. The acrylic acid recovery rate of the water separation tower (300) was 98.7%.

REFERENCE NUMERALS

[0124] 1: (meth)acrylic acid-containing mixed gas [0125] 100: (meth)acrylic acid absorption tower [0126] 102: high concentration (meth)acrylic acid aqueous solution transfer line [0127] 103: low concentration (meth)acrylic acid aqueous solution transfer line [0128] 150: acetic acid absorption tower [0129] 200: (meth)acrylic acid extraction tower [0130] 201: raffinate transfer line [0131] 203: extract transfer line [0132] 250: solvent recovery tower [0133] 251: flow excluding the reflux among the upper flow of the solvent recovery tower [0134] 252: reflux flow among the upper flow of the solvent recovery tower [0135] 253: lower flow of the solvent recovery tower [0136] 300: water separation tower [0137] 301: azeotropic solvent transfer line [0138] 302: extraction solvent transfer line [0139] 303: lower flow of the water separation tower [0140] 304: upper flow of the water separation tower [0141] 305: absorption solvent (water) transfer line [0142] 350: phase separation tank [0143] 400: heavies separation tower