Circulation-purification-type cleaning apparatus and circulation-purification-type cleaning method

Abstract

To provide a cleaning apparatus capable of significantly reducing the usage amount of organic solvent for cleaning, and also of remarkably reducing the amount of impurities eluted from a cleaning target after cleaning.SOLUTION: Provided is a circulation-purification-type cleaning apparatus for cleaning a cleaning target, the apparatus comprising: an ion exchange device that produces a treated liquid by ion-exchanging a cleaning organic solvent; a liquid-to-be-treated line that is connectable to an outlet of the cleaning target and connected to an inlet of the ion exchange device; a first treated liquid line that is connectable to an inlet of the cleaning target and connected to an outlet of the ion exchange device; and a circulation device. When the liquid-to-be-treated line is connected to the outlet of the cleaning target and the inlet of the ion exchange device, and the first treated liquid line is connected to the inlet of the cleaning target and the outlet of the ion exchange device, the cleaning organic solvent circulates through a circulation path including the first treated liquid line, the cleaning target, the liquid-to-be-treated line, and the ion exchange device, by the driving of the circulation device, and is purified by the ion exchange device.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a circulating purification type cleaning apparatus and a circulating purification type cleaning method. [Background technology]

[0002] When a non-aqueous liquid such as an organic solvent is used in contact with a container or pipe made of a metal such as fluororesin or SUS, the container or pipe must be thoroughly washed in advance. In particular, for storage containers for non-aqueous liquids used in semiconductor manufacturing processes and components such as pipes used when passing the non-aqueous liquid, it is necessary to reduce the amount of impurities such as metals and fine particles as much as possible. In general, containers made of fluororesin are washed using an acid. Containers made of metal such as SUS are washed by polishing or by further washing with water, acid, etc. after polishing. In addition, as described in Patent Document 1, it has also been proposed to use an electrolytic polishing liquid for metals in which alcohol, a surfactant, an organic acid, etc. are mixed as a cleaning liquid. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-220448 A [Patent Document 2] International Publication No. 2022 / 030380 Summary of the Invention [Problem to be solved by the invention]

[0004] For cleaning the containers, piping, etc., it is desirable to use a cleaning organic solvent (hereinafter also referred to as "cleaning liquid") with a low impurity content. However, according to the method described in Patent Document 1, the clean level is on the order of ppm, which is not sufficient as the clean level (ppb or ppt level) required for storage containers used in semiconductor manufacturing processes. In addition, if impurities are eluted into the cleaning liquid, there is a concern of re-contamination, such as re-adhesion to the container, so a process of repeatedly rinsing the inside of the container using a cleaning liquid with a low impurity content is required. That is, in order to reduce the amount of impurity elution in the object to be cleaned and to increase the cleanliness, more cleaning liquid with a low impurity content is required. However, when a large amount of organic solvent is used, problems arise such as increased costs and increased environmental load. Furthermore, if the amount of organic solvent handled increases, the tank for storing the organic solvent also becomes larger, which may cause management and safety issues.

[0005] An object of the present invention is to provide a circulating purification-type cleaning apparatus and a circulating purification-type cleaning method which can significantly reduce the amount of organic solvent used for cleaning and significantly reduce the amount of impurities eluted from an object to be cleaned after cleaning. [Means for solving the problem]

[0006] The present invention provides a circulation purification type cleaning apparatus for cleaning an object having an inlet and an outlet, an ion exchange device having an ion exchanger for ion-exchanging an organic cleaning solvent as a liquid to be treated to obtain a treatment liquid; a line for a liquid to be treated that is connectable to an outlet of the object to be cleaned and that is connected to an inlet of the ion exchange device; a first processing liquid line connectable to an inlet of the object to be cleaned and connected to an outlet of the ion exchange device; A circulation device for circulating and delivering the organic solvent for cleaning; Equipped with The circulation purification type cleaning apparatus is characterized in that, when the line for the treated liquid is connected to the outlet of the object to be cleaned and the inlet of the ion exchange device, and the first treatment liquid line is connected to the inlet of the object to be cleaned and the outlet of the ion exchange device, the organic cleaning solvent is purified by the ion exchanger while being circulated through a circulation path including the first treatment liquid line, the object to be cleaned, the line for the treated liquid, and the ion exchange device by driving the circulation device.

[0007] The present invention also provides an ion exchange device having an ion exchanger, a line for a liquid to be treated, which is connectable to an outlet of the object to be cleaned and is connected to an inlet of the ion exchange device; a first processing liquid line connectable to an inlet of the object to be cleaned and connected to an outlet of the ion exchange device; A circulation device; A circulating purification type cleaning method for cleaning an object to be cleaned using a circulating purification type cleaning apparatus comprising: a preparation step of connecting the line for the liquid to be treated to an outlet of the object to be cleaned and an inlet of the ion exchange device, and connecting the first processing liquid line to the inlet of the object to be cleaned and an outlet of the ion exchange device; a purging step of purging the cleaning organic solvent into the object to be cleaned; a cleaning step of cleaning the object to be cleaned with the cleaning organic solvent purged into the object to be cleaned; a purification step of purging the cleaning organic solvent as the liquid to be treated after the cleaning step into the ion exchange device through the line for the liquid to be treated to obtain a liquid that has been ion-exchanged by the ion exchanger; the organic solvent for cleaning is circulated through a circulation path including the first treatment liquid line, the object to be cleaned, the treatment liquid line, and the ion exchange device by driving the circulation device, thereby repeatedly carrying out the cleaning step and the purification step. Effect of the Invention

[0008] According to the present invention, it is possible to provide a circulating purification-type cleaning apparatus and a circulating purification-type cleaning method which can significantly reduce the amount of organic solvent used for cleaning and significantly reduce the amount of impurities eluted from an object to be cleaned after cleaning. [Brief description of the drawings]

[0009] [Figure 1] 1 shows a schematic diagram of a circulation purification type cleaning device according to one embodiment of the present invention. [Diagram 2] 1 shows a schematic diagram of a circulation purification type cleaning device according to one embodiment of the present invention. [Diagram 3] 1 shows a schematic diagram of a circulation purification type cleaning device according to one embodiment of the present invention. [Figure 4] 1 is a graph showing the results of Example 1. [Diagram 5] 1 is a graph showing the results of Example 2. [Figure 6] 1 is a graph showing the results of Example 3. [Figure 7] 1 is a graph showing the results of Example 4. [Figure 8] 1 is a graph showing the results of Example 5. [Figure 9] 1 is a graph showing the results of Example 1, Example 2 and Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Circulation purification type cleaning equipment> FIG. 1 shows a schematic diagram of a circulating purification type cleaning apparatus (hereinafter, also abbreviated as "cleaning apparatus") according to one embodiment of the present invention. The cleaning apparatus 1 according to the present invention is a cleaning apparatus for cleaning an object 2 having at least an inlet 2A and an outlet 2B, and includes at least an ion exchange apparatus 3, a line 4 for a liquid to be treated, a first processing liquid line 5, and a pump P (circulation apparatus). The ion exchange apparatus 3 has an ion exchanger that ion-exchanges a cleaning organic solvent as a liquid to be treated to obtain a processing liquid. The line 4 for a liquid to be treated is a line that can be connected to the outlet 2B of the object to be cleaned and is connected to the inlet 3A of the ion exchange apparatus. The first processing liquid line 5 is a line that can be connected to the inlet 2A of the object to be cleaned and is connected to the outlet 3B of the ion exchange apparatus. The pump P is a circulation apparatus for circulating and sending the cleaning organic solvent. The cleaning apparatus 1 may further include a second processing liquid line 6 for sampling branched off from the first processing liquid line 5 or the treated liquid line 4, a filter F provided in the first processing liquid line 5, a pressure detector PI provided in the treated liquid line 4, a flow meter (not shown), and other valves, etc. The cleaning apparatus shown in Fig. 1 shows an example in which the object to be cleaned is a tank and a pump P is used as a circulation device, but the object to be cleaned and the circulation device are not limited to this.

[0011] The inlet and the outlet of the object to be cleaned 2 and the ion exchange device 3 are openings through which the cleaning organic solvent enters the object to be cleaned and the ion exchange device, respectively, when the cleaning organic solvent is passed through the inlet and the opening through which the liquid to be treated exits the ion exchange device 3. The cleaning organic solvent may be passed through the ion exchange device 3 in a downward flow manner as shown in Fig. 1 or in an upward flow manner as shown in Fig. 2.

[0012] It is preferable to clean the cleaning apparatus 1 itself in advance by a known method before using the cleaning apparatus 1 to clean the object to be cleaned. It is also possible to perform pre-cleaning of the cleaning apparatus 1, for example, by directly connecting the line 4 for the liquid to be treated and the line 5 for the liquid to be treated with the object to be cleaned without connecting the line 4 for the liquid to be treated and the line 5 for the liquid to be treated with the object to be cleaned with the line 5 for the liquid to be treated ...

[0013] In the cleaning apparatus 1 according to the present invention having the above-mentioned configuration, when the line 4 for the liquid to be treated is connected to the outlet 2B of the object to be cleaned and the inlet 3A of the ion exchange device, and the first line 5 for the liquid to be treated is connected to the inlet 2A of the object to be cleaned and the outlet 3B of the ion exchange device, the organic solvent for cleaning is circulated through a circulation path including the first line 5 for the liquid to be treated, the object to be cleaned, the line 4 for the liquid to be treated, and the ion exchange device 3 by driving the pump P (circulation device). On the other hand, the organic solvent for cleaning after being used for cleaning the object to be cleaned is purified by the ion exchanger in the ion exchange device 3. That is, according to the present invention, the organic solvent for cleaning used for cleaning the object to be cleaned can be repeatedly used for cleaning the object to be cleaned while being circulated and purified by the ion exchange device. As a result, the amount of the organic solvent for cleaning can be significantly reduced. In addition, according to the present invention, the amount of impurities eluted from the object to be cleaned after cleaning can be significantly reduced. Specifically, according to the present invention, the amount of impurities eluted from the object to be cleaned after cleaning can be reduced to the ppt level, preferably the total amount of impurities eluted to 100 ppt or less. The cleaning of the object to be cleaned using the cleaning device according to the present invention may be performed at room temperature or may be appropriately heated. When performed at room temperature, the present invention is a method for recycling cleaning organic solvents with low power consumption and low environmental impact. Each component of the cleaning device according to the present invention will be described in detail below.

[0014] [Item to be cleaned] The cleaning object 2 in the present invention has an inlet 2A and an outlet 2B, and is not limited as long as it is present in the flow path of the nonaqueous liquid and can come into contact with the nonaqueous liquid when the nonaqueous liquid is passed through the cleaning object when it is used after cleaning. Specific examples of the cleaning object include containers such as storage containers for nonaqueous liquids used in semiconductor manufacturing processes, and various components such as piping, valves, packing, and O-rings used when passing the nonaqueous liquid. The cleaning object can be made of metal such as fluororesin or SUS, provided that it has resistance to the cleaning organic solvent. The cleaning object may be one or more. For example, when one of the cleaning objects is a container such as a tank, cleaning according to the present invention can be performed in a state where various components such as piping, valves, packing, or O-rings are placed in the tank as other cleaning objects. Furthermore, cleaning using the cleaning device according to the present invention can be performed in a state where various components such as necessary piping, valves, packing, or O-rings are connected to the tank.

[0015] [Organic solvent for cleaning] Examples of the organic solvent for cleaning include alcohols such as isopropyl alcohol (IPA), methanol, ethanol, and propanol; esters such as propylene glycol monomethyl ether acetate (PGMEA); ethers such as propylene glycol monomethyl ether (PGME); polyethers; N-methylpyrrolidone; and mixed solvents of two or more selected from these solvents. The organic solvent for cleaning is preferably a solvent that can be mixed with water. Among these, the organic solvent for cleaning is preferably alcohols such as IPA, methanol, and ethanol, and IPA is particularly preferred because it is a commercially available product with high cleanliness and is easily available.

[0016] A small amount of acid may be added to the organic solvent for cleaning. By adding an acid, metal impurities are easily eluted from the object to be cleaned, and the metal impurities eluted in the organic solvent for cleaning can be prevented from reattaching to the liquid-contacting part. Examples of the acid that can be used include mineral acids such as nitric acid, hydrochloric acid, and sulfuric acid, and organic acids such as citric acid and acetic acid. However, the type of acid needs to be appropriately selected in consideration of the effect when combined with the organic solvent for cleaning. The amount of acid added can be, for example, 0.001 to 10 mass% with respect to the total amount of the organic solvent for cleaning. When an organic solvent for cleaning to which an acid has been added is used, it is preferable to immediately wash the system with an organic solvent with high cleanliness or ultrapure water after cleaning to remove the impurities in the system eluted by the acid and the remaining acid. The organic solvent for cleaning to which an acid has been added is particularly effective when the object to be cleaned is a container made of resin or the like. In addition, as described in Patent Document 2, water may be added to the organic solvent for cleaning. By adding water, the ion exchange group of the ion exchanger in the ion exchange device is hydrated, and the amount of impurities adsorbed can be increased. The amount of water added is preferably an amount such that the water content in the organic solvent for washing after the addition of water is 0.01 to 20% by mass.

[0017] The impurities contained in the object to be cleaned and the organic solvent for cleaning are mainly metal impurities, and examples of such impurities include metal ions of Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, etc. The object to be cleaned and the organic solvent for cleaning may contain other metal ions besides these.

[0018] [Ion exchange device] The ion exchange device 3 has an ion exchanger for ion-exchanging a liquid to be treated (mainly a used organic solvent for cleaning) for cleaning an object to be cleaned, to obtain a treatment liquid (a purified organic solvent for cleaning). The ion exchange device 3 is, for example, a column, a cartridge, or a resin tower filled with an ion exchanger. As shown in FIG. 3, a sealed pressure-feeding device such as a cylinder or a metal canister can can also be used as the ion exchange device 3. In that case, since the ion exchange device itself is configured to have a circulation device, it is not necessary to separately provide a circulation device such as a pump. Such a pressure-feeding device is not particularly limited, and a commercially available product can be appropriately selected and used. As an example of the pressure-feeding device, a cartridge-type cartridge water purifier (G series, manufactured by Organo Corporation) can be mentioned. In addition, a batch-type ion exchange device is not suitable for the present invention in consideration of the installation space and the need to perform circulation purification.

[0019] (Ion exchanger) As the ion exchanger, one or more selected from the group consisting of a cation exchanger and an anion exchanger can be used. As the ion exchanger, specifically, one or more selected from the group consisting of a granular ion exchange resin, a monolithic ion exchanger, a molded product obtained by pulverizing a granular ion exchange resin, an ion exchange fiber, and an ion adsorption membrane can be used. The cation exchanger may be a strongly acidic cation exchanger having a strongly acidic cation exchange group, or a weakly acidic cation exchanger having a weakly acidic cation exchange group. In addition, the anion exchanger may be a strongly basic anion exchanger having a strongly basic anion exchange group, or a weakly basic anion exchanger having a weakly basic anion exchange group. The ion exchanger can be recycled using a known method. That is, the organic solvent for cleaning remaining in the ion exchanger after use in purifying the organic solvent for cleaning is replaced with water, and then an appropriate regenerant (such as an acid or an alkali) is passed through the ion exchanger to regenerate the ion exchanger, which can be reused for purifying the organic solvent for cleaning. The flash point of the mixture of the organic solvent for cleaning and water must be room temperature or higher.

[0020] Granular ion exchange resins (hereinafter also simply referred to as "ion exchange resins") include cation exchange resins and anion exchange resins. The ion exchange resin preferably contains at least a cation exchange resin, and a cation exchange resin and an anion exchange resin can also be used in combination. When a cation exchange resin and an anion exchange resin are used in combination, the cation exchange resin and the anion exchange resin may be packed as a mixed bed in one ion exchange device, or may be packed as a single bed in separate ion exchange devices.

[0021] From the viewpoint of removing impurities, the ion form of the cation exchange resin is preferably H-type. The cation exchange resin may be a strong acid cation exchange resin or a weak acid cation exchange resin. The base material of the cation exchange resin is preferably a styrene-divinylbenzene copolymer. The base material of the cation exchange resin may be any of a gel type, a macroporous type, and a porous type structure. The ion exchange capacity of the cation exchange resin in a wet state is preferably 0.5 eq / LR or more, more preferably 1.0 eq / LR or more. The ion exchange capacity of the cation exchange resin in a wet state is preferably as high as possible, and may be appropriately selected. The harmonic mean diameter of the cation exchange resin is preferably 200 to 900 μm, more preferably 300 to 700 μm. The ion exchange resin is usually manufactured in a state containing water. The ion exchange resin exists in a state containing water even when the ion exchange resin is filled at the sales, distribution, and use site. In the present invention, the ion exchange resin in such a state is called a wet ion exchange resin.

[0022] Examples of the strongly acidic cation exchange resin include Amberlite IR120B, IR124, 200CT, HPR1200, HPR1006NNC (all trade names), Amberjet 1020, 1024, 1060, and 1220 (all trade names) manufactured by DuPont de Nemours; Diaion SK104, SK1B, SK110, SK112, PK208, PK212L, PK216, and P (all trade names) manufactured by Mitsubishi Chemical Corporation. Examples of the fluoride-containing polymers include, but are not limited to, K218, PK220, PK228, UBK08, UBK10, and UBK12 (all trade names); Orlite DS-1, DS-4 (all trade names), and Amberlyst 15JS-HG·DRY (trade name) manufactured by Organo Corporation; C100, C100E, C120E, C100x10, C100x12MB, C150, C160, and SGC650 (all trade names) manufactured by Purolite Corporation; and Lewatit Monoplus S108H, Monoplus SP112, and S1668 (all trade names) manufactured by Lanxess AG. Examples of weakly acidic cation exchange resins include, but are not limited to, Amberlite FPC3500 and IRC76 (all trade names) manufactured by DuPont de Nemours; Orlite DS-21 and DS-22 (all trade names) manufactured by Organo Corporation; Diaion WK10, WK11, WK100 and WK40L (all trade names) manufactured by Mitsubishi Chemical Corporation; C104, C106, C107E, C115E and SSTC104 (all trade names) manufactured by Purolite Corporation; and Lewatit CNP80WS (trade name) manufactured by Lanxess.

[0023] The ion form of the anion exchange resin may be OH form, Cl form, organic acid form, carbonate form, or mineral acid form, and is preferably OH form or organic acid form (e.g., citric acid form, acetic acid form, etc.). The anion exchange resin may be a strongly basic anion exchange resin or a weakly basic anion exchange resin. The base of the anion exchange resin is preferably a styrene-divinylbenzene copolymer. The base of the anion exchange resin may have any of a gel type, macroporous type, and porous type structure. The ion exchange capacity of the anion exchange resin in a wet state is preferably 0.5 eq / LR or more, more preferably 0.9 eq / LR or more. The harmonic mean diameter of the anion exchange resin is preferably 200 to 900 μm, more preferably 300 to 700 μm.

[0024] Examples of anion exchange resins include Amberlite IRA900, IRA402, IRA96SB, and IRA98 (all trade names) manufactured by DuPont de Nemours; Amberjet 4400, 4002, and 4010 (all trade names); AmberSep IRA743 (trade name); Diaion UBA120, PA306S, PA308, PA312, PA316, and PA318L manufactured by Mitsubishi Chemical Corporation. Examples of such antibacterial agents include, but are not limited to, WA21J and WA30 (all trade names); Orlite DS-2, DS-5, and DS-6 (all trade names) manufactured by Organo Corporation; Amberlyst B20-HG·DRY (trade name); A400, A600, SGA550, A500, A501P, A502PS, A503, A100, A103S, A110, A111S, and A133S (all trade names) manufactured by Purolite Corporation; and Lewatit Monoplus M500, Monoplus M800, MP62WS, and Monoplus MP64 (all trade names) manufactured by Lanxess AG.

[0025] When a cation exchange resin and an anion exchange resin are used as a mixed bed, a commercially available mixed bed resin can be used. Examples of such mixed bed resins include, but are not limited to, Orlite DS-3, DS-7 (both trade names) and Amberlyst MSPS2-1·DRY (trade name) manufactured by Organo Corporation.

[0026] Examples of monolithic ion exchangers (organic porous ion exchangers) include organic porous cation exchangers having cation exchange groups introduced therein, organic porous anion exchangers having anion exchange groups introduced therein, and organic porous chelate exchangers having functional groups having chelating ability introduced therein. The exchange capacity of the organic porous cation exchanger is preferably 1 to 3 mg equivalents / mL (dry state), more preferably 1.5 to 3 mg equivalents / mL (dry state). The exchange capacity of the organic porous anion exchanger is preferably 1 to 6 mg equivalents / mL (dry state), more preferably 2 to 5 mg equivalents / mL (dry state). The exchange capacity of the H-type organic porous chelate exchanger is preferably 0.3 to 2 mg equivalents / mL (water-wet state), more preferably 1 to 2 mg equivalents / mL (water-wet state). As the organic porous ion exchanger, a known one, for example, one described in Patent Document 2, can be appropriately selected and used.

[0027] The molded product obtained by crushing granular ion exchange resin refers to a product obtained by mixing a support such as polyethylene with crushed ion exchange resin and molding it into a block shape. The shape may be a shape that can be filled into a column or a resin tower, or a shape in which the liquid to be treated flows from the outside to the inside like a filter. When the liquid to be treated can be treated at a required flow rate under a given pressure, the crushed ion exchange resin may be molded by placing it in a container without using a support. Examples of commercially available molded products include 3M metal ion removal filter MIP series SCP series (product name, manufactured by 3M).

[0028] The ion exchange fiber may be a cation exchange fiber or anion exchange fiber having a structure in which a functional group (ion exchange group) is introduced into a fiber as a base material. From the viewpoint of physical strength, the base material of the ion exchange fiber is preferably a polyester, polyethylene, polypropylene, polyolefin, or polyacrylonitrile resin. As the ion exchange fiber, a known fiber may be appropriately selected and used.

[0029] Examples of the ion adsorption membrane include a porous membrane material (base material) having a cation exchange group or anion exchange group introduced on the surface of the membrane material, and a membrane made of fibers having a cation exchange group or anion exchange group. Examples of the base material constituting the ion adsorption membrane include one or more selected from polyethylene, polypropylene, cellulose, nylon, polystyrene, fluororesin, polytetrafluoroethylene, polyethersulfone, polyamide, etc. As the ion adsorption membrane, a known one can be appropriately selected and used.

[0030] Among the above, ion exchange resins are preferred as the ion exchanger in terms of versatility. As described above, the ion exchanger used for purifying the cleaning organic solvent can be regenerated using an acid or an alkali. By regenerating the ion exchanger and repeatedly using it for purifying the cleaning organic solvent, impurities that are more likely to dissolve into an organic solvent than an aqueous solution are gradually eluted from the ion exchanger, and the amount of such impurities eluted is reduced. As a result, a cleaner cleaning organic solvent can be obtained. That is, by recycling the ion exchanger, the purification ability of the ion exchanger can be improved. The regeneration treatment of the ion exchanger may be performed at the same place where the cleaning device according to the present invention is used, or at a different place. However, if it is performed at a different place, it is preferable to perform an operation of temporarily replacing the cleaning organic solvent remaining inside the ion exchanger with water before transportation.

[0031] (Regeneration of ion exchanger) Hereinafter, the regeneration of ion exchange resins in the case where a mixed bed of cation exchange resins and anion exchange resins is used as an ion exchanger will be described. When a mixed bed resin of H-type cation exchange resins and organic acid-type anion exchange resins is used, both resins can be regenerated simultaneously by passing an organic acid aqueous solution through the mixed bed resin after use without extracting and separating the resins. In addition, when an ion exchange resin containing an organic acid-type anion exchange resin is used, the organic acid ions eluted in the cleaning solution during purification of the cleaning solution are bound to polyvalent metal ions such as copper ions and iron ions in the object to be cleaned by chelation, and the cleaning property of the object to be cleaned can be improved. Metal impurities bound to organic acid ions by chelation can be removed by adsorption to the ion exchange resin in the ion exchange device, or by rinsing or ultrapure water washing performed after the end of circulation washing and the withdrawal of the cleaning solution. On the other hand, when the cation exchange resin and the anion exchange resin are used as single beds, regeneration treatment can be performed in each resin tower. The ion exchange resin thus regenerated can be reused in the cleaning device according to the present invention.

[0032] [Line for treated liquid, first treated liquid line] The treated liquid line 4 is a pipe that can be connected to the outlet 2B of the object to be cleaned and is connected to the inlet 3A of the ion exchange device. The first treated liquid line 5 is a pipe that can be connected to the inlet 2A of the object to be cleaned and is connected to the outlet 3B of the ion exchange device. The material of these lines is usually selected based on chemical resistance and cleanliness, and metal pipes such as SUS or PFA pipes made of fluororesin are used. Each line can be arbitrarily removed from the ion exchange device, the object to be cleaned, etc. As will be described later, the treated liquid line 4 also functions as a "second organic solvent for cleaning filling line" when filling the organic solvent for cleaning.

[0033] [Second processing liquid line] The circulation purification type cleaning apparatus 1 may have a second processing liquid line 6 for sampling, which is branched from the processing liquid line 4 or from the first processing liquid line 5. A part of the ion exchanger filled in the ion exchanger device 3 is taken out as a sample from the second processing liquid line 6, and the deterioration state of the resin in the sample is checked, so that the time to replace the ion exchanger can be predicted. The deterioration state of the resin can be checked, for example, by measuring the perfect sphericity rate (PBC: the ratio of resin that maintains a spherical shape to the total resin) of the resin or the remaining amount of ion exchange groups. Note that the deterioration state of the resin may be checked by installing an analytical device (for example, an image recognition sensor or a device equipped with the sensor) for determining the deterioration of the resin instead of the second processing liquid line. If deterioration of the resin is found as a result of checking the deterioration state of the resin for the sample taken out from the second processing liquid line, it is preferable to replace the ion exchanger in the ion exchanger device with another ion exchanger. In this case, the other ion exchanger may be a new ion exchanger or a reused product obtained by regenerating a used ion exchanger. The second processing liquid line 6 may be a line branched from the processing liquid line 4 or may be a line branched from the first processing liquid line 5. The circulation purification type cleaning apparatus 1 may have two second processing liquid lines 6, the second processing liquid line 6 branched from the processing liquid line 4 and the second processing liquid line 6 branched from the first processing liquid line 5. In particular, when the size of the ion exchange apparatus is large, it is preferable to provide both the inlet and the outlet of the ion exchange apparatus, that is, both the second processing liquid line 6 branched from the processing liquid line 4 and the second processing liquid line 6 branched from the first processing liquid line 5. As described later, the second processing liquid line 6 also functions as a "first organic solvent for cleaning filling line" when filling the organic solvent for cleaning.

[0034] [Circulation device] A pump such as an air-driven diaphragm pump can be used as the circulation device P for circulating and sending the organic solvent for cleaning. When using an electric pump other than an air-driven pump, it is preferable to select an explosion-proof product. As described above, when a pressure-feeding device such as a canister is used as the ion exchange device, the ion exchange device itself plays the role of a circulation device, so there is no need to provide a separate circulation device. That is, in a canister, when an inert gas is injected into the canister, the organic solvent for cleaning is discharged out of the system in an amount corresponding to the amount of inert gas injected into the canister. From the viewpoint of easy adaptation to scale-up, a configuration using a column or the like as the ion exchange device and a pump as the circulation device, as shown in FIG. 1 or FIG. 2, is preferable.

[0035] [Filter] The cleaning device according to the present invention may have a filter (particulate removal filter) F for purifying the cleaning organic solvent after use. The filter F is usually provided in the subsequent stage of the ion exchange device 3. The filter is not particularly limited as long as it has chemical resistance to the target cleaning organic solvent, but the pore size is preferably 100 nm or less. A plurality of ion exchange devices and filters may be connected together for use.

[0036] [others] The cleaning device according to the present invention may include necessary components such as a valve, a pressure detector PI, and a flow meter, as necessary.

[0037] [Recycling and refining organic solvents for cleaning] In the cleaning apparatus 1 having the above-mentioned configuration, the line 4 for the treated liquid is connected to the outlet 2B of the object to be cleaned and the inlet 3A of the ion exchange device, and the first line 5 for the treated liquid is connected to the inlet 2A of the object to be cleaned and the outlet 3B of the ion exchange device, thereby forming a circulation path for the cleaning organic solvent including the first line 5 for the treated liquid, the object to be cleaned 2, the line 4 for the treated liquid, and the ion exchange device 3. Then, by driving the circulation device, the cleaning organic solvent is circulated and sent through the circulation path, whereby the object to be cleaned is cleaned and the cleaning organic solvent is purified by the ion exchanger in the ion exchange device. The time for circulating and purifying the cleaning organic solvent can be appropriately set, and can be, for example, 2 hours or more.

[0038] [How to purge organic solvents used for cleaning] Methods for purging (filling) the cleaning organic solvent into the object to be cleaned include, for example, the following methods A to D. Each method will be described with reference to a cleaning apparatus having a second processing liquid line 6 branched off from a first processing liquid line 5 as shown in Fig. 1. Methods B and C can reduce the number of pumps used compared to methods A and D.

[0039] (Method A) 1) A first processing liquid line 5 is connected to the inlet 2A for the object to be cleaned. 2) A line 4 for the liquid to be treated is connected to the outlet 2B of the object to be cleaned. 3) An organic solvent for cleaning is pumped from one end of the second processing liquid line (first organic solvent for cleaning filling line) 6, and purged into the object to be cleaned from the inlet 2A for the object to be cleaned via the first processing liquid line 5. In the method A, the organic solvent for washing is delivered by a pump separate from the pump P in the washing device 1.

[0040] (Method B) 1) A first processing liquid line 5 is connected to the inlet 2A for the object to be cleaned. 2) The line 4 for the liquid to be treated is not connected to the outlet 2B of the object to be cleaned, and the organic solvent for cleaning is fed from one end of the line for the liquid to be treated (second organic solvent for cleaning filling line) 4, and purged from the inlet 2A of the object to be cleaned into the object to be cleaned via the first processing liquid line 5. In method B, the organic solvent for cleaning is delivered by a pump P in the cleaning apparatus 1. According to method B, the organic solvent for cleaning is purged into the object to be cleaned through the ion exchange device 3 and the filter F in the cleaning apparatus 1, so that the amount of impurities in the organic solvent for cleaning can be further reduced compared to method A.

[0041] (Method C) 1) A first processing liquid line 5 is connected to the inlet 2A for the object to be cleaned. 2) A line 4 for the liquid to be treated is connected to the outlet 2B of the object to be cleaned. 3) A three-way valve (not shown) is provided between the needle valve V1 of the treated liquid line 4 and the pump P. 4) One end of a new line (third organic solvent filling line for washing) 7 is connected to the three-way valve. 5) An organic solvent for cleaning is fed from the other end of the third organic solvent for cleaning filling line 7 and purged into the object to be cleaned from the inlet 2A for the object to be cleaned via the first processing liquid line 5. In method C, the organic cleaning solvent is delivered by a pump P in the cleaning apparatus 1. According to method C, similarly to method B, the organic cleaning solvent is purged into the object to be cleaned through the ion exchange device 3 and the filter F in the cleaning apparatus 1, so that the amount of impurities in the organic cleaning solvent can be reduced more than in method A. On the other hand, according to this method, compared to method B, it is possible to save the trouble of removing the line 4 for the treated liquid from the outlet 2B of the object to be cleaned every time the organic cleaning solvent is purged.

[0042] (Method D) 1) The organic solvent for cleaning is purged into the object to be cleaned from the inlet 2A of the object to be cleaned using a pump or the like, without passing through the cleaning device 1.

[0043] When the object to be cleaned is a container such as a tank, the cleaning of the object to be cleaned may be started by connecting each line in a state where the cleaning organic solvent has been purged into the container in advance by the above-mentioned method D. Alternatively, the cleaning organic solvent may be purged into the object to be cleaned via the first cleaning organic solvent filling line 6 and the first processing liquid line 5 (the above-mentioned method A), via the second cleaning organic solvent filling line 4 and the first processing liquid line 5 (the above-mentioned method B), or via the third cleaning organic solvent filling line 7 and the first processing liquid line 5 (the above-mentioned method C). When the cleaning organic solvent is purged from an empty space (the object to be cleaned), an air vent valve (not shown) is used to discharge the air in the object to be cleaned from which the cleaning organic solvent is purged to the outside of the system. If air remains inside the object to be cleaned, there may be a portion where the cleaning organic solvent does not completely come into contact with the liquid. Therefore, it is preferable to completely replace the air in the object to be cleaned with the cleaning organic solvent. The air vent valve is usually installed at the highest position in the system. That is, for example, when the object to be cleaned is a tank, the organic solvent for cleaning may be purged into the tank while removing air from an air vent valve provided at the top of the tank, until the tank is filled with the organic solvent for cleaning. When the object to be cleaned is a pipe, the end of the pipe may be fixed at the highest position and an air vent valve may be attached to that part.

[0044] <Circulation purification type cleaning method> The circulating purification type cleaning method according to the present invention is a circulating purification type cleaning method for cleaning an object to be cleaned using the above-mentioned circulating purification type cleaning apparatus according to the present invention, and includes at least a preparation step, a purging step, a cleaning step, and a purification step. The preparation step is a step of connecting a line for the liquid to be cleaned to an outlet of the object to be cleaned and an inlet of an ion exchange device, and connecting a first processing liquid line to an inlet of the object to be cleaned and an outlet of the ion exchange device. The purging step is a step of purging an organic solvent for cleaning into the object to be cleaned 2. The cleaning step is a step of cleaning the object to be cleaned 2 with the organic solvent for cleaning purged into the object to be cleaned 2. The purification step is a step of purging the organic solvent for cleaning as the liquid to be cleaned after being used in the cleaning step into the ion exchange device 3 through the line for the liquid to be cleaned 4, thereby obtaining a processing liquid ion-exchanged by the ion exchanger. In the cleaning method according to the present invention, the organic solvent for cleaning is circulated and sent through a circulation path including the first processing liquid line, the object to be cleaned, the line for the liquid to be cleaned, and the ion exchange device by driving the circulation device, whereby the cleaning step and the purification step are repeatedly performed. The preparation step may be performed before or after the purging step, so long as it is performed before the cleaning step. That is, in the cleaning method according to the present invention, each step is performed in the order of "preparation step → purging step → cleaning step → purification step → repetition of the cleaning step and purification step" or "purge step → preparation step → cleaning step → purification step → repetition of the cleaning step and purification step."

[0045] [Preparation process] The preparation step is a step of preparing for circulation cleaning by connecting the treated liquid line 4 to the outlet 2B of the object to be cleaned and the inlet 3A of the ion exchange device, and connecting the first treated liquid line 5 to the inlet 2A of the object to be cleaned and the outlet 3B of the ion exchange device. When the object to be cleaned is a container such as a tank and it is possible to purge the organic solvent for cleaning into the object to be cleaned in advance, the purging step may be carried out first, and then the preparation step may be carried out.

[0046] [Purge process] As explained about the cleaning apparatus according to the present invention, in the purging step, the cleaning organic solvent can be purged into the cleaning object 2 by using, for example, the above-mentioned methods A to D. In this case, an air vent valve can be used as appropriate to discharge the air in the cleaning object into which the cleaning organic solvent is purged to the outside of the system. Alternatively, as described above, when the cleaning object is a container such as a tank, the cleaning step may be started after the cleaning organic solvent has been purged into the tank in advance and the respective lines are connected (preparation step).

[0047] [Cleaning process] In the washing step, the object to be washed is washed with the washing organic solvent purged into the object to be washed in the purging step. The washing organic solvent used in the washing step becomes a liquid to be treated in the subsequent purification step.

[0048] [Refining process] The purification step is a step in which the cleaning organic solvent (liquid to be treated) used in the cleaning step is purged into the ion exchanger 3 through the line 4 for the liquid to be treated, to obtain a treated liquid that has been ion-exchanged by the ion exchanger. The cleaning organic solvent purified in the purification step is purged again into the object to be cleaned through the first treated liquid line 5, and is reused as the cleaning organic solvent.

[0049] In the washing step and the purification step, the circulation device may be preset so that the supply of the washing organic solvent by the circulation device is stopped when a predetermined time is reached. By setting in this way, the process can be automatically shifted to the next step (from the washing step to the purification step, or from the purification step to the washing step).

[0050] In addition, the circulation-purification type cleaning method according to the present invention may appropriately employ the items described above for the circulation-purification type cleaning apparatus according to the present invention. For example, the circulation-purification type cleaning method according to the present invention may include, prior to the preparation step, a step of cleaning the cleaning apparatus 1 itself by a known method before using the cleaning apparatus for cleaning an object to be cleaned.

[0051] Thus, in the cleaning method according to the present invention, the cleaning organic solvent is circulated through a circulation path including the first processing liquid line, the object to be cleaned, the processing liquid line, and the ion exchange device by driving the circulation device, thereby repeatedly performing the cleaning step and the purification step. That is, according to the present invention, the cleaning organic solvent used for cleaning the object to be cleaned can be repeatedly used for cleaning the object to be cleaned while being circulated and purified by the ion exchange device. As a result, the amount of the cleaning organic solvent used can be significantly reduced. Furthermore, according to the cleaning method according to the present invention, the amount of impurities eluted from the object to be cleaned after cleaning can be significantly reduced. EXAMPLES

[0052] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0053] [Examples 1 and 2] The following test was carried out to confirm that the amount of metal impurities in the cleaning organic solvent can be reduced even when an anion exchange resin with a different ion form is used as the ion exchanger. Note that the citrate form of the anion exchange resin is expected to reduce the amount of multivalent ions in the object to be cleaned because the citrate ions released by the ion exchange have a chelating effect.

[0054] <Equipment used in the test> · Cleaning target: SUS container (made of SUS304, electrolytically polished and acid-cleaned) Ion exchange device: Fluororesin column (diameter 25 mm, height 200 mm) Ion exchanger: Orlite DS-3 (trade name, manufactured by Organo Corporation, a mixed bed of strongly acidic cation exchange resin and strongly basic anion exchange resin), 90 mL (Ionic form of resin) Example 1: RH type, R-OH type (R represents the resin base) Example 2: RH type, R-citric acid type (R represents the resin base). Filter: Optimizer D filter (product name, manufactured by Entegris), pore size 50 nm Cleaning organic solvent: IPA SE grade (product name, manufactured by Tokuyama Corporation) Circulation device: Smoothflow Pump Q Series (product name, manufactured by Takumina Corporation) ·Liquid passing conditions: Circulating liquid passing, SV5 Pressure detector: USL-DL fluororesin pressure gauge R3 / 8 00N-228 series (product name, manufactured by Universal Corporation)

[0055] (Process 1) First, IPA, an organic solvent for cleaning, was poured into the above SUS container as the object to be cleaned, and the container was left to soak in IPA for 24 hours. The concentrations of various metals in the IPA after 24 hours of soaking were measured using an Agilent 8900 Triple Quadrupole ICP-MS (product name, manufactured by Agilent Technologies, Inc.). The obtained concentrations of various metals were designated as "A [ppt]". A includes the amount of metal impurities eluted from the object to be cleaned before the cleaning process and the amount of metal impurities contained in the IPA itself ("B" described below). (Process 2) Next, 24-hour circulating cleaning was performed using the circulating purification type cleaning apparatus according to the present invention shown in FIG. 2. Note that IPA was purged into the SUS container from the inlet 2A before the preparation process. After circulating cleaning, the IPA used for circulating cleaning was extracted and discarded. Then, similar to process 1, IPA (not used for cleaning) was poured into the SUS container after the above cleaning, and the IPA was immersed for 24 hours. The concentrations of various metals in the IPA after immersion for 24 hours were measured, and the obtained concentrations of various metals were designated as "C [ppt]". C includes the amount of metal impurities eluted from the object to be cleaned after the cleaning process and the amount of metal impurities contained in the IPA itself used ("B" described later).

[0056] When the concentration of various metals in the IPA (IPA before pouring into the SUS container) used as the organic solvent for cleaning is designated as "B [ppt]," the concentration of various metals X (AB) [ppt] eluted from the SUS container before cleaning and the concentration of various metals Y (CB) [ppt] eluted from the SUS container after cleaning are shown in Figure 4 (Example 1) and Figure 5 (Example 2), respectively. The reduced concentration (XY) [ppt] and reduction rate ((XY) / X×100) [%] of various metals by cleaning are shown in Table 1.

[0057] [Table 1]

[0058] As shown in Table 1, Figures 4 and 5, it was found that the amount of metal eluted from the object to be cleaned into the organic solvent for cleaning was significantly reduced by performing the circulating purification-type cleaning according to the present invention, regardless of whether the ionic form of the anion exchange resin contained in the mixed bed resin was the OH type (Example 1) or the citric acid type (Example 2). In other words, it was found that the object to be cleaned was sufficiently cleaned by performing the circulating purification-type cleaning according to the present invention.

[0059] [Examples 3 and 4] In step 2 of Examples 1 and 2, IPA was sampled from the second treatment liquid line 6 at 2 hours, 6 hours, and 24 hours after the start of circulation purification, respectively, and the concentrations of various metals in the IPA were measured using the same device as in Example 1. The results are shown in Figures 6 and 7.

[0060] As shown in Figures 6 and 7, the metal concentrations in the cleaning organic solvents repeatedly used through circulation and purification were all 5 ppt or less in Example 3 and all 15 ppt or less in Example 4, and thus the cleaning liquid had sufficient cleanliness. The cleanliness remained almost constant throughout the 24-hour circulation and purification. The metal concentrations in the cleaning liquid in Example 4 were slightly higher than those in Example 3, suggesting the possibility that citric acid in Example 4 promoted the elution of metals from the objects to be cleaned.

[0061] [Example 5] The RH type cation exchange resin and the R-citric acid type anion exchange resin used in Example 2 were not separated, but were regenerated as a mixed bed using a citric acid solution, and then used again to clean a SUS container.

[0062] (Recycling resin) First, the mixed bed resin used in Example 2 was washed with water, and then regenerated into an RH-type cation exchange resin and an R-citric acid-type anion exchange resin by the following procedure. The used mixed bed resin (50 mL) was packed into a column, and 10 BV of a 5% by mass citric acid aqueous solution was passed through the mixed bed resin at SV5. Then, ultrapure water washing was performed to wash out the citric acid remaining in the resin.

[0063] (Cleaning of objects to be cleaned) Using the regenerated mixed bed resin, a SUS container was washed (24-hour circulation washing) in the same manner as in Example 2. Then, similar to Example 4, IPA was sampled 2 hours, 6 hours, and 24 hours after the start of circulation purification, and the concentrations of various metals in the IPA were measured using the same device as in Example 2. The results are shown in FIG.

[0064] As shown in FIG. 8, it was found that the amount of metal eluted from the object to be cleaned into the organic solvent for cleaning can be significantly reduced, as in Example 4, even when a used ion exchange resin is recycled as the ion exchanger. That is, it was shown that the ion exchanger can be recycled in the cleaning of the object to be cleaned according to the present invention. It was also shown that the organic solvent for cleaning is highly purified by recycling the ion exchanger, and the eluted impurities are not concentrated in the organic solvent for cleaning. In Example 5, the amount of eluted Fe in particular was significantly reduced (reduction rate measured by the same method as in Example 1: 71%).

[0065] [Comparative Example 1] The cleaning object was washed in a batch manner without circulating and purifying the cleaning organic solvent using an ion exchanger. The cleaning object and the cleaning organic solvent were the same as those in Example 1.

[0066] (Process 1) First, IPA, an organic solvent for cleaning, was poured into a SUS container as a cleaning target, and the container was left soaked in IPA for 24 hours. Using the same device as in Example 1, the concentrations of various metals in the IPA after 24 hours of immersion were measured, and the obtained concentrations of various metals were designated as "A [ppt]". (Process 2) Next, 1 L of IPA was poured into the SUS container from step 1, lightly stirred, and then the IPA was discharged from the container. This operation was repeated three times (total amount of cleaning liquid: 3 L).

[0067] After three washing operations in step 2, the IPA used for washing was extracted and discarded. IPA not used for washing was poured into the above-mentioned washed SUS container and soaked for 24 hours. The concentrations of various metals in the IPA after 24 hours of immersion were measured, and the obtained concentrations of various metals were designated as "C [ppt]". The concentrations of various metals in the IPA after washing treatment Y(CB) [ppt] are shown in FIG. 9 together with the concentrations of various metals in the IPA after washing treatment in Examples 1 and 2 Y(CB) [ppt].

[0068] As shown in FIG. 9, in Comparative Example 1, in which the object to be cleaned was cleaned without circulating and refining the cleaning organic solvent using an ion exchange resin, many metals remained even when three times the amount of IPA was used compared to Examples 1 and 2, in which the object to be cleaned was cleaned while circulating and refining, and the effect of reducing the amount of metal elution was low. That is, in the present invention, in which the object to be cleaned is cleaned while circulating and refining the cleaning organic solvent using an ion exchange resin, the amount of metal elution could be reduced more effectively by increasing the processing amount using 1 / 3 the amount of IPA compared to when circulating and refining is not performed. Note that the total amount of cleaning is 3 L when immersion cleaning is repeated three times using 1 L of the cleaning organic solvent as in Comparative Example 1. On the other hand, the total amount of cleaning is 10.8 L when circulating and cleaning is performed for 24 hours at a circulation rate of 450 mL / hour using 1 L of the cleaning organic solvent as in Examples 1 and 2.

[0069] The present invention includes the following configurations. [Configuration 1] A circulating purification type cleaning apparatus for cleaning an object having an inlet and an outlet, an ion exchange device having an ion exchanger for ion-exchanging an organic cleaning solvent as a liquid to be treated to obtain a treatment liquid; a line for a liquid to be treated that is connectable to an outlet of the object to be cleaned and that is connected to an inlet of the ion exchange device; a first processing liquid line connectable to an inlet of the object to be cleaned and connected to an outlet of the ion exchange device; A circulation device for circulating and delivering the organic solvent for cleaning; Equipped with a first processing liquid line connected to the inlet of the object to be cleaned and the outlet of the ion exchange device, and a second processing liquid line connected to the inlet of the object to be cleaned and the outlet of the ion exchange device, the cleaning organic solvent being purified by the ion exchanger while being circulated through a circulation path including the first processing liquid line, the object to be cleaned, the processing liquid line, and the ion exchange device by driving the circulation device. [Configuration 2] The circulation-purification type cleaning apparatus according to configuration 1, further comprising a second processing liquid line for sampling, branched off from the first processing liquid line or the line 4 for the liquid to be processed. [Configuration 3] 3. The circulating purification type cleaning apparatus according to claim 1 or 2, wherein the ion exchanger comprises one or more selected from the group consisting of a granular ion exchange resin, a monolithic ion exchanger, a molded product obtained by pulverizing a granular ion exchange resin, an ion exchange fiber, and an ion adsorption membrane. [Configuration 4] 4. The circulation-purification-type cleaning apparatus according to any one of configurations 1 to 3, wherein the ion exchanger contains an H-type cation exchanger and an organic acid-type anion exchanger. [Configuration 5] an ion exchange device having an ion exchanger; a line for a liquid to be treated that is connectable to an outlet of the object to be cleaned and that is connected to an inlet of the ion exchange device; a first processing liquid line connectable to an inlet of the object to be cleaned and connected to an outlet of the ion exchange device; A circulation device; A circulating purification type cleaning method for cleaning an object to be cleaned using a circulating purification type cleaning apparatus comprising: a preparation step of connecting the line for the liquid to be treated to an outlet of the object to be cleaned and an inlet of the ion exchange device, and connecting the first processing liquid line to the inlet of the object to be cleaned and an outlet of the ion exchange device; a purging step of purging the cleaning organic solvent into the object to be cleaned; a cleaning step of cleaning the object to be cleaned with the cleaning organic solvent purged into the object to be cleaned; a purification step of purging the cleaning organic solvent as the liquid to be treated after the preparation step and the cleaning step into the ion exchange device through the line for the liquid to be treated, thereby obtaining a liquid that has been ion-exchanged by the ion exchanger; the organic solvent for cleaning is circulated through a circulation path including the first treatment liquid line, the object to be cleaned, the treatment liquid line, and the ion exchange device by driving the circulation device, thereby repeatedly carrying out the cleaning step and the purification step. [Configuration 6] 6. The circulation purification type cleaning method according to claim 5, wherein the ion exchanger comprises an H-form cation exchanger and an organic acid-form anion exchanger. [Configuration 7] 7. The circulating purification type cleaning method according to claim 5 or 6, wherein the ion exchanger used in purifying the cleaning organic solvent is regenerated and then reused in the ion exchange apparatus. [Configuration 8] 6. The circulation-purification type cleaning method according to claim 5, wherein in the cleaning step and the purification step, when a predetermined time is reached, the supply of the cleaning organic solvent by the circulation device is stopped and the step proceeds to a next step. [Explanation of symbols]

[0070] 1. Circulation purification type cleaning equipment 2. Objects to be cleaned 2A Inlet for cleaning object 2B Exit for cleaning object 3. Ion exchange device 3A Ion exchanger inlet 3B Outlet of ion exchanger 4. Line for treated liquid / Second cleaning organic solvent filling line 5. First processing liquid line 6 Second processing liquid line / First cleaning organic solvent filling line 7. Third cleaning organic solvent filling line P Pump (circulation device) F Filter PI Pressure Detector V1 Needle Valve

Claims

1. A circulating purification type cleaning apparatus for cleaning an object to be cleaned, having an inlet and an outlet, An ion exchange apparatus having an ion exchanger that obtains a treated solution by ion-exchanging an organic solvent for washing, which is the liquid to be treated, A line of liquid to be treated, which can be connected to the outlet of the object to be cleaned and is connected to the inlet of the ion exchange device, A first processing liquid line is connected to the inlet of the object to be cleaned and to the outlet of the ion exchange device, A circulation device for circulating and delivering the aforementioned cleaning organic solvent, Equipped with, A circulating purification type washing apparatus characterized in that, when the liquid to be treated line is connected to the outlet of the object to be washed and the inlet of the ion exchange device, and the first processing liquid line is connected to the inlet of the object to be washed and the outlet of the ion exchange device, the washing organic solvent is purified by the ion exchanger while being circulated through a circulation path including the first processing liquid line, the object to be washed, the liquid to be treated line, and the ion exchange device by the drive of the circulation device.

2. Furthermore, the circulating purification type washing apparatus according to claim 1, further comprising a second processing liquid line for sampling, branched from the first processing liquid line or the liquid to be processed line.

3. The circulating purification type washing apparatus according to claim 1, wherein the ion exchanger comprises one or more selected from the group consisting of granular ion exchange resin, monolithic ion exchange resin, molded product obtained by crushing granular ion exchange resin, ion exchange fiber, and ion adsorption membrane.

4. The circulating purification washing apparatus according to claim 1, wherein the ion exchanger comprises an H-type cation exchanger and an organic acid-type anion exchanger.

5. An ion exchange apparatus having an ion exchanger, A line of liquid to be treated, which can be connected to the outlet of the object to be cleaned and is connected to the inlet of the ion exchange device, A first processing liquid line that can be connected to the inlet of the object to be cleaned and is connected to the outlet of the ion exchange device, Circulation device and A circulating purification type cleaning method for cleaning an object to be cleaned using a circulating purification type cleaning apparatus equipped with the following: A preparation step of connecting the liquid to be treated line to the outlet of the object to be cleaned and the inlet of the ion exchange device, and connecting the first processing liquid line to the inlet of the object to be cleaned and the outlet of the ion exchange device, A purging step in which a cleaning organic solvent is purged into the object to be cleaned, A cleaning step of cleaning the object to be cleaned with the cleaning organic solvent purged into the object to be cleaned, After the preparation step, the cleaning organic solvent used in the cleaning step is purged into the ion exchange apparatus through the liquid to be treated line to obtain a treated liquid that has been ion-exchanged by the ion exchanger, in a purification step, A circulating purification type cleaning method characterized in that the cleaning organic solvent is circulated and delivered by the drive of the circulation device through a circulation path including the first processing liquid line, the object to be cleaned, the liquid to be processed line, and the ion exchange device, thereby repeatedly performing the cleaning step and the purification step.

6. The circulating purification washing method according to claim 5, wherein the ion exchanger comprises an H-type cation exchanger and an organic acid-type anion exchanger.

7. The circulating purification type washing method according to claim 6, wherein the ion exchanger used for the purification of the washing organic solvent is regenerated and then reused in the ion exchange apparatus.

8. The circulating purification type washing method according to claim 5, wherein in the washing step and the purification step, when a predetermined time is reached, the supply of the washing organic solvent by the circulation device is stopped and the process moves to the next step.

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