Operation management method of solution purification device, operation management device, solution purification method, and solution purification device

Abstract

To provide an operation control method for solution purification apparatus that can determine when to regenerate or replace an ion-exchange resin in a solution purification apparatus using an ion-exchange resin.SOLUTION: Provided is an operation control method for solution purification apparatus, which is an operation control method for solution purification apparatus using an ion exchange resin for performing purification of a solution to be treated, and in which the inlet pressure of the resin tower 10 containing the ion exchange resin 42 for performing purification by passing through the solution to be treated is measured, and based on the measured inlet pressure, at least one of the timing of regeneration or replacement of the ion-exchange resin is determined.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an operation management method, an operation management device, a solution purification method, and a solution purification device for purifying a solution using an ion exchange resin.

Background Art

[0002] Ion exchange resins are effective for removing metals from solutions and are widely used for purifying solutions such as aqueous solutions, organic solvents, acid solutions, and alkaline solutions.

[0003] Purification of acid solutions using anion exchange resins and cation exchange resins, and recovery of acids using chelating resins are known.

[0004] As purification of acid solutions, removal of metals from inorganic acids, organic acids, mixed solutions of organic acids and organic solvents, etc. is known. In the purification of inorganic acids, it is known that various metals exist as chloride complexes in hydrochloric acid in particular and can be removed by anion exchange resins (see Patent Document 1 and Non-Patent Document 1). In addition, a method for removing metals in phosphoric acid has also been reported (see Patent Document 2).

[0005] It has also been reported that metal impurities can be removed using anion exchange resins in the purification of organic acids. Cases where the anion exchange resin is used in the form of the organic acid to be purified (see Patent Document 3), cases where it is used in the Cl form (see Patent Document 4), etc. have been reported. In Patent Document 5, metals are reduced from a mixed solution of an organic acid and an organic solvent using a non-metal form ion exchange resin (H form, OH form).

[0006] On the other hand, regarding the operation management of water treatment devices, operation management using analysis data such as treated water quality has been reported (see Patent Document 6). Regarding back pressure, a method for suppressing the generation of bubbles due to changes in the solubility of gas when an ion exchange resin in a water-wet state and a non-aqueous liquid are mixed by applying back pressure has been reported (see Patent Document 7), but it is not a technique for using the measured value of back pressure for operation management.

[0007] However, there are no reports referring to the pressure fluctuations on the resin column due to the volume change of the ion exchange resin in the purification of solutions such as organic acids, nor are there reports on the operation management method for determining and managing the regeneration time and exchange time of the ion exchange resin in the purification of solutions such as organic acids.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Non-Patent Documents

[0009]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] An object of the present invention is to provide an operation management method, an operation management device, a solution purification method, and a solution purification device for a solution purification device using an ion exchange resin, which can determine the regeneration time or exchange time of the ion exchange resin.

Means for Solving the Problems

[0011] The present invention is a method for operating and managing a solution purification apparatus using an ion exchange resin for purifying a solution to be treated, The solution to be treated contains an organic acid, and the ion exchange resin contains an anion exchange resin. measuring an inlet pressure of a resin tower in which the ion exchange resin for purifying the solution to be treated by passing the solution to be treated is stored, and determining at least one of a regeneration time and an exchange time of the ion exchange resin based on the measured inlet pressure, which is a method for operating and managing a solution purification apparatus.

[0012] In the method for operating and managing the solution purification apparatus, at least one of the regeneration time and the exchange time of the ion exchange resin may be determined based on whether the measured inlet pressure has deviated from a preset reference value range for a preset time or more.

[0013] In the method for operating and managing the solution purification apparatus, when the measured inlet pressure has deviated from a preset reference value range for a preset time or more, the feeding of the solution to be treated to the solution purification apparatus may be stopped.

[0014] In the method for operating and managing the solution purification apparatus, a liquid contact portion of the solution purification apparatus may be formed or coated with a material inert to the solution to be treated.

[0015] In the method for operating and managing the solution purification apparatus, the solution to be treated is passed through the resin column at a flow rate of 4 L / L-resin·hr or more may also be.

[0017] In the method for operating and managing the solution purification apparatus, the ion exchange resin may be configured to include an acrylic resin.

[0018] The present invention is an operation management device for a solution purification apparatus using an ion exchange resin for purifying a solution to be treated, The solution to be treated contains an organic acid, and the ion exchange resin contains an anion exchange resin. Pressure measuring means for measuring the inlet pressure of a resin column in which the ion exchange resin for purifying the solution to be treated is stored, and determination means for determining at least one of the regeneration time and the replacement time of the ion exchange resin based on the measured inlet pressure. It is an operation management device for a solution purification device.

[0019] In the operation management device of the solution purification device, the determination means may determine at least one of the regeneration time and the replacement time of the ion exchange resin based on whether or not the measured inlet pressure deviates from a preset reference value range for a preset time or more.

[0020] The operation management device of the solution purification device may further include control means for stopping the feeding of the solution to be treated to the solution purification device when the measured inlet pressure deviates from a preset reference value range for a preset time or more.

[0021] In the operation management device of the solution purification device, the wetted part of the solution purification device may be formed or coated with a material inert to the solution to be treated.

[0024] In the operation management device of the solution purification device, the ion exchange resin may be configured to include an acrylic resin.

[0025] The present invention is a solution purification method using an ion exchange resin for purifying a solution to be treated, The solution to be treated contains an organic acid, and the ion exchange resin contains an anion exchange resin. including a purification step of passing the solution to be treated through a resin column in which the ion exchange resin is stored for purification, measuring the inlet pressure of the resin column, and determining at least one of the regeneration time and the replacement time of the ion exchange resin based on the measured inlet pressure. It is a solution purification method.

[0026] The present invention is a solution purification device using an ion exchange resin for purifying a solution to be treated, The solution to be treated contains an organic acid, and the ion exchange resin contains an anion exchange resin. Purification means for purifying the solution to be treated by passing the solution to be treated through a resin column in which the ion exchange resin is housed, pressure measurement means for measuring the inlet pressure of the resin column, and determination means for determining at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure. A solution purification apparatus comprising:

Advantages of the Invention

[0027] According to the present invention, it is possible to provide an operation management method, an operation management device, a solution purification method, and a solution purification apparatus for determining the regeneration time or the exchange time of an ion exchange resin in a solution purification apparatus using an ion exchange resin.

Brief Description of the Drawings

[0028]

Figure 1

Embodiments for Carrying Out the Invention

[0029] Embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

[0030] An outline of an example of a solution purification apparatus including an operation management apparatus for the solution purification apparatus according to an embodiment of the present invention is shown in FIG. 1, and its configuration will be described.

[0031] The purification device 1 of FIG. 1 is a solution purification device using an ion exchange resin for purifying a solution to be treated, for example, reducing metal impurities in the solution to be treated. As a purification means for performing purification by passing the solution to be treated, it includes a resin tower 10 in which an ion exchange resin 42 is stored; a pressure gauge 26 as a pressure measuring means for measuring the inlet pressure of the resin tower 10, and a control device 20 as a determination means for determining at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure, and an operation management device 3 of the solution purification device having the above; The purification device 1 may include a solution tank 12 for storing the solution to be treated and a treated solution tank 18 for storing the treated solution. The purification device 1 may further include a pretreatment solution tank 14 for storing the pretreatment solution and a drain tank 16 for storing the drain liquid.

[0032] In the purification device 1, the outlet of the solution tank 12 to be treated and the inlet of the solution to be treated, for example, at the upper part of the resin tower 10 are connected by a pipe 30 via a pump 22, and the outlet of the treated solution, for example, at the lower part of the resin tower 10 and the inlet of the treated solution tank 18 are connected by a pipe 36. A pressure gauge 26 for measuring the inlet pressure of the resin tower 10 is installed on the downstream side of the pump 22 in the pipe 30.

[0033] The pressure gauge 26 and the control device 20 are connected by a wired or wireless electrical connection or the like. The pump 22 and the control device 20 may be connected by a wired or wireless electrical connection or the like.

[0034] The outlet of the pretreatment solution tank 14 and the inlet of the pretreatment solution, for example, at the upper part of the resin tower 10 are connected by a pipe 32 via a pump 24, and the outlet of the drain, for example, at the lower part of the resin tower 10 and the inlet of the drain tank 16 are connected by a pipe 38.

[0035] A pipe 34 is connected to the inlet of the washing water, for example, at the upper part of the resin tower 10, and a pipe 40 is connected to the outlet of the washing drain, for example, at the lower part of the resin tower 10. A resistivity / conductivity meter 46 may be installed in the pipe 40 as resistivity / conductivity measuring means for measuring the resistivity or conductivity of the washing drain.

[0036] In the treatment solution tank 12, the treatment solution to be purified is stored. In the pretreatment solution tank 14, the pretreatment solution is stored.

[0037] The resin column 10 is configured to have a storage chamber. The storage chamber is made of a resin material such as a fluororesin, and has an inlet for supplying the treatment solution therein and an outlet for discharging it to the outside. Inside the storage chamber, the ion exchange resin 42 is stored and filled on the screen / mesh 44. The resin column 10 is configured such that the treatment solution supplied from the inlet passes through and contacts the ion exchange resin 42 and is discharged to the outside from the outlet, whereby the treatment solution is purified.

[0038] When the pump 22 is driven in the purification apparatus 1, the treatment solution in the treatment solution tank 12 is supplied through the pipe 30 toward the inlet of the resin column 10. A plurality of pumps 22 may be provided in the pipe path according to the flow rate of the treatment solution required for purification.

[0039] The treatment solution is supplied from the inlet, and the treatment solution passes through (flows through) the ion exchange resin 42, for example, in a downward flow and is discharged from the outlet, whereby the treatment solution to be purified is brought into contact with the ion exchange resin 42 for purification (purification step). The inlet is provided at the lower part of the storage chamber of the resin column 10, and the storage chamber is filled with the treatment solution or a solution having the same composition as the treatment solution or a solution that can be quickly replaced with the treatment solution in an upward flow, and after the air bubbles inside the resin are pushed out of the storage chamber, it passes through (flows through) in a downward flow and is discharged from the outlet, whereby the treatment solution to be purified may be brought into contact with the ion exchange resin 42 for purification. The treated solution discharged from the outlet is stored in the treatment solution tank 18 through the pipe 36 as necessary. The treated solution before reaching the target moisture content, the mixed solution of the following pretreatment solution and the treatment solution, etc. may be stored in the drain tank 16 through the pipe 38 as necessary.

[0040] By this purification process (treatment for reducing metal impurities contained), the amount of metal impurities contained in the solution to be treated (for example, the content of each metal element is 200 μg / L or less) is, for example, 20 μg / L or less. Thereby, a high-quality treatment liquid with a small amount of metal impurities contained can be obtained.

[0041] When using a solution to be treated with low affinity for water, a pretreatment liquid with higher affinity for water than the solution to be treated may be used. When the pump 24 is driven in the purification apparatus 1, the pretreatment liquid in the pretreatment liquid tank 14 is supplied through the pipe 32 toward the inlet of the resin tower 10.

[0042] The pretreatment liquid is supplied from the inlet, and the pretreatment liquid passes through the ion exchange resin 42 (flows through) in a downward flow, for example, and is discharged from the outlet, whereby the pretreatment liquid is brought into contact with the ion exchange resin 42 to perform pretreatment (pretreatment step). The pretreatment drainage discharged from the outlet is stored in the drainage tank 16 through the pipe 38 as necessary.

[0043] By this pretreatment, the solution to be treated and the ion exchange resin become more compatible, and ionic impurities are more likely to diffuse into the ion exchange resin. Also, when using a solution to be treated with low affinity for water, by using a pretreatment liquid with higher affinity for water than the solution to be treated, it becomes easier to replace the small amount of moisture remaining inside the resin with the pretreatment liquid.

[0044] When the ion exchange resin 42 immersed in the solution to be treated is to be converted back to the H form and used again when the solution to be treated is a non-aqueous liquid, it may be washed with washing water such as ultrapure water and then regenerated to the H form with a mineral acid or the like. For example, the washing water is supplied through the pipe 34 toward the washing water inlet of the resin tower 10. The washing water is supplied from the washing water inlet, and the washing water passes through the ion exchange resin 42 (flows through) in a downward flow, for example, and is discharged from the washing water outlet, whereby the washing water is brought into contact with the ion exchange resin 42 to be washed to perform washing (washing step). In the washing step, the resin tower 10 functions as a washing means. The washing drainage discharged from the washing water outlet is discharged through the pipe 40.

[0045] By this cleaning process, it can be regenerated into the H shape again. The ion exchange resin 42 may be used in a disposable manner without being regenerated.

[0046] In the operation management method and operation management device of the solution purification apparatus according to the present embodiment, the inlet pressure of the resin tower 10 in which the ion exchange resin 42 is stored and filled is measured by a pressure gauge 26 for measuring the inlet pressure of the resin tower 10, and based on the measured inlet pressure, at least one of the regeneration timing and replacement timing of the ion exchange resin is determined. For example, the control device 20 determines at least one of the regeneration timing and replacement timing of the ion exchange resin based on the inlet pressure measured by the pressure gauge 26.

[0047] The inventors of the present invention focused on the fact that in the purification process of reducing metal impurities and the like in a solution to be treated such as an organic acid with an ion exchange resin, the functional group of the ion exchange resin contracts when it is converted from the regenerated form or solution form to the metal ionized form during the purification process, and swells when it is converted from the metal ionized form to the regenerated form or solution form, resulting in pressure fluctuations at the inlet of the resin tower 10. In particular, the swelling and shrinkage rate of the anion exchange resin in an aqueous organic acid solution is larger than that in pure water or the like. In the purification of an organic acid, when the anion exchange resin converted from the Cl form or OH form to the organic acid form is converted to the metal ionized form during the purification process, pressure fluctuations occur at the inlet of the resin tower 10. By managing the pressure fluctuations, at least one of the regeneration timing and replacement timing of the ion exchange resin can be determined. Further, the anion exchange resin, particularly the anion exchange resin having an acrylic-based matrix, is less likely to be crushed due to swelling and shrinkage when the ion form is converted from the organic acid form to the metal ionized form. Therefore, in the purification process of an organic acid using an anion exchange resin, particularly an anion exchange resin having an acrylic-based matrix, a method of determining and managing at least one of the regeneration timing and replacement timing of the ion exchange resin from the pressure fluctuations at the inlet and outlet of the resin tower 10 is effective.

[0048] In purification aimed at reducing metal impurities in an acid solution such as an organic acid, when the concentration of the acid itself, which is a conductive substance other than metal impurities, is high, it is difficult to manage metal concentration fluctuations in the order of ppb in terms of conductivity and specific resistance in the treatment solution. However, according to the operation management method and operation management device of the solution purification apparatus according to the present embodiment, it is possible to appropriately determine the regeneration time or replacement time of the ion exchange resin in the solution purification apparatus using the ion exchange resin. In the case of pressure fluctuations, it is less likely to be affected by conductivity and specific resistance due to organic acids or the like.

[0049] At least one of the regeneration time and replacement time of the ion exchange resin may be determined based on whether the measured inlet pressure deviates from the preset reference value range for a preset time or more. For example, the control device 20 may determine at least one of the regeneration time and replacement time of the ion exchange resin based on whether the inlet pressure measured by the pressure gauge 26 deviates from the preset reference value range for a preset time or more.

[0050] When the measured inlet pressure deviates from the preset reference value range for a preset time or more, the feeding of the solution to be treated to the resin tower 10 of the purification apparatus may be stopped. For example, when the inlet pressure measured by the pressure gauge 26 deviates from the preset reference value range for a preset time or more, the control device 20 may control the pump 22 to stop the feeding of the solution to be treated to the resin tower 10 of the purification apparatus.

[0051] The ion exchange resin used for purification is an anion exchange resin or a cation exchange resin.

[0052] Examples of the anion exchange resin include strong anion exchange resins, weak anion exchange resins, boron-selective resins (weak anion exchange resins), polyamine resins, and the like.

[0053] Examples of the functional group of the weak anion exchange resin include primary to tertiary amino groups.

[0054] Examples of the weak anion exchange resin include IRA67 (functional group: tertiary amino group) (manufactured by DuPont), IRA96SB (functional group: tertiary amine group) (manufactured by DuPont), DIAION WA10 (functional group: tertiary amino group) (manufactured by Mitsubishi Chemical Corporation), DIAION WA20 (functional group: polyamine group) (manufactured by Mitsubishi Chemical Corporation), DIAION WA21J (functional group: polyamine group) (manufactured by Mitsubishi Chemical Corporation), DIAION WA30 (functional group: polyamine group) (manufactured by Mitsubishi Chemical Corporation), DIAION WA30C (functional group: polyamine group) (manufactured by Mitsubishi Chemical Corporation), DIAION WA30LL (functional group: polyamine group) (manufactured by Mitsubishi Chemical Corporation), SEPABEADS FPDA13 (functional group: tertiary amine group) (manufactured by Mitsubishi Chemical Corporation), and the like. The weak anion exchange resin may be used after pretreatment such as regeneration treatment is performed as necessary.

[0055] Examples of the functional group of the strong anion exchange resin include a quaternary ammonium group and the like.

[0056] Examples of strong anion exchange resins include, for example, HPR4002 Cl (functional group: quaternary amine group) (manufactured by DuPont), IRA900J Cl (functional group: quaternary amino group, tertiary amino group) (manufactured by DuPont), HPR4580 Cl (functional group: quaternary amino group) (manufactured by DuPont), IRA400J Cl (functional group: quaternary amino group, tertiary amino group) (manufactured by DuPont), IRA402BL Cl (functional group: quaternary amino group, tertiary amino group) (manufactured by DuPont), A400 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A600 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), SFA550 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A500 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A501P (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A502PS (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A503 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A520E (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A850 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), A860 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), SSTA63 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), SSTA64 (functional group: quaternary amino group) (manufactured by Purolite Co., Ltd.), etc. An anion exchange resin in which a strong anion exchange group and a weak anion exchange group coexist may also be used. For example, HPR4780 Cl (functional group: quaternary amino group, tertiary amino group) (manufactured by DuPont), DIAION WA55 (functional group: tertiary, quaternary amine group) (manufactured by Mitsubishi Chemical Corporation), etc. may be used. The strong anion exchange resin may be used after being subjected to pretreatment such as regeneration treatment as necessary.

[0057] Examples of boron-selective resins (weak anion exchange resins) include, for example, AmberSep IRA743 (functional group: glucamine group) (manufactured by DuPont), DIAION CRB03 (functional group: glucamine group) (manufactured by Mitsubishi Chemical Corporation), DIAION CRB05 (functional group: glucamine group) (manufactured by Mitsubishi Chemical Corporation), etc.

[0058] Examples of cation exchange resins include strong cation exchange resins, weak cation exchange resins, and chelating resins.

[0059] Chelating resin is a resin having a functional group capable of forming a chelate (complex) with metal ions. As this functional group, any functional group capable of forming a chelate (complex) with metal ions may be used, and there is no particular limitation. For example, aminomethylphosphonic acid group, iminodiacetic acid group, thiol group, polyamine group, etc. can be mentioned.

[0060] As the chelating resin, for example, AmberSep IRC747UPS (chelating group: aminomethylphosphonic acid group), AmberSep IRC748 (chelating group: iminodiacetic acid group) (both manufactured by DuPont), S930 / 4922 (chelating group: iminodiacetic acid) (PuroLite Co., Ltd.), S950 (chelating group: aminophosphonic acid) (PuroLite Co., Ltd.), etc. can be used. The chelating resin may be used after pretreatment such as regeneration treatment as necessary. In addition, as the H-form chelating resin, Orlite (registered trademark) DS-21 (trade name, manufactured by Organo Co., Ltd.) (chelating group: aminomethylphosphonic acid group), Orlite (registered trademark) DS-22 (trade name, manufactured by Organo Co., Ltd.) (chelating group: iminodiacetic acid group), S920 (chelating group: thiouronium) (PuroLite Co., Ltd.), S957 (chelating group: phosphonic acid, sulfonic acid) (PuroLite Co., Ltd.) may also be used.

[0061] Examples of the functional group of the weak cation exchange resin include a carboxyl group and the like.

[0062] Examples of weak cation exchange resins include Amberlite IRC76 (functional group: carboxylic acid group) (manufactured by DuPont), Amberlite FPC3500 (functional group: carboxylic acid group) (manufactured by DuPont), DIAION WK10 (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), DIAION WK100 (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), DIAION WK10S (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), DIAION WK11 (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), DIAION WT01S (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), Relite WK60L (functional group: carboxylic acid group) (manufactured by Mitsubishi Chemical Corporation), etc. The weak cation exchange resin may be used after pretreatment such as regeneration treatment as necessary.

[0063] Examples of the functional groups of strong cation exchange resins include sulfonic acid groups and the like.

[0064] Examples of strong cation exchange resins include Amberlite IR124 (functional group: sulfonic acid group) (manufactured by DuPont), Amberlite 200CT (functional group: sulfonic acid group) (manufactured by DuPont), Orlite (registered trademark) DS-1 (trade name, manufactured by Organo Corporation) (functional group: sulfonic acid group), Orlite (registered trademark) DS-4 (trade name, manufactured by Organo Corporation) (functional group: sulfonic acid group), etc. The strong cation exchange resin may be used after pretreatment such as regeneration treatment as necessary.

[0065] Depending on the metal, there are elements that become anionic as oxides or complexes, and anionic impurities. Therefore, purification may be insufficient with only cation exchange resin. Thus, an anion exchange resin may be used, and the anion exchange resin and the cation exchange resin may be used in combination.

[0066] For example, combinations in the order of anion exchange resin - cation exchange resin, combinations in the order of cation exchange resin - anion exchange resin, combinations in the order of anion exchange resin or cation exchange resin - mixed bed of anion exchange resin and cation exchange resin, combinations in the order of mixed bed of anion exchange resin and cation exchange resin - anion exchange resin or cation exchange resin, etc. can be mentioned.

[0067] An anion exchange resin and a cation exchange resin may be used in a mixed bed, or the treatment may be carried out in the order of anion exchange resin → cation exchange resin. It is effective to first remove the anion component using an anion exchange resin that is easy to ion-exchange in an acidic solution, and then remove the cation component using a cation exchange resin. If zwitterions are present, reducing them first with an anion exchange resin will reduce the load on the subsequent cation exchange resin. Also, since the cation exchange resin captures metal impurities with the cation exchange group, it may be arranged at the rear stage as a polisher. A chelating resin may be used instead of the cation exchange resin, or a combination of a cation exchange resin and a chelating resin may be used after the anion exchange resin.

[0068] Examples of the matrix of the cation exchange resin and the anion exchange resin include styrene resin, acrylic resin, etc. In an organic acid, the ionic form of the anion exchange resin is converted into an acid form and a metal ion form, so swelling and shrinkage due to the conversion of the ionic form occur, and the resin may be crushed when liquid passing and regeneration are repeated. The anion exchange resin may be composed of an acrylic resin that is resistant to swelling and shrinkage and has flexibility, for example, it has less crushing even when swelling from the OH form to the organic acid form. Also, by using an acrylic-based anion exchange resin with large swelling and shrinkage, it is easy to detect pressure fluctuations.

[0069] The solution to be purified is a liquid purified by an ion exchange resin, such as a liquid for manufacturing, etc., and is used in the manufacture of flat panel displays (FPD) such as semiconductor integrated circuits (IC), liquid crystal displays (LCD), electronic components such as imaging devices (CCD, CMOS), and various recording media such as CD-ROM, DVD-ROM, etc. (collectively referred to as electronic industrial products), including chemical solutions, solvents such as dissolution solvents, and electronic materials (including raw materials of electronic materials and their dissolution solvents).

[0070] The chemical solutions include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as citric acid, oxalic acid, succinic acid, tartaric acid, lactic acid, malonic acid, and formic acid, and organic alkalis such as tetramethylammonium hydroxide (TMAH) and tetramethylammonium chloride (TMAC).

[0071] The acids to be purified, etc., can be organic acids, inorganic acids, or organic alkalis. However, the operation management method and operation management device of the solution purification apparatus according to this embodiment are effective technologies in the purification of organic acids with a large swelling ratio.

[0072] There are also organic alkalis that can be managed by the same differential pressure. For example, in TMAH solutions and TMAC solutions, the cation exchange resin is converted into the TMA form and swells. Therefore, the operation management method and operation management device of the solution purification apparatus according to this embodiment can be preferably applied.

[0073] The solvents include organic solvents such as acetone, 2-butanone, n-butyl acetate, ethanol, methanol, 2-propanol, toluene, xylene, propylene glycol methyl ether acetate, N-methyl-2-pyrrolidinone, ethyl lactate, phenolic compounds, dimethyl sulfoxide, tetrahydrofuran, γ-butyrolactone, polyethylene glycol monomethyl ether (PGME), polyethylene glycol monomethyl ether acetate (PGMEA), etc., and mixtures thereof.

[0074] Examples of electronic materials include semiconductor-related materials (such as resists, strippers, antireflection films, interlayer insulation film coating agents, buffer coat film coating agents, etc.), flat panel display (FPD) materials (such as photoresists for liquid crystals, materials for color filters, alignment films, sealing materials, liquid crystal mixtures, polarizing plates, reflectors, overcoat agents, spacers, etc.).

[0075] The term "metal impurities" is a concept that includes metal impurity ions in addition to metals. Typical examples include sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe), etc.

[0076] Particularly when targeting the purification of organic acids for the electronic industry at the ppb level or below, the ion exchange resin itself may be thoroughly washed with acids and alkalis (such as acids like mineral acids and alkali solutions like NaOH and TMAH) to reduce the contained metals.

[0077] The resin tower 10 may be any device that can store and fill ion exchange resin and allow the solution to be treated to pass through, without particular limitation. However, in order to easily detect pressure fluctuations, it is preferable to use a resin tower with a large LV, for example, a resin tower with a bed height of 60 cm or more. Also, a material or structure with less metal elution and high pressure resistance is preferable.

[0078] Due to pressure fluctuations, pressure relief means such as a relief valve may be provided, for example, at the upper part of the resin tower 10 to relieve the pressure of the resin tower 10 when the pressure exceeds the control pressure.

[0079] The control device 20 is composed of, for example, a microcomputer including an arithmetic means such as a CPU that calculates a program, and a storage means such as a ROM and a RAM that store the program and arithmetic results, and an electronic circuit. The control device 20 can function as a determination means for determining at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure, and a determination means for determining at least one of the regeneration time and the exchange time of the ion exchange resin based on whether or not the measured inlet pressure has deviated from the range of a preset reference value for a preset time or more. When the measured inlet pressure has deviated from the range of the preset reference value for the preset time or more, it can function as a control means for stopping the feeding of the solution to be treated to the resin column 10 of the solution purification device 1.

[0080] The operation management device 3 may include an output unit as an output means for performing a predetermined output. As the output in the output unit, in addition to a visually and auditorily recognizable alarm such as a display or sound indicating the regeneration time and the exchange time of the ion exchange resin, a corresponding method for corresponding to the regeneration and exchange of the ion exchange resin may be displayed. The output unit may be, for example, any device that can display and output information, and there is no particular limitation. For example, a display device such as a liquid crystal display or an organic EL display, or an audio output device such as a speaker. For example, as a method of alarm, it may be displayed on the touch panel of the control panel, notified to the operator by email or the like via Internet communication, notified of a visually and auditorily recognizable alarm to a small communication device such as a smartphone, or notified of a visually and auditorily recognizable alarm to the output unit in a monitoring room or the like.

[0081] The wetted parts where the refining device 1 comes into contact with the solution to be treated or the treatment liquid (for example, the internal flow path of the pump 22, the inner walls of the pipes 30 and 36, the wetted parts such as the inner wall of the storage chamber of the resin column 10, the inside of the solution tank 12 to be treated and the treatment liquid tank 18, the wetted part of the pressure gauge 26, etc.) may be formed or coated with a material that is inert to the solution to be treated. Thereby, the wetted parts are inert to the solution to be treated, and the influence such as elution of metal impurities from the wetted parts into the solution to be treated can be reduced. When metal elution occurs from measuring instruments such as pressure gauges for determining the regeneration time or replacement time, the quality of the treatment liquid may deteriorate. In particular, in an acid solution, metal elution from measuring instruments such as pressure gauges may become a source of contamination. Therefore, if the inlet pressure of the resin column 10 is measured with a pressure gauge in which the wetted parts and the like are formed or coated with a material that is inert to the solution to be treated so that there is little metal elution, the change in the ionic form of the ion exchange resin can be appropriately detected by pressure through in-line analysis, and the regeneration time or replacement time can be determined.

[0082] Examples of the material that is inert to the solution to be treated and used for the wetted parts include fluororesins, polypropylene resins, polyethylene resins, etc., and fluororesins can be mentioned from the viewpoint of metal elution and the like. Examples of fluororesins include PTFE (tetrafluoroethylene resin), PFA (tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin), ETFE (tetrafluoroethylene-ethylene copolymer resin), FEP (tetrafluoroethylene-hexafluoropropylene copolymer resin), PVDF (vinylidene fluoride resin), ECTFE (ethylene-chlorotrifluoroethylene resin), PCTFEP (chlorotrifluoroethylene resin), PVF (vinyl fluoride resin), etc.

[0083] As the pressure gauge, for example, a pressure gauge made of a fluororesin such as the wetted parts can be used. Also, for example, pipes lined with a resin such as a fluororesin can be used. Thereby, metal elution can be suppressed and the inlet pressure of the resin column 10 can be measured.

[0084] When the purification device 1 further has a filtering means such as a filter for removing impurity fine particles contained in the treatment liquid after the resin tower 10, not only the eluted metal impurities in the treatment liquid but also the impurity fine particles can be reduced, and a higher-purity treatment liquid can be obtained. Alternatively, when a filtering means such as a filter for removing impurity fine particles contained in the treatment liquid is provided in the front stage of the purification device 1 or the front stage of the resin tower 10, contamination such as the adsorption of fine particles to the ion exchange resin matrix can be suppressed. In particular, fine particles with an anion charge may adsorb to the functional groups or matrix of the anion exchange resin. By providing filtering means such as filters for removing impurity fine particles at both the front and rear stages of the resin tower 10, both of the above effects can be obtained.

Example

[0085] Hereinafter, examples and comparative examples will be given to describe the present invention more specifically and in detail, but the present invention is not limited to the following examples.

[0086] <Example 1> [Swelling ratio of ion exchange resin in organic acid] (Anion exchange resin (acrylic resin, styrene resin)) The volume of each anion exchange resin in the chloride ion form in ultrapure water was measured. Strong base and medium base anion exchange resins are in the Cl form, and weak base resins are in the HCl (hydrochloric acid) form. Then, 100 g of each organic acid and 10 g of the anion exchange resin in a saturated wet state were mixed in a beaker and left standing for 1 hour. The supernatant was discarded, and after decantation several times with ultrapure water, the volume of each anion exchange resin in the organic acid form was measured. The volume change from the Cl form or HCl form to the organic acid form was expressed as the swelling ratio (%).

[0087] The results are shown in Table 1 below. As a result of the test, both strong base and weak base swelled more in the organic acid form than in the Cl form or HCl form.

[0088]

Table 1

[0089] <Example 2> [Swelling ratio of ion exchange resin in organic acid] (Anion exchange resin (acrylic resin, styrene resin)) The volume of the regenerated form of each anion exchange resin in ultrapure water was measured. Strong base and medium base anion exchange resins are in the OH form, and weak base resins are in the free base form. Then, 100 g of each organic acid and 10 g of the anion exchange resin in a saturated wet state were mixed in a beaker and left standing for 1 hour. The supernatant was discarded, and after decantation several times with ultrapure water, the volume of each anion exchange resin in the organic acid form was measured. The volume change from the OH or free base form to the organic acid form was expressed as the swelling ratio (%).

[0090] The results are shown in Table 2 below. The volume of the anion exchange resin based on weak base acrylic resin was larger in the organic acid form than that of the anion exchange resin based on styrene resin.

[0091] [Table 2]

[0092] <Example 3> [Back pressure of anion exchange resin in organic acid] (Anion exchange resin (acrylic resin, styrene resin)) To confirm the differential pressure at the initial stage of liquid flow (many of the ion exchange groups are in the citric acid form) in the purification of citric acid using the citric acid form resin, an acrylic or styrene-based anion exchange resin was prepared in advance in the citric acid form and packed into a fluororesin column. A 30% aqueous citric acid solution was passed through the citric acid form anion exchange resin at a flow rate of 2 L / L-resin·hr to 14 L / L-resin·hr, and the pressure at the column inlet was measured. The back pressure at the end of liquid flow was 0 kPa. The results are shown in Table 3 below.

[0093] It was confirmed that both styrene-based anion exchange resins and acrylic-based anion resins had backpressure even at a relatively low flow rate of 4 L / L-resin·hr. At 4 L / L-resin·hr and above, the pressure of the acrylic-based anion resin was more than twice as high as that of the styrene-based resin, confirming that the difference in the matrix affected the pressure applied to the column during liquid flow.

[0094] Also, in the same way, to confirm the differential pressure in the later stage of liquid flow (where many of the ion exchange groups are not in the citrate form) in the purification using citrate-form resin, a simulated solution obtained by dissolving 2% NaCl in 30% aqueous citric acid solution was passed through the citrate-form resin at a rate of 30 L / L-resin, and the backpressure of styrene-based and acrylic-based anion exchange resins converted from the citrate form to the Cl form in 30% aqueous citric acid solution was measured. The backpressure at the stop of liquid flow was 0 kPa. The results are shown in Table 3 below.

[0095] It was confirmed that both styrene-based anion exchange resins and acrylic-based anion resins had backpressure even at a relatively low flow rate of 4 L / L-resin·hr. At 4 L / L-resin·hr and above, the pressure of the acrylic-based anion resin was more than twice as high as that of the styrene-based resin, and the effect of the pressure during liquid flow due to the difference in the matrix was confirmed.

[0096] When comparing the backpressure at the initial stage and the later stage of liquid flow, the backpressure of the styrene-based anion exchange resin was slightly higher in the later stage, and that of the acrylic-based anion exchange resin was higher in the initial stage. Due to the difference in the matrix, a difference was observed in the tendency of pressure fluctuation. Since a difference was observed in the pressure at the initial and later stages of liquid flow for both styrene-based and acrylic-based anion exchange resins, it was confirmed that the change in ion form affected the pressure applied to the column.

[0097]

Table 3

[0098] In this way, it was possible to measure the pressure applied to the resin column in which the ion exchange resin was stored and to confirm the change in back pressure during liquid flow due to the change in ionic form. Therefore, based on the measured pressure, it is possible to determine the regeneration timing or replacement timing of the ion exchange resin in the solution purification apparatus using the ion exchange resin.

Explanation of Signs

[0099] 1 Purification apparatus, 3 Operation management apparatus, 10 Resin column, 12 Treated solution tank, 14 Pretreatment liquid tank, 16 Drainage tank, 18 Treated liquid tank, 20 Control apparatus, 22, 24 Pumps, 26 Pressure gauge, 30, 32, 34, 36, 38, 40 Pipes, 42 Ion exchange resin, 44 Sieve plate / mesh, 46 Specific resistance meter (conductivity meter).

Claims

1. A method for operating and managing a solution purification apparatus using an ion exchange resin for purifying a solution to be treated, wherein the solution to be treated contains an organic acid, the ion exchange resin contains an anion exchange resin, measuring an inlet pressure of a resin tower in which the ion exchange resin for purifying the solution to be treated by passing the solution to be treated is stored, and based on the measured inlet pressure, determining at least one of a regeneration time and an exchange time of the ion exchange resin. A method for operating and managing a solution purification apparatus, characterized by this.

2. A method for operating and managing a solution purification apparatus according to claim 1, determining at least one of a regeneration time and an exchange time of the ion exchange resin based on whether or not the measured inlet pressure has deviated from a preset reference value range for a preset time or more. A method for operating and managing a solution purification apparatus, characterized by this.

3. A method for operating and managing a solution purification apparatus according to claim 1 or 2, when the measured inlet pressure has deviated from a preset reference value range for a preset time or more, stopping the feeding of the solution to be treated to the solution purification apparatus. A method for operating and managing a solution purification apparatus, characterized by this.

4. A method for operating and managing a solution purification apparatus according to any one of claims 1 to 3, wherein a wetted part of the solution purification apparatus is formed or coated with a material inert to the solution to be treated. A method for operating and managing a solution purification apparatus, characterized by this.

5. A method for operating and managing a solution purification apparatus according to any one of claims 1 to 4, wherein the solution to be treated is passed through the resin tower at a flow rate of 4 L / L-resin·hr or more. A method for operating and managing a solution purification apparatus, characterized by this.

6. A method for operating and managing a solution purification apparatus according to any one of claims 1 to 5, A method for operating and managing a solution purification apparatus, characterized in that the ion exchange resin comprises an acrylic resin. **Claim 7** An operation management device for a solution purification apparatus using an ion exchange resin for purifying a solution to be treated, wherein the solution to be treated contains an organic acid, the ion exchange resin contains an anion exchange resin, pressure measuring means for measuring the inlet pressure of a resin tower in which the ion exchange resin for purifying the solution to be treated by passing the solution to be treated is stored; judgment means for judging at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure; An operation management device for a solution purification apparatus, comprising the above. **Claim 8** A solution purification method using an ion exchange resin for purifying a solution to be treated, wherein the solution to be treated contains an organic acid, the ion exchange resin contains an anion exchange resin, including a purification step of passing the solution to be treated through a resin tower in which the ion exchange resin is stored to perform purification; measuring the inlet pressure of the resin tower, and judging at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure. A solution purification method characterized by this. **Claim 9** A solution purification apparatus using an ion exchange resin for purifying a solution to be treated, wherein the solution to be treated contains an organic acid, the ion exchange resin contains an anion exchange resin, purification means for passing the solution to be treated through a resin tower in which the ion exchange resin is stored to perform purification; pressure measuring means for measuring the inlet pressure of the resin tower; judgment means for judging at least one of the regeneration time and the exchange time of the ion exchange resin based on the measured inlet pressure; A solution purification apparatus characterized by comprising

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