Processing liquid evaluation method, processing liquid management method, processing liquid evaluation device and processing device

Abstract

To provide a processing liquid evaluation method in which quantitative determination of nonvolatile impurities in a processing liquid exhausted from an ion exchanger can be performed.SOLUTION: A processing liquid evaluation method is characterized to comprise a measurement step, in which nonvolatile impurities in an ion exchange processing liquid that is obtained by passing a processed liquid through an ion exchanger filling device 10 are measured by an electrically charged particle detector 16, and that performs quantitative determination of the nonvolatile impurities.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a method for evaluating a treatment liquid, a method for managing a treatment liquid, an apparatus for evaluating a treatment liquid, and a technology of a treatment apparatus.

Background Art

[0002] Ion exchangers such as ion exchange resins are used for purifying water by removing ionic impurities from water. In recent years, ion exchangers have also been used for purifying organic solvents used in manufacturing electronic materials.

[0003] In purifying a liquid to be treated such as water or an organic solvent, it is essential to manage the impurities in the treatment liquid discharged from the ion exchanger. In the analysis of impurities in a liquid, ICP-MS (Inductively Coupled Plasma Mass Spectrometry) is generally used for analyzing metals, and GC (Gas Chromatography) is generally used for analyzing organic substances. However, the impurities in the treatment liquid discharged from the ion exchanger may include non-volatile organic substances that are the matrix of the ion exchanger, and GC is inappropriate for analyzing non-volatile organic substances. Also, LC (Liquid Chromatography) is used for analyzing non-volatile organic substances, but it is difficult to quantify non-volatile organic substances because the sensitivity varies depending on the type of non-volatile organic substance.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, an object of the present disclosure is to enable quantification of non-volatile impurities in the treatment liquid discharged from the ion exchanger.

Means for Solving the Problem

[0006] An evaluation method of a treatment liquid according to an aspect of the present disclosure includes a measurement step of measuring non-volatile impurities in an ion-exchanged treatment liquid obtained by passing a liquid to be treated through an ion-exchanger filling device with a charged particle detector and quantifying the non-volatile impurities, which is characterized by this.

[0007] Further, in the above evaluation method of the treatment liquid, in the measurement step, it is preferable to pass the ion-exchanged treatment liquid through a liquid chromatography column and introduce the treatment liquid discharged from the liquid chromatography column into the charged particle detector.

[0008] Further, in the above evaluation method of the treatment liquid, it is preferable to directly introduce the ion-exchanged treatment liquid into the charged particle detector without passing it through a liquid chromatography column.

[0009] Further, in the above evaluation method of the treatment liquid, it is preferable to quantify the non-volatile impurities in the treatment liquid by a calibration curve method.

[0010] A management method of a treatment liquid according to an aspect of the present disclosure is characterized by managing the operating conditions of the ion-exchanger filling device based on the amount of the non-volatile impurities obtained by the above evaluation method of the treatment liquid.

[0011] A management method of a treatment liquid according to an aspect of the present disclosure is characterized by managing the treatment conditions of the ion-exchanged treatment liquid in the subsequent stage of the ion-exchanger filling device based on the amount of the non-volatile impurities obtained by the above evaluation method of the treatment liquid.

[0012] An evaluation device of a treatment liquid according to an aspect of the present disclosure is characterized by including a charged particle detector that measures non-volatile impurities in an ion-exchanged treatment liquid obtained by passing a liquid to be treated through an ion-exchanger filling device.

[0013] Further, a processing apparatus according to one aspect of the present disclosure includes an ion exchanger filling apparatus through which a liquid to be processed is passed, and a charged particle detector that measures non-volatile impurities in the ion-exchanged processing liquid obtained by passing the liquid to be processed through the ion exchanger filling apparatus.

Effect of the Invention

[0014] According to the present disclosure, non-volatile impurities in the processing liquid discharged from the ion exchanger can be quantified.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0016] 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.

[0017] FIG. 1 is a schematic diagram showing an example of a processing apparatus according to the present embodiment. The processing apparatus 1 shown in FIG. 1 includes an ion exchanger filling apparatus 10 and a processing liquid evaluation apparatus 12. A pipe 14a is connected to the inlet of the ion exchanger filling apparatus 10, and a pipe 14b is connected to the outlet of the ion exchanger filling apparatus 10. The processing liquid evaluation apparatus 12 includes a charged particle detector 16, and a pipe 14c branched from the pipe 14b is connected to the charged particle detector 16.

[0018] The treatment process of the liquid to be treated using the treatment apparatus 1 shown in Fig. 1 will be described. It is assumed that the liquid to be treated contains ionic impurities. The liquid to be treated is passed through the ion exchanger filling device 10 via the pipe 14a. At this time, the liquid to be treated comes into contact with the ion exchanger filled in the ion exchanger filling device 10, and the ionic impurities in the liquid to be treated are ion-exchanged and removed by the ion exchanger. The liquid to be treated from which the ionic impurities have been removed is discharged from the ion exchanger filling device 10 to the pipe 14b as a treated liquid (hereinafter referred to as an ion-exchanged treated liquid).

[0019] The liquid to be treated is not particularly limited, and examples thereof include water, sugar solution, organic solvents, etc. Organic solvents include, for example, alcohols such as isopropyl alcohol, methanol, ethanol, etc., ketones such as cyclohexanone, methyl isobutyl ketone, acetone, methyl ethyl ketone, etc., alkene-based organic solvents such as 2,4-diphenyl-4-methyl-1-pentene, 2-phenyl-1-propene, etc., N-methylpyrrolidone, and mixed organic solvents thereof. The organic solvent may be either a polar organic solvent or a nonpolar organic solvent. Further, as the polar organic solvent, it may be a protic polar organic solvent or an aprotic polar organic solvent.

[0020] The ionic impurities contained in the liquid to be treated are not particularly limited, and examples thereof include monovalent ionic metal impurities such as Na, K, Li, etc., divalent or higher ionic metal impurities such as Cr, As, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Zn, etc. (cationic impurities), anionic impurities such as sulfate ions, nitrate ions, chloride ions, boron, fluorine, organic acids such as formic acid, acetic acid, etc.

[0021] The ion exchanger filled in the ion exchanger filling device 10 includes, for example, granular ion exchange resin, non-granular organic porous ion exchanger, activated carbon, carbonized resin, zeolite, etc. The granular ion exchange resin includes, for example, cation exchange resin, anion exchange resin, chelate exchange resin, etc. The non-granular organic porous ion exchanger is, for example, a monolithic organic porous body having a continuous skeleton phase and a continuous pore phase with an ion exchange group introduced therein. The ion exchange group includes, for example, an anion exchange group, a cation exchange group, etc.

[0022] Non-volatile impurities may be mixed into the ion exchange treatment liquid obtained from the ion exchanger filling device 10. For example, when using granular ion exchange resin or non-granular organic porous ion exchanger as the ion exchanger, depending on the liquid to be treated passed through the ion exchanger filling device 10, it may react with the non-volatile organic matter that is the matrix of the ion exchanger, and non-volatile organic matter may be mixed into the ion exchange treatment liquid. Also, when the liquid to be treated contains a large amount of non-volatile impurities or the ion exchanger deteriorates, non-volatile impurities may be mixed into the ion exchange treatment liquid. Therefore, quantifying the non-volatile impurities in the ion exchange treatment liquid discharged from the ion exchanger filling device 10 is important for managing the operating conditions of the ion exchanger filling device 10 and the treatment conditions of the ion exchange treatment liquid.

[0023] The following describes a method for evaluating the treatment liquid for quantifying non-volatile impurities in the ion exchange treatment liquid.

[0024] A part of the ion exchange treatment liquid discharged from the ion exchanger filling device 10 passes through the pipe 14c and is introduced into the charged particle detector 16. The non-volatile impurities in the ion exchange treatment liquid are measured by the charged particle detector 16, and the non-volatile impurities are quantified (measurement step). The frequency of measuring non-volatile impurities by the charged particle detector 16 may be, for example, about once a day to once a month.

[0025] FIG. 2 is a block diagram showing the configuration of a charged particle detector. The configuration of the charged particle detector shown in FIG. 2 is an example and is not limited thereto, and a conventionally known charged particle detector can be applied. The charged particle detector 16 shown in FIG. 2 includes a nebulizer 20, a drying tube 22, a mixing chamber 24, a collector 26, an electrometer 28, and a detection unit 30. The measurement of nonvolatile impurities by the charged particle detector 16 is performed, for example, as follows. The ion exchange treatment liquid discharged from the ion exchanger filling device 10 is sprayed by the nebulizer 20 with a carrier gas of nitrogen or air to form droplets. The droplets are sent to the drying tube 22, and by passing through the drying tube 22, the solvent in the droplets evaporates, and residual particles of nonvolatile impurities in the droplets are formed. The residual particles are sent to the mixing chamber 24 and collide with positively charged nitrogen gas to be positively charged. The stream of positively charged residual particles moves to the collector 26, and the charge imparted to the residual particles in the collector 26 is measured as a current value by the electrometer 28. Then, the detection unit 30 creates and stores a spectrum with the retention time on the horizontal axis and the current value (signal intensity) detected by the electrometer on the vertical axis. Since the current value measured by the electrometer is directly proportional to the amount of detected residual particles, that is, the amount of nonvolatile impurities, the nonvolatile impurities can be quantified from the area of the peak in the spectrum created by the detection unit 30.

[0026] The quantification of nonvolatile impurities is preferably performed by a calibration curve method. An example of the procedure of the calibration curve method will be described below. (1) As described above, obtain the peak area in the spectrum of nonvolatile impurities obtained by the charged particle detector 16. (2) Prepare a plurality of standard solutions containing substances soluble in the liquid to be treated at different concentrations. For example, when the liquid to be treated is isopropanol, as the soluble substance, for example, LiBr is preferable. That is, prepare a plurality of isopropanols containing LiBr with different concentrations. (3) Analyze the above standard solution with the charged particle detector 16 in the same manner as described above, and create a calibration curve showing the relationship between the peak area of the obtained spectrum and the concentration of LiBr. (4) Using the calibration curve created in (3), convert the peak area obtained in (1) into the concentration of non-volatile impurities. Note that the quantification of non-volatile impurities may be performed by an operator, or an arithmetic unit may be provided in the treatment liquid evaluation device 12 and the quantification may be performed by the arithmetic unit.

[0027] Also, the ion exchange treatment liquid discharged from the ion exchanger filling device 10 may be analyzed by ICP-MS to quantify the metal impurities in the treatment liquid. By calculating the concentration of the metal impurities in the treatment liquid through the analysis by ICP-MS, the concentration of the non-volatile organic substances contained in the non-volatile impurities can be estimated from the concentration of the non-volatile impurities described above.

[0028] In this embodiment, the ion exchange treatment liquid discharged from the ion exchanger filling device 10 may be directly introduced into the charged particle detector 16, or the ion exchange treatment liquid may be passed through a liquid chromatography column, and the treatment liquid discharged from the liquid chromatography column may be sequentially introduced into the charged particle detector 16. In the former case, the total amount of non-volatile impurities contained in the ion exchange treatment liquid can be measured. In the latter case, since the components of the non-volatile impurities are separated by the liquid chromatography column, the amount of each component of the non-volatile impurities contained in the ion exchange treatment liquid can be measured. The liquid chromatography column may be appropriately selected according to the components of the non-volatile impurities, and conventionally known ones such as a gel filtration column, a cation exchange column, and an anion exchange column can be applied.

[0029] The method for managing the treatment liquid in this embodiment is characterized by managing the operating conditions of the ion exchanger filling device 10 based on the amount of non-volatile impurities in the ion exchanger treatment liquid obtained by the above-described method for evaluating the treatment liquid. As the management of the operating conditions, for example, during the actual operation of the ion exchanger filling device 10, if the result of quantifying the non-volatile impurities in the ion exchanger treatment liquid shows that the amount of non-volatile impurities exceeds a predetermined value, the operation of the ion exchanger filling device 10 may be stopped, the regeneration treatment of the ion exchanger may be performed, or the ion exchanger may be replaced, etc. Also, as the management of the operating conditions, during the actual operation of the ion exchanger filling device 10, the non-volatile impurities in the ion exchanger treatment liquid are quantified, and the liquid passing speed of the water to be treated is adjusted according to the amount of non-volatile impurities, etc. is also included. Further, as the management of the operating conditions, for example, during the design stage of the ion exchanger filling device 10, that is, during the test operation of the ion exchanger filling device 10, if the result of quantifying the non-volatile impurities in the ion exchanger treatment liquid shows that the amount of non-volatile impurities exceeds a predetermined value, changing the material or filling amount of the ion exchanger is also included.

[0030] Also, the method for managing the treatment liquid in this embodiment is characterized by managing the treatment conditions of the ion exchange treatment liquid in the subsequent stage of the ion exchanger filling device 10 based on the amount of non-volatile impurities in the ion exchanger treatment liquid obtained by the above-described method for evaluating the treatment liquid. As the management of the treatment conditions of the ion exchange treatment liquid, for example, during the test operation of the ion exchanger filling device 10, which is the design stage of the device, if the result of quantifying the non-volatile impurities in the ion exchanger treatment liquid shows that the amount of non-volatile impurities exceeds a predetermined value, adopting the installation of equipment for treating non-volatile impurities in the subsequent stage of the ion exchanger filling device 10, etc. can be mentioned. The equipment in the subsequent stage is, for example, devices such as coagulation sedimentation, biological treatment, photooxidation, wet catalytic oxidation, pressure flotation, activated carbon adsorption, microfiltration, ultrafiltration, etc. Also, as the management of the treatment conditions of the ion exchange treatment liquid, during the actual operation of the ion exchanger filling device 10, if the result of quantifying the non-volatile impurities in the ion exchanger treatment liquid shows that the amount of non-volatile impurities exceeds a predetermined value, changing the treatment conditions of the equipment installed in the subsequent stage of the ion exchanger filling device 10, etc. is also included.

Example

[0031] Hereinafter, examples will be given to more specifically explain the present disclosure, but the present disclosure is not limited to the following examples.

[0032] Three samples (a sample in which resin A was dissolved, a sample in which resin B was dissolved, and a sample in which resin C was dissolved) were prepared by dissolving 100 mL each of resin A, resin B, and resin C in 500 mL of isopropanol. These samples were analyzed with a charged particle detector to determine the peak areas of resins A, B, and C in the samples. <Measurement conditions> Mobile phase: Isopropanol / ultrapure water = 50 / 50 Flow rate: 0.5 mL / min Charged particle detector: Vanquish CAD H (Thermo Scientific TM Vanquish TM Flex UHPLC system) Concentration measurement method: Calibration curve method

[0033] Isopropanol standard solutions with concentrations of 0.05, 0.1, 0.5, 1, 10, 50, and 100 μg / mL of Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate were prepared. Each standard solution was analyzed with a charged particle detector to determine the peak area of Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate in each standard solution, and a calibration curve defining the relationship between the concentration and peak area of Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate was created. Using the created calibration curve, the peak areas of resins A, B, and C described above were converted to concentrations in the samples. As a result, resin A was 1100 ppm, resin B was 2100 ppm, and resin C was 170 ppm. The values were close to the concentrations of resins A, B, and C in the prepared samples, resulting in highly accurate measurement results.

[0034] [Appendix] (1) A method for evaluating a processing liquid, comprising a measurement step of measuring non-volatile impurities in an ion-exchange processed liquid obtained by passing a liquid to be processed through an ion-exchanger filling device using a charged aerosol detector, and quantifying the non-volatile impurities. (2) In the measurement step, the ion-exchange processed liquid is passed through a liquid chromatography column, and the processed liquid discharged from the liquid chromatography column is introduced into the charged aerosol detector. The method for evaluating a processing liquid according to (1) above. (3) In the measurement step, the ion-exchange processed liquid is directly introduced into the charged aerosol detector without passing it through a liquid chromatography column. The method for evaluating a processing liquid according to (1) above. (4) Quantifying the non-volatile impurities in the processing liquid by a calibration curve method. The method for evaluating a processing liquid according to any one of (1) to (3) above. (5) A method for managing a processing liquid, characterized in that the operating conditions of the ion-exchanger filling device are managed based on the amount of the non-volatile impurities obtained by the method for evaluating a processing liquid according to any one of (1) to (4) above. (6) A method for managing a processing liquid, characterized in that the processing conditions of the ion-exchange processed liquid in the subsequent stage of the ion-exchanger filling device are managed based on the amount of the non-volatile impurities obtained by the method for evaluating a processing liquid according to any one of (1) to (4) above. (7) A processing liquid evaluation device, comprising a charged aerosol detector for measuring non-volatile impurities in an ion-exchange processed liquid obtained by passing a liquid to be processed through an ion-exchanger filling device. (8) An ion-exchanger filling device through which a liquid to be processed is passed, A processing device, comprising a charged aerosol detector for measuring non-volatile impurities in an ion-exchange processed liquid obtained by passing the liquid to be processed through the ion-exchanger filling device.

Explanation of symbols

[0035] 1 Processing device, 10 Ion exchanger filling device, 12 Processing liquid evaluation device, 14a - 14c Pipes, 16 Charged particle detector, 20 Nebulizer, 22 Drying tube, 24 Mixing chamber, 26 Collector, 28 Electrometer, 30 Detection unit.

Claims

1. A method for evaluating a treatment liquid, comprising a measurement step of measuring non-volatile impurities in an ion exchange treatment liquid obtained by passing the treatment liquid through an ion exchanger filling device using a charged aerosol detector, and quantifying the non-volatile impurities.

2. 2. The method for evaluating a treatment liquid according to claim 1, wherein in the measurement step, the ion exchange treatment liquid is passed through a liquid chromatography column, and the treatment liquid discharged from the liquid chromatography column is introduced into the charged particle detector.

3. 2. The method for evaluating a treatment liquid according to claim 1, wherein in the measuring step, the ion-exchange treatment liquid is introduced directly into the charged particle detector without being passed through a liquid chromatography column.

4. 4. The method for evaluating a processing liquid according to claim 1, wherein the amount of non-volatile impurities in the processing liquid is determined by a calibration curve method.

5. 2. A method for managing a treatment liquid, comprising the steps of: managing operating conditions of said ion exchanger-filled device based on the amount of said non-volatile impurities obtained by the method for evaluating a treatment liquid according to claim 1.

6. 2. A method for managing a treatment liquid, comprising: managing treatment conditions for the ion-exchange treatment liquid in a downstream stage of the ion exchanger filling device based on the amount of the non-volatile impurities obtained by the method for evaluating the treatment liquid according to claim 1.

7. An apparatus for evaluating a treated liquid, comprising a charged particle detector for measuring non-volatile impurities in an ion-exchange treated liquid obtained by passing a liquid to be treated through an ion exchanger-packed device.

8. an ion exchanger packing device through which the liquid to be treated is passed; a charged particle detector for measuring non-volatile impurities in an ion-exchanged liquid obtained by passing the liquid to be treated through the ion exchanger-filled device.

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