JPH1190160A - Collecting method and collector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a collecting method and a collector for effectively collecting acidic or basic compounds contained in a gas such as the atmosphere. SOLUTION: This collector has a first collecting member 3 in which a basic or an acidic solid collecting agent for forming salts with the acidic or basic objectives in the atmosphere is supported on a supporting body, a first elution means for supplying first elution liquid for dissolving the salts formed in the first collecting member 3 in a first elution liquid storage vessel 7 to the first collecting member 3, a second collecting member 5 for collecting the objectives from the first elution liquid in which the salts are dissolved by ion adsorption, and a second elution means for supplying second elution liquid for eluting the objectives adsorbed on the second collecting member 5 from the second collecting member 5 in a second elution liquid storage vessel 11 to the second collecting member 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a collecting method and a collecting apparatus for collecting and analyzing acidic or basic compounds contained in a gas such as air.

[0002]

2. Description of the Related Art One of the bad odor substances that can sometimes be contained in the atmosphere is a basic compound such as ammonia and amines, and the odor is known as the rotten odor of fresh fish. The foul odor of amines generated from fish ilium bone processing plants and chemical plants is a serious problem, and it is desired to purify the ambient air. To that end, it collects and analyzes ammonia and amines in the air. It is necessary to establish the technology to perform.

On the other hand, in the VLSI manufacturing process, it is essential to establish a technology for managing and analyzing impurity gas in a clean room. For the analysis of inorganic ions, a technique is used in which ion components in the atmosphere are collected in ultrapure water by an impinger or the like and detected by ion chromatography (IC). However, it has become clear that contamination by ultra-trace amounts of organic matter in the atmosphere, which has been of little importance until now, also causes various defects in semiconductor devices and lowers the yield of the VLSI manufacturing process. Also required the same level of sensitivity as inorganic substances. In particular, amines such as ammonia, alkanolamines, aliphatic amines and aromatic amines, which are ionic organic compounds, have high reactivity and clearly cause problems such as hindering resist curing in the lithography process. And the development of analytical methods has become particularly important.

[0004] Ammonia contamination in the clean room is considered to be caused by outside air, wafer cleaning liquid, CVD source gas and the like. Further, it is considered that the amines are derived from components contained in the additive of the boiler water of the clean room and components generated from the human body. These ammonia and amines as trace gases contribute to a decrease in the yield of the semiconductor manufacturing process.

As a conventional collecting method for the purpose of analyzing ammonia and amines, an impinger pure water collecting method or a filter paper absorption method in which air is passed through a filter paper coated with sulfuric acid has been used. However, in the impinger method, since ultrapure water is used in a large amount of 100 ml or more in order to increase the collection efficiency, concentration was difficult. Also, in the filter paper absorption method, the filter paper removed from the holder after collection is put in a beaker, immersed in a sufficient amount of solvent (10 ml to 20 ml with a 5 cm diameter filter paper), extracted, and then applied to an analyzer. There is a concern about contamination from air and containers, and there is a problem as a highly sensitive detection method for trace gas.

[0006] As an apparatus capable of reducing such contamination during the operation and automating all the operations, there is disclosed an apparatus in which a diffusion scrubber method using a gas permeable membrane and ion chromatography are integrated ( JP 8
-54380). By using this device, it is possible to automatically monitor ammonia having an air concentration of 0.1 ppb level every 20 minutes.

[0007]

Ammonia and amine contained in the air often react with acidic substances (eg, hydrochloric acid) in the air and exist in the form of particles or mist.
However, the diffusion scrubber method cannot trap particles or mist due to its mechanism. For this reason, when simultaneous measurement is actually performed at the same location by the impinger method and the diffusion scrubber method, the concentration detected by the impinger collection often gives a higher result. In such a state, it is impossible to accurately measure the amounts of ammonia and amine, and consequently, it must be used in combination with an impinger.

Recently, in order to test the gas generated from the component material, a very small box (15 cm) made of the component material is used.
(X 15 cm x 15 cm) and there is a need to analyze the air in it. However, there is a problem that the impinger and the diffusion scrubber are large in size and cannot be collected in such a small box.

An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a collecting method and a collecting device for enabling high-sensitivity analysis of compounds contained in gases such as air. I do.

[0010]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, have found that a gas-permeable porous support has an acidic or basic solid collecting agent supported thereon. Then, a basic or acidic gas component is collected by the formation of a salt with the collector, and the gas component is re-collected with high efficiency through salt elution and ion adsorption of the gas component to achieve high concentration. It was found that the sample can be prepared.

The collection method of the present invention is a collection method for collecting an acidic or basic target substance in the air and preparing a sample solution containing the target substance, wherein the target substance and a salt are formed. Contacting the target with a possible basic or acidic solid collector to form a salt, dissolving the salt in a first solvent, and ionizing the salt in a first solvent in which the salt is dissolved. A step of contacting an adsorption member having an adsorption ability to adsorb the target object to the adsorption member,
Eluting the ion-adsorbed target substance into the second solvent.

Further, the collecting device of the present invention is a collecting device for collecting an acidic or basic target substance in the air and preparing a sample solution containing the target substance, wherein the target substance and a salt are collected. A first or second collecting member in which a basic or acidic solid collecting agent capable of generating a salt is supported on a support, and a first eluent for dissolving the salt formed in the first collecting member is used as a first eluent. A first eluting means for supplying to the collecting member, a second collecting member for collecting the target substance by ion adsorption from the first eluate in which the salt is dissolved, and a second collecting member. A second eluting unit that supplies a second eluent for eluting the adsorbed target object from the second collection member to the second collection member.

As the support, a fluororesin porous filter subjected to a hydrophilic treatment is used.

When the above object is a basic compound selected from ammonia and an amine compound, the solid collecting agent is phosphonic acid, sulfuric acid, perchloric acid, tartaric acid, phosphoric acid, boric acid, oxalic acid, adipine. It is an acidic compound selected from the group consisting of acids, quinaldic acid, citric acid, cinnamic acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, and malic acid.

The first trapping member is prepared by preparing a solid trapping agent in an alcohol solution, supplying the solid trapping agent to a hydrophilized fluororesin filter, and removing the solvent by decompression, heating, or gas purging. You.

In addition to the centralized automatic control of the collecting device,
A control unit for taking in data obtained by analyzing the sample liquid prepared by the collection device with the detection device and performing data processing can be added.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the case of analyzing ammonia and the like using an ion chromatograph, when an extract of a trapped component is injected into the ion chromatograph, the extract is concentrated by a concentration column built in the apparatus main body, and the concentrated trapped component is detected. The method of detecting with a vessel is adopted. This method has drawbacks such as a large amount of contamination in the extraction step, a long flow path to the internal concentrator, and an increase in the amount of extract to be used, so that it takes a long time for concentration. An automatic injection device having a concentration device for performing concentration outside the ion chromatograph device is also commercially available.However, since it is a method of storing in the form of being absorbed in an extract and concentrating it in the process of automatic injection, the ion chromatography is performed. It has the same disadvantages as having a concentrator inside the graph.

In the present invention, two types of collection members, a first collection member and a second collection member, are used.
Is a member in which a trapping agent for trapping a component to be trapped in the air, that is, an acidic or basic gas, is supported on a porous support, and the trapping agent is a compound that forms a solid phase. It is. The second collection member is a member for preparing a sample in which the capture target collected by the first collection member is contained in a small amount of liquid. The trapping agent of the first trapping member collects the trapped components in the air by forming a salt with the trapped components, and the trapping component and the trapping agent are brought into contact with the eluent that dissolves the salt, whereby the trapped component and the trapping agent are eluent And leave the porous support. The second collection member captures the collection target component by an ion adsorption action and does not form a salt.

In this configuration, by using a solid collecting agent having excellent collecting performance, it is easy to concentrate all the collected target components into a small amount of liquid, and to collect the collecting target components. By arranging two types of collecting members for performing extraction and concentration in close proximity, the amount of eluent used for collection, extraction and concentration can be small. For example, in the ammonia analysis using the present invention, the amount of pure water to be used can be reduced to about 1 to 2 ml, which is 1/10 or less of that of the prior art, and therefore, high-sensitivity analysis with little background can be performed. Automatic analysis is also possible by employing a computer.

When an acidic collecting agent is used as a collecting agent of the first collecting member, a basic substance such as ammonia or amine is captured, and when a basic collecting agent is used, an acidic substance is captured.
The trapping agent must be non-volatile in terms of stability at room temperature, volatility, and the like, and therefore, a solid at room temperature is used. For example, as an acidic trapping agent that traps a basic trapping target, phosphonic acid, perchloric acid, tartaric acid, boric acid, oxalic acid, adipic acid, quinaldic acid, citric acid, cinnamic acid,
Examples include succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid and the like. Acetic acid, formic acid and the like having a low melting point are not suitable because the life of the collecting agent is short and air pollution due to volatilization in the air is considered.
Examples of the basic compound which can be captured by such an acidic capturing agent are ammonia, primary amine,
Secondary amine, tertiary amine, quaternary amine, sodium salt, potassium salt and the like can be mentioned. The amines that can be collected in the present invention may be liquids or solids at normal temperature and normal pressure, or may have vapor pressure in a gas, or may be mist-like amines. Examples of the primary amine include saturated aliphatic primary amines such as methylamine, ethylamine, and propylamine; unsaturated aliphatic primary amines such as allylamine; and aromatic primary amines such as aniline; Examples of the amine include a saturated aliphatic secondary amine such as dimethylamine and diethylamine, an unsaturated aliphatic secondary amine such as diallylamine, and an aromatic secondary amine such as methylaniline. Examples of the tertiary amine include trimethylamine, triethylamine, and methylpiperidine, and examples of the quaternary amine include benzyltrimethylammonium chloride. In the present invention, a primary amine, a secondary amine, a tertiary amine,
All basic compounds in the air such as quaternary amines, sodium salts and potassium salts can be collected.

The basic collecting agent for collecting the acidic capturing target is an alkali metal hydroxide, preferably potassium hydroxide or calcium hydroxide, such as hydrochloric acid, hydrofluoric acid, acetic acid, lactic acid or formic acid. Of organic acids are to be captured.

The porous support for supporting the above-mentioned collecting agent is
A porous filter that allows gas to permeate is used. As this porous material, a fluororesin is excellent. As the fluorine resin, polytetrafluoroethylene (PTF
E), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FE
P), tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinylether copolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (P
CTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyvinylidene difluoride (PVDF), polyvinyl fluoride (PVF) and the like. Since these fluororesins have excellent chemical resistance, they are durable to acid coating or repeated extraction with an organic solvent, and contain few impurities. However, these fluororesins commonly have very high water repellency. Therefore, it is necessary to impart hydrophilicity to the surface of the fluororesin-made porous support so that the trapping agent can easily contact the capture target and the eluent.

As the method of hydrophilizing the above-mentioned fluororesin porous support, a method of immersing the support in an aqueous solution of NaAl (OH) ₄ and then irradiating an ArF laser, or a method of performing a low-temperature plasma treatment, Examples include a chemical activation method in which an alkali metal is immersed in a solution in an organic solvent, and a method in which an alkali metal is immersed in a humectant such as polyvinylpyrrolidone.

As a method for forming a layer of an acidic scavenger on the surface of the porous support having been subjected to the hydrophilization treatment as described above, a solution of the above-described acidic scavenger is passed through the porous support or After dropping or dipping, a method of removing the solvent by decompression, heating, or gas barge may be used.
At this time, examples of the solvent that can be used for the preparation process of the collecting agent layer include water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, and the like. Considering the low boiling point of methanol, methanol is optimal. In the case of a basic collector, a layer is formed in the same manner, and the solvent used at this time is preferably water, methanol, ethanol or the like.

The fluororesin constituting the porous support preferably has a porous surface, that is, a porous structure in which substantially circular holes are connected to each other. The porous support is formed by knitting a fibrous material into a filter shape, or
Tube-shaped ones are easy to use. It is preferable to use a porous film filter generally called a membrane filter, which has a pore structure in which pores close to a circle are interconnected. In the case of a membrane filter used for collecting a trace component in the air, the pore size is 0.025 to
10 μm, film thickness 10-170 μm, diameter 5-50 mm
Something is good. In addition, as a tube-shaped thing,
It is desirable that the porous inner tube be placed inside an outer tube made of plastic or the like so that gas does not pass outside the tube. Here, the reason why porous is preferable is that the surface area is large. In the case of the tube used in the present invention, it is preferable that the inner tube has a hole diameter of 0.025 to 10 μm, a film thickness of 10 to 170 μm, an inner tube diameter of 2 to 10 mm, and an inner tube length of about 5 mm to 50 cm. If the length of the tube is long, the collection efficiency will increase,
A blank having a length of about 10 cm is preferable because the size of the blank also increases. Further, when the tube is formed in a spiral shape or a zigzag shape, the probability of contact between the measured air and the tube surface is increased, and the collection efficiency is good.

When a gas containing a basic substance to be trapped is brought into contact with the first trapping member having the above-mentioned acidic trapping agent layer, the basic substance in the gas is trapped by the first trapping member. It is trapped by the collector to form a salt. The salt on the first collecting member is eluted into the eluent by bringing the eluent (first eluent) into contact with the first collecting member. The eluent may be any solvent that can elute salts and does not contain substances that hinder measurement and analysis.
Can be used as an eluent, but usually pure water is used. When the first eluent comes into contact with the first collecting member, the salt to be captured and the collecting agent are eluted into the first eluent. In the case of eluting an amine salt with water as an eluent, in the case of a filter having a diameter of 13 mmφ, use 99 ml of water with 2 ml of water.
More than 5% of the amine salt is eluted into the eluent and recovered.

The second trapping member is formed of a material having an ion-adsorbing ability such as an ion-exchange resin, and a material having a cation-adsorbing ability such as a cation-exchange resin is used for a basic trapping object. In the case of an acidic capture target, a material having an anion adsorption ability such as an anion exchange resin is used. When the first eluent containing the trapping agent and the trapping agent eluted from the first trapping member comes into contact with the second trapping member, the trapping target is adsorbed to the second trapping member. After the capture target is adsorbed by the second collection member, the first eluent is removed from the second collection member, and the second collection member that has adsorbed the capture target has a strongly acidic group or a strongly basic group. By bringing the eluent (second eluent) containing a solvent having a group into contact, the capture target elutes into the eluent. When the capture target is basic, a solvent such as methylsulfonic acid or diaminopropionate is used.When the capture target is acidic, a solvent such as an aqueous solution of Na ₂ CO ₃ , NaHCO ₃ , cyanophenol is used. Can be
Thus, the capture target is detected by introducing the second eluent from which the capture target has eluted into the detector.

As an analysis method, liquid chromatography (HPLC) or ion chromatography (IC) can be considered. For example, in the case of analysis by HPLC, it is impossible to analyze inorganic substances such as sodium, but IC
It is possible to measure amines having a large number of carbon atoms which cannot be measured by the method. In this case, the collected amine usually has low sensitivity to ultraviolet absorption, so it is preferable to perform fluorescent labeling.

The method of forming a layer of an acidic or basic collecting agent on the surface of the porous support and capturing the components in the gas as in the first collecting member described above is extremely effective. ,
In particular, it is effective as a method for collecting a basic substance such as ammonia or amine, which requires a very small amount of control in a semiconductor process. However, in order to achieve higher sensitivity and automation, an automation system that can prevent contamination in the process of extracting and analyzing captured components from the first capturing member is indispensable. In the present invention, a configuration is proposed in which the eluent in the process from extraction to analysis can be minimized, the contamination is small, the concentration time is short, and the measurement can be performed with high sensitivity and in a short time. . This can be realized, for example, as an apparatus described below.

FIG. 1 is a conceptual diagram showing a first embodiment of the trapping device according to the present invention. The collection device 1 includes a first collection member 3, a second collection member 5, a first eluent storage container 7, a drain 9, and a second eluate storage container 11, and a first collection member. The 3 and 2nd collection members 5 are each comprised as a removable cartridge.

The first trapping member 3 has an ion adsorption column 15 and a first
It is connected to the eluent storage container 7 and the liquid sending pump 17, and is connected to the switching valve 19 on the downstream side. In this embodiment, pure water is used as the first eluent,
By disposing the ion adsorption column 15 between the collecting member 3 and the first eluent storage container 7, ionic impurities in pure water as the first eluent can be removed, and contamination can be reduced. .

The switching valve 19 is connected to a detecting device D such as an ion chromatograph and the second collecting member 5. Further, the second collection member 5 is connected to the drain 9, the second eluent storage container 11, and the liquid sending pump 23 via the switching valve 21. Switching valve 13, 19, 2
The switching operation of 1 and the operation of the liquid feed pumps 17 and 23 are automatically performed by a computer (not shown). As the switching valves 13, 19, and 21, normally used switching valves such as a three-way switching valve are appropriately used.

In order to collect the trapping target, first, the gas to be measured passes through the first trapping member 3 and passes through the first trapping member 3.
The switching valve 13 is switched so that the acidic or basic collecting agent reacts with the capturing target to generate a salt, and a predetermined amount of the gas to be measured flows. Next, the first collecting member 3 is connected to the first eluent storage container 6 side,
To supply the first eluent from the first eluent storage container 7 to the first collection member 3 through the ion adsorption column 5. After the salt and the collecting agent on the first collecting member 3 are eluted into the first eluent and dissociated into ions, they come into contact with the second collecting member 5 and the capture target is the second collecting member 5 Is ion-adsorbed.
The collecting agent is discharged to the drain together with the first eluent. At this time, the flow rate of the first eluent is controlled by controlling the drive time of the liquid feed pump 17 and the switching valve 13 by a computer.

After a lapse of a predetermined time, the valve is switched, and the second eluent in the second eluent storage container 11 is switched by the liquid sending pump 23 through the switching valve 21 to the second collecting member 5.
Supplied to The second eluent elutes the capture target ion-adsorbed by the second collection member 5, is injected into the detector (analyzer) D via the switching valve 19, and is simultaneously analyzed by the detector D. Is started.

The first collecting member and the second collecting member are arranged close to each other, and the path to the detector D is set short, so that a large amount of the first eluate and the second eluate can be obtained. Use is avoided.

FIG. 2 shows an example in which the first collection member 3 of the collection device 1 of FIG. 1 is configured as a detachable cartridge. The cartridge 25 has a cylindrical collecting chamber 27 to which the first collecting member 3 is attached, and an inlet 29 and an outlet 31 communicating with the collecting chamber 27. The first trapping member 3 includes a disc-shaped porous support 33 and a trapping agent 35 supported on one surface on the upstream side.
Is mounted on the collection device 1 so that the gas to be analyzed and the first eluent flow into the collection chamber 27 from the inlet 29. The cartridge is formed of a plastic such as polypropylene. When the gas to be analyzed flows into the collection chamber 27, the trapping target in the gas forms a salt with the trapping agent 35, and the gas from which the trapping target has been removed is discharged from the outlet 31 through the porous support 33. Thereafter, when the first eluent is supplied from the inflow port 29 to the collection chamber 27, the salt and the trapping agent to be trapped elute into the first eluent, and the porous support 33
Through the outlet 31 and is supplied to the second collection member 5.

The first collecting member and the second collecting member of the present invention can be provided in one cartridge. An example of the collecting device in this case is shown below.

FIG. 3 shows a second example of the trapping device 41 according to the present invention.
In this trapping device 41, the first trapping member 3 ′ accommodated in one detachable cartridge 43 is shown.
And a second collecting member 5 '.

The collection device 41 includes a first collection member 3 ′, a second collection member 5 ′, a first eluent storage container 7, a drain 9, and a second eluate storage container 11. The arrangement of one collection member 3 'is different from that of the collection device 1 of FIG. That is,
The first collection member 3 ′ is connected on one side to the ion adsorption column 15, the first eluent storage container 7 and the liquid sending pump 17 via the switching valves 13 and 19, and on the other side to the second collection member 3 ′. It is arranged so as to be connected to the collecting member 5 '. The first eluent from which the ionic impurities have been removed by the ion adsorption column 15 is supplied to the first collection member 3 ′,
The contamination of the first eluent is reduced.

The switching valve 19 is connected to a detecting device D such as an ion chromatograph and the first collecting member 3 ′ of the cartridge 43. Further, the second collection member 5 '
Is connected to the drain 9, the second eluent storage container 11, and the liquid sending pump 23 via the switching valve 21. The switching operation of the switching valves 13, 19, 21 and the operation of the liquid feed pumps 17, 23 are automatically performed by a computer (not shown).

In order to collect the trapping target, first, the gas to be measured passes through the first trapping member 3 ′, and the gas to be measured is mixed with the acidic or basic trapping agent on the first trapping member 3 ′. The switching valves 13 and 19 are switched so that the capture target reacts to generate salt, and a predetermined amount of the gas to be measured flows. next,
Connecting the first collection member 3 ′ to the first eluent storage container 7,
By operating the pump 17, the first eluent is supplied from the first eluent storage container 7 to the first collection member 3 ′ through the ion adsorption column 5. After the salt and the collecting agent on the first collecting member 3 'are eluted into the first eluent and dissociated into ions, they come into contact with the second collecting member 5', and the capture target is the second collecting member. The ions are adsorbed to the member 5 '. The collecting agent is discharged to the drain 9 together with the first eluent. At this time, the flow rate of the first eluent is controlled by controlling the drive time of the liquid feed pump 17 and the switching valve 13 by a computer.

After a lapse of a predetermined time, the valve is switched, and the second eluent in the second eluent storage container 11 is supplied to the second collecting member 5 ′ through the switching valve 21 by the liquid sending pump 23. The second eluent contains the second collection member 5 ′
The first trapping member 3 ′ and the switching valve 19, which elute the trapping target ion-adsorbed by the trapping agent and have no trapping agent.
, The analysis by the detector D is started at the same time as the injection into the detector D.

The first collection member 3 'of the collection device 41 shown in FIG.
FIG. 4 shows an example in which the second collection member 5 ′ is configured as a detachable cartridge. This cartridge 43
Is a first cylindrical member to which the first collecting member 3 'is attached.
A collection chamber 45, a cylindrical second collection chamber 47 to which the second collection member 5 'is attached, a first port 49 communicating with the first collection chamber 45, and a communication with the second collection chamber. It has a second port 51.
The second collection chamber 47 is formed smaller in diameter than the first collection chamber 45,
They are arranged coaxially. The first collecting member 3 ′ includes a disc-shaped porous support 53 and a collecting agent 55 supported on one surface of the first port 49 side, and the cartridge 43 is mounted on the collecting device 41. Then, the configuration is such that the gas to be analyzed and the first eluent flow into the first collection chamber 45 from the first port 49. When the gas to be analyzed flows into the first collection chamber 45, the trapping target in the gas forms a salt with the trapping agent 55, and the gas from which the trapping target has been removed becomes the porous support 53 and the second trapping member. It is discharged from the second port 31 through 5 '. Thereafter, when the first eluent is supplied from the inlet 49 to the first collection chamber 45, the salt and the trapping agent to be trapped elute into the first eluent, pass through the porous support 53, and pass through the porous support 53. 2 are collected. The trapping target is ion-adsorbed by the second trapping member 5 ′, and the trapping material is discharged from the second port 51 to the outside of the cartridge 43. Thereafter, when the second eluent is supplied from the second port 51, the capture target on the second collection member 5 'is eluted into the second eluate, and the porous support 53 having no collection agent is removed. The liquid is discharged from the first port 49 and sent to the detector D.

In the configuration shown in FIGS. 3 and 4, the first collection member and the second collection member are contained in one cartridge, and if the target to be captured is basic, it has an acidic collector. A first collection member and a second collection member having a cation adsorption ability are incorporated, and in the case of an acidic trapping target, a first collection member having a basic collection agent and an anion adsorption ability And a second collection member having Therefore, the capture target can be easily changed by exchanging the cartridge.

The cartridges 25 and 43 described above may be mounted on the collection devices 1 and 41 after collecting the capture target using a gas sampler separate from the collection devices 1 and 41. In this case, the collection, concentration, and analysis of a large number of gas samples can be performed continuously by replacing the cartridge, so that the analysis operation can be performed efficiently. In the collecting devices 1 and 41 of FIGS. 1 and 3, a plurality of cartridges may be arranged in parallel so that the connection can be switched sequentially. Alternatively, in the collecting device 41 of FIG.
A pair of cartridges for acidic and basic capture targets is configured to be connected in parallel between the switching valves 19 and 21, and measurement of acidic and basic capture targets can be performed sequentially by switching the switching valves 19 and 21. You may do so.

In the present invention, mist-like and particulate amines, which cannot be analyzed by the diffusion scrubber method, can be collected. Only a small amount of liquid is required, and the preparation time of the sample liquid for measurement can be shortened. Further, the first collecting member can be regenerated by supplying the solution of the collecting agent again to the used cartridge and placing the collecting agent on the porous support and drying it, so that the cost can be reduced. is there.

[0047]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

The analysis according to the present invention was carried out using the following instruments.

[High Performance Liquid Chromatography (HPLC)] HPLC 610E system column manufactured by Waters Co., Ltd .: L-Column O (trade name, manufactured by Chemical Inspection Association)
DS) (4.6 mmφ × 250 mm) Column temperature: 40 ° C., flow rate: 1 ml / min, mobile phase solvent: acetonitrile / water = 45/55 Injection volume: 20 μl / time Detector: Waters 474 scanning fluorescence detector ( [Excitation wavelength: 450 nm, Fluorescence wavelength: 530 nm] [Reagents] acetonitrile, water, methanol: solvent for high-performance liquid chromatography manufactured by Wako Pure Chemical Industries, Ltd. NBD-F: manufactured by Dojindo Corporation Other reagents: Wako Pure Chemical Industries, Ltd. Was used.

Concentration of standard amine: methylamine = 4 μg
/ Ml, ethylamine = 5 μg / ml, propylamine = 7
μg / ml Internal standard: butylamine concentration = 7 μg / ml Buffer solution: borate buffer / methanol solution (pH 8.5) [Pump] Mini pump (MP-603P) manufactured by Shibata Chemical Co., Ltd. [Disposable membrane filter] Toyo Roshi Kaisha ), 13HP020AN Diameter: 13 mmφ, Pore size: 0.2 μm, Thickness: 35 μm, Material: hydrophilic PTFE, Housing material: Polypropylene [ion chromatography] Apparatus: Dionex DX-100 Guard column: CG-12, Separation column: CA-12 Concentration column: CG-12 Eluent: methanesulfonic acid (10 mM), flow rate: 1.0
(Ml / min) Detector: Conductivity detector (Example 1) -Filter collection and recovery test- After passing 5 ml of methanol through the disposable filter cartridge using a syringe, 0.3% methanol tartaric acid solution 1 ml of the solution was passed, put in a desiccator, and dried under reduced pressure for 1 hour with a vacuum pump. When the vacuum was released, the atmosphere was replaced with high-purity nitrogen.

The two cartridges prepared as described above were connected in series, 10 μl of the mixed amine was spread on glass wool placed in a tube connected to the two cartridges, and 300 L of nitrogen was applied to the glass wool at 2 L / min. A stream of nitrogen was blown through the glass wool and passed through the two cartridges.

Thereafter, the cartridge was loaded with 2.5 mg / ml of N
Elution was carried out with 1 ml of BD-F / buffer solution, 10 μl of butylamine was added as an internal standard substance, and the mixture was reacted at 70 ° C. for 15 minutes, followed by HPLC measurement. The amine was taken in a sample bottle as it was, and the peak area subjected to the labeling reaction was calculated as 100% collection. Table 1 shows the results.

[0053]

Table 1 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Cartridge Amine recovery (%) Methylamine Ethylamine Propylamine ----------------------------------------------------------- 1st 97.6 101.0 97.7 2nd 1 .87 0.00 0.91 ------------------------------------------------------ 0.3% tartaric acid coated By doing so, it was found that the amine was obtained with a recovery of 98 to 100%. An extract volume of 1 ml was sufficient.

(Example 2)-Ammonia recovery test with water-The above cartridge was washed with 5 ml of methanol, and then washed with 0.5 ml of methanol.
1 ml of a 3% methanolic tartaric acid solution was passed through. It was dried in a desiccator for 30 minutes using a vacuum pump to remove methanol.

A 25% aqueous ammonia solution was diluted with methanol to prepare a 25 μg / ml methanol solution. 40 μl of this solution was placed on glass wool placed in a tube connected to two cartridges connected in series in the same manner as in Example 1, and the atmosphere was ventilated at a rate of 2 L / min for 150 minutes.

Thereafter, pure water is added to the first cartridge for 1 hour.
Ammonia was recovered from the cartridge by supplying three times each ml.

On the other hand, as a standard, three samples were prepared by directly adding 40 μl of the above-mentioned ammonia solution to 1 ml of pure water, and the recovery rate of ammonia recovered from the cartridge was calculated based on these samples. Table 2 shows the results.

[0058]

Table 2 Ammonia recovery rate (%) 1st ml 2nd ml 3ml 3rd-------------------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− First time 94.3 5.3 0.4 Second time 95.6 3.90 .5 ------------------------------------

In the case of recovery with water, 9 ml of extract was used for 2 ml of extract.
A recovery of 9.5% or more was obtained. In other words, an eluate of 2 ml is sufficient for introduction into the ion chromatograph. Compared with the conventional impinger method, the amount of liquid required to capture the trapped substance in the air is reduced and the concentration is 100 times or more. It can be.

(Example 3) -Comparison with the impinger method- An actual measurement of atmospheric substances in a clean room was performed as follows.

First, a hydrophilic PTFE cartridge treated with 0.3% methanol tartaric acid in the same manner as in Example 1 was used as a collecting member. The air was collected at a flow rate of 1.1 L / min for 120 minutes using an air collecting pump.
After the sampling, 1 ml of a 2 mg / ml NBD-F borate buffer (pH 8.52) solution was added to the collecting member, 5 μl of butylamine was added as an internal standard, the mixture was heated at 60 ° C. for 15 minutes, and measured by HPLC. Note that a calibration curve using methylpropanolamine was prepared by repeating the measurement by HPLC by performing the same operation.

On the other hand, in the impinger method, the air is sucked into 140 ml of pure water at a rate of 2 L / min for 120 minutes by bubbling to absorb the gas in 480 l of the atmosphere, and the substances collected by the ion chromatography method are measured. did. Table 3 shows the results
Shown in

[0063]

Table 3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Cumulative flow ) Methylpropanolamine Ammonia (L) The present method The impinger method The present method The impinger method --------------------------------------------------- Clean room A 203 16.7 13.0 8.0 8.1 Clean room B 114 1.0 0.87 1.3 1.4 1.4 -------------------------------------------------------------------- −−−−−−−−−−−−−−−− Compared with the impinger method collected at the same time, the measured values almost matched. When a hydrophilic PTFE cartridge is used,
The blank value was sufficiently low for both ammonia and methylpropanolamine, and the lower detection limits when using ion chromatography were 0.06 and 0.07 [air pp, respectively].
b], and the detection ability was high.

Example 4 After 5 ml of methanol was passed through the disposable filter cartridge using a syringe, 1 ml of a 0.3% methanol solution of tartaric acid was passed through, placed in a desiccator, and dried under reduced pressure with a vacuum pump for 1 hour. did. When the vacuum was released, the atmosphere was replaced with high-purity nitrogen. This cartridge was incorporated as a cartridge 25 into the collection device 1 having the configuration shown in FIG. 1 and the following operation was performed. A cation exchange resin column (styrene-vinyl copolymer-sulfonic acid type, exchange capacity: 2 g) was used as the second collection member 5 of the collection device 1.

Pure water was charged into the first eluent storage container 7, and a 10 mM methanesulfonic acid aqueous solution was charged into the second eluent storage container 11. After the air in the clean room A measured in Example 3 was allowed to flow into the cartridge 25 at a rate of 2 L / min for 30 minutes, the liquid sending pump 17 was operated to dispense 2 ml of pure water from the first eluate storage container 7. It was supplied to the cartridge 25 at the speed. The water passes through the cartridge 25 and the second
And was discharged to the drain 9 through the collecting member 5 of FIG. Thereafter, the switching valves 19 and 21 are switched, and the liquid sending pump 23 is operated to move the second eluent storage container 11 by 10 m.
1 ml of an aqueous solution of M methanesulfonic acid was supplied to the second collection member 5. The aqueous solution of methanesulfonic acid that passed through the second collection member 5 was sent from the switching valve 19 to the ion chromatograph detector and analyzed. Table 4 shows the analysis results.

The collecting agent of the present method can be prepared by a simple operation, and is small in size and easy to carry and handle as compared with the impinger method. In addition, since extraction can be performed with a small amount of pure water, the concentration time for IC measurement can be reduced. In this law,
Since volatile ammonia and amines are collected in a state where salts are formed on the surface of the first collection member, long-term storage is stable, and long-distance sample transport can be performed without any problem. Also,
The collected ammonia and amines can be extracted with an organic solvent such as methanol, so that not only ion chromatography but also various kinds of analysis such as HPLC and GC can be performed.

[0067]

According to the present invention, an acidic or basic compound in a gas can be efficiently collected and concentrated at a high concentration, so that it is most suitable for a highly sensitive analysis of a basic compound. Therefore,
Environmental management of ammonia, amines, and the like in an indoor room, an outdoor room, a clean room, and the like is improved, the yield of a semiconductor manufacturing process such as a resist process is improved, and a high-quality semiconductor device can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing a first embodiment of a collection device of the present invention.

FIG. 2 is a schematic configuration diagram illustrating an example of a cartridge used in the collection device of FIG.

FIG. 3 is a schematic configuration diagram showing a second embodiment of the collection device of the present invention.

FIG. 4 is a schematic configuration diagram illustrating an example of a cartridge used in the collection device of FIG. 3;

[Explanation of symbols]

 1,41 Collection device 3,3 'First collection member 5,5' Second collection member 7 First eluent storage container 9 Drain 11 Second eluent storage container 13,19,21 Switching valve 15 Ion adsorption column 17, 23 Liquid feed pump 25, 43 Cartridge 27 Collection chamber 29 Inlet 31 Discharge port 33, 53 Porous support 35, 55 Collector 45, 47 First collection chamber, Second collection chamber 49,51 1st mouth, 2nd mouth

Claims (2)

[Claims] 1. A collection method for collecting an acidic or basic target substance in the air and preparing a sample liquid containing the target substance,
Contacting the target with a basic or acidic solid collecting agent capable of forming the target and a salt to form a salt, dissolving the salt in a first solvent, dissolving the salt; A step of contacting the adsorption member having ion adsorption ability with the first solvent to adsorb the target object to the adsorption member, and a step of eluting the ion-adsorbed target object to the second solvent. A collection method characterized by the following. 2. A collection device for collecting an acidic or basic target substance in the air and preparing a sample liquid containing the target substance,
A first collection member in which a basic or acidic solid collection agent capable of forming the target substance and a salt is supported on a support; and a first collection member for dissolving the salt formed in the first collection member. A first eluting means for supplying an eluent to the first collection member, and a first eluent containing the salt dissolved therein.
A second collecting member for collecting the target substance from the eluent by ion adsorption, and a second eluent for eluting the target substance adsorbed on the second collecting member from the second collecting member. The second
And a second eluting means for supplying to the collecting member.