WO2013140560A1 - AUTOMATIC pH ADJUSTMENT APPARATUS - Google Patents

AUTOMATIC pH ADJUSTMENT APPARATUS Download PDF

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WO2013140560A1
WO2013140560A1 PCT/JP2012/057276 JP2012057276W WO2013140560A1 WO 2013140560 A1 WO2013140560 A1 WO 2013140560A1 JP 2012057276 W JP2012057276 W JP 2012057276W WO 2013140560 A1 WO2013140560 A1 WO 2013140560A1
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Prior art keywords
sample
container
automatic
intensity
adjustment
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PCT/JP2012/057276
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French (fr)
Japanese (ja)
Inventor
彦北 朱
光一 千葉
寿晴 黒田
道雄 堀内
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システム・インスツルメンツ株式会社
独立行政法人産業技術総合研究所
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Priority to PCT/JP2012/057276 priority Critical patent/WO2013140560A1/en
Publication of WO2013140560A1 publication Critical patent/WO2013140560A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
    • G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means

Definitions

  • the present invention relates to an automatic pH adjusting device, and more particularly to an automatic pH adjusting device that can be suitably used for pH adjustment as a pretreatment for solid phase extraction.
  • trace elements including heavy metals is conducted for the study of material circulation in the ocean, water quality inspection of tap water, water quality survey of lake water and river water.
  • a chelate resin or the like for the purpose of separation from interference components and improvement of analysis sensitivity.
  • Patent Document 1 discloses an automatic pH adjusting device that automatically adjusts the pH of boiler water.
  • This automatic pH adjusting device includes a water supply device that supplies water containing ammonium ions to a boiler water system, and a pH measurement device that measures the pH of boiler water flowing through the boiler water system.
  • the amount of water supplied from the water supply device is controlled based on the pH measured by the pH measurement device, and the acidic components contained in the boiler water are neutralized and reduced.
  • Non-Patent Document 1 discloses an electrode insertion type pH measurement device in which an electrode is directly inserted into a sample.
  • Non-Patent Document 2 discloses a portable pH measurement device that enables pH measurement of a very small amount of sample.
  • Non-Patent Document 3 discloses a flow-type pH measuring device capable of measuring the pH of a sample flowing in a pipe.
  • the amount of sample required for analysis of trace elements is usually several ⁇ l to several tens of ml. Therefore, in the separation and concentration described above, it is sufficient if a sample exceeding the required sample amount can be prepared in a short time, and it is not necessary to use a large-scale apparatus such as Patent Document 1.
  • Patent Document 1 since ammonium ion-containing water is directly supplied to the boiler water system, there is a possibility that the hydrogen ion concentration distribution in the boiler water is biased and a long time is required for pH adjustment. Therefore, it is not suitable for adjusting the pH of the sample for separation and concentration.
  • the measurement device of Non-Patent Document 2 is portable and the device itself is small. Therefore, it is necessary to take a small amount from the sample during pH adjustment and perform pH measurement, and as a result, the pH adjustment may take a long time. Therefore, it is not suitable for pH measurement of a sample during separation and concentration.
  • Non-Patent Documents 1 to 3 it is necessary to directly contact the pH measurement device with the sample, and the possibility of contamination derived from the apparatus cannot be excluded. Therefore, it is not suitable for pH measurement of a sample during separation and concentration.
  • an object of the present invention is to provide an automatic pH adjusting device that can prepare a sample for separation and concentration in a short time or can minimize contamination factors during sample preparation.
  • a first invention is an automatic pH adjusting device, a container capable of containing a pH adjustment target solution; A stirring device capable of stirring the solution to be adjusted for pH contained in the container; When the pH adjustment target solution is accommodated in the container, a spraying device having an injection port arranged at a location where the pH adjusting agent atomized with respect to the liquid surface can be injected, It is characterized by providing.
  • the second invention is the first invention, wherein
  • the pH adjustment target solution is one to which an indicator that changes color according to pH is added,
  • a light irradiation device for irradiating light from outside the container into the container;
  • An intensity detection device that is disposed opposite to the light irradiation device and the container and detects the intensity of transmitted light that has passed through the container;
  • a pH calculator that calculates the pH of the pH adjustment target solution contained in the container using the intensity of transmitted light detected by the intensity detector; It is characterized by providing.
  • the third invention is the first or second invention, wherein
  • the light irradiation device includes a light irradiation unit that emits light
  • the intensity detector includes an intensity detector that detects the intensity of transmitted light
  • the intensity detection unit and the light irradiation unit are arranged perpendicular to the opposing surface of the container to which the intensity detection device and the light irradiation device respectively face, and the intensity detection unit is connected to the light irradiation unit. It is arrange
  • the spray apparatus which has the injection port arrange
  • the bias of the hydrogen ion concentration distribution can be reduced. Accordingly, the pH condition can be adjusted more stably, so that an amount of sample necessary for separation and concentration can be prepared in a short time. Further, since the spray device does not come into contact with the pH adjustment target solution, it is possible to eliminate a cross-contamination factor between samples.
  • the device for calculating the pH of the pH adjustment target solution contained in the container that is, the light irradiation device and the intensity detection device are arranged outside the container, the contamination derived from the device. Factors can be eliminated. Therefore, contamination factors during sample preparation can be minimized.
  • the intensity detection unit and the light irradiation unit are arranged perpendicularly to the opposing surfaces of the container facing the intensity detection device and the light irradiation device, respectively, and the intensity detection unit is Since it arrange
  • FIG. 2 is an enlarged schematic diagram of the nebulizer 28 of FIG. 1.
  • FIG. 2 is an example of the flowchart which shows the pH adjustment process routine performed by PC42.
  • FIG. 1 is a schematic diagram illustrating a configuration of an automatic pH adjusting device 10 according to the present embodiment.
  • the automatic pH adjusting device 10 of this embodiment is a device for automatically adjusting the pH of the sample 12 to which a pH indicator is added.
  • the pH automatic adjustment device 10 includes a container 14 including a rectangular main body portion 14 a that can store a sample 12 and an opening portion 14 b for taking in and out the sample 12.
  • the container 14 is a transparent container made of PET.
  • the material of the container 14 can be used instead of PET as long as it shows a high transmittance with respect to the specific wavelength light described later.
  • the main body 14 a is installed on the stirrer 16.
  • a stirrer 18 is installed inside the main body 14a.
  • the stirrer 16 rotates the stirrer 18 at a low speed by an electromagnetic coil, and the sample 12 can be gently stirred by rotating the stirrer 18 at a low speed.
  • the stirrer 18 is of a shape and material that does not wear due to contact with the main body 14a during rotation.
  • a light source unit 20 that generates an illumination light beam for irradiating the sample 12 and a pinhole plate 22 are installed.
  • the light source unit 20 for example, an LED light source, a halogen light source, a tungsten lamp, a single wavelength laser device, or the like is employed.
  • an optical diffraction device such as a mirror may be used in combination with the light sources according to the enumeration.
  • the light diffraction device is provided at a location where the light source unit 20 in FIG. 1 is disposed, and functions as the light source unit 20. Accordingly, such a light diffraction device can also be adopted as the light source unit 20.
  • a pinhole 22a that transmits part of the illumination light beam generated by the light source unit 20 is provided.
  • a pinhole plate 24 having a pinhole 24a formed at the center thereof and a spectroscope 26 for measuring the intensity of specific wavelength light out of the light flux that has passed through the pinhole 24a are installed on the other side surface of the main body portion 14a.
  • a spectroscope 26 for measuring the intensity of specific wavelength light out of the light flux that has passed through the pinhole 24a.
  • a photodiode, an optical sensor or the like having sufficient sensitivity to the specific wavelength light is employed.
  • the opening 14b is provided with a nebulizer 28 capable of injecting a liquid in a mist form.
  • the nebulizer 28 is attached to a height adjusting member (not shown). The height adjusting member is adjusted so that the liquid surface of the sample 12 and the injection port 28a do not come into contact with each other during the liquid injection.
  • FIG. 2 is an enlarged schematic view of the nebulizer 28 of FIG.
  • the nebulizer 28 includes a gas supply pipe 30 through which compressed air, an inert gas, and the like can be circulated, and a liquid supply pipe 32 through which a liquid can be circulated.
  • the gas supply pipe 30 includes a gas supply port 30a and a gas injection port 30b.
  • the gas supply port 30a is connected to an inert gas tank (not shown) such as nitrogen.
  • the liquid supply pipe 32 includes a liquid supply port 32a and a liquid ejection port 32b.
  • the liquid supply port 32 a is connected to a non-metallic tube 34.
  • FIG. 2 shows a coaxial nebulizer having a double-pipe structure, a coaxial type having a multi-pipe structure and a nebulizer characterized by a cross-flow type fine spray are also employed.
  • the nebulizer 28 is connected via a tube 34 to a container 38 that contains a pH adjusting liquid 36 therein.
  • a solenoid-type opening / closing valve 40 is provided in the middle of the tube 34. When the opening / closing valve 40 is opened while gas is flowing through the gas supply pipe 30, the pH adjustment liquid refined by the gas suction pressure is ejected from the liquid ejection port 32 b toward the liquid surface of the sample 12.
  • the pH automatic adjusting device 10 includes a PC 42 for controlling the entire device.
  • the spectroscope 26 is connected to the input side of the PC 42, and the transmitted light signal 44 from the spectroscope 26 is input to the PC 42.
  • an opening / closing valve 40 is connected to the output side of the PC 42 via an I / O board 46, and an opening / closing signal 48 from the PC 42 is generated from the PC 42.
  • the stirrer 16 and the height adjusting member may be connected to the output side of the PC 42.
  • a substrate integrated controller may be used instead of the PC 42 and the I / O board 46.
  • a valve opening degree conversion model for converting the valve opening degree of the opening / closing valve 40 into the opening / closing signal 48, or the difference between the target transmitted light intensity I tar corresponding to the adjustment target pH and the measured transmitted light intensity I mv A supply amount map that defines the relationship between ⁇ I and the supply amount of the pH adjusting liquid 36, a valve opening map that defines the relationship between the supply amount of the pH adjusting solution 36 and the valve opening of the opening / closing valve 40, etc. It is assumed that it is stored in
  • the amount of sample required for analysis of trace elements is usually several ⁇ l to several tens of ml, and this is necessary for pH adjustment for separation and concentration. It is sufficient if the amount exceeding the sample amount can be prepared in a short time.
  • the pH adjustment liquid 36 is added to the sample 12 in a droplet state using an auto burette or the like to adjust the pH.
  • the pH of the solution for separating and concentrating trace elements is in the vicinity of neutrality, and the injection of the adjustment liquid having a droplet size (about 0.1 to 0.3 ml) causes a drastic change in the solution pH.
  • the pH automatic adjusting device 10 of the present embodiment the pH adjusting liquid 36 can be sprayed in the form of a mist toward the liquid surface of the sample 12, so that the intensity fluctuation is reduced and the target pH is stably adjusted Can be reached. Therefore, the amount necessary for separation and concentration can be prepared in a short time.
  • the light source unit 20 and the spectroscope 26 used for pH measurement are installed outside the container 14. Further, the injection port 28 a of the nebulizer 28 does not come into contact with the liquid level of the sample 12. As described above, in the automatic pH adjusting device 10 of the present embodiment, since the device used for pH adjustment is not in contact with the sample 12, contamination factors during pH adjustment can be minimized.
  • FIG. 3 is an example of a flowchart showing a pH adjustment processing routine executed in the PC 42 in the present embodiment. Note that the routine shown in FIG. 3 is repeatedly executed at predetermined intervals.
  • a difference ⁇ I between the target transmitted light intensity I tar and the measured transmitted light intensity I mv is calculated (step 110). Specifically, first, the spectroscope 26 obtains the intensity of the specific wavelength light (measured transmitted light intensity I mv ), and the difference between the measured transmitted light intensity I mv and the target transmitted light intensity I tar is calculated as ⁇ I. It should be noted that a value that is separately set and stored in advance in the PC 42 is used as the target transmitted light intensity I tar .
  • step 120 it is determined whether or not the absolute value
  • > ⁇ I th ⁇ I is applied to the supply amount map, and the supply amount of the pH adjusting liquid 36 is calculated (step 130).
  • ⁇ ⁇ I th in this step the process proceeds to step 140.
  • the threshold value ⁇ I th used in this step can be changed as appropriate according to the pH adjustment accuracy.
  • the opening degree of the on-off valve 40 is changed (step 150). Specifically, first, the valve opening degree of the on-off valve 40 is calculated by applying the supply amount of the pH adjusting liquid 36 calculated in step 130 to the valve opening degree map. Next, the calculated valve opening is applied to the valve opening conversion model to be converted into an opening / closing signal 48 and transmitted to the opening / closing valve 40. Thereby, the supply amount of the pH adjusting liquid 36 from the nebulizer 28 is changed. Following this step, a counter value described later is reset (step 160).
  • step 140 it is determined whether or not the counter value is equal to a predetermined value.
  • the counter value used in this step is counted when
  • the automatic pH adjusting device of this embodiment will be further described with reference to experimental examples.
  • the sample for trace element analysis is basically prepared and stored under acidic conditions, and the separation and concentration of trace elements by solid phase extraction is in a weakly acidic to neutral pH range.
  • the pH of the sample is adjusted by increasing the pH of the sample by adding ammonia water as the pH adjusting liquid 36.
  • pH automatic adjustment device 10 pH automatic adjustment device 12 Sample (solution for pH adjustment) 14,38 container 16 stirrer (stirring device) 18 Stirrer (stirring device) 20 Light source part (light irradiation device, light irradiation part) 26 Spectrometer (Intensity detector, Intensity detector) 28 Nebulizer (spraying device) 28a injection port 36 pH adjusting liquid 42 PC (pH calculation device) 44 Transmitted light signal 48 Open / close signal

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Abstract

The present invention pertains to an automatic pH adjustment apparatus, and provides an automatic pH adjustment apparatus which enables short-time preparation of a sample for separation and concentration or which can minimize the contamination factors during the preparation of the sample. In an automatic pH adjustment apparatus (10) according to one embodiment, a pH -adjusting fluid (36) can be jetted in the form of a mist toward the liquid surface of a sample (12) to adjust the pH of the sample (12) to a target level stably with reduced fluctuations in the intensity of transmitted light. Thus, a sample in an amount necessary for separation and concentration can be prepared in a short time. Further, a light source unit (20) and a spectroscope (26), which are used in pH measurement, are located in the outside of a vessel (14), while a jet orifice (28a) of a nebulizer (28) does not come into contact with the liquid surface of the sample (12). In the automatic pH adjustment apparatus (10), as described above, the devices used in pH adjustment do not come in contact with the sample (12), so that the contamination factors during pH adjustment can be minimized.

Description

ｐＨ自動調整装置pH automatic adjustment device
　本発明は、ｐＨ自動調整装置に関し、より詳細には、固相抽出の前処理としてのｐＨ調整に好適に使用できるｐＨ自動調整装置に関する。 The present invention relates to an automatic pH adjusting device, and more particularly to an automatic pH adjusting device that can be suitably used for pH adjustment as a pretreatment for solid phase extraction.
　重金属を含む微量元素の分析は、海洋における物質循環研究・水道水の水質検査・湖水や河川水の水質調査などのために行われている。この微量元素の分析に際し、干渉成分からの分離や分析の感度向上を目的として、キレート樹脂などを用いた固相抽出による微量元素の分離濃縮が必要となる場合がある。この分離濃縮を行う際には、サンプルを予め最適なｐＨ条件に調整することが要求される。 The analysis of trace elements including heavy metals is conducted for the study of material circulation in the ocean, water quality inspection of tap water, water quality survey of lake water and river water. When analyzing this trace element, it may be necessary to separate and concentrate the trace element by solid-phase extraction using a chelate resin or the like for the purpose of separation from interference components and improvement of analysis sensitivity. When performing this separation and concentration, it is required to adjust the sample to an optimum pH condition in advance.
　ｐＨ条件の調整に関し、例えば特許文献１には、ボイラ水のｐＨを自動的に調整するｐＨ自動調整装置が開示されている。このｐＨ自動調整装置は、アンモニウムイオンを含む水をボイラ水系に供給する水供給装置と、当該ボイラ水系を流れるボイラ水のｐＨを測定するｐＨ測定装置とを備えている。このｐＨ自動調整装置においては、該ｐＨ測定装置で測定したｐＨに基づいて該水供給装置からの水供給量を制御し、ボイラ水中に含まれる酸性成分を中和低減している。 Regarding the adjustment of pH conditions, for example, Patent Document 1 discloses an automatic pH adjusting device that automatically adjusts the pH of boiler water. This automatic pH adjusting device includes a water supply device that supplies water containing ammonium ions to a boiler water system, and a pH measurement device that measures the pH of boiler water flowing through the boiler water system. In this automatic pH adjustment device, the amount of water supplied from the water supply device is controlled based on the pH measured by the pH measurement device, and the acidic components contained in the boiler water are neutralized and reduced.
　また、ｐＨ測定装置に関し、例えば非特許文献１には、サンプルに電極を直接挿入する電極挿入型のｐＨ測定装置が開示されている。また、例えば非特許文献２には、微量サンプルのｐＨ測定を可能とした携帯型のｐＨ測定装置が開示されている。更に、例えば非特許文献３には、配管中を流れるサンプルのｐＨを測定可能なフロー式のｐＨ測定装置が開示されている。 Further, regarding the pH measurement device, for example, Non-Patent Document 1 discloses an electrode insertion type pH measurement device in which an electrode is directly inserted into a sample. Further, for example, Non-Patent Document 2 discloses a portable pH measurement device that enables pH measurement of a very small amount of sample. Further, for example, Non-Patent Document 3 discloses a flow-type pH measuring device capable of measuring the pH of a sample flowing in a pipe.
日本特開２０１１－２００１２号公報Japanese Unexamined Patent Publication No. 2011-20012
　ところで、微量元素の分析に必要となるサンプル量は通常、数μｌ～数十ｍｌである。そのため、上述した分離濃縮においては、必要サンプル量を上回る量のサンプルを短時間で準備できれば十分であり、上記特許文献１のような大掛かりな装置を用いる必要はない。特に上記特許文献１では、アンモニウムイオン含有水を直接ボイラ水系に供給するので、ボイラ水中の水素イオン濃度分布に偏りが生じｐＨ調整に長時間を要する可能性がある。よって、分離濃縮用サンプルのｐＨ調整には不向きである。また、上記非特許文献２の測定装置は携帯型であり装置自体が小さい。そのため、ｐＨ調整中のサンプルから少量分取してｐＨ測定を行う必要があり、結果的にｐＨ調整に長時間を要する可能性がある。よって、分離濃縮中のサンプルのｐＨ測定には不向きである。 By the way, the amount of sample required for analysis of trace elements is usually several μl to several tens of ml. Therefore, in the separation and concentration described above, it is sufficient if a sample exceeding the required sample amount can be prepared in a short time, and it is not necessary to use a large-scale apparatus such as Patent Document 1. In particular, in Patent Document 1, since ammonium ion-containing water is directly supplied to the boiler water system, there is a possibility that the hydrogen ion concentration distribution in the boiler water is biased and a long time is required for pH adjustment. Therefore, it is not suitable for adjusting the pH of the sample for separation and concentration. Further, the measurement device of Non-Patent Document 2 is portable and the device itself is small. Therefore, it is necessary to take a small amount from the sample during pH adjustment and perform pH measurement, and as a result, the pH adjustment may take a long time. Therefore, it is not suitable for pH measurement of a sample during separation and concentration.
　また、微量元素の分析目的に鑑みれば、その分析に至るまでのコンタミネーション要因は極力排除しておくことが望ましい。この点を考慮すると、上記非特許文献１乃至３ではサンプルにｐＨ測定機器を直接接触させる必要があり、装置由来のコンタミネーション可能性を排除できない。よって、分離濃縮中のサンプルのｐＨ測定には不向きである。 Also, in view of the purpose of analyzing trace elements, it is desirable to eliminate as much contamination factors as possible until the analysis. In consideration of this point, in Non-Patent Documents 1 to 3, it is necessary to directly contact the pH measurement device with the sample, and the possibility of contamination derived from the apparatus cannot be excluded. Therefore, it is not suitable for pH measurement of a sample during separation and concentration.
　本発明は、上述の課題の少なくとも１つを解決するために鑑みなされたものである。即ち、分離濃縮用のサンプルを短時間で準備でき、または、サンプル準備中のコンタミネーション要因を最小化できるｐＨ自動調整装置を提供することを目的とする。 The present invention has been made in order to solve at least one of the above-described problems. That is, an object of the present invention is to provide an automatic pH adjusting device that can prepare a sample for separation and concentration in a short time or can minimize contamination factors during sample preparation.
　第１の発明は、上記の目的を達成するため、ｐＨ自動調整装置であって、
　ｐＨ調整対象溶液を収容可能な容器と、
　前記容器内に収容したｐＨ調整対象溶液を撹拌可能な撹拌装置と、
　前記容器内にｐＨ調整対象溶液を収容した場合に、その液面に対して霧状にしたｐＨ調整剤を噴射可能な箇所に配置された噴射口を有する噴霧装置と、
　を備えることを特徴とする。 In order to achieve the above object, a first invention is an automatic pH adjusting device,
a container capable of containing a pH adjustment target solution;
A stirring device capable of stirring the solution to be adjusted for pH contained in the container;
When the pH adjustment target solution is accommodated in the container, a spraying device having an injection port arranged at a location where the pH adjusting agent atomized with respect to the liquid surface can be injected,
It is characterized by providing.
　また、第２の発明は、第１の発明において、
　前記ｐＨ調整対象溶液は、ｐＨに応じて変色する指示薬を添加したものであり、
　前記容器外から前記容器内に向かって光を照射する光照射装置と、
　前記光照射装置と前記容器を隔てて対向配置され、前記容器を透過した透過光の強度を検出する強度検出装置と、
　前記強度検出装置で検出した透過光の強度を用いて、前記容器内に収容したｐＨ調整対象溶液のｐＨを算出するｐＨ算出装置と、
　を備えることを特徴とする。 The second invention is the first invention, wherein
The pH adjustment target solution is one to which an indicator that changes color according to pH is added,
A light irradiation device for irradiating light from outside the container into the container;
An intensity detection device that is disposed opposite to the light irradiation device and the container and detects the intensity of transmitted light that has passed through the container;
A pH calculator that calculates the pH of the pH adjustment target solution contained in the container using the intensity of transmitted light detected by the intensity detector;
It is characterized by providing.
　また、第３の発明は、第１または第２の発明において、
　前記光照射装置は光を照射する光照射部を備え、
　前記強度検出装置は透過光の強度を検出する強度検出部を備え、
　前記強度検出部および前記光照射部は、前記強度検出装置および前記光照射装置がそれぞれ対向する前記容器の対向面に対して垂直に配置されると共に、前記強度検出部は、前記光照射部からの光照射方向の延長線上に配置されることを特徴とする。 The third invention is the first or second invention, wherein
The light irradiation device includes a light irradiation unit that emits light,
The intensity detector includes an intensity detector that detects the intensity of transmitted light,
The intensity detection unit and the light irradiation unit are arranged perpendicular to the opposing surface of the container to which the intensity detection device and the light irradiation device respectively face, and the intensity detection unit is connected to the light irradiation unit. It is arrange | positioned on the extension line | wire of the light irradiation direction.
　第１の発明によれば、ｐＨ調整対象溶液の液面に対して霧状にしたｐＨ調整剤を噴射可能な箇所に配置された噴射口を有する噴霧装置を備えるので、ｐＨ調整対象溶液中の水素イオン濃度分布の偏りを小さくできる。従って、ｐＨ条件をより安定的に調整できるので、分離濃縮に必要な量のサンプルを短時間で準備できる。また、噴射装置はｐＨ調整対象溶液と接触しないので、サンプル間のクロスコンタミネーション要因を排除できる。 According to 1st invention, since the spray apparatus which has the injection port arrange | positioned in the location which can inject the pH adjuster made into the mist with respect to the liquid level of the pH adjustment object solution is provided, in the pH adjustment object solution The bias of the hydrogen ion concentration distribution can be reduced. Accordingly, the pH condition can be adjusted more stably, so that an amount of sample necessary for separation and concentration can be prepared in a short time. Further, since the spray device does not come into contact with the pH adjustment target solution, it is possible to eliminate a cross-contamination factor between samples.
　第２の発明によれば、容器内に収容したｐＨ調整対象溶液のｐＨを算出するための機器、即ち、光照射装置や強度検出装置を容器の外部に配置したので、当該機器由来のコンタミネーション要因を排除できる。よって、サンプル準備中のコンタミネーション要因を最小化できる。 According to the second aspect of the invention, since the device for calculating the pH of the pH adjustment target solution contained in the container, that is, the light irradiation device and the intensity detection device are arranged outside the container, the contamination derived from the device. Factors can be eliminated. Therefore, contamination factors during sample preparation can be minimized.
　第３の発明によれば、強度検出部および光照射部が上記強度検出装置および上記光照射装置がそれぞれ対向する上記容器の対向面に対して垂直に配置されると共に、上記強度検出部が上記光照射部からの光照射方向の延長線上に配置されるので、上記容器を透過する透過光の強度を安定的に検出できる。 According to the third invention, the intensity detection unit and the light irradiation unit are arranged perpendicularly to the opposing surfaces of the container facing the intensity detection device and the light irradiation device, respectively, and the intensity detection unit is Since it arrange | positions on the extension line | wire of the light irradiation direction from a light irradiation part, the intensity | strength of the transmitted light which permeate | transmits the said container can be detected stably.
実施形態のｐＨ自動調整装置の構成を示す概略図である。It is the schematic which shows the structure of the pH automatic adjustment apparatus of embodiment. 図１のネブライザ２８の拡大模式図である。FIG. 2 is an enlarged schematic diagram of the nebulizer 28 of FIG. 1. 本実施形態において、ＰＣ４２により実行されるｐＨ調整処理ルーチンを示すフローチャートの一例である。In this embodiment, it is an example of the flowchart which shows the pH adjustment process routine performed by PC42.
［ｐＨ自動調整装置の構成］
　以下、図１乃至図３や実験例を参照しながら、本発明の実施の形態について説明する。図１は、本実施形態のｐＨ自動調整装置１０の構成を示す概略図である。本実施形態のｐＨ自動調整装置１０は、ｐＨ指示薬を添加した試料１２のｐＨを自動的に調整するための装置である。図１に示すように、ｐＨ自動調整装置１０は、試料１２を収容可能な四角形状の本体部１４ａと、試料１２を出し入れするための開口部１４ｂとから構成される容器１４を備えている。容器１４はＰＥＴ製の透明容器である。但し、容器１４の材料は、後述する特定波長光に対して高い透過性を示すものであればＰＥＴの代わりに採用できる。 [Configuration of pH automatic adjustment device]
Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 3 and experimental examples. FIG. 1 is a schematic diagram illustrating a configuration of an automatic pH adjusting device 10 according to the present embodiment. The automatic pH adjusting device 10 of this embodiment is a device for automatically adjusting the pH of the sample 12 to which a pH indicator is added. As shown in FIG. 1, the pH automatic adjustment device 10 includes a container 14 including a rectangular main body portion 14 a that can store a sample 12 and an opening portion 14 b for taking in and out the sample 12. The container 14 is a transparent container made of PET. However, the material of the container 14 can be used instead of PET as long as it shows a high transmittance with respect to the specific wavelength light described later.
　本体部１４ａは撹拌器１６上に設置されている。本体部１４ａの内部には撹拌子１８が設置されている。撹拌器１６は電磁コイルによって撹拌子１８を低速回転させるものであり、撹拌子１８を低速回転させることで試料１２を緩やかに撹拌することができる。なお、撹拌子１８としては、回転中に本体部１４ａとの接触によって磨耗することの無いような形状、材料のものが採用される。
　本体部１４ａの一方の側面には、試料１２を照射するための照明光束を発生させる光源部２０と、ピンホール板２２とが設置されている。光源部２０としては、例えばＬＥＤ光源、ハロゲン光源、タングステンランプ、単波長レーザ装置などが採用される。なお、光路長の増加による検出感度向上を図る場合は、例えばミラーといった光回折装置を、列挙に係る光源と組み合わせて用いることがある。この場合、当該光回折装置は、図１の光源部２０の配置箇所に設けられ、光源部２０として機能することになる。従って、光源部２０としては、このような光回折装置も採用できる。ピンホール板２２の中心には、光源部２０で発生させた照明光束のうちの一部を透過するピンホール２２ａが設けられている。
　本体部１４ａの他方の側面には、その中心にピンホール２４ａが形成されたピンホール板２４と、ピンホール２４ａを通過した光束のうちの特定波長光の強度を測定する分光器２６とが設置されている。分光器２６としては、上記特定波長光に十分な感度を有するフォトダイオード、光センサなどが採用される。 The main body 14 a is installed on the stirrer 16. A stirrer 18 is installed inside the main body 14a. The stirrer 16 rotates the stirrer 18 at a low speed by an electromagnetic coil, and the sample 12 can be gently stirred by rotating the stirrer 18 at a low speed. The stirrer 18 is of a shape and material that does not wear due to contact with the main body 14a during rotation.
On one side surface of the main body portion 14a, a light source unit 20 that generates an illumination light beam for irradiating the sample 12 and a pinhole plate 22 are installed. As the light source unit 20, for example, an LED light source, a halogen light source, a tungsten lamp, a single wavelength laser device, or the like is employed. In order to improve the detection sensitivity by increasing the optical path length, an optical diffraction device such as a mirror may be used in combination with the light sources according to the enumeration. In this case, the light diffraction device is provided at a location where the light source unit 20 in FIG. 1 is disposed, and functions as the light source unit 20. Accordingly, such a light diffraction device can also be adopted as the light source unit 20. In the center of the pinhole plate 22, a pinhole 22a that transmits part of the illumination light beam generated by the light source unit 20 is provided.
On the other side surface of the main body portion 14a, a pinhole plate 24 having a pinhole 24a formed at the center thereof and a spectroscope 26 for measuring the intensity of specific wavelength light out of the light flux that has passed through the pinhole 24a are installed. Has been. As the spectroscope 26, a photodiode, an optical sensor or the like having sufficient sensitivity to the specific wavelength light is employed.
　開口部１４ｂには、液体を霧状に噴射可能なネブライザ２８が設けられている。ネブライザ２８は高さ調節部材（不図示）に取り付けられている。この高さ調節部材により、試料１２の液面と噴射口２８ａとが液体噴射中に接触することのないように調節される。ここで、図２を参照しながら、ネブライザ２８の構成について説明する。図２は、図１のネブライザ２８の拡大模式図である。図２に示すように、ネブライザ２８は、圧縮空気、不活性ガス等を流通可能なガス供給管３０と、液体を流通可能な液体供給管３２とを備えている。ガス供給管３０は、ガス供給口３０ａとガス噴射口３０ｂとを備えている。ガス供給口３０ａは、窒素等の不活性ガスタンク（不図示）と接続されている。同様に、液体供給管３２は、液体供給口３２ａと液体噴射口３２ｂとを備えている。液体供給口３２ａは、非金属製のチューブ３４と接続されている。なお、図２には二重管構造を有する同軸型のネブライザを示しているが、このほか多重管構造を有する同軸型や、クロスフロー型の微細噴霧を特徴とするネブライザも採用される。 The opening 14b is provided with a nebulizer 28 capable of injecting a liquid in a mist form. The nebulizer 28 is attached to a height adjusting member (not shown). The height adjusting member is adjusted so that the liquid surface of the sample 12 and the injection port 28a do not come into contact with each other during the liquid injection. Here, the configuration of the nebulizer 28 will be described with reference to FIG. FIG. 2 is an enlarged schematic view of the nebulizer 28 of FIG. As shown in FIG. 2, the nebulizer 28 includes a gas supply pipe 30 through which compressed air, an inert gas, and the like can be circulated, and a liquid supply pipe 32 through which a liquid can be circulated. The gas supply pipe 30 includes a gas supply port 30a and a gas injection port 30b. The gas supply port 30a is connected to an inert gas tank (not shown) such as nitrogen. Similarly, the liquid supply pipe 32 includes a liquid supply port 32a and a liquid ejection port 32b. The liquid supply port 32 a is connected to a non-metallic tube 34. Although FIG. 2 shows a coaxial nebulizer having a double-pipe structure, a coaxial type having a multi-pipe structure and a nebulizer characterized by a cross-flow type fine spray are also employed.
　再び図１に戻り、ｐＨ自動調整装置１０の構成について説明する。ネブライザ２８は、ｐＨ調整液３６を内部に収納した容器３８とチューブ３４を介して接続されている。チューブ３４の途中には、ソレノイド式の開閉バルブ４０が設けられている。
　ガス供給管３０にガスを流しつつ開閉バルブ４０を開くと、ガスの吸引圧によって微細化されたｐＨ調整液が液体噴射口３２ｂから試料１２の液面に向けて噴射される。 Returning to FIG. 1 again, the configuration of the automatic pH adjusting device 10 will be described. The nebulizer 28 is connected via a tube 34 to a container 38 that contains a pH adjusting liquid 36 therein. A solenoid-type opening / closing valve 40 is provided in the middle of the tube 34.
When the opening / closing valve 40 is opened while gas is flowing through the gas supply pipe 30, the pH adjustment liquid refined by the gas suction pressure is ejected from the liquid ejection port 32 b toward the liquid surface of the sample 12.
　また、ｐＨ自動調整装置１０は、装置全体をコントロールするためのＰＣ４２を備えている。ＰＣ４２の入力側には分光器２６が接続されており、分光器２６からの透過光信号４４がＰＣ４２に入力される。一方、ＰＣ４２の出力側にはＩ／Ｏボード４６を介して開閉バルブ４０が接続されており、ＰＣ４２からの開閉信号４８がＰＣ４２から発せられる。なお、開閉バルブ４０同様、ＰＣ４２の出力側に撹拌器１６や、上記高さ調節部材が接続されていてもよい。また、ＰＣ４２およびＩ／Ｏボード４６の代わりに、基板集積コントローラを使用してもよい。
　ＰＣ４２の内部には、各種計算モデル、関係マップなどが予め構築、設定等された上で記憶されているものとする。例えば、開閉バルブ４０のバルブ開度を開閉信号４８に変換するためのバルブ開度変換モデルや、調整目標ｐＨに対応する目標透過光強度Ｉｔａｒと、測定した透過光の強度Ｉｍｖとの差ΔＩと、ｐＨ調整液３６の供給量との関係を規定した供給量マップ、ｐＨ調整液３６の供給量と開閉バルブ４０のバルブ開度との関係を規定したバルブ開度マップなどがＰＣ４２の内部に記憶されているものとする。 Moreover, the pH automatic adjusting device 10 includes a PC 42 for controlling the entire device. The spectroscope 26 is connected to the input side of the PC 42, and the transmitted light signal 44 from the spectroscope 26 is input to the PC 42. On the other hand, an opening / closing valve 40 is connected to the output side of the PC 42 via an I / O board 46, and an opening / closing signal 48 from the PC 42 is generated from the PC 42. As with the opening / closing valve 40, the stirrer 16 and the height adjusting member may be connected to the output side of the PC 42. Further, instead of the PC 42 and the I / O board 46, a substrate integrated controller may be used.
It is assumed that various calculation models, relationship maps, and the like are preliminarily constructed and set in the PC 42 and stored. For example, a valve opening degree conversion model for converting the valve opening degree of the opening / closing valve 40 into the opening / closing signal 48, or the difference between the target transmitted light intensity I tar corresponding to the adjustment target pH and the measured transmitted light intensity I mv A supply amount map that defines the relationship between ΔI and the supply amount of the pH adjusting liquid 36, a valve opening map that defines the relationship between the supply amount of the pH adjusting solution 36 and the valve opening of the opening / closing valve 40, etc. It is assumed that it is stored in
［ｐＨ自動調整装置の特徴］
　上述したように、微量元素の分析に必要となるサンプル量（例えば、分析機器に投入されるサンプル量）は通常数μｌ～数十ｍｌであり、分離濃縮のためのｐＨ調整においては、この必要サンプル量を上回る量を短時間で準備できれば十分である。ここで、オートビュレット等を用いてｐＨ調整液３６を液滴状態で試料１２に添加しｐＨ調整すると仮定する。微量元素の分離濃縮用溶液のｐＨは中性付近の場合が多く、液滴サイズ（約０．１～０．３ｍｌ）の調整液の注入は、溶液ｐＨの激しい変化を引き起こす。そうすると、試料１２を通過する特定波長光の強度が変動し、その結果、ｐＨ調整に長時間（例えば１０分～３０分）を要する可能性がある。この点、本実施形態のｐＨ自動調整装置１０によれば、試料１２の液面に向けてｐＨ調整液３６を霧状に噴射できるので、上記の強度変動を小さくして安定的に調整目標ｐＨに到達させることができる。よって、分離濃縮に必要な量を短時間で準備できる。 [Features of automatic pH adjuster]
As described above, the amount of sample required for analysis of trace elements (for example, the amount of sample put into the analytical instrument) is usually several μl to several tens of ml, and this is necessary for pH adjustment for separation and concentration. It is sufficient if the amount exceeding the sample amount can be prepared in a short time. Here, it is assumed that the pH adjustment liquid 36 is added to the sample 12 in a droplet state using an auto burette or the like to adjust the pH. In many cases, the pH of the solution for separating and concentrating trace elements is in the vicinity of neutrality, and the injection of the adjustment liquid having a droplet size (about 0.1 to 0.3 ml) causes a drastic change in the solution pH. Then, the intensity of the specific wavelength light passing through the sample 12 varies, and as a result, it may take a long time (for example, 10 to 30 minutes) for pH adjustment. In this respect, according to the pH automatic adjusting device 10 of the present embodiment, the pH adjusting liquid 36 can be sprayed in the form of a mist toward the liquid surface of the sample 12, so that the intensity fluctuation is reduced and the target pH is stably adjusted Can be reached. Therefore, the amount necessary for separation and concentration can be prepared in a short time.
　また、上述したように、微量元素の分析目的に鑑みれば、その分析に至るまでのコンタミネーション要因を極力排除しておくことが望ましい。この点、本実施形態のｐＨ自動調整装置１０では、ｐＨ測定に使用する光源部２０や分光器２６が容器１４の外部に設置されている。また、ネブライザ２８の噴射口２８ａが試料１２の液面に接触することもない。このように、本実施形態のｐＨ自動調整装置１０では、ｐＨ調整に使用する機器を試料１２と非接触としたので、ｐＨ調整中のコンタミネーション要因を最小化できる。 Also, as described above, in view of the purpose of analyzing trace elements, it is desirable to eliminate as much contamination factors as possible until the analysis. In this regard, in the pH automatic adjustment device 10 of the present embodiment, the light source unit 20 and the spectroscope 26 used for pH measurement are installed outside the container 14. Further, the injection port 28 a of the nebulizer 28 does not come into contact with the liquid level of the sample 12. As described above, in the automatic pH adjusting device 10 of the present embodiment, since the device used for pH adjustment is not in contact with the sample 12, contamination factors during pH adjustment can be minimized.
［実施の形態における具体的処理］
　次に、図３を参照しながら、ｐＨ自動調整装置１０によるｐＨ自動調整を実現するための具体的な処理について説明する。図３は、本実施形態において、ＰＣ４２において実行されるｐＨ調整処理ルーチンを示すフローチャートの一例である。なお、図３に示すルーチンは、所定間隔にて繰り返し実行されるものとする。 [Specific processing in the embodiment]
Next, specific processing for realizing automatic pH adjustment by the automatic pH adjusting device 10 will be described with reference to FIG. FIG. 3 is an example of a flowchart showing a pH adjustment processing routine executed in the PC 42 in the present embodiment. Note that the routine shown in FIG. 3 is repeatedly executed at predetermined intervals.
　図３に示すルーチンにおいて、先ず、目標透過光強度Ｉｔａｒと測定透過光強度Ｉｍｖとの差ΔＩが算出される（ステップ１１０）。具体的には先ず、分光器２６において特定波長光の強度（測定透過光強度Ｉｍｖ）が求められ、測定透過光強度Ｉｍｖと目標透過光強度Ｉｔａｒとの差分がΔＩとして算出される。なお、目標透過光強度Ｉｔａｒには、別途設定され予めＰＣ４２の内部に記憶されている値が用いられるものとする。 In the routine shown in FIG. 3, first, a difference ΔI between the target transmitted light intensity I tar and the measured transmitted light intensity I mv is calculated (step 110). Specifically, first, the spectroscope 26 obtains the intensity of the specific wavelength light (measured transmitted light intensity I mv ), and the difference between the measured transmitted light intensity I mv and the target transmitted light intensity I tar is calculated as ΔI. It should be noted that a value that is separately set and stored in advance in the PC 42 is used as the target transmitted light intensity I tar .
　続いて、ステップ１１０で算出したΔＩの絶対値｜ΔＩ｜が閾値ΔＩｔｈよりも大きいか否かが判定される（ステップ１２０）。本ステップにおいて、この｜ΔＩ｜＞ΔＩｔｈの場合には、ΔＩが上記供給量マップに適用されｐＨ調整液３６の供給量が算出される（ステップ１３０）。一方、本ステップにおいて、｜ΔＩ｜≦ΔＩｔｈの場合には、ステップ１４０に進む。なお、本ステップで用いる閾値ΔＩｔｈは、ｐＨ調整精度に応じて適宜変更が可能である。 Subsequently, it is determined whether or not the absolute value | ΔI | of ΔI calculated in step 110 is larger than a threshold value ΔI th (step 120). In this step, when | ΔI |> ΔI th , ΔI is applied to the supply amount map, and the supply amount of the pH adjusting liquid 36 is calculated (step 130). On the other hand, if | ΔI | ≦ ΔI th in this step, the process proceeds to step 140. The threshold value ΔI th used in this step can be changed as appropriate according to the pH adjustment accuracy.
　ステップ１３０に続いて、開閉バルブ４０の開度が変更される（ステップ１５０）。具体的には先ず、ステップ１３０で算出したｐＨ調整液３６の供給量を上記バルブ開度マップに適応して開閉バルブ４０のバルブ開度を算出する。次いで、算出したバルブ開度を上記バルブ開度変換モデルに適用して開閉信号４８に変換され、開閉バルブ４０に発信される。これにより、ネブライザ２８からのｐＨ調整液３６の供給量が変更される。本ステップに続いて、後述のカウンタ値がリセットされる（ステップ１６０）。 Following step 130, the opening degree of the on-off valve 40 is changed (step 150). Specifically, first, the valve opening degree of the on-off valve 40 is calculated by applying the supply amount of the pH adjusting liquid 36 calculated in step 130 to the valve opening degree map. Next, the calculated valve opening is applied to the valve opening conversion model to be converted into an opening / closing signal 48 and transmitted to the opening / closing valve 40. Thereby, the supply amount of the pH adjusting liquid 36 from the nebulizer 28 is changed. Following this step, a counter value described later is reset (step 160).
　ステップ１４０では、カウンタ値が所定値と等しいか否かが判定される。本ステップで用いるカウンタ値は、｜ΔＩ｜≦ΔＩｔｈの場合にカウントされるものである。また、本ステップで用いる所定値は、ｐＨ調整精度に応じて別途設定され、予めＰＣ４２の内部に記憶されているものとする。本ステップにおいて、カウンタ値が所定値と等しい場合、ｐＨ調整が終了したと判断できるので、閉信号としての開閉信号４８が開閉バルブ４０に発信される（ステップ１７０）。一方、本ステップにおいて、カウンタ値が所定値と等しくない場合、カウンタ値に１が加算される（ステップ１８０）。 In step 140, it is determined whether or not the counter value is equal to a predetermined value. The counter value used in this step is counted when | ΔI | ≦ ΔI th . Further, it is assumed that the predetermined value used in this step is set separately according to the pH adjustment accuracy and stored in advance in the PC 42. In this step, if the counter value is equal to the predetermined value, it can be determined that the pH adjustment has been completed, so an open / close signal 48 as a close signal is transmitted to the open / close valve 40 (step 170). On the other hand, if the counter value is not equal to the predetermined value in this step, 1 is added to the counter value (step 180).
［実験例］
　次に、実験例を参照しながら、本実施形態のｐＨ自動調整装置について更に説明する。
　なお、本実験例においては、微量元素分析用の試料が基本的に酸性条件に調製し保存されていること、および、固相抽出による微量元素の分離濃縮が弱酸性から中性のｐＨ範囲で行われることを考慮し、アンモニア水をｐＨ調整液３６として添加することで試料ｐＨを上昇させてｐＨ調整を実現している。 [Experimental example]
Next, the automatic pH adjusting device of this embodiment will be further described with reference to experimental examples.
In this experimental example, the sample for trace element analysis is basically prepared and stored under acidic conditions, and the separation and concentration of trace elements by solid phase extraction is in a weakly acidic to neutral pH range. In consideration of what is performed, the pH of the sample is adjusted by increasing the pH of the sample by adding ammonia water as the pH adjusting liquid 36.
　ｐＨ調整に際しては、先ず、０．２％硝酸溶液１００ｍｌ中に、メチルレッド指示薬（０．１％）および酢酸（９９％）０．５ｍｌ、アンモニア水（２８％）０．８５ｍｌを添加してテスト試料を調製した。次いで、調製したテスト試料を容器１４に収容し、アンモニア水（２８％）をネブライザ２８から添加した。分光器２６での計測波長は５６０ｎｍを用いた。透過光信号４４の計測および開閉バルブ４０のコントロールは、目的透過光強度の２／３に到達するまでは３００ｍｓ間隔で行い、その後は１００ｍｓ間隔で行った。直近３回の透過光信号強度が目標強度となった場合にｐＨ調整が完了するとした。
　調整目標ｐＨ＝６．０としてｐＨ調整を行ったところ、１０個の独立したテスト試料のうち、ｐＨ＝５．９となったものが２個、ｐＨ＝６．０となったものが５個、ｐＨ＝６．１となったものが３個であった。この結果から、本実施形態のｐＨ自動調整装置によれば、固相抽出における微量元素の回収率の再現性を確保するのに十分な精度でｐＨ調整できることが明らかとなった。また、各テスト試料の調整は２分以内に完了できた。そのため、固相抽出に必要な量を短時間で準備できることも明らかとなった。 When adjusting the pH, first, add 100 ml of 0.2% nitric acid solution, 0.5 ml of methyl red indicator (0.1%), acetic acid (99%), and 0.85 ml of aqueous ammonia (28%). Samples were prepared. Next, the prepared test sample was placed in the container 14, and aqueous ammonia (28%) was added from the nebulizer 28. The measurement wavelength at the spectroscope 26 was 560 nm. The measurement of the transmitted light signal 44 and the control of the open / close valve 40 were performed at intervals of 300 ms until reaching 2/3 of the target transmitted light intensity and thereafter at intervals of 100 ms. The pH adjustment was completed when the last three transmitted light signal intensities reached the target intensity.
When pH adjustment was performed with the adjustment target pH = 6.0, of the 10 independent test samples, 2 were pH = 5.9 and 5 were pH = 6.0. There were 3 samples with pH = 6.1. From this result, according to the pH automatic adjustment device of the present embodiment, it became clear that the pH can be adjusted with sufficient accuracy to ensure the reproducibility of the trace element recovery rate in the solid-phase extraction. Moreover, the adjustment of each test sample was completed within 2 minutes. Therefore, it became clear that the amount required for solid phase extraction can be prepared in a short time.
　１０　ｐＨ自動調整装置
　１２　試料（ｐＨ調整対象溶液）
　１４，３８　容器
　１６　撹拌器（撹拌装置）
　１８　撹拌子（撹拌装置）
　２０　光源部（光照射装置、光照射部）
　２６　分光器（強度検出装置、強度検出部）
　２８　ネブライザ（噴霧装置）
　２８ａ　噴射口
　３６　ｐＨ調整液
　４２　ＰＣ（ｐＨ算出装置）
　４４　透過光信号
　４８　開閉信号 10 pH automatic adjustment device 12 Sample (solution for pH adjustment)
14,38 container 16 stirrer (stirring device)
18 Stirrer (stirring device)
20 Light source part (light irradiation device, light irradiation part)
26 Spectrometer (Intensity detector, Intensity detector)
28 Nebulizer (spraying device)
28a injection port 36 pH adjusting liquid 42 PC (pH calculation device)
44 Transmitted light signal 48 Open / close signal

Claims (3)

  1. 　ｐＨ調整対象溶液を収容可能な容器と、
    　前記容器内に収容したｐＨ調整対象溶液を撹拌可能な撹拌装置と、
    　前記容器内にｐＨ調整対象溶液を収容した場合に、その液面に対して霧状にしたｐＨ調整剤を噴射可能な箇所に配置された噴射口を有する噴霧装置と、
    　を備えることを特徴とするｐＨ自動調整装置。     a container capable of containing a pH adjustment target solution;
    A stirring device capable of stirring the solution to be adjusted for pH contained in the container;
    When the pH adjustment target solution is accommodated in the container, a spraying device having an injection port arranged at a location where the pH adjusting agent atomized with respect to the liquid surface can be injected,
    An automatic pH adjusting device comprising:
  2. 　前記ｐＨ調整対象溶液は、ｐＨに応じて変色する指示薬を添加したものであり、
    　前記容器外から前記容器内に向かって光を照射する光照射装置と、
    　前記光照射装置と前記容器を隔てて対向配置され、前記容器を透過した透過光の強度を検出する強度検出装置と、
    　前記強度検出装置で検出した透過光の強度を用いて、前記容器内に収容したｐＨ調整対象溶液のｐＨを算出するｐＨ算出装置と、
    　を備えることを特徴とする請求項１に記載のｐＨ自動調整装置。     The pH adjustment target solution is one to which an indicator that changes color according to pH is added,
    A light irradiation device for irradiating light from outside the container into the container;
    An intensity detection device that is disposed opposite to the light irradiation device and the container and detects the intensity of transmitted light that has passed through the container;
    A pH calculator that calculates the pH of the pH adjustment target solution contained in the container using the intensity of transmitted light detected by the intensity detector;
    The pH automatic adjusting device according to claim 1, comprising:
  3. 　前記光照射装置は光を照射する光照射部を備え、
    　前記強度検出装置は透過光の強度を検出する強度検出部を備え、
    　前記強度検出部および前記光照射部は、前記強度検出装置および前記光照射装置がそれぞれ対向する前記容器の対向面に対して垂直に配置されると共に、前記強度検出部は、前記光照射部からの光照射方向の延長線上に配置されることを特徴とする請求項１または２に記載のｐＨ自動調整装置。     The light irradiation device includes a light irradiation unit that emits light,
    The intensity detector includes an intensity detector that detects the intensity of transmitted light,
    The intensity detection unit and the light irradiation unit are arranged perpendicular to the opposing surface of the container to which the intensity detection device and the light irradiation device respectively face, and the intensity detection unit is connected to the light irradiation unit. The automatic pH adjusting device according to claim 1, wherein the automatic pH adjusting device is disposed on an extended line in the light irradiation direction.
PCT/JP2012/057276 2012-03-22 2012-03-22 AUTOMATIC pH ADJUSTMENT APPARATUS WO2013140560A1 (en)

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EP3719607A1 (en) * 2019-04-02 2020-10-07 Covestro Deutschland AG Smart container device, transportation tool, user terminal and management system

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WO2015029624A1 (en) * 2013-08-30 2015-03-05 システム・インスツルメンツ株式会社 Automatic ph adjustment device
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