WO2022264584A1 - 微粒子測定装置とこれを備えた超純水製造装置、及び微粒子測定方法 - Google Patents
微粒子測定装置とこれを備えた超純水製造装置、及び微粒子測定方法 Download PDFInfo
- Publication number
- WO2022264584A1 WO2022264584A1 PCT/JP2022/012519 JP2022012519W WO2022264584A1 WO 2022264584 A1 WO2022264584 A1 WO 2022264584A1 JP 2022012519 W JP2022012519 W JP 2022012519W WO 2022264584 A1 WO2022264584 A1 WO 2022264584A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particle
- ultrapure water
- particle counter
- particles
- counter
- Prior art date
Links
- 238000005259 measurement Methods 0.000 title claims abstract description 73
- 229910021642 ultra pure water Inorganic materials 0.000 title claims abstract description 49
- 239000012498 ultrapure water Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000691 measurement method Methods 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 278
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004364 calculation method Methods 0.000 claims abstract description 12
- 239000010419 fine particle Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 13
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 239000011859 microparticle Substances 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 description 71
- 238000001914 filtration Methods 0.000 description 33
- 238000000108 ultra-filtration Methods 0.000 description 20
- 238000005342 ion exchange Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/22—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
Definitions
- the present invention relates to a particle measuring apparatus, an ultrapure water production apparatus equipped with the same, and a particle measurement method, and more particularly to an apparatus for measuring the number of particles in ultrapure water produced by the ultrapure water production apparatus.
- a light scattering liquid particle counter (LPC) is used, which utilizes the scattered light emitted from fine particles when the target fine particles are irradiated with laser light (International Publication No. 2020/241476).
- LPC light scattering liquid particle counter
- a direct spectroscopy method is used to determine not only the number of fine particles in ultrapure water but also the particle size and shape of the fine particles (Japanese Patent Application Laid-Open No. 2016-55240). In the direct microscopy method, fine particles captured by the filtration membrane are observed with an optical microscope, a scanning electron microscope, or the like.
- LPC when detecting particles with a small particle size range, such as a particle size of 50 nm or less, a small area in the flow cell is irradiated with laser light that has been focused and increased in light density.
- Such an LPC is also called a partial counting light scattering LPC.
- Partially-counting light scattering LPC suffers from uncertainties in particle number and concentration measurements, such as the intensity of light detected by the same size of particles depending on where they pass through the laser beam, or that particles that do not pass through the laser beam are not detected. It's big.
- the number of fine particles can be accurately evaluated for each particle size range by using a filtration membrane having a pore size smaller than the particle size of the fine particles to be measured.
- a long period of filtration is required to obtain a sample, and it is difficult to quickly grasp the fluctuations in the number of fine particles in ultrapure water.
- An object of the present invention is to provide a fine particle measuring device capable of increasing the measurement accuracy of the number of fine particles regardless of the particle size and capable of rapid measurement.
- the particle measuring apparatus of the present invention comprises first and second particle counters for obtaining the number of particles contained in water flowing through a predetermined section of an ultrapure water production apparatus, and measurement results of the first and second particle counters. Based on this, the first particle counter and the second particle counter have different counting efficiencies.
- the present invention it is possible to provide a fine particle measuring device capable of improving the measurement accuracy of the number of fine particles regardless of the particle size and allowing rapid measurement.
- FIG. 1 is a schematic diagram of a subsystem of an ultrapure water production apparatus according to one embodiment of the present invention
- FIG. 1 is a schematic configuration diagram of a particle measuring device
- FIG. It is a schematic block diagram of the microparticles
- 1 is a schematic diagram of a system used in Examples;
- FIG. It is a graph which shows the measurement result of the particle counter in the measurement point P1. It is a graph which shows the measurement result of the particle counter in the measurement point P1. It is a graph which shows the measurement result of the particle counter in the measurement point P1. It is a graph which shows the measurement result of the particle counter in the measurement point P1. It is a graph which shows the measurement result of the particle counter in the measurement point P2.
- P2 shows the measurement result of the particle counter in the measurement point P2.
- FIG. 1 shows an overview of a subsystem 1 of an ultrapure water production system according to one embodiment of the present invention.
- Subsystem 1 is a system for producing ultrapure water supplied to point of use 21 from pure water produced in the primary pure water system, and is also called a secondary pure water system.
- the subsystem 1 includes a primary pure water tank 2, a pure water supply pump 3, an ultraviolet oxidation device 4, a hydrogen peroxide removal device 5, and a non-regenerative mixed-bed first ion exchange device 6 (cartridge polisher), a membrane degassing device 7, a booster pump 8, a second ion exchange device 9, an ultrafiltration membrane device 10, and a final stage filtration membrane device 11, which are connected to the mother pipe L1 are arranged in series along the flow direction D of the water to be treated in this order.
- a branch portion of the main pipe L1 to the point of use 21 is connected to the primary pure water tank 2 by a return line L2 for returning the ultrapure water not used at the point of use 21 to the primary pure water tank 2. .
- the primary pure water tank 2 stores pure water produced by the primary pure water system.
- the ultraviolet oxidation device 4 irradiates the water to be treated with ultraviolet rays to decompose the organic substances contained in the water to be treated.
- the hydrogen peroxide remover 5 is equipped with a catalyst such as palladium (Pd), platinum (Pt), etc., and decomposes hydrogen peroxide generated by ultraviolet irradiation. This prevents the subsequent first ion exchange device 6 from being damaged by the oxidizing substances.
- the first ion exchange device 6 is filled with a mixed bed of cation exchange resin and anion exchange resin, and removes ion components in the water to be treated.
- the membrane deaerator 7 removes dissolved oxygen and carbon dioxide contained in the water to be treated.
- the booster pump 8 is provided, for example, to pressurize the water to be treated when the point of use 21 is provided at a high place.
- the second ion exchange device 9 mainly removes fine particles and particulate components generated by the booster pump 8 . Since fine particles and particulate components can be removed by the ultrafiltration membrane device 10, the second ion exchange device 9 can be omitted.
- the ultrafiltration membrane device 10 one using a membrane having a molecular weight cutoff of about 4000 to 6000 (corresponding to a pore diameter of 2 to 4 nm) can be mentioned, and this can remove fine particles with a particle size of 10 nm or more with a high probability. It becomes possible.
- the membrane may be a hollow fiber membrane, a flat membrane, or a pleated membrane.
- the ultrafiltration membrane is preferably one with little elution from the membrane itself, and polysulfone can be suitably used.
- ultrafiltration membranes examples include OLT-6036H manufactured by Asahi Kasei Corporation and NTU-3306-K6R manufactured by Nitto Denko Corporation. Since the ultrafiltration membrane device 10 removes organic matter eluted from the resin of the first ion exchange device 6, the quality of the ultrapure water supplied to the point of use 21 is further improved, and the final stage filtration membrane The load on device 11 is reduced.
- the final stage filtration membrane device 11 is a purification unit provided at the final stage of the subsystem 1.
- the filtration membrane of the final filtration membrane device 11 is made of materials such as polyethylene (PE), high density polyethylene (HDPE), tetrafluoroethylene (PTFE), polypropylene (PP), polyarylsulfone (PAS), and nylon. .
- the membrane may be a hollow fiber membrane, a flat membrane, or a pleated membrane.
- the final-stage filtration membrane device 11 has a membrane cartridge attached to a housing.
- a pipe filled with filtration membranes can be used as the final-stage filtration membrane device 11 .
- the piping is preferably made of polyvinylidene fluoride (PVDF), PTFE, CLVP (clean vinyl chloride pipe), perfluoroalkoxy fluororesin (PFA), or the like.
- PVDF polyvinylidene fluoride
- PTFE polyvinylidene fluoride
- CLVP clean vinyl chloride pipe
- PFA perfluoroalkoxy fluororesin
- the retention diameter of the filtration membrane of the final filtration membrane device 11 is 5 nm or less, preferably 3 nm or less, more preferably 1 nm or less.
- the retention diameter is measured as follows. First, the particle removal efficiency (PRE) of the filtration membrane to be measured is measured by SEMI (Semiconductor Equipment and Materials International) standard C89-0116 "TEST METHOD FOR PARTICLE ROMOVAL PERFORMANCE OF LIQUID DILTER RATED BELOW 30 nm WITH INDUCITIVELY COUPLED PLASMA- MASS SPECTROSCOPY (ICP-MS)”.
- SEMI Semiconductor Equipment and Materials International
- the retained diameter means the particle diameter at which the PRE is 80% or more, preferably 90%, ie the particle diameter at which at least 80% of the particles are captured. Therefore, the fact that the retention diameter is 5 nm means that particles with a particle size of 5 nm are captured with a probability of 80% or more, preferably 90%, or the rejection rate is 80% or more, preferably 90%.
- a Guardian (registered trademark) PS filter manufactured by Entegris can be used.
- the final stage filtration membrane device 11 is connected to the point of use 21 .
- the final-stage filtration membrane device 11 is the most downstream membrane filtration device that constitutes the ultrapure water production device. .
- the term "most downstream” means the most downstream of various purification units constituting the subsystem 1 with respect to the flow direction D of the water to be treated.
- Either one of the ultrafiltration membrane device 10 and the final-stage filtration membrane device 11 can be omitted.
- the ultrafiltration membrane device 10 becomes the most downstream membrane filtration device constituting the ultrapure water production device.
- the ultrapure water production device (subsystem 1) is equipped with a particle measuring device 12.
- the particle measuring device 12 includes a final-stage filtration membrane device 11 (ultrafiltration membrane device 10 when the final-stage filtration membrane device 11 is omitted), which is the most downstream membrane filtration device constituting the ultrapure water production device, and a use point. 21 (the section indicated by the thick line in FIG. 1).
- FIG. 2A shows a schematic configuration of the particle measuring device 12.
- Particle counter 12 includes a first particle counter 12A and a second particle counter 12B.
- the first particle counter 12A and the second particle counter 12B measure the number of particles contained in the water flowing through the section S.
- the first particle counter 12A and the second particle counter 12B are laser light scattering particle counters (LPC).
- the LPC irradiates the target fine particles with a laser beam, converts the scattered light emitted from the fine particles by the irradiation of the laser light into electric signals, and measures the number and particle size of the fine particles from the electric signals.
- a branch pipe L3 is branched from the main pipe L1, and the branch pipe L3 is further branched into two parallel branch pipes L4 and L5. is set up. Therefore, the first particle counter 12A and the second particle counter 12B are installed at substantially the same point, and the same ultrapure water is introduced. As will be described in detail later, since the second particle counter 12B has a smaller rated flow rate than the first particle counter 12A, the branch pipes L4 and L5 are provided with flow rate adjusting valves (not shown).
- the pipe diameters and lengths of the branch pipes L4 and L5 may be determined in advance so as to obtain the rated flow rates of the first particle counter 12A and the second particle counter 12B.
- the ultrapure water that has passed through the first particle counter 12A and the second particle counter 12B is discharged outside the system, but may be returned to the main pipe L1.
- the substantially same point is a section in which the number of particles does not fluctuate. Even if they are separated from each other, they can be considered to be arranged at substantially the same point.
- the first particle counter 12A and the second particle counter 12B are provided in the section between the final filtration membrane device 11 and the point of use 21, even if the positions of these particle counters are separated from each other, , so long as there is no variation in the number of fine particles, it can be considered that they are arranged at substantially the same point.
- the same consideration can be applied to the case where the first particle counter 12A and the second particle counter 12B are provided in other sections.
- substantially the same point means any two points in the section between two water treatment means arranged in series without another water treatment means intervening.
- the section between the ultraviolet oxidation device 4 and the hydrogen peroxide removal device 5, the section between the first ion exchange device 6 and the membrane deaerator 7, the section between the membrane deaeration device 7 and the second ion exchange device 9 In the section between the ultrafiltration membrane device 10 and the final stage filtration membrane device 11, the first particle counter 12A and the second particle counter 12B are provided at any position in each section. , it can be considered that the first particle counter 12A and the second particle counter 12B are arranged at substantially the same point as long as the number of particles does not fluctuate.
- the first particle counter 12A and the second particle counter 12B may be arranged in series on the branch pipe L3.
- the first particle counter 12A is positioned upstream of the second particle counter 12B in FIG. 2B, either the first particle counter 12A or the second particle counter 12B can be upstream.
- a bypass pipe L6 bypassing the first particle counter 12A and a second A bypass pipe L7 is provided to bypass the particle counter 12B.
- the particle measuring device 12 has a particle counting means 12C connected to the first particle counter 12A and the second particle counter 12B.
- Calculation means 12C is provided as a control unit of a personal computer or a subsystem, and is substantially configured as software.
- the calculation means 12C calculates the number of particles contained in the water flowing through the section S for each particle size range based on the measurement results of the first particle counter 12A and the second particle counter 12B. A specific calculation method will be described later.
- the system 101 shown in FIG. 3 the number of fine particles in ultrapure water was measured.
- the system 101 used is a simplified version of the subsystem 1 shown in FIG. .
- the most downstream membrane filtration device constituting the ultrapure water production apparatus is the ultrafiltration membrane device 10, and the filtration membrane devices 11A and 11B having the same filtration performance as the final stage filtration membrane device 11 are the ultrafiltration membrane devices. 10 and the point of use 21, it is installed in a branch pipe L7 branching from the main pipe L1.
- the ultrafiltration membrane device 10 is OLT-6036HA manufactured by Asahi Kasei Corporation, the filtration membrane device 11A is an Entegris Guardian (registered trademark) PS filter (retention diameter 5 nm), and the filtration membrane device 11B is Entegris Guardian ( (registered trademark) PS filter (retention diameter 1 nm).
- the number of fine particles in ultrapure water was measured at measurement points P1 to P3 in the figure. At each measurement point P1 to P3, the number of particles was measured by two particle counters (A) and (B).
- the particle meter (A) is Ultra DI-20 (manufactured by PMS), which can measure particles of 20 nm or more.
- the particle meter (B) is KS-16 (manufactured by RION) and can measure particles of 100 nm or more. Further, in order to obtain a reference value, ultrapure water sampled at measurement points P1 and P3 was analyzed with a scanning electron microscope (SEM).
- the particle size categories in the particle counters (A) and (B) indicate the measurement range.
- the particle counter (A) can simultaneously measure the number of particles with a particle size of 20 nm or more, 50 nm or more, 75 nm or more, and 100 nm or more. is.
- Rated flow refers to the flow of ultrapure water introduced into the particle counter.
- Effective flow rate means the flow rate that contributes to the measurement of the particle count. Specifically, the effective flow rate is the flow rate of the portion of the ultrapure water introduced into the particle counter that is irradiated with a laser beam and the number of particles is measured, or the flow rate of the portion that is irradiated with a laser beam and the number of particles is measured per unit time.
- the particle counter (A) with a small minimum measurable particle size needs to focus the laser light and irradiate a very narrow area with a strong laser light. As a result, most of the ultrapure water introduced into the particle counter is not irradiated with the laser beam and does not contribute to the measurement.
- the counting efficiency is defined as effective flow rate/rated flow rate x 100 (%).
- the particle counter (A) has a very low counting efficiency.
- the particle counter (B) irradiates a wider area with a weaker laser beam than the particle counter (A). a large value.
- FIG. 4 shows the measurement results (relationship between time and number of particles) of particle counter (A) and particle counter (B) at measurement point P1.
- the particle counter (A) measured the number of particles of 20 nm or more and the number of particles of 100 nm or more.
- 5A to 5C show the graphs of FIG. 4 separately for each measurement data, FIG. As a result of measuring the number of fine particles described above, FIG. 5C shows the result of measuring the number of fine particles of 100 nm or more with the fine particle meter (B).
- FIG. 6 shows the measurement results of the particle counter (A) and the particle counter (B) at the measurement point P2.
- 7A to 7C show the graphs of FIG. 6 separately for each measurement data, and were created in the same manner as FIGS.
- FIG. 8 shows the measurement results of the particle counter (A) and the particle counter (B) at the measurement point P3.
- 9A-9C show the graphs of FIG. 8 separately for each measurement data, and were created in the same manner as FIGS. 5A-5C.
- Table 2 shows the average values of the measured values after the number of fine particles stabilized (average values at time T shown in FIGS. 4, 6 and 8).
- a centrifugal filter equipped with a fine particle trapping membrane with a pore size of 10 nm was passed through for a predetermined period of time. It was watered and the fine particles were sampled and observed.
- " ⁇ 50" means that the number of fine particles is so small that it cannot be distinguished from signal noise, and is understood to be below the false count.
- the number of detected particles is smaller at the measurement point P3 than at the measurement point P1, and this tendency is captured by both the particle meter (A) and the particle meter (B).
- fine particles with a particle size of 100 nm or more were hardly detected by the fine particle meter (A), but were detected by the fine particle meter (B) and the SEM method.
- These large particles with a particle size of 100 nm or more are presumed not to have passed through the ultrafiltration membrane device 10 but to be fine particles generated from the ultrafiltration membrane device 10 itself.
- the reason why particles with a particle size of 100 nm or more were hardly detected by the particle counter (A) is that the area irradiated with the laser beam, that is, the particle detection area, is limited in the particle counter (A). It is conceivable that existing particles with a particle size of 100 nm or more were not detected.
- the particle counter (B) irradiates a wide area with the laser beam, so the particle detection area is large, and more particles with a diameter of 100 nm or more can be detected than the particle counter (A). Conceivable. Moreover, it can be seen from the measurement data at the measurement points P1 and P3 that the measurement results of the particle counter (B) are correlated with the measurement results of the SEM method.
- the microparticle meter (A) hardly detected microparticles of 100 nm or more existing at a low concentration.
- the particle counter (A) can detect particles with a small particle size, but the measurement accuracy of particles with a large particle size tends to decrease. It is difficult to accurately measure the number of fine particles of all particle sizes. Therefore, in order to accurately measure the number of large fine particles, the SEM method must be used. In the SEM method, even fine particles with small particle diameters can be detected by using a filter membrane with a pore size smaller than the particle diameter of the fine particles to be measured. It is possible. However, the SEM method requires a long time for sampling a sample using a centrifugal filter, and the smaller the target particle size, the longer the filtration required. Therefore, it is difficult to quickly grasp the variation in the number of fine particles in ultrapure water.
- the inventors of the present application came up with the idea of measuring particles with large particle sizes and particles with small particle sizes using separate particle counters with different counting efficiencies. That is, the particle counter (A) has the advantage of being able to detect small particles, although it has a narrow particle detection area, while the particle counter (B) has the advantage of having a wide particle detection area, although it is difficult to detect small particles. , The number of fine particles with a small particle size is measured by a fine particle meter with a low counting efficiency but a small measurable particle size, such as a fine particle meter (A), and the number of fine particles with a large particle size is measured by a fine particle meter (B), etc.
- the measurable particle diameter is large, but the particle size is measured with a particle counter that has high counting efficiency. As a result, it becomes possible to perform the measurement, which conventionally used the SEM method, only with the particle counter, so that the measurement accuracy of the number of particles can be improved regardless of the particle size, and the measurement can be performed quickly.
- the first particle counter 12A (corresponding to the particle counter (A)) and the second particle counter 12B (corresponding to the particle counter (B)) of the particle measuring device 12 have different counting efficiencies.
- the counting efficiency of the second particle counter 12B is greater than the counting efficiency of the first particle counter 12A.
- the counting efficiencies of the first particle counter 12A and the second particle counter 12B are not limited at all, for example, the counting efficiency of the first particle counter 12A is in conflict with the measurable particle diameter, It is preferable to select from 10% or less, 5% or less, 1% or less, etc. according to the required measurable particle size.
- the second particle counter 12B is characterized by high particle counting efficiency, it is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.
- the measurable particle diameters of the first particle counter 12A and the second particle counter 12B are not limited at all, for example, the measurable particle diameter of the first particle counter 12A is preferably 50 nm or less, and preferably 20 nm or less. More preferred. The measurable particle diameter of the second particle counter 12B is preferably 100 nm or more.
- the calculation means 12C uses the measurement result of the first particle counter 12A for the number of particles with a particle size of less than 100 nm, and the measurement result of the second particle counter 12B for the number of particles with a particle size of 100 nm or more. Calculate the distribution of the number of fine particles of particle size. That is, the first particle counter 12A measures the number of particles of 20 nm or more, 50 nm or more, 75 nm or more, and 100 nm or more, and thus measures the number of particles of 20 nm or more and less than 50 nm, 50 nm or more and less than 75 nm, 75 nm or more and less than 100 nm, and 100 nm or more. can be measured.
- the measurement result of the second particle counter 12B is adopted instead of the measurement result of the first particle counter 12A.
- the number of fine particles of 20 nm or more and less than 50 nm, 50 nm or more and less than 75 nm, 75 nm or more and less than 100 nm, and 100 nm or more can be obtained with high accuracy using different particle counters. If the measurable particle diameter of the first particle counter 12A and the measurable particle diameter of the second particle counter 12B partially overlap, the measurement of the second particle counter 12B (particle counter with high counting efficiency) It is preferred to adopt the results.
- the ultrapure water production apparatus (subsystem 1) has a control unit 12D that manages the operation of the ultrapure water production apparatus based on the measurement result of the calculation means 12C of the particle measuring device 12. Information about the number of particles for each particle size range calculated by the particle number calculation means 12C is input to the control unit 12D. A determination is made whether the number of particles in the area exceeds a predetermined threshold. When the controller 12D determines that the predetermined threshold has been exceeded, it generates a signal indicating that the predetermined threshold has been exceeded. Based on this signal, the control unit 12D stops the supply of ultrapure water from the ultrapure water production apparatus to the point of use 21, stops the operation of the ultrapure water production apparatus, and operates the ultrapure water production apparatus.
- the ultrapure water production apparatus (subsystem 1) includes the controller 12D, but the particle measuring apparatus 12 may include the controller 12D.
- the set of first particle counter 12A and second particle counter 12B may be installed at multiple locations.
- a set of the first particle counter 12A and the second particle counter 12B may be installed at the inlet and outlet of the ultrafiltration membrane device 10 .
- the particle number calculation means 12C may be installed for each set, or only one may be installed to receive information (particle number) from each set and output or display it for each set.
- the second particle counter 12B is omitted.
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Description
2 1次純水タンク
3 純水供給ポンプ
4 紫外線酸化装置
5 過酸化水素除去装置
6 第1のイオン交換装置
7 膜脱気装置
8 ブースターポンプ
9 第2のイオン交換装置
10 限外ろ過膜装置
11 最終段ろ過膜装置
12 微粒子測定装置
12A 第1の微粒子計
12B 第2の微粒子計
12C 微粒子数算出手段
21 ユースポイント
Claims (10)
- 超純水製造装置の所定の区間を流れる水に含まれる微粒子数を取得する第1及び第2の
微粒子計と、
前記第1及び第2の微粒子計の計測結果に基づき、前記所定の区間を流れる水に含まれる微粒子数を粒径範囲ごとに算出する微粒子数算出手段と、を有し、
前記第1の微粒子計と前記第2の微粒子計は計数効率が互いに異なる、微粒子測定装置。 - 前記区間は前記超純水製造装置を構成する最下流の膜ろ過装置と前記ユースポイントとの間の区間である、請求項1に記載の微粒子測定装置。
- 前記第2の微粒子計の前記計数効率は前記第1の微粒子計の前記計数効率より大きい、請求項1または2に記載の微粒子測定装置。
- 前記第1及び第2の微粒子計は、前記所定の区間において同じ地点に設置される、請求項1から3のいずれか1項に記載の微粒子測定装置。
- 前記第2の微粒子計の可測粒子径が100nm以上である、請求項1から4のいずれか1項に記載の微粒子測定装置。
- 前記第1の微粒子計の可測粒子径が20nm以下である、請求項5に記載の微粒子測定装置。
- 請求項1から6のいずれか1項に記載の微粒子測定装置と、前記超純水製造装置を構成する最下流の膜ろ過装置と、を有する超純水製造装置。
- 前記微粒子測定装置の前記微粒子数算出手段が算出した粒径範囲ごとの微粒子数のうち、少なくとも一部の粒径範囲における微粒子数が所定の閾値を超えたときに、その旨を示す信号を生成する制御部を有する、請求項7に記載の超純水製造装置。
- 前記制御部は前記信号に基づき前記超純水製造装置の運転を管理する、請求項8に記載の超純水製造装置。
- 超純水製造装置の所定の区間を流れる水に含まれる微粒子数を第1及び第2の微粒子計で計測することと、
前記第1及び第2の微粒子計の計測結果に基づき、前記所定の区間を流れる水に含まれる微粒子数を微粒子数算出手段によって、粒径範囲ごとに算出することと、を有し、
前記第1の微粒子計と前記第2の微粒子計は計数効率が互いに異なる、超純水中の微粒子測定方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023529567A JPWO2022264584A1 (ja) | 2021-06-14 | 2022-03-18 | |
CN202280040880.8A CN117480374A (zh) | 2021-06-14 | 2022-03-18 | 微粒测定装置和具备其的超纯水制造装置以及微粒测定方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-098602 | 2021-06-14 | ||
JP2021098602 | 2021-06-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022264584A1 true WO2022264584A1 (ja) | 2022-12-22 |
Family
ID=84527030
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/012519 WO2022264584A1 (ja) | 2021-06-14 | 2022-03-18 | 微粒子測定装置とこれを備えた超純水製造装置、及び微粒子測定方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2022264584A1 (ja) |
CN (1) | CN117480374A (ja) |
TW (1) | TW202322891A (ja) |
WO (1) | WO2022264584A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08159949A (ja) * | 1994-11-30 | 1996-06-21 | Midori Anzen Co Ltd | 粒子検出装置 |
JPH08252440A (ja) * | 1995-03-16 | 1996-10-01 | Japan Organo Co Ltd | 膜破損検出方法及び装置 |
WO2015064628A1 (ja) * | 2013-10-31 | 2015-05-07 | 栗田工業株式会社 | 超純水中の微粒子数の測定方法及び装置 |
WO2017164361A1 (ja) * | 2016-03-25 | 2017-09-28 | 栗田工業株式会社 | 超純水製造システム |
-
2022
- 2022-03-18 JP JP2023529567A patent/JPWO2022264584A1/ja active Pending
- 2022-03-18 CN CN202280040880.8A patent/CN117480374A/zh active Pending
- 2022-03-18 WO PCT/JP2022/012519 patent/WO2022264584A1/ja active Application Filing
- 2022-06-14 TW TW111121931A patent/TW202322891A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08159949A (ja) * | 1994-11-30 | 1996-06-21 | Midori Anzen Co Ltd | 粒子検出装置 |
JPH08252440A (ja) * | 1995-03-16 | 1996-10-01 | Japan Organo Co Ltd | 膜破損検出方法及び装置 |
WO2015064628A1 (ja) * | 2013-10-31 | 2015-05-07 | 栗田工業株式会社 | 超純水中の微粒子数の測定方法及び装置 |
WO2017164361A1 (ja) * | 2016-03-25 | 2017-09-28 | 栗田工業株式会社 | 超純水製造システム |
Also Published As
Publication number | Publication date |
---|---|
JPWO2022264584A1 (ja) | 2022-12-22 |
TW202322891A (zh) | 2023-06-16 |
CN117480374A (zh) | 2024-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2685482B2 (ja) | 粒子状物質の分析方法及び装置 | |
KR102287709B1 (ko) | 초순수 제조 시스템 | |
US20020134722A1 (en) | Ultrapure water producing apparatus | |
JP6477487B2 (ja) | 超純水中の微粒子数の測定方法及び装置 | |
JP3672158B2 (ja) | 濁度の測定方法および装置 | |
TWI762594B (zh) | 中空纖維薄膜裝置之潔淨度的評估方法、清洗方法及中空纖維薄膜裝置之清洗裝置 | |
CN105051519A (zh) | 微粒测定方法及微粒测定系统、以及超纯水制造系统 | |
Lee et al. | Evaluation of concentration measurement techniques of colloidal nanoparticles for microfiltration and ultrafiltration applications: Inductively coupled plasma-mass spectrometry, nanoparticle tracking analysis and electrospray-scanning mobility particle sizer | |
WO2022264584A1 (ja) | 微粒子測定装置とこれを備えた超純水製造装置、及び微粒子測定方法 | |
Troester et al. | Laser-Induced Breakdown-Detection for reliable online monitoring of membrane integrity | |
US20050228610A1 (en) | Method and device for measuring fine particles in ultrapure water | |
JP2006087988A (ja) | 光反応管内蔵型光反応装置及びこれを用いる水質モニタリング装置 | |
JP2005087949A (ja) | 膜ろ過装置の膜損傷の検知方法およびそのための装置 | |
JP2009222566A (ja) | 微生物計測方法およびシステム | |
JP2014185904A (ja) | 水質測定方法 | |
JP2008292215A (ja) | 測定ガス希釈装置およびその方法ならびに水銀分析装置およびその方法 | |
JP4591702B2 (ja) | 膜処理装置及び膜損傷検知方法 | |
JP5168952B2 (ja) | 膜ろ過装置の運転方法及び膜ろ過装置 | |
JP2021084045A (ja) | 超純水製造装置とその水質管理方法 | |
Ebie et al. | New measurement principle and basic performance of high-sensitivity turbidimeter with two optical systems in series | |
KR102235405B1 (ko) | 미량의 과산화수소수의 농도를 측정하는 장치 및 방법 | |
JPH0493638A (ja) | 低濃度吸光度連続測定装置 | |
JP6943119B2 (ja) | 膜モジュールの評価方法、評価装置および超純水製造装置 | |
KR20200116730A (ko) | 미량의 과산화수소수의 농도를 측정하는 장치 및 방법 | |
JP2021053547A (ja) | 不純物検知装置及び不純物検知方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22824580 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023529567 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18565684 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280040880.8 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |