JP2022177660A - Filtration device and filtration method - Google Patents

Abstract

To provide a filtration device and a filtration method, which allow for preventing intrusion of a gas and eliminate the need to replace a filter material for each sample.SOLUTION: A filtration device is provided, comprising a sample supply unit (110), a filter material sheet (120) provided below the sample supply unit (110), and a suction unit (130) for sucking a filtered fluid sample from a side opposite to the sample supply unit (110) with respect to the filter material sheet (120).SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a filtering device and a filtering method.

In quantitative analysis, separation of the substance to be analyzed from other inhibitory substances is very important for accurate analysis. There are various separation methods such as solvent extraction, solid-phase extraction, chelate extraction, chromatogram separation, etc. Filtration is frequently used as a physical separation method for suspended solids and solutions. .

In qualitative and quantitative analyses, filtration is used to separate suspended solids from solutions, even when samples are supplied to analyzers. Filtration is usually performed on a sample-by-sample basis, and the filtered sample is supplied to an analyzer.

As an apparatus for continuously filtering samples to be analyzed continuously, for example, Patent Document 1 discloses a filtering apparatus for separating insoluble components from a fluid sample. Moreover, Patent Document 2 describes the use of a filter in a flow injection method (FIA), which is a type of flow analysis method.

JP-A-9-192415 JP-A-62-113066

However, in the conventional technology as described above, since the entire amount is filtered, it is necessary to periodically replace the filter medium. In addition, a large-scale mechanism is required to periodically replace the filter medium. If the timing of the passage of the sample through the filter medium and the replacement of the filter medium do not match, the measurement target of the previous sample will affect the measurement results of the next sample. In addition, when a large amount of gas that affects the measurement is mixed in the sample at irregular timing, it is sufficient to perform continuous filtration with a filtration device for each sample for accurate analysis. It wasn't.

In one embodiment of the present invention, by solving the above problems, a large-scale and complicated device is not required, there is no need to match the timing of the passage of the sample through the filter medium and the replacement of the filter medium, and the mixture of gas can be prevented. It is an object of the present invention to provide a filtration device and a filtration method that can be used without changing the filter medium for each sample.

One embodiment of the present invention includes the following configurations.

[1] A filtration device for filtering a fluid sample, comprising: a sample supply unit; a filter medium sheet provided below the sample supply unit; and a suction unit for sucking the filtered fluid sample, the sample supply unit and the filter material sheet are not in contact with each other, the filter material sheet can be continuously transported, and the sample supply The filtering device, wherein a supply speed of the fluid sample supplied from the unit is set to be higher than a suction speed of the fluid sample that passes through the filter medium sheet and is sucked.

[2] The filtering device according to [1], wherein the filter medium sheet is inclined downward from the top toward the destination from the source of transportation.

[3] A support member for supporting the filter medium sheet is provided, the support member being a pedestal having a support surface for the filter medium sheet, and a through hole for sucking the fluid sample through the filter medium sheet. The filtering device according to [1] or [2], wherein a hole is provided in the pedestal.

[4] Any one of [1] to [3], wherein the filter medium sheet is continuously conveyed by winding the filter medium sheet wound into a roll with a winding device. Filtration device according to.

[5] A flow analysis device comprising a sampling device for introducing a sample into a pipeline, and an analysis device for analyzing the sample transported in the pipeline, wherein the flow analysis device of [1] to [4] A flow analysis device comprising a filtration device according to any of the claims.

[6] A filtration method for filtering a fluid sample, comprising a step of supplying the fluid sample from a sample supply unit; and filtering with a sheet, wherein in the filtering step, the filtered fluid sample is sucked from the side opposite to the sample supply unit with respect to the filter medium sheet, and the sample supply unit and the filter medium sheet The filter medium sheet is continuously conveyed, and the supply speed of the fluid sample supplied from the sample supply unit is the speed of the fluid sample sucked through the filter medium sheet. A filtration method that is set to be greater than the suction rate.

[7] The filtration method according to [6], wherein the filter medium sheet is inclined downward from the top toward the destination.

[8] A flow analysis method according to [6] or [7], comprising a sample introduction step of introducing a sample into a pipeline, and an analysis step of analyzing the sample transported in the pipeline. A method of flow analysis, comprising a filtration step of filtering according to the filtration method of .

According to one embodiment of the present invention, there is no need for a large-scale and complicated device, there is no need to match the timing of passage of a sample through a filter medium with replacement of the filter medium, and it is possible to prevent gas from entering the filter medium. It is possible to provide a filtration device and a filtration method that do not require replacement.

It is a side view showing a schematic structure of a filter concerning one embodiment of the present invention. 1 is a perspective view showing a configuration of part of a filtering device according to an embodiment of the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows schematic structure of the flow analysis apparatus which concerns on Embodiment 1 of this invention. It is a figure which shows schematic structure of the flow analysis apparatus which concerns on Embodiment 2 of this invention.

For example, the present inventors introduce the sample and the reagent into a continuous flow in a capillary tube in which the sample liquid and the reagent are segmented by air bubbles, respectively, perform reaction operations, and then remove the air bubbles. or a continuous flow analysis method ( CFA), when filtering is performed by providing a continuous filtration device downstream of the sample after heating, the sample may not flow continuously through the channel. Further, when thermal decomposition is performed, the gas generated by the decomposition is irregularly contained in the liquid, so that the gas may be irregularly mixed in the CFA that is periodically segmented in the gas phase. In addition, in CFA, it is necessary to replace the filter paper quickly and accurately when switching between samples, and a large-scale mechanism is required that takes into consideration the prevention of dripping and carryover to the next sample.

As a result of intensive studies to solve these problems, it was found that it does not require a large-scale and complicated device, does not need to match the timing of the passage of the sample through the filter medium and the replacement of the filter medium, and can prevent gas contamination. The present invention has been completed by discovering a filtering device and a filtering method that do not require replacement of the filter medium for each sample.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to this, and various modifications are possible within the scope described, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also present. included in the technical scope of

(I) Filtration Device A filtration device according to one embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a side view showing a schematic configuration of a filtering device according to one embodiment of the present invention. FIG. 2 is a perspective view showing a configuration of part of a filtering device according to one embodiment of the present invention.

A filtering device 10 according to one embodiment of the present invention is a filtering device for filtering a fluid sample. A "flowable sample" is not particularly limited as long as it is a sample having fluidity, but is, for example, a suspended sample containing soluble and insoluble components. By "filtering" is intended to separate and remove insoluble components from a flowable sample. As shown in FIG. 1, the filtration device 10 according to one embodiment of the present invention includes a sample supply section 110, a filter medium sheet 120, a suction section 130, a support member 140, and a winding device 150. .

The sample supply unit 110 is a member for supplying the fluid sample to the filter medium sheet 120 . The sample supply unit 110 has a sample supply port 111 for discharging the fluid sample.

A filter medium sheet 120 is provided below the sample supply section 110 . Specifically, the filter medium sheet 120 is located between the sample supply section 110 and the suction section 130 at a position where it can receive the fluid sample that has been ejected from the sample supply port 111 and dropped.

The winding device 150 is a device for winding the filter medium sheet 120 and continuously conveying the filter medium sheet 120 . The filter material sheet 120 can be continuously transported by winding the filter material sheet 120 in a roll shape with a winding device 150 . By continuously conveying the filter medium sheet 120, a new filter medium sheet 120 is always conveyed between the sample supply section 110 and the suction section 130, so that excess fluid sample that has not been sucked into the suction section 130 is removed. The surface of the filter medium sheet 120 is discharged together with the filtered filter medium sheet 120 (waste filter medium sheet) without diffusing the surface of the filter medium sheet 120 toward the conveying source side. Therefore, it is not necessary to install a new filter medium sheet for each fluid sample. In the filtering device shown in FIGS. 1 and 2, the filter medium sheet 120 is wound up by the winding device 150 so that it can be continuously transported. For example, the mechanism does not necessarily depend on being wound by the winding device 150 . For example, the filter medium sheet 120 may be conveyed by a belt conveyor.

The conveying speed of the filter medium sheet 120 may be any speed at which the excess fluid sample that has not been sucked into the suction unit 130 is not diffused on the surface of the filter medium sheet 120 toward the conveying source side. The conveying speed of the filter medium sheet 120 may be appropriately set according to the supply speed of the fluid sample supplied from the sample supply unit 110 and the suction speed of the fluid sample passed through the filter material sheet 120 and sucked. The conveying speed of the filter medium sheet 120 may be, for example, 0.5 cm/min or more and 10 cm/min or less, 1 cm/min or more and 5 cm/min or less, or 2 cm/min or more and 4 cm/min or less. may

The filter medium sheet 120 is inclined downward from the top toward the destination from the source of transport. As a result, excess fluid sample that has not been sucked by the suction unit 130 flows toward the winding device 150, so that it is possible to more effectively prevent the filter medium sheet 120 from flowing from the transfer destination to the transfer source. can be done. Therefore, the filter medium sheet 120 is continuously conveyed, and the flowable sample discharged from the sample supply port 111 and dropped can be received by the portion of the filter medium sheet 120 that is not used for filtration. Excess fluid sample that has not soaked into the filter medium sheet 120 is discharged below the winding device 150 as waste liquid together with the waste filter medium sheet.

The angle of inclination of the filter medium sheet 120 with respect to the horizontal direction is not particularly limited. It is even more preferable to have By setting the inclination angle of the filter medium sheet 120 within such a range, the filter medium sheet 120 can reliably receive the flowable sample discharged from the sample supply port 111 and dropped, and the above-described effects can be obtained. . 1 and 2, the filter medium sheet 120 is inclined from top to bottom from the source to the destination. As long as the surface of the filter material sheet 120 is not greatly diffused toward the conveying source side, the filter material sheet 120 does not necessarily have to be inclined.

The filter medium sheet 120 is preferably strip-shaped. The width of the filter medium sheet 120 may be any size as long as it can sufficiently receive the flowable sample discharged from the sample supply port 111 and dropped. The width of the filter medium sheet 120 may be, for example, 5 mm or more and 100 mm or less, 10 mm or more and 40 mm or less, 15 mm or more and 35 mm or less, or 20 mm or more and 30 mm or less.

The filter medium sheet 120 may be any material as long as it can separate the soluble and insoluble components contained in the fluid sample. Examples of the filter medium sheet include a filter paper sheet, a cloth sheet, a membrane sheet and the like. Examples of materials for the filter medium sheet 120 include cellulose, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polyester, rayon, pulp, cotton, hemp, and silk.

The suction unit 130 sucks the filtered fluid sample from the opposite side of the filter medium sheet 120 to the sample supply unit 110 . A pump (not shown) is connected to the suction unit 130, and the suction unit 130 can suck the filtered fluid sample by the pump.

The sample supply part 110 and the filter medium sheet 120 are not in contact with each other. A fluid sample supplied from the sample supply unit 110 drops and is filtered by the filter medium sheet 120 . As a result, gas contained in the fluid sample (for example, gas for segmentation, air mixed irregularly, gas generated during decomposition, etc.) is released into the air.

The supply speed of the fluid sample supplied from the sample supply unit 110 is set to be higher than the suction speed of the fluid sample that passes through the filter medium sheet 120 and is sucked. Thereby, the suction unit 130 can suck the filtered fluid sample without taking in gas.

The supply speed of the fluid sample supplied from the sample supply unit 110 is, for example, 1.05 to 3 times the suction speed of the fluid sample sucked through the filter medium sheet 120. Preferably, it is more preferably 1.1 times or more and 2 times or less. As a result, the suction unit 130 can suck the filtered fluid sample without taking in gas, and waste of the sample supplied to the filtering device 10 can be reduced. The supply speed of the fluid sample supplied from the sample supply unit 110 is preferably faster than the suction speed of the fluid sample passed through the filter medium sheet 120 and sucked by 0.1 mL/min or more. Thereby, the suction unit 130 can suck the filtered fluid sample without taking in gas. For example, when the supply speed of the fluid sample supplied from the sample supply unit 110 is 0.3 mL/min or more and 5 mL/min or less, the suction speed of the fluid sample sucked through the filter medium sheet 120 is 0. 0.2 mL/min or more and 4.5 mL/min or less. Further, when the supply speed of the fluid sample supplied from the sample supply unit 110 is 0.5 mL/min or more and 5 mL/min or less, the suction speed of the fluid sample sucked through the filter medium sheet 120 is 0. .3 mL/min or more and 4 mL/min or less. Further, when the supply speed of the fluid sample supplied from the sample supply unit 110 is 1 mL/min or more and 3 mL or less, the suction speed of the fluid sample sucked through the filter medium sheet 120 is 0.5 mL/min. minute or more and 2 mL/minute or less.

The support member 140 is a member for supporting the filter medium sheet 120 . Support member 140 is a pedestal having a support surface 141 for the filter media sheet. The support member 140 is provided with through holes 142 for sucking the fluid sample through the filter medium sheet 120 . A tubular suction portion 130 is inserted into the through hole 142 so as to be in close contact with the through hole 142 .

The width of the support member 140 is not particularly limited as long as it can stably support the filter medium sheet 120, and may be the same as the width of the filter medium sheet 120 or larger than the width of the filter medium sheet 120. and can be smaller.

The inclination angle of the support member 140 is not particularly limited as long as it is an angle that does not create a gap with the filter medium sheet 120 .

The inner diameter of the through-hole 142 may be any size as long as the aspirator 130 can be inserted thereinto and all of the filtered fluid sample can be aspirated into the aspirator 130 without leaking out. The inner diameter of the through hole 142 may be, for example, 0.2 mm or more and 10 mm or less, 1 mm or more and 5 mm or less, or 2 mm or more and 4 mm or less.

The outer diameter of the suction part 130 may be any size as long as it can be inserted into the through-hole 142 and sucked into the suction part 130 without all of the filtered fluid sample leaking out. Therefore, the inner diameter of through hole 142 and the outer diameter of suction portion 130 are preferably the same. The outer diameter of the suction part 130 may be, for example, 0.2 mm or more and 10 mm or less, 1 mm or more and 5 mm or less, or 2 mm or more and 4 mm or less.

The inner diameter of the suction unit 130 may be any size as long as it is possible to suck all of the filtered fluid sample into the suction unit 130 and to perform stable filtration. The inner diameter of the suction part 130 may be, for example, 0.05 mm or more and 5 mm or less, 0.1 mm or more and 2 mm or less, or 0.2 mm or more and 1.5 mm or less.

Alternatively, instead of inserting the suction portion 130 into the through-hole 142, the through-hole 142 itself may be the suction portion 130, and the through-hole 142 may be connected to a pipeline to which a pump is connected.

Although the filtering device shown in FIGS. 1 and 2 is provided with the support member 140, the support member 140 may not necessarily be provided as long as the filter medium sheet is held. Further, even when the support member 140 is provided, the support member 140 does not necessarily have to be a pedestal, and its shape is not particularly limited as long as it can support the filter medium sheet. Furthermore, in the filtering device shown in FIG. 2, the width of the support member 140 is the same as the width of the filter medium sheet 120, but the width of the support member 140 does not necessarily have to be the same as the width of the filter medium sheet 120. It may be wider or narrower than the width of the sheet 120 .

(II) Filtration method A filtration method according to an embodiment of the present invention will be described below. For convenience of explanation, the description of the items already described in the filtering device (I) will not be repeated.

A filtration method according to an embodiment of the present invention is a filtration method for filtering a fluid sample, comprising a step of supplying the fluid sample from a sample supply unit 110; and filtering with a filter medium sheet 120 provided below the sample supply unit 110 .

In the filtering step, the filtered fluid sample is sucked from the side opposite to the sample supply unit 110 with respect to the filter medium sheet. The sample supply unit 110 and the filter material sheet 120 are not in contact with each other, and the filter material sheet 120 is continuously conveyed. The supply speed of the fluid sample supplied from the sample supply unit 110 is set to be higher than the suction speed of the fluid sample that passes through the filter medium sheet 120 and is sucked. The filter medium sheet 120 is inclined downward from the top toward the destination from the source of transport.

A filtration method according to an embodiment of the present invention may include a step of washing the filter medium sheet 120 before the step of supplying the fluid sample from the sample supply unit 110 . As a result, impurities contained in the filter medium sheet 120 (for example, metals such as aluminum, iron, copper, etc.) can be removed. Therefore, it is possible to prevent the impurities from being mixed with the fluid substance filtered by the cleaned filter medium sheet 120 . For washing the filter medium sheet 120, for example, water, a solvent contained in the fluid sample, or the like can be used.

(III) Flow Analyzer A flow analyzer according to an embodiment of the present invention will be described below. For convenience of explanation, the description of the items already described in the filtering device (I) will not be repeated.

[Embodiment 1]
A filtering device according to Embodiment 1 of the present invention will be described with reference to the drawings. FIG. 3 is a diagram showing a schematic configuration of the flow analyzer 1 according to Embodiment 1 of the present invention.

A flow analysis device 1 according to one embodiment of the present invention includes a sampling device 11, a bubble segmentation device 12, a reagent addition device 13, a heating device 14, a filtration device 10, and an analysis device 15. FIG.

The sampling device 11 is a device for sampling a sample and introducing it into the pipeline 16 . In one embodiment of the present invention, the sampling device 11 comprises a collection tube that introduces the sample into the line 16 and a sampling pump that applies a suction force to the collection tube. A sample is introduced into the conduit 16 at a predetermined flow rate by the sampling pump. The sample is a liquid containing a substance or element to be analyzed.

The bubble segmentation device 12 is a device for performing bubble segmentation on the sample introduced into the pipe line 16 to produce a plurality of segments partitioned by bubbles within the pipe line 16 . In one embodiment of the present invention, the bubble segmentation device 12 includes a gas introduction tube that introduces gas into the conduit 16 and a gas introduction pump that applies a suction force to the gas introduction tube. By performing air bubble segmentation, reagents and the like can be suitably mixed by swirling in the segmented liquid separated by air bubbles. In addition, since the segmented liquid is separated by air bubbles and independently flows through the conduit 16, mutual diffusion between samples can be prevented. The bubble segment gas is preferably air, but can be inert gases such as argon and helium, and various gases such as nitrogen and oxygen can also be used. These gases may be used alone, or two or more of them may be mixed and used. In this way, the reagent is introduced into the continuous flow in the pipe where the sample is segmented by air bubbles, and after the reaction operation is performed, the air bubbles are removed, and the analysis is performed by the detector provided downstream. The method by which it is done is called Continuous Flow Analysis (CFA).

The reagent addition device 13 is a device for adding a reagent into the sample flow transported along the conduit 16 . The reagent addition device 13 includes a reagent introduction tube that guides the reagent to the conduit 16 and a reagent introduction pump that applies a suction force to the reagent introduction tube. The reagent may be a reagent added in sample pretreatment. Examples of the reagent include, but are not limited to, acids such as hydrogen peroxide, nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, and hydrofluoric acid; sodium peroxide, calcium carbonate, and carbonate; Alkali, such as sodium, etc. can be mentioned.

The heating device 14 heats the sample transported along the pipeline 16 . The heating device 14 may be a constant temperature bath equipped with a heater. However, the configuration of the heating device 14 is not limited to this, and may be an ultrasonic decomposition device, a microwave decomposition device, an autoclave decomposition device, or the like. Also, within the heating device 14, the conduit 16 forms a coil or spiral. In one embodiment of the invention, a heating device 14 is provided downstream of the reagent addition device 13 . By heating the sample to which the reagent has been added, the reaction of the sample with the reagent can be accelerated and pretreatment can be performed. In the example of FIG. 3, the flow analyzer comprises a pretreatment unit 17 consisting of one reagent addition device 13 and one heating device 14, but instead of one reagent addition device 13, a plurality of reagent A plurality of reagent addition devices 13 may be provided to add the . In addition, although the flow analyzer includes one pretreatment unit 17 in the example of FIG. 3 , the flow analyzer may include a plurality of pretreatment units 17 . In such a case, the flow analyzer may have a filtration device 10 for each pretreatment unit 17, and a plurality of pretreatment units 17 may have different numbers of reagent addition devices 13, respectively. By providing a plurality of pretreatment units 17, for example, after performing acid decomposition under heating, it is possible to perform pretreatment in the form of acid decomposition by adding acid again and performing acid decomposition under heating. When a plurality of reagent addition devices 13 are provided, the reagents added by each reagent addition device 13 may be the same or different.

Further, in the example of FIG. 3, the reagent addition device 13 is provided downstream of the bubble segmentation device 12, but the arrangement of the reagent addition device 13 is not limited to this. The reagent addition device 13 may be provided upstream of the bubble segmentation device 12 . Alternatively, the reagent introduced by the reagent addition device 13 may be provided downstream of the heating device 14 . Alternatively, one or more reagent addition devices 13 for introducing reagents used for pretreatment are provided upstream of the heating device 14, and one or more reagent addition devices 13 are provided downstream of the heating device 14. may be

The filtering device 10 filters a heated sample (fluid sample) to which a reagent has been added. The details of the filtering device 10 are as described in (I). By removing the insoluble components from the flowable sample by means of the filtering device 10, it is possible to prevent clogging of the insoluble components in the conduit 16 and/or in the downstream analysis device 15, thereby preventing the analysis from becoming impossible. can. By supplying the filtered fluid sample to the analyzer 15, the analyzer 15 can appropriately analyze the filtered fluid sample. Moreover, in the example of FIG. 3, the filtering device 10 is provided downstream of the heating device 14, but the arrangement of the filtering device 10 is not limited to this. The filtration device 10 may be provided upstream of the bubble segmentation device 12 .

The analysis device 15 is a device that analyzes the filtered fluid sample. In one embodiment of the invention, analyzer 15 is an inductively coupled plasma-mass spectrometer (ICP-MS). However, the analysis device 15 is not limited to this, and may be any analysis device, such as an atomic absorption photometer, an inductively coupled plasma optical emission spectrometer (ICP-OES), an inductively coupled plasma It may be a triple quadrupole mass spectrometer, an ion electrode meter, or a spectrophotometer. Further, the analysis device 15 is not limited to a device for measuring the presence or absence or concentration of metal elements, and the measurement target is not particularly limited. Also, the analysis may be quantitative analysis or qualitative analysis.

According to the flow analyzer according to the first embodiment described above, the sample is continuously introduced into the conduit 16, the bubbles are segmented, the reagent is introduced, the reaction is accelerated by the heating device, and the flow is caused by the filtering device. The analytical data can be continuously measured by the analytical instrument after filtering the biological sample.

In Embodiment 1 described above, the flow analyzer comprises the reagent addition device 13 and the heating device 14 . However, the flow analyzer does not necessarily need to include the reagent addition device 13 and the heating device 14, and may be configured to include neither the reagent addition device 13 nor the heating device 14. FIG. When analyzing a sample that does not need to be pretreated or a sample that has already been pretreated, the configuration may be such that neither the reagent addition device 13 nor the heating device 14 is provided. Even in such a case, the flow analysis device is equipped with the filtering device 10 . Alternatively, the flow analyzer may have a configuration including only the heating device 14 and not including the reagent addition device 13, or conversely, a configuration including only the reagent addition device 13 and not including the heating device 14. There may be. Even in such a case, the flow analysis device is equipped with the filtering device 10 . For example, when introducing a sample to which a reagent such as an acid or an alkali has been added in advance into the conduit 16, or when pretreatment requires heating but does not require a reagent, only the heating device 14 is provided, A configuration without the reagent adding device 13 is possible. Which configuration should be used may be appropriately selected according to the sample pretreatment method.

In embodiments without reagent addition device 13 and heating device 14 , the flow analysis device comprises a sampling device 11 for introducing a flowable sample into line 16 and a sample transported along line 16 . and an analysis device 15 for performing an analysis on a sample, which further includes a filtration device 10 for filtering the flowable sample.

Although not provided in the example of FIG. 3, the flow analyzer according to one embodiment of the present invention may further include a pool tank (liquid reservoir) in the middle of the pipeline 16 . Since the flow analyzer is a method of performing analysis by flowing a sample in a closed space, the pressure may become high. Even in such a case, by providing the pool tank, the pressure can be released, and the volume required for each step can be suitably dispensed and collected. The arrangement of the pool tank is not particularly limited as long as it is in the middle of the pipeline 16, but is preferably downstream of the heating device 14, more preferably the heating device 14 (when a plurality of heating devices 14 is provided between the most downstream heating device 14 ) and the analysis device 15 . As a means for releasing the pressure in the flow analyzer, a debubbler, a pressure reducing valve, or the like for discharging an appropriate amount of air (gas) and liquid can be provided in addition to the pool tank.

The flow analyzer according to one embodiment of the present invention may also include a pressurizing device that applies pressure against the flow of the sample from the downstream side of the heating device 14 . The pressurizing device includes, for example, a compressor and a valve. By providing such a pressurizing device, it is possible to suppress expansion of bubbles in the heating device 14 and promote the reaction in the heating device 14 due to the synergistic effect of heating and pressurization. The pressure applied by the pressurizing device is not particularly limited, but is, for example, 0.14 MPa or less.

Also, in the flow analyzer according to one embodiment of the present invention, an autosampler can be used as the sampling device 11 . Also, prior to sampling, an ultrasonic homogenizer or stirrer may be provided to pulverize and/or stir the sample.

Alternatively, the flow analyzer according to one embodiment of the present invention may further include a diluter in the middle of line 16 . This allows the desired dilution to be performed automatically in the flow analyzer when dilution is required depending on the concentration of the sample. A commercially available automatic diluter can be suitably used as such a diluter.

Furthermore, the flow analysis device according to one embodiment of the present invention is a device in which a device for pretreating a sample other than a liquid such as a solid to prepare a liquid sample is incorporated in the sampling device 11, or an upstream of the sampling device 11. It may be a device incorporated in a A flow analysis apparatus is an apparatus that analyzes a liquid sample using a flow analysis method, and a sample other than a liquid such as a solid cannot be measured as it is. Therefore, by incorporating an apparatus for pretreating a sample other than a liquid, such as a solid, to prepare a liquid sample, it is possible to consistently perform from pretreatment to analysis of a sample other than a liquid, such as a solid. As such an apparatus, an apparatus for fully automatic pretreatment of samples other than liquids such as solids is more preferable. For example, a fully automatic pretreatment apparatus for acid decomposition that performs reagent addition, mixing, heating, and diluting fully automatically is preferable. can be used.

In the present embodiment, the case where the flow analyzer uses CFA was exemplified, but it is not limited to CFA, and is not particularly limited as long as it is a continuous analyzer in which gas is mixed in the sample.

[Embodiment 2]
FIG. 4 is a diagram showing a schematic configuration of a flow analyzer 2 according to Embodiment 2 of the present invention. For convenience of description, members having the same functions as the members described in the first embodiment are denoted by the same reference numerals, and description thereof will not be repeated.

The flow analyzer 2 according to Embodiment 2 of the present invention further includes a marker introduction device 18, a high-temperature and high-pressure decomposition device 19, and a suspended matter trap, in addition to the configuration of the flow analysis device 1 according to Embodiment 1 described above. It includes a collection cartridge 20 , a surfactant addition device 21 , a mixing coil 22 , a marker detection device 23 and a degassing device 24 . In addition, between the sampling device 11 and the high-temperature and high-pressure decomposition device 19, and between the suspension collection cartridge 20 and the surfactant addition device 21, a bubble segmentation device 12 is further included.

A marker introduction device 18 is a device for introducing a marker into the conduit 16 . In one embodiment of the present invention, marker introduction device 18 includes a collection tube that introduces markers into line 16 and a pump that applies suction to the collection tube. The marker may contain a substance that can be detected by the marker detection device 23, and may be the substance, a solution containing the substance, or a dispersion containing the substance. good too.

Here, the marker introduction device 18 and the sampling device 11 are capable of alternately introducing the marker and a predetermined number of one or more samples into the pipeline 16 . That is, introduction of a marker from the marker introduction device 18 into the conduit 16 and introduction of a predetermined number of one or more samples from the sampling device 11 into the conduit 16 are alternately switched. . This switching may be performed manually or may be performed automatically.

When the marker and one sample can be alternately introduced into the conduit 16, the marker is introduced into the conduit 16 before each sample. For each sample, the marker detection device 23 that has detected the marker outputs a marker detection signal to the analysis device 15, and the analysis device 15 acquires analysis data based on the detection signal. As a result, even if the liquid cannot be sent in a stable and uniform time from sample introduction to the analyzer, the timing of obtaining analysis data will not be off, so samples can be measured stably and continuously. can do.

In addition, when the marker and a predetermined number of two or more samples can be alternately introduced into the conduit 16, the marker is introduced into the conduit 16 once before the predetermined number of two or more samples. be introduced. After detecting the marker, the marker detection device 23 outputs a marker detection signal to the analysis device 15, and based on the detection signal, the analysis device 15 sequentially acquires the analysis data of the predetermined number of samples. As a result, even if the liquid cannot be sent stably and uniformly from the introduction of the sample to the analyzer, it is possible to reduce the lag in the timing of obtaining analysis data to within a certain range. samples can be measured continuously. The upper limit of the predetermined number may be appropriately selected depending on the type of sample, pretreatment method, etc., and may be 80, 77, 50, 20, 15, or 10, for example.

Although the marker detectable by the marker detection device 23 is not particularly limited, it is preferably a substance that is not contained in the sample. Also, the marker is preferably a substance that is not decomposed by reagents and heat that are added between introduction into the conduit 16 and the marker detection device 23 . For example, the marker can be a spectrophotometrically detectable substance. Such substances are not particularly limited, and examples thereof include rhodium, nickel, copper, chromium, manganese, iodine, cobalt, nitrate ions, phosphate ions, and silicate ions. Alternatively, the substance may be a voltammetrically detectable substance. Such substances are also not particularly limited, and examples thereof include copper, cadmium, nickel, mercury, arsenic, and selenium. Alternatively, the substance can be a substance detectable with an ion electrode meter. Such substances are also not particularly limited, and examples thereof include calcium, potassium, fluorine, and ammonia. Alternatively, the substance may be a substance detectable by ion chromatography. Such substances are not particularly limited, and examples thereof include ions of inorganic acids and organic acids, phenols, hydrazines, amino acids, and polysaccharides. Alternatively, the substance may be a turbidimeter detectable substance. Such a substance is not particularly limited, and examples thereof include silica, which is a fine particle substance that does not dissolve in acids other than hydrofluoric acid. Alternatively, the substance may be a substance detectable with a fluorometer. Such substances are also not particularly limited, and examples thereof include benzene, coumarin, and naphthalene. Among these, rhodium, cobalt, nickel, copper, and the like are particularly preferred markers because of their ease of detection.

The high-temperature and high-pressure decomposing device 19 is a device for dissolving metal components and decomposing organic substances, suspended solids, metal complexes, etc. coexisting in the sample as a pretreatment. The high temperature and high pressure decomposition device 19 separates the sample into a waste liquid and a sample from which the waste liquid has been removed. The high-temperature and high-pressure decomposition device 19 discharges the waste liquid and supplies the sample from which the waste liquid has been removed to the pipeline 16 .

The suspended matter collection cartridge 20 is a device for removing the residue of the filter medium sheet 120 from the filtered fluid sample. Depending on the material of the filter medium sheet 120, residue of the filter medium sheet 120 may be mixed into the filtered fluid sample. In this case, by removing the residue of the filter medium sheet 120 from the fluid sample filtered by the suspension collection cartridge 20, clogging and contamination of the marker detection device 23 and the analysis device 15 due to the inclusion of the residue can be prevented. can be done.

In this embodiment, the filtration device 10 is arranged between the heating device 14 and the suspension collection cartridge 20 . However, the arrangement of the filtration device 10 is not limited to this, and may be between the sampling device 11 and the analysis device 15 . The filtration device 10 may be arranged appropriately according to the type of the analysis device 15. For example, the filtration device 10 may be placed between the sampling device 11 and the bubble segmentation device 12, or between the marker detection device 23 and the degassing device 24. It can be in between.

The suspension collection cartridge 20 is not particularly limited as long as it can collect the residue of the filter medium sheet 120 and does not contaminate the filtered fluid sample. Quartz wool, cellulose, or the like, for example, can be used as the suspension collection cartridge 20 .

The surfactant addition device 21 is a device for adding a surfactant to the fluid sample. By adding a surfactant to the fluid sample, the liquid can be stably flowed, the adhesion of dirt can be prevented, and clogging in the channel 16 can be prevented. .

The mixing coil 22 is a device for mixing the fluid sample and surfactant. When the fluid sample and the surfactant with different liquid properties pass through the helically wound mixing coil 22, the fluid sample and the surfactant can be mixed by stirring.

The marker detection device 23 and the analysis device 15 are arranged in series. After the sample is pretreated and before it is introduced into the analyzer 15, the marker detection device 23 continuously measures the liquid introduced from the conduit 16 to detect the marker. Then, a detection signal is output to the analyzer 15 . After receiving the detection signal, the analysis device 15 starts acquiring analysis data. In this case, the timing of starting acquisition of analysis data may be adjusted so that the sample that has reached the analyzer 15 can be measured. For example, after the analysis device 15 receives the detection signal, it may be set to start acquisition of analysis data after a predetermined time.

In one embodiment of the present invention, the marker detection device 23 is a spectrophotometer, and outputs a detection signal to the analysis device 15 when rhodium is detected when the marker contains rhodium. However, the marker detection device 23 is not limited to spectrophotometers and can be, for example, voltammeters, ion electrodemeters, ion chromatography, turbidimeters and fluorometers. The marker and the sample that flow sequentially are introduced into the analysis device 15 and the marker detection device 23 at the same timing from the conduit 16 and the branch pipe, respectively. Alternatively, the timings at which the markers and the sample sequentially flowing to the analyzer 15 and the marker detection device 23 are introduced may not be the same but may be different. In addition, the markers and the samples flowing sequentially must be introduced at an early timing. In the above-described embodiment, the analysis device 15 starts acquiring analysis data when it receives the detection signal. can be set to start

In one embodiment of the present invention, analyzer 15 and marker detection device 23 are arranged in series as previously described. However, the analysis device 15 and the marker detection device 23 may be arranged in parallel.

The degassing device 24 is a device for discharging air bubbles that partition the segments. The degassing device 24 includes a degassing pipe for discharging air bubbles from the conduit 16 and a degassing pump for determining the air bubble discharging speed. The air bubbles are discharged by the degassing device 24 so that air bubbles do not mix with the analyzer 15 .

(IV) Flow Analysis Method A flow analysis method according to an embodiment of the present invention will be described below. For convenience of explanation, the descriptions of the items already described in (I) the filtering device, (II) the filtering method, and (III) the flow analysis device will not be repeated.

A flow analysis method according to an embodiment of the present invention is a flow analysis method including a sample introduction step of introducing a sample into a pipeline, and an analysis step of analyzing the sample transported through the pipeline. , includes a filtration step of performing filtration by the filtration method of (II) described above.

The sample introduction step is a step of introducing a sample into a pipeline. For example, a plurality of samples are sampled by a sampling device, and sequentially and continuously introduced into the pipeline at a predetermined flow rate.

The analysis step is a step of analyzing the sample transferred along the pipeline. Here, the analysis includes detection of the presence or absence of the analyte or measurement of its concentration. Also, the analysis may be quantitative analysis or qualitative analysis. The analysis method is not particularly limited, and any analysis may be used. Mention may be made of polar mass spectrometry, ion electrode spectrometry or spectrophotometry.

Also, the analysis target is not particularly limited, but can be, for example, a method for measuring the concentration of a metal element.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a marker introduction step of introducing a marker into the conduit 16 between the sample introduction step and the next sample introduction step. Here, the marker introducing step and the sample introducing step are preferably performed such that the marker and a predetermined number of one or more samples are alternately introduced into the pipeline.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a high temperature and high pressure decomposition step of performing high temperature and high pressure decomposition processing on the sample transported along the pipeline. The heating temperature, pressure, and time in the high-temperature and high-pressure decomposition step may be appropriately selected according to the object to be analyzed, and are not particularly limited. The heating temperature is, for example, 110° C. to 130° C., the pressure is, for example, 0.11 MPa to 0.15 MPa, and the time is, for example, 15 minutes to 25 minutes.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a reagent addition step of adding a reagent into the sample flow transported along the pipeline.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a heating step of heat-treating the sample transferred along the pipeline. In such a case, the analysis step is performed on the sample after heat treatment. The heating temperature and heating time in the heating step may be appropriately selected according to the analysis target, the pretreatment method, and the like, and are not particularly limited. The heating temperature is, for example, 25° C. to 150° C., and the heating time is, for example, 5 minutes to 1 hour.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a suspended matter collection step of collecting residue of the filter medium sheet from the flowable sample transported along the conduit.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a surfactant addition step of adding a surfactant to the fluid sample transported along the pipeline.

Furthermore, the flow analysis method according to one embodiment of the present invention includes a mixing step of mixing the flowable sample transported along the pipeline with the surfactant added in the surfactant addition step. good too.

Furthermore, the flow analysis method according to one embodiment of the present invention may include a marker detection step of detecting markers and outputting detection signals to the analyzer. In such a case, the analysis step acquires analysis data based on the detection signal.

Furthermore, the flow analysis method according to an embodiment of the present invention may include a degassing step of expelling air bubbles that have defined the segments.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the examples.

(Examples 1 to 4)
Using the flow analyzer shown in FIG. 4, each component in the sample was quantified by continuous flow analysis (CFA). The filtration device included in the flow analyzer was the filtration device shown in FIGS. The supply speed of the fluid sample supplied from the sample supply unit was 1.2 mL/min, the suction speed of the fluid sample sucked through the filter medium sheet 120 was 1 mL/min, and the transport speed of the filter medium sheet was 3 cm/min. minutes. The width of the filter medium sheet and the support member was 25 mm, the inclination angle of the filter medium sheet and the support member was 12 degrees, the inner diameter of the through hole was 1 mm, the outer diameter of the suction portion was 3 mm, and the inner diameter of the suction portion was 1 mm. A filter paper sheet (JIS P3801, for quantitative analysis, 5 type B) was used as the filter medium sheet. 100 mg/L rhodium and 1 M nitric acid were used as markers, 30% hydrogen peroxide was used as reagent, and 0.1% Triton-X was used as surfactant. The analyzer used was an inductively coupled plasma mass spectrometer.

It is known that samples 1 to 3, which are three types of factory wastewater, and Cd, Pb, As, Se, Cr, Zn, Fe, Cu, Mn, B, and Al each contain 25 μg/L. was used. A calibration curve was prepared for each component, and each component in the sample was quantified. BL1-4 represent pure blanks. A rhodium peak, which was used as a marker, was well observed in all measurements. Table 1 shows the results. The lower limit of quantitative determination for Fe was 10 μg/L, and the lower limit of quantitative determination for components other than Fe was 5 μg/L.

It was found that any sample can be measured without any problem using the flow analyzer including the filtration device described above.

A filtering device and a filtering method according to an embodiment of the present invention can be used in the field of analysis.

Reference Signs List 1, 2 flow analysis device 10 filtration device 11 sampling device 12 bubble segmentation device 13 reagent addition device 14 heating device 15 analysis device 110 sample supply unit 111 sample supply port 120 filter medium sheet 130 suction unit 140 support member 141 support surface 142 through hole 150 Take-up device

Claims (8)

A filtration device for filtering a flowable sample, comprising:
A sample supply unit, a filter material sheet provided below the sample supply unit, and a suction unit for sucking the filtered fluid sample from the opposite side of the filter material sheet to the sample supply unit,
The sample supply unit and the filter medium sheet are not in contact,
The filter medium sheet can be continuously transported,
The filtering device, wherein a supply speed of the fluid sample supplied from the sample supply unit is set to be higher than a suction speed of the fluid sample sucked through the filter medium sheet. 2. The filtering device according to claim 1, wherein the filter medium sheet is inclined downward from above toward the transfer destination from the transfer source. A support member for supporting the filter medium sheet,
3. The method according to claim 1, wherein the support member is a pedestal having a support surface for the filter medium sheet, and the pedestal is provided with a through hole for sucking the fluid sample through the filter medium sheet. Filtration device as described. 4. The filter medium sheet according to any one of claims 1 to 3, wherein the filter medium sheet is continuously transportable by winding a roll-shaped filter medium sheet with a winding device. filtration device. a sampling device for introducing a sample into the conduit;
an analysis device that analyzes the sample transferred through the pipe;
A flow analysis device comprising a filtration device according to any one of claims 1-4. A filtration method for filtering a flowable sample, comprising:
a step of supplying the fluid sample from a sample supply unit;
and filtering the supplied fluid sample with a filter medium sheet provided below the sample supply unit,
In the filtering step, the filtered fluid sample is sucked from the side opposite to the sample supply unit with respect to the filter medium sheet,
The sample supply unit and the filter medium sheet are not in contact,
The filter medium sheet is continuously conveyed,
The filtering method, wherein a supply speed of the fluid sample supplied from the sample supply unit is set to be higher than a suction speed of the fluid sample sucked through the filter medium sheet. 7. The filtration method according to claim 6, wherein the filter medium sheet is inclined downward from the top toward the destination from the source of transport. a sample introduction step of introducing the sample into the pipeline;
an analysis step of analyzing the sample transferred in the pipe;
A flow analysis method comprising:
A flow analysis method comprising a filtration step of performing filtration by the filtration method according to claim 6 or 7.

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