Refining device

Abstract

The present invention relates to a compound purification device having a crystallizer in which N crystallization tanks are connected in series, and a cleaning column for forcibly transporting crystals, wherein the cleaning column has a line for delivering products and a line for returning a mother liquid to an N-th crystallization tank, and the crystallizer has: a line for supplying slurry from the N-th crystallization tank to the cleaning column; a line for feeding slurry from a downstream crystallization tank to an one upstream crystallization tank via a solid-liquid separator; a line for returning, to the original crystallization tank, the mother liquid in which the crystal has been removed in the solid-liquid separator; and a line including, as a line for feeding the mother liquid from the upstream crystallization tank to each of the first to N-1th crystallization tanks, at least one among a line for directly feeding the mother liquid from one upstream crystallization tank and a line for feeding the mother liquid from one upstream crystallization tank via the solid-liquid separator, and further has a line for feeding the mother liquid to the outside of the purification device. The present invention can obtain a compound with high purity and at high yield and low cost.

Description

[Technical field]

[0001] The present invention relates to a purification apparatus that can be suitably used for purifying industrially produced compounds. [Background technology]

[0002] Currently, various kinds of chemical compounds are widely produced and used industrially. For industrially produced chemical compounds, high quality products with reduced impurities are required depending on the application, and various improved purification technologies for that purpose are being investigated.

[0003] As a purification technique for a compound, a purification method has been disclosed in which a cooling type crystallization tank having a clarification section at the top and a vertical purification tower having a clarification section at the top and a heater at the bottom are connected in series, the crystals generated in the crystallization tank are sent to the crystallization tank connected to the purification tower in sequence, the crystals sent from the crystallization tank are allowed to settle by gravity in the purification tower, and a part of the crystals heated and melted by the heater at the bottom of the purification tower is raised as a reflux liquid and contacted with the crystals settling by gravity, and the crystals are washed (see Patent Documents 1 and 2). In addition, a purification method for acrylic acid has been disclosed in which a suspension containing crystals of acrylic acid generated in a crystallization tank and a crude acrylic acid melt is sent to a washing column, the crystals are forcibly transported in the washing column, and the melt obtained by melting the crystals at the bottom of the column is used as a washing liquid to wash the crystals in the washing column (see Patent Document 3). In addition, a purification method has been disclosed in which the purity of acrylic acid is increased by repeating suspension crystallization or layer crystallization multiple times from an aqueous solution containing acrylic acid (see Patent Document 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 59-66305 [Patent Document 2] Japanese Patent Application Publication No. 6-91103 [Patent Document 3] Special Publication No. 2003-530376 [Patent Document 4] Special Publication No. 2010-501526 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, various purification techniques have been disclosed, but in industrial production, it is required to produce high-purity compounds at high yield and low cost. As a result of the inventors' studies, it has become clear that the purification apparatus using the gravity settling type washing column described in Patent Documents 1 and 2 does not provide industrially sufficient purification effect and production amount when purifying organic compounds that generate crystals with relatively fine particle size or when purifying crude compound solutions with low purity. In addition, the purification apparatus described in Patent Document 3 does not provide a high yield in the crystallization process, and the operating cost of the process of treating the crystallization residue increases. In order to obtain a high yield in the crystallization process, it is necessary to increase the purity of the crude compound solution to be provided to the crystallization process, which increases the purification cost of the pre-crystallization process, which is disadvantageous. In addition, in the method of repeating crystallization multiple times described in Patent Document 4, the purity of the crude compound solution to be provided to the crystallization process can be low, but the process includes a process of melting the crystals once and a process of discharging the mother liquor during the crystallization process, which complicates the equipment, and therefore increases the equipment investment and energy consumption, which is disadvantageous. The present invention has been made in consideration of the above-mentioned current situation, and has an object to provide a compound purification apparatus capable of obtaining a high-purity compound in high yield and at low cost. [Means for solving the problem]

[0006] The present inventors have studied purification apparatuses capable of obtaining high-purity compounds at high yields and low cost, and have found that in a purification apparatus having N crystallization tanks or maturation tanks including at least one crystallization tank connected in series, with the most upstream crystallization tank or maturation tank connected to a washing column, at least one of the lines for sending slurry from the crystallization tank or maturation tank to the tank one upstream is a line for sending the slurry via a solid-liquid separation device, and a line for returning the mother liquor from which the crystals have been removed in the solid-liquid separation device to the original tank, and a line for returning the mother liquor from the washing column to at least the Nth tank of the crystallization apparatus, and further, at least one of a line for directly sending the mother liquor from the tank one tank above to each of the 1st to N-1th tanks of the crystallization apparatus and a line for sending the mother liquor from the tank one upstream via a solid-liquid separation device, and a line for sending the mother liquor to the outside of the purification apparatus, can be provided, and thus the present invention has been completed.

[0007] That is, the present invention relates to a compound purification apparatus having a crystallizer having a crystallization section and a washing column for forcibly transporting crystals, the crystallizer having N (N≧2) tanks, which are connected in series with a first tank downstream and an Nth tank upstream, at least the first tank is a crystallization tank equipped with a cooling mechanism, the second and subsequent tanks are crystallization tanks or maturation tanks, at least one tank has a line for supplying a compound-containing purified liquid, the washing column has a line for carrying out a product and a line for returning mother liquor to the crystallizer, and the line for returning mother liquor to the crystallizer is connected to at least the Nth tank, the crystallizer has a line for supplying a slurry from the Nth tank to the washing column, a line for returning mother liquor from the downstream tank, The purification apparatus has a line for sending slurry to the tank one tank upstream, and a line for sending mother liquor from the upstream tank to each of the 1st to N-1th tanks, and at least one of the lines for sending slurry from the N-1 downstream tanks to the tank one tank upstream is a line for sending slurry to the tank one tank upstream via a solid-liquid separation device, and has a line for returning the mother liquor from which crystals have been removed in the solid-liquid separation device to the original tank, and the lines for sending mother liquor from the upstream tank to each of the 1st to N-1th tanks include at least one of a line for directly sending mother liquor from the tank one tank upstream and a line for sending mother liquor from the tank one tank upstream via a solid-liquid separation device, and further has a line for sending mother liquor to the outside of the purification apparatus.

[0008] It is preferable that all of the 1st to (N-1th) tanks included in the crystallization apparatus have a line for sending the slurry to the tank immediately upstream via a solid-liquid separation device, and a line for returning at least a part of the mother liquor discharged from the solid-liquid separation device to the original tank.

[0009] Of the lines for sending the mother liquor from upstream tanks to each of the 1st to N-1th tanks, at least one is preferably a line for sending the mother liquor from the tank one upstream via a solid-liquid separator.

[0010] At least one of the solid-liquid separation devices provided in the line for transporting the slurry from the downstream tank to the upstream tank has one or more additional lines for transporting the mother liquor in addition to a line for returning the mother liquor to the original tank, and it is preferable that the additional lines are connected to a downstream tank and / or to the outside of the purification device relative to the original tank.

[0011] At least one of the 1st to (N-1th) tanks included in the crystallizer preferably has a line for directly transferring the mother liquor from the tank immediately upstream.

[0012] It is preferable that the crystallizer has a line for sending the mother liquor from the first tank to the outside of the purification apparatus via a solid-liquid separator.

[0013] The cooling mechanism is preferably of a type that cools the contents of the vessel outside the vessel.

[0014] The wash column may or may not have a mechanical mechanism for scraping off the crystal bed.

[0015] The compound is preferably (meth)acrylic acid.

[0016] Of the lines in the crystallization apparatus that transfer the slurry from a downstream tank to a tank one tank upstream, at least the line that transfers the slurry from the (N-1)th tank to the (N)th tank is a line that transfers the slurry to the tank one tank upstream via a solid-liquid separation device, and it is preferable that the solid-liquid separation device provided in the line that transfers the slurry from the (N-1)th tank to the (N)th tank is a basket centrifuge or a decanter centrifuge. Effect of the Invention

[0017] The compound purification apparatus of the present invention can obtain a high purity compound in high yield with reduced amount of discharged crystallization residue even when purifying an organic compound that produces crystals with a relatively small particle size or when purifying a crude compound solution with low purity. In addition, the amount of washing liquid in the washing column can be reduced, thereby reducing the operating cost of the apparatus. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Diagram 2] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Diagram 3] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Figure 4] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Diagram 5] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Figure 6] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Figure 7] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. [Figure 8] FIG. 1 is a diagram showing an example of a refining apparatus of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0020] The purification apparatus of the present invention has a crystallizer in which N (N≧2) tanks are connected in series and a washing column for forcibly transporting crystals, and at least the first tank included in the crystallizer is a crystallization tank equipped with a cooling mechanism, and the second and subsequent tanks are crystallization tanks or maturation tanks, and the Nth tank is connected to a washing column, and the slurry is sent from the downstream tank to the tank one upstream in sequence, and the slurry is sent from the Nth tank to the washing column. Furthermore, at least one of the lines for sending the slurry from the downstream tank to the tank one upstream in sequence is a line for sending the slurry to the upstream tank via a solid-liquid separator, and has a line for returning at least a part of the mother liquor discharged from the solid-liquid separator to the original tank. Furthermore, the purification apparatus of the present invention has at least one of a line for directly sending the mother liquor from the tank one upstream and a line for sending the mother liquor from the tank one upstream via a solid-liquid separator for all of the 1st to N-1th tanks included in the crystallization apparatus, and further has a line for sending the mother liquor outside the purification apparatus.

[0021] By connecting multiple crystallization tanks or maturation tanks in series and sending the slurry, which is a suspension of compound crystals and mother liquor, to the tanks one step upstream in sequence, and sending the mother liquor from the upstream tank to the downstream tank while being in countercurrent contact with the crystals, the purity of the crystals and mother liquor can be improved the further upstream. Here, by using as many solid-liquid separators as possible and concentrating the slurry through the solid-liquid separators and sending it to the tank one step upstream, the purity of the crystals and mother liquor can be improved more effectively.

[0022] Therefore, in the purification apparatus of the present invention, the line for sending the mother liquor outside the purification apparatus is preferably a line for sending the mother liquor from the most downstream tank to the outside of the purification apparatus, whereby a smaller amount of low-purity mother liquor (crystallization residue) in which impurities are concentrated can be discharged from the most downstream tank, and a high-purity compound can be obtained in a high yield.

[0023] In the washing column, the purity of the crystals is increased by countercurrently contacting the crystal bed with a part of the liquid obtained by heating and melting the purified crystals, but the amount of this washing liquid can be reduced by supplying high-purity crystals and mother liquor from the Nth tank to the washing column, which reduces the amount of crystals produced in the crystallization tank and the operating costs of the refrigerator.

[0024] When using multiple tanks in this manner and sending the crystals upstream while concentrating the crystals in the slurry to increase the purity of the crystals and mother liquor, lines are required to send the crystal-free mother liquor from the upstream side to the downstream side and from tanks within the purification apparatus to the outside of the purification apparatus (preferably from the most downstream tank to the outside of the purification apparatus) in order to bring the mother liquor into countercurrent contact with the crystals and to adjust the liquid level in each tank.

[0025] Regarding this point, a method is known as a conventional technique in which a crystal settling region is provided at the top of the tank, and the mother liquor not containing crystals (hereinafter sometimes referred to as clear mother liquor) is discharged from there by overflow from the upstream to the downstream tank, and then directly from the most downstream tank to the outside of the purification apparatus. This method has the advantage that no liquid delivery pump is required and the liquid level of each tank can be easily adjusted, but the tank structure becomes complicated because a crystal settling region is required at the top of each tank.

[0026] In particular, when refining a compound that produces fine crystals or a low-purity compound solution, the settling speed of the crystals is slow, so the tank itself needs to be overly large in order to design the settling region. If the crystals are too fine and the settling region is not formed properly, the crystals will be sent downstream, resulting in problems such as a decrease in the purification effect of the device.

[0027] In addition, in the purification apparatus of the present invention, at least one of the lines for sending the slurry from the downstream tank to the tank one step upstream has a line for sending the slurry to the tank one step upstream via a solid-liquid separator. This prevents crystals from being sent to the downstream tank, efficiently increases the purity in the upstream tank, and facilitates purification in the next step (washing column).

[0028] Of the N-1 lines that transfer the slurry from the downstream tank to the tank one upstream, the proportion of lines that transfer the slurry to the tank one upstream via a solid-liquid separator is preferably 60% or more. Most preferably, it is 100%, that is, all of the N-1 lines that transfer the slurry from the downstream tank to the tank one upstream are lines that transfer the slurry to the tank one upstream via a solid-liquid separator. Furthermore, among the lines that transport the slurry from the downstream tank to the tank one level upstream, it is preferable that at least the line that transports the slurry from the (N-1)th tank to the Nth tank is a line that transports the slurry to the tank one level upstream via a solid-liquid separation device.

[0029] Among the tanks included in the above crystallization apparatus, the one having a line for sending the slurry to the immediately upstream tank via a solid-liquid separation device has a line for returning at least a portion of the mother liquor discharged from the solid-liquid separation device to the original tank, and the slurry containing concentrated crystals separated in the solid-liquid separation device is sent to the immediately upstream tank, and at least a portion of the remaining mother liquor is returned to the original tank.

[0030] Furthermore, in the crystallization apparatus, all of the 1st to N-1th tanks have at least one of a line for directly sending the mother liquor from the tank one tank upstream and a line for sending the mother liquor from the tank one tank upstream via a solid-liquid separator. By having these lines, the liquid level in the tanks can be kept constant.

[0031] In the purification apparatus of the present invention, at least one of the 1st to N-1th tanks included in the crystallization apparatus preferably has a line for directly sending the mother liquor from the tank immediately upstream. More preferably, the N-1th tank has a line for directly sending the mother liquor from the tank immediately upstream (the Nth tank). The reason why it is preferable to have a line for directly sending the mother liquor from the Nth tank to the N-1th tank will be described later.

[0032] If the tank included in the crystallizer has a line for sending the mother liquor from the tank one upstream via a solid-liquid separator, the sending of crystals from the tank one upstream to the downstream side can be effectively suppressed by solid-liquid separation, so that even when the purification apparatus is used for purifying a compound whose crystals have a slow settling rate, the purification efficiency of the purification apparatus can be maintained high. Therefore, it is preferable that at least one of the lines for sending the mother liquor from the upstream tank to each of the 1st to N-1th tanks is a line for sending the mother liquor from the tank one upstream via a solid-liquid separator.

[0033] When a line for sending the mother liquor from a tank included in a crystallizer to a tank one tank downstream via a solid-liquid separator is provided, it is preferable to share the solid-liquid separator provided on the line for sending the slurry to the tank one tank upstream from the crystallizer in view of the cost of the purification apparatus itself and the operating cost of the apparatus. By doing so, the number of pieces of equipment such as the solid-liquid separator and the liquid sending pump can be reduced.

[0034] In this case, the apparatus may be configured such that one or more additional lines for sending the mother liquor are provided on a line for sending the slurry to the tank one tank upstream from a solid-liquid separator, and the additional lines are connected to a tank one tank downstream from the original tank. The additional lines may be further branched to be connected to two or more tanks downstream from the original tank in addition to the tank one tank downstream. The additional lines may be connected to the outside of the purification apparatus.

[0035] A crystallization apparatus having such a configuration, i.e., at least one of the solid-liquid separation devices provided in the line for delivering the slurry from the downstream tank to the upstream tank, has one or more additional lines for delivering the mother liquor in addition to the line for returning the mother liquor to the original tank, and the additional lines are connected to the downstream tank and / or to the outside of the purification apparatus relative to the original tank, is one of the preferred embodiments of the purification apparatus of the present invention.

[0036] Of the solid-liquid separation devices provided in the line for transporting the slurry from the downstream tank to the upstream tank, the proportion of those having such an additional line is preferably 30% or more, more preferably 60% or more, and even more preferably 100%.

[0037] The solid-liquid separation device may be a commonly used device such as a basket centrifuge, a decanter centrifuge, a liquid cyclone, a filter, etc. An example of a basket centrifuge is the Escher-Wyss pusher centrifuge manufactured by Tsukishima Kikai Co., Ltd., and an example of a decanter centrifuge is the Bird decanter centrifuge manufactured by Tsukishima Kikai Co., Ltd., and a screw decanter centrifuge manufactured by IHI Corporation.

[0038] When a basket centrifuge is used, the crystal concentration in the cake after solid-liquid separation is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.When a decanter centrifuge is used, the crystal concentration after concentration is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.

[0039] When using a liquid cyclone, the crystal concentration in the concentrated slurry is preferably 25% or more, more preferably 30% or more, and more preferably 35% or more. If the slurry concentration is too high, the fluidity decreases and the risk of pipe clogging increases, so the concentrated slurry concentration is preferably 55% or less, more preferably 50% or less, and even more preferably 45% or less.

[0040] When a basket centrifuge or decanter centrifuge is used as a solid-liquid separation device, the initial investment and operating costs are high, but the efficiency of concentrating the slurry (crystals) is high, which has the advantage of improving the purification efficiency of the compounds. On the other hand, when a liquid cyclone is used, the efficiency of concentrating the slurry (crystals) is low, and many tanks must be installed in the crystallization device to obtain a sufficient purification effect, but the initial investment and operating costs are reduced, and there are no problems caused by the rotating machine.

[0041] As described above, in the crystallization apparatus, among the lines for transferring the slurry from a downstream tank to the tank one tank upstream, at least the line for transferring the slurry from the (N-1)th tank to the Nth tank is preferably a line for transferring the slurry to the tank one tank upstream via a solid-liquid separation device, and in this case, the solid-liquid separation device provided on the line for transferring the slurry from the (N-1)th tank to the Nth tank is preferably a basket type centrifuge or a decanter type centrifuge.

[0042] The crystallization apparatus includes a plurality of crystallization tanks or maturation tanks including at least one crystallization tank. The total number of crystallization tanks and maturation tanks is not particularly limited, but from the viewpoint of sufficiently improving the purity of the crystals and mother liquor, it is preferable that the number is 2 or more when a basket type centrifuge or a decanter type centrifuge is used as a solid-liquid separation apparatus, and 3 or more in other cases. In addition, the effect of improving the purity of the crystals and mother liquor increases as the number of tanks increases, but if there are too many tanks, the equipment investment increases and the power consumption of pumps, agitators, etc. associated with the tanks also increases, which is disadvantageous. Therefore, the total number of crystallization tanks and maturation tanks is preferably 6 or less regardless of the type of solid-liquid separation apparatus. More preferably, it is 5 or less.

[0043] As long as the crystallizer includes at least one crystallization tank, the other tanks may be either crystallization tanks or aging tanks, but the number of aging tanks included in the crystallizer is preferably 0 to 2, and more preferably 0 to 1.

[0044] The tanks included in the crystallizer preferably have a structure capable of forming a clear mother liquor layer at the top, and when any of the 1st to N-1th tanks included in the crystallizer has a line for directly transferring the mother liquor from the tank one upstream, the line is preferably a line for directly transferring the clear mother liquor layer at the top of the tank one upstream by overflow. In addition, one of the preferred embodiments of the purification apparatus of the present invention is that the line for transferring the mother liquor to the outside of the purification apparatus is a line for transferring the mother liquor to the outside of the purification apparatus by overflow.

[0045] As described above, the purification apparatus of the present invention preferably has a line for sending the mother liquor from the most downstream first tank included in the crystallization apparatus to the outside of the purification apparatus. In one preferred embodiment of the purification apparatus of the present invention, the line is a line for sending the clear mother liquor layer at the top of the first tank included in the crystallization apparatus to the outside of the purification apparatus by overflow.

[0046] In the case where the tank included in the crystallization apparatus does not form a clear layer of mother liquor at the top, a solid-liquid separation device can be installed, and the mother liquor and crystals can be separated from the slurry taken out of the tank by the solid-liquid separation device, and the mother liquor can be sent to one or more downstream tanks. The mother liquor separated by the solid-liquid separation device can be discharged outside the purification apparatus, and a preferred embodiment of the purification apparatus of the present invention is to have a line that sends the mother liquor from the first tank included in the crystallization apparatus to the outside of the purification apparatus via the solid-liquid separation device.

[0047] Of the 1st to N-1th tanks included in the crystallizer, preferably 30% or more, more preferably 60% or more, and most preferably all of the N-1th tanks are structured to send the mother liquor to the tank one downstream (or two or more downstream tanks in addition) via a solid-liquid separator and / or discharge it outside the crystallizer. This makes it possible to reduce the size of the tanks, thereby reducing the investment amount and construction area. As described above, in this case, it is preferable to share the solid-liquid separator with the solid-liquid separator installed in the line that sends the slurry to the tank one upstream from the viewpoint of cost.

[0048] However, since the Nth tank preferably has a larger capacity than the downstream tanks in order to hold / age the slurry to be sent to the washing column, and the purity of the slurry is improved and the crystals tend to grow larger than in the downstream tanks, it is relatively easy to design the crystal settling region in the upper part of the tank, i.e., the clear mother liquor layer. Therefore, it is preferable that the Nth tank has a structure in which the mother liquor is sent directly to the downstream tank by overflow.

[0049] The crystallization tank included in the crystallization apparatus of the present invention is not particularly limited as long as it is equipped with a cooling mechanism and can cool a solution of a compound to precipitate crystals and generate a slurry containing the crystals and the mother liquor. It can be broadly classified into a type in which a cooling jacket is attached to the tank itself and the inside of the tank is directly cooled to generate crystals, and a type in which the cooling mechanism is separate from the tank and connected by piping to circulate the cooling / crystallization.

[0050] Although the method in which the tank itself is equipped with a cooling jacket has the advantage of requiring fewer pieces of equipment, the tank itself needs to be made larger in order to increase the heat transfer area.When high production capacity is required, the tank size becomes excessively large, which is a disadvantage in terms of initial investment and site area.

[0051] Therefore, when the size of the tank itself is limited or when purifying a compound that requires high production capacity, a system in which the contents of the tank are cooled outside the tank is preferable. In this way, if the tank and the cooling mechanism are connected by piping, and part of the solution of the compound in the tank (or the slurry containing crystals) is sent to the cooling mechanism to generate crystals in the cooling mechanism, and the slurry containing the generated crystals is returned to the tank, the heat transfer area can be easily increased by increasing the number of cooling mechanisms, and the crystallization tank can be easily scaled up.

[0052] In this case, the cooling mechanism is not particularly limited as long as it can cool the compound solution and precipitate crystals. However, it is preferable to use a shell-and-tube heat exchanger, a spiral heat exchanger, or the like that can ensure a large heat transfer area, a cooling disk crystallizer that performs crystallization while scraping the cooling surface, or a scraping type cooling crystallizer.

[0053] The cooling disk type crystallizer may be any device that cools a solution of a compound to precipitate crystals and scrapes off the precipitated crystals, but it may be a device that is composed of a tube and multiple cooling plates that divide the tube, in which crystals are formed on the wall surfaces of the cooling plates and in which agitating blades with wipers are rotated inside the tube to scrape off the crystals.

[0054] The scraping-type cooling crystallizer may be any device that cools a solution of a compound to precipitate crystals and scrapes off the precipitated crystals, but it may be a device that is composed of a double-walled tube in which a refrigerant is passed through the outer tube and a solution of the compound in a tank (or a slurry containing the crystals) is passed through the inner tube to form crystals on the wall of the inner tube, and a shaft with a scraping blade is rotated inside the inner tube to scrape off the crystals.

[0055] The crystallization apparatus of the present invention may or may not have an aging tank, but it is preferable that it has an aging tank. In the present invention, the aging tank is a tank that does not have a cooling mechanism for precipitating crystals, and grows crystals of a compound by holding the crystals of the compound for a certain period of time. By growing the crystals to be as uniform as possible and then sending the crystals to the washing column, impurities can be efficiently removed in the washing column, and a compound with higher purity can be obtained in a high yield. Therefore, it is preferable that the tank that sends the liquid to the washing column, i.e., the Nth tank, is an aging tank.

[0056] The aging tank is not particularly limited as long as it can hold the crystals of the compound in a suspended state in the tank. By holding the crystals for a certain period of time, fine crystals melt due to Ostwald ripening, and larger crystals grow further, narrowing the crystal size distribution and further improving the purification efficiency in the washing column. In addition, even if the crystals are held in a crystallization tank for a certain period of time, the same effect as that of the aging tank can be expected.

[0057] A slurry containing crystals of a compound is sent from the Nth tank of the crystallizer to the washing column included in the purification apparatus of the present invention, and the crystals are washed, and high-purity crystals of the compound are obtained as a product. In a preferred embodiment of the washing column of the present invention, when the specific gravity of the crystals is greater than that of the mother liquor, the crystals move downward in the column to form a crystal bed. Then, at the bottom of the column, a portion of the crystals is withdrawn from the crystal bed while being suspended in a circulating liquid (a washing liquid circulating in the washing column) and melted by heating, and a portion of the circulating liquid containing the obtained melt is withdrawn as a product. A portion of the remaining circulating liquid (a washing liquid) is brought into countercurrent contact with the crystal bed to wash the crystals. In addition, the mother liquor in the washing column is returned to the crystallizer through a line that returns the mother liquor to the crystallizer. The line for returning the mother liquor to the crystallizer is connected to at least the Nth tank, but may be connected to a further downstream tank. Also, a line for returning a part of the mother liquor to the washing column may be provided.

[0058] When the specific gravity of the crystals is less than that of the mother liquor, the crystals move upward in the column in the opposite manner to the above, and the crystal bed is suspended and melted at the top of the column, and the product is withdrawn.

[0059] The washing column included in the purification apparatus of the present invention is a column that forcibly transports the crystal bed. Specifically, there are mechanical washing columns that compress the crystals with a piston to form / transport the crystal bed, and hydraulic washing columns (water pressure washing columns) that send slurry to the column with a pump and extract the mother liquor from a filter placed in the column to form / transport the bed. The operating principle of these washing columns is described in the book Melt Crystallization (Edited by Joachim Ulrich, Heike Glade, Shaker Verlag, Aachen 2003).

[0060] The washing column is not particularly limited as long as it can wash the crystals, and may be either a mechanical washing column or a hydraulic washing column. A mechanical washing column is characterized by high stability during operation and high purification efficiency of compounds. On the other hand, a hydraulic washing column is characterized by high production capacity per column cross-sectional area and few moving parts in the washing column, so that troubles caused by the device are few. In purifying an easily polymerizable substance, the generation of polymers in the washing column may be suppressed by using a hydraulic washing column with few moving parts.

[0061] A preferred embodiment of the washing column is one having a mechanical mechanism for scraping off the crystal bed (see U.S. Pat. No. 3,872,009A). In washing columns having a forced transport mechanism for the crystal bed, the crystal bed after purification is scraped off with a scraper or the like, resuspended, and then melted.

[0062] Another preferred form of washing column is one that does not have a mechanical mechanism for scraping off the crystal bed (see U.S. Patent No. 7,425,273 B2). In this method, the crystal bed is scraped off by the dynamic pressure of the circulating liquid. There are no sliding surfaces such as shaft seals, and when purifying easily polymerizable substances, the generation of polymers due to liquid retention and sliding heat can be suppressed.

[0063] The solution of the compound to be purified may be supplied to any tank in the crystallizer, but it is preferable to supply it to the second or subsequent tank from the viewpoint of purification efficiency. The optimal location varies depending on the composition of the supply liquid, the crystallization yield, and the concentration efficiency of the crystals in the solid-liquid separator, so it can be selected appropriately.

[0064] The crystallization temperature in the crystallization tank in the purification apparatus of the present invention may be appropriately adjusted depending on the type of compound to be purified, but is generally in the range of -1 to -15°C relative to the melting point of the pure substance, preferably -1.5 to -13.5°C, more preferably -3.5°C to -12.5°C, and even more preferably -5 to -11.5°C. When the compound to be purified is (meth)acrylic acid, the temperature is preferably 0 to 12°C, more preferably 1 to 10°C, and even more preferably 2 to 8.5°C.

[0065] If the temperature of the crystallization tank is high, crystals with high purity are produced, but for example, when the crystallization tank is a scraping-type cooling crystallizer described later, problems such as the need for a lot of power to scrape the crystals in the crystallization tank may occur. In addition, if the temperature difference between the refrigerant and the inside of the crystallization tank is too high, problems such as blocking of the scraper for scraping may occur when the crystallization tank is a scraping-type cooling crystallizer, and it may be difficult to continue operation.

[0066] Therefore, under conditions where the temperature of the crystallization tank is high, it is necessary to reduce the temperature difference between the refrigerant and the inside of the crystallization tank and to reduce the amount of crystals produced per heat transfer area. If the temperature of the crystallization tank is low, the purity of the crystals produced will decrease, but if the crystallization tank uses a scraping-type cooling crystallizer, the power required to scrape the crystals in the crystallization tank is small, and scraper blocking is unlikely to occur even if the temperature difference between the refrigerant and the inside of the crystallization tank is increased. As a result, the temperature difference between the refrigerant and the inside of the crystallization tank can be increased, and the amount of crystals produced per heat transfer area can be increased. However, if the crystallization temperature is too low, the grain size of the produced crystals will be small, and the crystals will tend to be difficult to settle.

[0067] The residence time of the compound in the crystallization tank and maturation tank can be adjusted appropriately depending on the type of compound to be purified, but is generally 0.02 to 6 hours, taking into consideration the yield of the compound obtained after purification, the purification efficiency, and the capital investment costs.

[0068] In the Nth tank, in order to adjust the particle size distribution of the slurry sent to the washing column and to reduce the reflux ratio (flow rate of washing liquid / flow rate of purified acrylic acid) in the washing column, the residence time is preferably longer than a certain time, preferably 0.5 to 6 hours, more preferably 1 to 5 hours, and further preferably 1.2 to 4.5 hours.

[0069] In addition, the 1st to N-1th tanks do not necessarily need to have a long residence time because they are not connected to a washing column. A shorter residence time allows the size of the tank itself to be smaller, which is advantageous in terms of capital investment costs. Therefore, the residence time of the 1st to N-1th tanks is preferably 0.03 to 4 hours, more preferably 0.04 to 3 hours, even more preferably 0.05 to 2 hours, and most preferably 0.1 to 1.5 hours.

[0070] The residence time of a compound in a crystallization tank means the residence time in the tank and in the cooling mechanism outside the tank when the crystallization tank is of a type in which the contents of the tank are cooled outside the tank, as described below. The residence time of each tank is calculated as the total capacity of the tank and the cooling mechanism outside the tank divided by the sum of the flow rate of the slurry supplied from the tank to the upstream tank or washing column and the flow rate of the liquid sent / discharged from each tank to the lower tank or outside the purification device.

[0071] The purification apparatus of the present invention may be used for purifying any compound, but as described above, it can be suitably used for purifying crystals that have poor sedimentation properties, and therefore it can be suitably used for purifying (meth)acrylic acid. Therefore, one of the preferred embodiments of the present invention is that the compound purified by the purification apparatus of the present invention is (meth)acrylic acid.

[0072] In this case, the solution of the compound fed to the purification apparatus of the present invention is an aqueous (meth)acrylic acid solution or a crude (meth)acrylic acid solution. The aqueous (meth)acrylic acid solution refers to a solution in which (meth)acrylic acid is dissolved in water. The crude (meth)acrylic acid solution refers to a solution made of (meth)acrylic acid and containing impurities such as by-products during the production of (meth)acrylic acid. These can be obtained, for example, by collecting in an absorption tower and distilling, as necessary, the gas of a compound that is a reaction product obtained by the gas phase oxidation reaction of propylene and isobutylene, but are not limited to those obtained by self-synthesis and may be those procured from elsewhere. The aqueous (meth)acrylic acid solution or the crude (meth)acrylic acid solution can be cooled, for example, to obtain a slurry containing crystals of (meth)acrylic acid.

[0073] Examples of the by-products include acids such as propionic acid, acetic acid, maleic acid, benzoic acid, and acrylic acid dimer, aldehydes such as acrolein, furfural, formaldehyde, and glyoxal, acetone, protoanemonin, etc. In addition, solvents such as toluene and methyl butyl ketone may be contained. In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid.

[0074] Examples of the purification apparatus of the present invention are shown in FIGS. FIG. 1 shows a crystallization apparatus having one crystallization tank and one aging tank. A line is installed to directly deliver mother liquor from the aging tank, which is the tank one tank upstream, to the crystallization tank, and a line is installed to directly discharge the residue (mother liquor) from the crystallization tank, which is the most downstream tank. A solution 1 of a compound to be fed to a purification apparatus is introduced into an aging tank 21. The solution 1 is cooled in a crystallization tank 11 equipped with a cooling mechanism, and the slurry containing the precipitated crystals is sent to a solid-liquid separation apparatus 31 via a line 51. In the solid-liquid separation apparatus 31, the slurry is separated into a mother liquor and a concentrated crystal slurry, and the concentrated crystal slurry is sent to the adjacent aging tank 21 via a line 52, and the mother liquor is returned to the crystallization tank 11 via a line 61. In addition, a residue 2 is discharged from the crystallization tank 11 to the outside of the purification apparatus via a line 71, and the liquid level of the crystallization tank 11 is adjusted. After the crystals are grown in the aging tank 21, the crystal slurry is sent to a mechanical washing column 41 via a line 53. In addition, in order to adjust the liquid level of the aging tank 21, the mother liquor is sent directly from the aging tank 21 to the crystallization tank 11 via a line 72. In the mechanical washing column 41, the crystals are compressed by a piston to form a crystal bed. Then, at the bottom of the column, the crystal bed is scraped off, suspended in the circulating liquid, and melted by heating. A part of the circulating liquid containing the resulting melt is discharged as a high-purity compound 3. A part of the remaining circulating liquid (washing liquid) is returned to the mechanical washing column 41, where the crystals are washed by countercurrent contact with the crystal bed. In addition, the mother liquor in the washing column is returned to the aging tank 21 through a line 75 that returns the mother liquor to the crystallizer. In this way, the compound is purified to obtain a high-purity compound.

[0075] Fig. 2 shows a crystallization apparatus having one crystallization tank and one maturation tank, in which a line is installed to directly send mother liquor from the maturation tank, which is the tank one tank upstream, to the crystallization tank, and a line is installed to directly discharge the residue (mother liquor) from the crystallization tank, which is the most downstream tank. In addition, the crystallization tank is one in which the contents of the tank are cooled outside the tank. Only the parts that are different from the purification apparatus in Fig. 1 will be explained below. The crystallization tank 11 is composed of tank 11A and a cooling mechanism 11B outside the tank, which are connected by lines 111 and 121. The solution of the compound (or a slurry containing crystals of the compound) sent from tank 11A to cooling mechanism 11B via line 111 is cooled in cooling mechanism 11B, and the slurry containing the precipitated crystals is sent to tank 11A via line 121. A portion of the slurry containing the compound crystals from tank 11A is sent to cooling mechanism 11B via line 111, and the remainder is sent to solid-liquid separation device 31 via line 51.

[0076] Figure 3 shows a crystallization apparatus having two crystallization tanks, in which a line is installed to send mother liquor directly from crystallization tank 12, which is the tank one tank upstream, to crystallization tank 11, and a line is installed to directly discharge the residue (mother liquor) from crystallization tank 11, which is the most downstream tank. In addition, the washing column is hydraulic and has a mechanical mechanism for scraping off the crystal bed. Only the parts that are different from the purification apparatus in Figure 1 will be explained below. A solution 1 of a compound to be supplied to a purification apparatus is introduced into a crystallization tank 12 . The crystallization tank 11 is composed of tank 11A and a cooling mechanism 11B outside the tank, which are connected by lines 111 and 121. The solution of the compound (or a slurry containing crystals of the compound) sent from tank 11A to cooling mechanism 11B via line 111 is cooled in cooling mechanism 11B, and the slurry containing the precipitated crystals is sent to tank 11A via line 121. A portion of the slurry containing the compound crystals from tank 11A is sent to cooling mechanism 11B via line 111, and the remainder is sent to solid-liquid separation device 31 via line 51. Similarly, the crystallization tank 12 is composed of a tank 12A and a cooling mechanism 12B outside the tank, which are connected by lines 112 and 122. A part of the slurry containing the compound crystals from the tank 12A is sent to the cooling mechanism 12B via line 112 and returned to the tank 12A via line 122. The crystal slurry is sent from the crystallization tank 12 to the hydraulic washing column 42 via line 53. At the bottom of the hydraulic washing column 42, the crystal bed is scraped off by a mechanical mechanism (scraper), and the crystals are withdrawn while suspended in the circulating liquid and melted by heating, and a part of the circulating liquid containing the resulting melt is discharged as a high-purity compound 3. A part of the remaining circulating liquid (washing liquid) is returned to the hydraulic washing column 42 and brought into countercurrent contact with the crystal bed to wash the crystals.

[0077] The crystallization apparatus shown in Fig. 4 has two crystallization tanks and one maturation tank, and a line is installed between the three tanks to directly send the mother liquor from the upstream tank, and a line is installed from the most downstream tank to directly discharge the residue (mother liquor). Only the parts that are different from the purification apparatus in Fig. 1 will be explained below. The crystallization tank 11 is cooled with a cooling mechanism, and the slurry containing the precipitated crystals is sent to the solid-liquid separator 31 via line 51. In the solid-liquid separator 31, the slurry is separated into a mother liquor and a concentrated crystal slurry, the concentrated crystal slurry is sent to the adjacent crystallization tank 12 via line 52, and the mother liquor is returned to the crystallization tank 11 via line 61. In addition, the residue 2 is discharged from the crystallization tank 11 to the outside of the purification apparatus via line 71, and the liquid level in the crystallization tank 11 is adjusted. In the crystallization tank 12, the same operation as in the crystallization tank 11 is performed, and the slurry containing the crystals is sent to the solid-liquid separator 32 via line 53 from the crystallization tank 12. In the solid-liquid separator 32, the slurry is separated into a mother liquor and a concentrated crystal slurry, the concentrated crystal slurry is sent to the adjacent maturation tank 21 via line 54, and the mother liquor is returned to the crystallization tank 12 via line 62. To adjust the liquid level in the crystallization tank 12, the mother liquor is sent directly from the crystallization tank 12 to the crystallization tank 11 through a line 72. After the crystals are grown in the aging tank 21, the crystal slurry is sent to the mechanical washing column 41 through a line 55. To adjust the liquid level in the aging tank 21, the mother liquor is sent directly from the aging tank 21 to the crystallization tank 12 through a line 73 connecting the aging tank 21 and the crystallization tank 12.

[0078] Figure 5 shows a crystallization apparatus having three crystallization tanks and one maturation tank. Between the four tanks, a line is installed to directly send mother liquor from the upstream tank, and a line is installed to directly discharge the residue (mother liquor) from the most downstream tank. In addition, the washing column is hydraulic and has a mechanical mechanism for scraping off the crystal bed. Below, only the parts that are different from the purification apparatus in Figure 4 will be explained. The solution 1 of the compound to be fed to the purification device is introduced into the crystallization tank 13. From the crystallization tank 12, which is the second tank from the most downstream, a slurry containing crystals is sent to the solid-liquid separation device 32 via line 53. In the solid-liquid separation device 32, the slurry is separated into a mother liquor and a concentrated crystal slurry, the concentrated crystal slurry is sent to the adjacent crystallization tank 13 via line 54, and the mother liquor is returned to the crystallization tank 12 via line 62. In addition, in order to adjust the liquid level in the crystallization tank 12, the mother liquor is sent directly from the crystallization tank 12 to the crystallization tank 11 via line 72. In the crystallization tank 13, the same operation as in the crystallization tank 12 is performed, and the slurry containing crystals is sent from the crystallization tank 13 to the solid-liquid separation device 33 via line 55. In the solid-liquid separation device 33, the slurry is separated into a mother liquor and a concentrated crystal slurry, the concentrated crystal slurry is sent to the adjacent maturation tank 21 via line 56, and the mother liquor is returned to the crystallization tank 13 via line 63. To adjust the liquid level in the crystallization tank 13, the mother liquor is sent directly from the crystallization tank 13 to the crystallization tank 12 through a line 73. After the crystals are grown in the aging tank 21, the crystal slurry is sent to the hydraulic washing column 42 through a line 57. To adjust the liquid level in the aging tank 21, the mother liquor is sent directly from the aging tank 21 to the crystallization tank 13 through a line 74 connecting the aging tank 21 and the crystallization tank 13. At the bottom of the hydraulic washing column 42, the crystal bed is scraped off by a mechanical mechanism (scraper), withdrawn while suspended in the circulating liquid, and heated and melted, and a part of the circulating liquid containing the resulting melt is discharged as high-purity compound 3. A part of the remaining circulating liquid (washing liquid) is returned to the hydraulic washing column 42 and brought into countercurrent contact with the crystal bed to wash the crystals.

[0079] The crystallization apparatus shown in Fig. 6 has two crystallization tanks and one maturation tank, and a line is installed between the three tanks to send the mother liquor from the upstream tank via a solid-liquid separator, and a line is installed from the most downstream tank to discharge the residue via a solid-liquid separator. Only the parts that are different from the purification apparatus shown in Fig. 4 will be explained below. In the crystallization tank 11 of FIG. 6, instead of a line for directly discharging the residue, a solid-liquid separator 33 for separating the residue from the slurry in the crystallization tank is installed. The slurry taken out of the crystallization tank 11 is sent to the solid-liquid separator 33 via a line 81. The residue 2 separated in the solid-liquid separator 33 is discharged outside the purification apparatus, while the remaining crystals are returned to the crystallization tank 11, and the liquid level in the crystallization tank 11 is adjusted. In place of a line for directly sending mother liquor to the crystallization tank 11, a solid-liquid separator 34 is installed in the crystallization tank 12. The slurry removed from the crystallization tank 12 is sent to the solid-liquid separator 34 via a line 83. The mother liquor separated in the solid-liquid separator 34 is sent to the crystallization tank 11 for adjusting the liquid level, and the remaining crystals are returned to the crystallization tank 12. In place of a line for directly sending the mother liquor to the crystallization tank 12, a solid-liquid separator 35 is installed in the aging tank 21. The slurry taken out from the aging tank 21 is sent to the solid-liquid separator 35 through a line 85. The mother liquor separated in the solid-liquid separator 35 is sent to the crystallization tank 12 for adjusting the liquid level, and the remaining crystals are returned to the aging tank 21. The wash column 43 is hydraulic and has no mechanical mechanism for scraping the crystal bed.

[0080] Figure 7 shows a crystallization apparatus having two crystallization tanks and one maturation tank, in which a line is installed between the three tanks to send the mother liquor from the tank one upstream via a solid-liquid separator, and a line is installed from the most downstream tank to discharge the residue via a solid-liquid separator, in which the solid-liquid separator for separating the mother liquor from the slurry taken out of the second crystallization tank and sending it to the most downstream (first) crystallization tank, and the solid-liquid separator for separating the residue discharged from the most downstream (first) crystallization tank to the outside of the purification apparatus are shared with the solid-liquid separator installed on the line for sending the slurry to the tank one upstream. Only the parts different from the purification apparatus in Figure 6 will be described below. In the apparatus of Figure 7, the slurry containing crystals that have been cooled and precipitated in the crystallization tank 11 is sent to the solid-liquid separation device 31 via line 51. In the solid-liquid separation device 31, the slurry is separated into mother liquor and concentrated crystal slurry, and the concentrated crystal slurry is sent to the adjacent crystallization tank 12 via line 52. A portion of the mother liquor separated in the solid-liquid separation device 31 is returned to the crystallization tank 11 via line 61, and the remainder is discharged outside the purification device via an additional line 101 connected to line 61. The slurry containing crystals cooled and precipitated in the crystallization tank 12 is sent to the solid-liquid separation device 32 via line 53. In the solid-liquid separation device 32, the slurry is separated into mother liquor and concentrated crystal slurry, and the concentrated crystal slurry is sent to the adjacent aging tank 21 via line 54. A portion of the mother liquor separated in the solid-liquid separation device 32 is returned to the crystallization tank 12 via line 62, and the remainder is sent to the crystallization tank 11 via an additional line 102 connected to line 62. In the refining apparatus of Fig. 7, line 51 → solid-liquid separator 31 → lines 61, 101 correspond to line 81 → solid-liquid separator 33 → lines 82, 91 in the apparatus of Fig. 6, and instead of installing solid-liquid separator 33, the number of pieces of equipment is reduced by sharing solid-liquid separator 31 provided on the line that sends the slurry to the upstream tank. Similarly, line 53 → solid-liquid separator 32 → lines 62, 102 correspond to line 83 → solid-liquid separator 34 → lines 84, 92 in the apparatus of Fig. 6, and instead of installing solid-liquid separator 34, the number of pieces of equipment is reduced by sharing solid-liquid separator 32 provided on the line that sends the slurry to the upstream tank.

[0081] FIG. 8 shows a crystallization apparatus having two crystallization tanks and one maturation tank, in which a line is installed to send the mother liquor from the second crystallization tank to the most downstream (first) crystallization tank via a solid-liquid separator, and a line is installed to discharge the residue from the most downstream tank via a solid-liquid separator, and a line is installed to send the mother liquor directly from the maturation tank to the second crystallization tank, and the solid-liquid separator for separating the mother liquor from the slurry taken out of the second crystallization tank and sending it to the most downstream crystallization tank, and the solid-liquid separator for separating the residue discharged from the most downstream crystallization tank to the outside of the purification apparatus are shared with the solid-liquid separator installed on the line for sending the slurry to the tank one upstream. In addition, the crystallization tank is a type that cools the contents of the tank outside the tank. Below, only the parts that are different from the purification apparatus in FIG. 7 will be described. 8, the crystallization tank 11 is composed of tank 11A and a cooling mechanism 11B outside the tank, which are connected by lines 111 and 121. The solution of the compound (or a slurry containing crystals of the compound) sent from tank 11A to cooling mechanism 11B via line 111 is cooled in cooling mechanism 11B, and the slurry containing the precipitated crystals is sent to tank 11A via line 121. A portion of the slurry containing the compound crystals from tank 11A is sent to cooling mechanism 11B via line 111, and the remainder is sent to solid-liquid separation device 31 via line 51. Similarly, the crystallization tank 12 is composed of a tank 12A and a cooling mechanism 12B outside the tank, which are connected by lines 112 and 122. A part of the slurry containing the compound crystals is sent from the tank 12A to the cooling mechanism 12B via line 112, and the remainder is sent to the solid-liquid separator 32 via line 53. The apparatus of FIG. 8 has a line 73 for sending the mother liquor directly from the aging tank 21 to the crystallization tank 12A, instead of the line for sending the mother liquor from the aging tank 21 to the crystallization tank 12 via the solid-liquid separator 35 as in the apparatus of FIG. [Explanation of symbols]

[0082] 1: Compound solution 2:Residue 3: High purity compounds 11-13: Crystallization tank with cooling mechanism 11A, 12A: Tank 11B, 12B: Cooling mechanism 21: Aging tank 31~35: Solid-liquid separator 41: Mechanical cleaning column 42: Hydraulic washing column (having a mechanical mechanism for scraping off the crystal bed) 43: Hydraulic washing column (without mechanical mechanism for scraping off the crystal bed) 51-57: Lines for pumping slurry (or crystals) from a downstream tank to an upstream tank or washing column 61~63: Lines for returning the mother liquor separated from the slurry by the solid-liquid separator to the original tank 71: Line that discharges the residue (mother liquor) directly from the most downstream tank to the outside of the refining equipment 72-74: Lines that directly pump mother liquor from the upstream tank to the downstream tank 75: Line that returns the mother liquor from the wash column to the crystallizer 81-86: Lines for separating crystals from the slurry taken out of the tank using a solid-liquid separator and returning them to the original tank 91: Line that discharges the residue (mother liquor) separated from the slurry taken out of the tank by the solid-liquid separator to the outside of the refining equipment 92, 93: Lines that send the mother liquor separated from the slurry taken out of the tank by the solid-liquid separator to the tank one step downstream 101: An additional line for discharging a part of the mother liquor separated from the slurry taken from the most downstream tank by the solid-liquid separator to the outside of the purification unit. 102: Additional line for sending a part of the mother liquor separated by a solid-liquid separator from the slurry taken from the second tank to the most downstream tank 111, 121, 112, 122: Lines connecting the crystallization tank and the cooling mechanism in a type of crystallization tank in which the contents of the tank are cooled outside the tank

Claims

1. A compound purification apparatus having a crystallization unit having a crystallization section for cooling a solution of a compound to precipitate crystals, and a washing column for forcibly transporting the crystals of the compound, The washing column is either a mechanical washing column in which the crystals are compressed with a piston to form / transport a crystal bed, or a hydraulic washing column in which a slurry is pumped into the column and mother liquor is extracted through a filter disposed in the column to form / transport a bed, The crystallization apparatus has N tanks (N≧2), which are connected in series with a first tank on the downstream side and an Nth tank on the upstream side in a direction of a slurry flow, at least the first tank being a crystallization tank equipped with a cooling mechanism, and the second and subsequent tanks being crystallization tanks or maturation tanks, A line is provided for supplying a compound-containing liquid to be purified from outside the purification apparatus to at least one tank, The wash column has a line for discharging the product and a line for returning the mother liquor to the crystallizer, the line for returning the mother liquor to the crystallizer being connected to at least the Nth tank; The crystallizer includes a line for supplying a slurry from the Nth tank to the washing column, a line for delivering the slurry from the downstream tank to the tank one upstream, and a line for delivering mother liquor from the upstream tank to each of the 1st to N-1th tanks; All of the 1st to (N-1th) tanks included in the crystallization apparatus have a line for sending a slurry to the tank one upstream via a solid-liquid separation device, and a line for returning at least a part of the mother liquor discharged from the solid-liquid separation device to the original tank; At least one of the solid-liquid separation devices provided in the line for sending the slurry from the downstream tank to the upstream tank has one or more additional lines for sending the mother liquor in addition to a line for returning the mother liquor to the original tank, and the additional lines are connected to the downstream tank and / or the outside of the purification device with respect to the original tank; the line for sending the mother liquor from an upstream tank to each of the 1st to N-1th tanks includes at least one of a line for directly sending the mother liquor from the tank one upstream and a line for sending the mother liquor from the tank one upstream via a solid-liquid separation device; The purification apparatus further comprises a line for sending the mother liquor to the outside of the purification apparatus.

2. The purification apparatus according to claim 1, characterized in that at least one of the lines for sending mother liquor from upstream tanks to each of the 1st to N-1th tanks is a line for sending mother liquor from the tank one upstream via a solid-liquid separation device.

3. The purification apparatus according to claim 1 or 2, wherein at least one of the 1st to N-1th tanks included in the crystallization apparatus has a line for directly sending mother liquor from the tank immediately upstream.

4. The purification apparatus according to any one of claims 1 to 3, further comprising a line for sending mother liquor from a first tank included in the crystallization apparatus to the outside of the purification apparatus via a solid-liquid separation apparatus.

5. 5. The refining apparatus according to claim 1, wherein the cooling mechanism is a type that cools the contents of the tank outside the tank.

6. 6. The purification apparatus according to claim 1, wherein the washing column comprises a mechanical mechanism for scraping off the crystal bed.

7. 6. The purification apparatus according to claim 1, wherein the washing column does not have a mechanical mechanism for scraping off the crystal bed.

8. The purification apparatus according to any one of claims 1 to 7, characterized in that the compound is (meth)acrylic acid.

9. Among the lines for transferring the slurry from the downstream tank to the tank one upstream of the crystallization apparatus, at least the line for transferring the slurry from the (N-1)th tank to the (N)th tank is a line for transferring the slurry to the tank one upstream via a solid-liquid separation apparatus, The purification apparatus according to any one of claims 1 to 8, characterized in that a solid-liquid separation device provided in a line for sending the slurry from the (N-1)th tank to the Nth tank is a basket type centrifuge or a decanter type centrifuge.

Images