JP2020204553A - Device and method for collecting and detecting hydrophilic substance in gas - Google Patents

Abstract

To provide a device for collecting and detecting hydrophilic substances in a gas that can efficiently collect a gaseous hydrophilic substance and a particulate hydrophilic substance in the gas at the same time and detect them with high accuracy, and a method for collecting and detecting the hydrophilic substances in the gas performed by the device for collecting and detecting.SOLUTION: A device collects and detects a gaseous hydrophilic substance and a particulate hydrophilic substance which are contained in a gas. The device for collecting and detecting the hydrophilic substances in the gas includes: a coil tube through which the gas passes; condensate collecting means connected to an outlet of the coil tube; cleaning means for cleaning the inside of the coil tube by making cleaning water pass through the coil tube; and hydrophilic substance detection means. The device for collecting and detecting the hydrophilic substance performs a method for collecting and detecting the hydrophilic substance in the gas.SELECTED DRAWING: Figure 1

Description

The present invention relates to a collection / detection device for collecting and detecting a gaseous or fine particle-like hydrophilic substance contained in a gas, and a collection / detection method.

To check the performance of the exhaust gas treatment process and treatment equipment that removes harmful gaseous and particulate substances contained in gas such as exhaust gas from the gas, the gaseous and particulate matter contained in the gas after removal Collection and detection of substances, as well as concentration measurement and quantification, have been studied, and various methods have been proposed.
For example, Non-Patent Document 1 describes a method of collecting and detecting cesium in incineration exhaust gas of waste containing radioactive cesium with a cylindrical filter paper and an impinger (gas suction bottle) provided in the subsequent stage. It is an official method for checking the performance of exhaust gas treatment equipment in waste treatment.

Further, in Patent Document 1, exhaust gas containing SO ₃ gas is passed through a spiral tube kept below the acid dew point temperature, and gaseous sulfuric acid is converted into liquid sulfuric acid by utilizing the inertial collision action in the tube to aggregate. after allowed to, SO ₃ for analyzing sampling method SO ₃ gas in the exhaust gas to be fractionated by washing the tube with washing water, and the sulfur oxides analyzer method ion chromatograph such washing water obtained by this method A method for analyzing the concentration is disclosed.
Further, in Non-Patent Document 2, a gas containing fine particles of hygroscopic alkali metal chloride such as NaCl and CsCl is passed through two glass coil tubes in series, and the alkali metal chloride contained in the gas by the glass coil tube is passed. A method of collecting fine particles of an object is disclosed.

Japanese Unexamined Patent Publication No. 8-210954

Waste-related guidelines 5-20 to 5-23 (Ministry of the Environment: December 27, 2011) Environmental Chemistry Vol. 28, No. 3, pp. 61-67, 2018

As described above, as a method of collecting the gaseous and fine particle hydrophilic substances contained in the gas, a method of filtering with a filter such as a cylindrical filter paper or a gas suction bottle such as an impinger is used to separate gas and water. A method of contacting with water to absorb gas and a method of utilizing an inertial collision action in a pipe such as a spiral pipe or a coil pipe are known.
It is said that the method using a filter is superior in the collection efficiency of particles to the method in which a gas and a liquid are brought into contact with each other, and the collection efficiency is particularly high in the region of fine particles. Therefore, this method is regarded as an official method for confirming the performance of exhaust gas treatment equipment in waste treatment.

However, it is considered difficult to collect gas by the filter method. In addition, cesium chloride, which is predicted to exist in the form of gas or fine particles in the waste incineration exhaust gas, is collected and removed by the bag filter, so its collection and removal performance (dust collection performance). ) Is not preferable to be evaluated and confirmed by collecting with a filter, and evaluation and confirmation by a principle completely different from that of a filter is desired.

It is considered that the method of bringing the gas into contact with water by a gas suction bottle such as an impinger and allowing the water to absorb the gas has a high collection efficiency of the hydrophilic gas in the gas. However, it has been pointed out that the collection of particles, especially fine particles, is insufficient.

On the other hand, as shown in Non-Patent Document 2, by passing a gas through the glass coil tube, hygroscopic alkali metal chloride fine particles contained in the gas can be collected. It is also shown that the particles smaller than 0.3 μm can be collected because the fine particles absorb moisture and grow by moistening the inside of the glass coil tube. From this result, it is considered that fine particles of hydrophilic substances such as alkali metal chloride contained in the gas can be collected by using a coil tube, particularly a coil tube in which the inside of the tube is moistened.

Therefore, the present inventor thinks that if a coil tube is connected to the gas suction bin, gaseous pollutants and particulate pollutants contained in the gas can be collected at the same time, and a glass coil tube is placed after the impinger. The gas or fine particles of ammonium chloride contained in the gas were collected by the connected device. As a result, although ammonium chloride gas and fine particles are collected, some ammonium chloride gas and fine particles are not collected, and it has been desired to develop a device having higher collection efficiency.

Further, in the conventional collection / detection method as described above, there is a problem that the blank value derived from the operation and the surrounding environment is high, the detection limit value is high, and as a result, the detection accuracy is low.

The present invention efficiently collects gaseous hydrophilic substances and / or particulate hydrophilic substances contained in a gas, and can collect the hydrophilic substances in a gas with high accuracy. -It is an object of the present invention to provide a detection device and a method for collecting / detecting a hydrophilic substance in a gas carried out by the collection / detection device.

As a result of repeated studies to solve the above problems, the present inventor has passed a gas through a device that combines a coil tube and a coagulated water collecting means connected to a gas outlet of the coil tube. The gaseous hydrophilic substance and / or the particulate hydrophilic substance contained therein can be efficiently collected, and the collected hydrophilic substance is washed by a washing means, and the obtained washing liquid is used as a hydrophilic substance detecting means. It was found that highly accurate detection and quantification are possible by detecting and quantifying with the above method.

The present inventors further perform cleaning of the coil tube or the like by the cleaning means before collecting the hydrophilic substance, and / and the hydrophilic substance detecting means of the aggregated water collecting means. It has been found that by connecting to the gas outlet, the blank value derived from the operation and the surrounding environment can be lowered, and more accurate detection and quantification become possible.
That is, the above-mentioned problem of the present invention is achieved by the following configuration.

The present invention is an apparatus for collecting and detecting a gaseous hydrophilic substance and a particulate hydrophilic substance contained in a gas, and is a coil tube through which the gas passes and agglomerated water connected to the outlet of the coil tube. The present invention provides a collecting / detecting apparatus for a hydrophilic substance in a gas, comprising a collecting means, a cleaning means for passing washing water through the coil tube to clean the inside of the coil tube, and a hydrophilic substance detecting means.

The coil tube is preferably a glass coil tube.

The device for collecting / detecting a hydrophilic substance in a gas is preferably provided with the hydrophilic substance detecting means connected to the outlet of the coagulated water collecting means.

It is preferable that the water-imparting means for imparting water to the gas is provided in front of the gas inlet of the coil tube (direction in which the gas flows in).

The present invention is also a method for collecting and detecting a gaseous hydrophilic substance and a particulate hydrophilic substance contained in a gas, in a step of passing the gas through a coil tube, and a gas flowing out from the coil tube. To obtain the collected water by passing the water droplets flowing out from the coil tube through the coagulated water collecting means, the cleaning step of passing the washing water through the coil tube to obtain the cleaning liquid, and the collected water and Provided is a method for collecting and detecting a gaseous hydrophilic substance in a gas, which comprises a hydrophilic substance detecting step of detecting the gaseous hydrophilic substance and the particulate hydrophilic substance contained in the cleaning liquid by a hydrophilic substance detecting means.

The method for collecting / detecting a hydrophilic substance in a gas preferably further includes a step of passing washing water through the coil tube to wash the coil tube before the step of passing the gas through the coil tube.

In the method for collecting / detecting a hydrophilic substance in a gas, the hydrophilic substance detecting means collects the gaseous hydrophilic substance and the particulate hydrophilic substance contained in the collected water and the cleaning liquid online (inside the apparatus). It is preferable that the means can be detected only by passing through the gas.

Gaseous hydrophilic substances and particles contained in the gas using the device for collecting and detecting hydrophilic substances in gas of the present invention or by the method for collecting and detecting hydrophilic substances in gas of the present invention. If the hydrophilic substance is collected, the hydrophilic substance can be efficiently collected, and highly accurate detection and quantification are possible.
In particular, the device for collecting / detecting a hydrophilic substance in a gas cleans the inside of the coil tube by a means for cleaning the inside of the coil tube before collecting / detecting the hydrophilic substance, and / or the aggregated water. By connecting a hydrophilic substance detecting means to the outlet of the collecting means, it is possible to reduce the blank value derived from the operation and the surrounding environment, and it is possible to detect and quantify the hydrophilic substance with higher accuracy. it can.

The figure which shows the schematic structure of the collection / detection apparatus of a hydrophilic substance in gas of this invention. The figure which shows the schematic structure of the method of collecting / detecting a hydrophilic substance in gas of this invention. The figure which shows schematic the detected gas generator used in an Example and a comparative example. The figure which shows typically the water addition means (impinger) used in an Example and a comparative example. The figure which shows typically the coil tube, the cleaning means, and the coagulated water collecting means used in an Example and a comparative example.

Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings, but the scope of the present invention is not limited to the following embodiments.

(Configuration of collection / detection device)
FIG. 1 is a diagram showing a schematic configuration of a device for collecting / detecting a hydrophilic substance in a gas of the present invention. FIG. 2 is a diagram showing a schematic configuration of a method for collecting / detecting a hydrophilic substance in a gas of the present invention.

As shown in FIG. 1, the device for collecting / detecting a hydrophilic substance in a gas of the present invention has a coil tube 3, a coagulated water collecting means 5, a cleaning means 4, and a hydrophilic substance detecting means 6 as essential configurations. Be prepared. The gas 7 flowing out from the exhaust gas treatment device or the like is introduced into the coil tube 3 from I3 of the coil tube 3 and flows out from the gas outlet O3. In the coil tube 3, particles of the hydrophilic substance contained in the gas 7 collide with the tube wall and are captured by the tube wall due to the centrifugal force generated when passing through the coil tube 3. When the inner wall of the pipe and the inside of the pipe are moistened with the water contained in the gas 7, the particles are dissolved in the water of the inner wall of the pipe, or the particles are aggregated and grown by the water in the inner wall of the pipe and the inside of the pipe. Is easier to capture and the collection efficiency is improved.

Further, when the inner wall of the pipe and the inside of the pipe are moist, the gaseous hydrophilic substance is also dissolved or absorbed in the inner wall of the pipe and the water in the pipe, or once grown into fine particles, the inside of the coil tube 3 is contained. It is collected by being condensed by the centrifugal force generated when passing through and being captured by the inner wall of the pipe.
As described above, the gaseous hydrophilic substance and / or the particulate hydrophilic substance is collected in the coil tube 3, but the inner wall of the tube in which the hydrophilic substance is absorbed and dissolved, and a part of the water in the tube. May flow out of the gas outlet O3 along with the flow of the gas 7. Further, a part of the hydrophilic substance, particularly the gaseous hydrophilic substance, may be contained in the flow of the gas 7 and flow out from the gas outlet O3 without being collected in the coil tube 3.

The gas 7 flowing out from the gas outlet O3 is introduced into the coagulated water collecting means 5 from the gas inlet I5 of the coagulated water collecting means 5. The hydrophilic substance flowing out from the outlet O3, that is, the water in which the gaseous hydrophilic substance and / or the particulate hydrophilic substance is absorbed and dissolved in the coil tube 3, and a part of the hydrophilic substance are contained in the aggregated water collecting means 5. It comes into contact with the water of the above, is absorbed and dissolved in the water in the aggregated water collecting means 5, and is collected. The "collected water" means the water in the coagulated water collecting means.
In this way, the gaseous hydrophilic substance and / or the particulate hydrophilic substance contained in the gas 7 is put into the collected water in the coil tube 3 or the aggregated water collecting means 5 with high collection efficiency. Be collected.

The cleaning means 4 is a means for cleaning the inside of the coil tube by passing water (cleaning water) through the coil tube 3. By this washing, the gaseous hydrophilic substance and / or the particulate hydrophilic substance collected in the coil tube 3 is dissolved in the washing water. By detecting the cleaning liquid of the coil tube 3 and the hydrophilic substance in the collected water in which the gaseous hydrophilic substance and / or the particulate hydrophilic substance collected in this manner are detected by the hydrophilic substance detecting means 6. , The gaseous hydrophilic substance and / or the particulate hydrophilic substance contained in the gas 7 can be detected with high accuracy. When the hydrophilic substance detecting means 6 has a quantification function, the total amount of the hydrophilic substances contained in the gas 7 can be quantified.

The cleaning liquid of the coil tube 3 may be taken out from the outlet O3 of the coil tube 3 and used for detection by the hydrophilic substance detecting means 6, or may be taken out from the take-out port O31 provided in the middle of the coil tube 3. Further, the washing water may be injected into the coil tube 3 from the outlet O3 side and taken out from the take-out port O32 (not shown) provided near the inlet I3 of the coil tube 3. Further, the cleaning liquid flowing out from the outlet O3 is introduced into the coagulated water collecting means 5 and combined with the collected water in the coagulated water collecting means 5, and then the collected water outlet of the coagulated water collecting means 5. It may be taken out from O5 and used for detection by the hydrophilic substance detecting means 6.
In this case, by connecting the hydrophilic substance detecting means 6 to the collecting water outlet O5, it is derived from the operation by coalescence and the environment between the coil tube 3 or the aggregated water collecting means 5 and the hydrophilic substance detecting means 6. It is possible to prevent an increase in the blank value, and it is possible to detect and quantify hydrophilic substances with higher accuracy.

Before supplying the gas 7 to a collecting / detecting device for a hydrophilic substance in a gas to collect / detect the gas 7, water (washing water) is passed through the coil tube 3 by the cleaning means 4 to pass the coil tube. Cleaning the inside of 3 is preferable because it can reduce an increase in the blank value due to contamination in the coil tube 3. When the cleaning means 4 can clean the coagulated water collecting means 5 together with the inside of the coil tube 3, if the coagulated water collecting means 5 is also cleaned, the increase in the blank value due to contamination in the apparatus can be further reduced. preferable.

(Coil tube)
The coil tube 3 is a tube formed by winding glass or the like in a spiral or spiral shape. The cross section of the coil tube 3 is usually circular, but the cross section is not limited to the circular shape and may be a tube having another shape.
The material for forming the coil tube of the hydrophilic substance collecting / detecting device of the present invention is not particularly limited as long as it can form a tube having an outer diameter smaller than about 1 cm and can form a spiral or a spiral smaller than about 20 cm in diameter. .. Considering ease of processing, strength, durability, price, availability, etc., metal materials such as copper and stainless steel and glass can be mentioned, but when a glass tube formed from glass is used, metal It is preferable to use a tube formed of a material because the collection efficiency of the particulate hydrophilic substance is higher.

The coil tube 3 of the hydrophilic substance collecting / detecting device of the present invention may include two or more coil tubes. In particular, it is preferable to connect two or more coil tubes in series (connecting the gas outlet of the coil tube in the front stage and the gas inlet of the coil tube in the rear stage) because the collection efficiency of the particulate hydrophilic substance is improved.

It is expected that the longer the total length of the coil tube 3, the higher the collection efficiency. It is expected that the larger the particle size of the particles in the gas, the better the collection efficiency. If the flow velocity of the gas passing through the coil tube 3 is the same, the smaller the winding diameter of the coil tube 3, the greater the centrifugal force acting on the particles in the gas, and it is expected that the collection efficiency will be improved. On the other hand, when the winding diameter of a coil tube, particularly a glass coil tube, is small, it becomes difficult to manufacture the coil tube.

The total length of the coil tube 3, its winding diameter (that is, the number of windings), the number of connections thereof, and the flow velocity of the gas to be passed are preferably selected so as to obtain a desired collection efficiency, and particularly preferably, agglomerated water collection. It is selected so that the collection efficiency close to 100% can be obtained in combination with the collection by means. Therefore, when collecting / detecting a hydrophilic substance, it is preferable to determine in advance the optimum total length, inner diameter, winding diameter (that is, number of turns), and number of connections of the coil tube 3 by a preliminary experiment or the like. Regarding the collection and detection conditions such as the gas flow velocity and the cooling temperature of the coil tube below, it is preferable to select the optimum conditions in advance by preliminary experiments or the like so that the desired collection efficiency can be obtained. ..

(Coil tube cooling means)
The device for collecting / detecting a hydrophilic substance in a gas of the present invention may be provided with a cooling means for a coil tube. The lower the temperature inside the coil tube, the higher the collection efficiency of particulate hydrophilic substances in many cases. In this case, depending on the environment in which the collection / detection device is installed, it is preferable to provide a cooling means for cooling the coil tube. Examples of the cooling means include various means such as an air-cooled type and a water-cooled type. For example, when the collection / detection device is installed in a high temperature environment, a method of providing a water tank filled with cold water as a cooling means and immersing the coil tube in the water tank can be mentioned.

(Aggregated water collecting means)
The structure and shape of the aggregated water collecting means 5 are not particularly limited as long as they can collect water droplets in which the hydrophilic substance flowing out from the coil tube 3 is dissolved. For example, a container such as a syringe with a glass, plastic or ceramic frit placed on the bottom, or a gas (including water droplets and gaseous hydrophilic substances) that flows out from a coil tube into the water filled therein, such as an impinger. The container to be passed through can be mentioned. In the case of a syringe in which the glass frit is arranged at the bottom, water droplets flowing out from the coil tube 3 together with the gas are introduced from the lower part of the glass frit, captured by the glass frit, and collected at the bottom of the syringe to be collected water. In the case of an impinger or the like, the water droplets flowing out from the coil tube 3 together with the gas are mixed with the water or the like contained in the impinger, and the mixed water becomes the collected water. When a gas is brought into contact with water to capture water droplets like an impinger, a gaseous hydrophilic substance contained in the gas, that is, a gaseous hydrophilic substance not captured by the coil tube 3 is also combined with the water. It is considered to be captured by the contact of.

(Cleaning means)
The cleaning means 4 for cleaning the inside of the coil tube 3 supplies a predetermined amount of cleaning water into the coil tube 3 and also discharges a cleaning solution from the coil tube 3 (the cleaning water contains water and hydrophilicity in the coil tube 3). It is not particularly limited as long as it is a means capable of recovering the entire amount of the solution in which the substance is dissolved. For example, a cleaning water supply unit that supplies a predetermined amount of cleaning water such as a syringe or a pump, a cleaning water introduction unit that introduces the cleaning water supplied from the cleaning water supply unit into the coil tube, and a cleaning liquid discharged from the coil tube. A means composed of a cleaning liquid recovery unit to be recovered can be mentioned.

Examples of the cleaning water introduction unit include a configuration including a three-way cock provided near the gas inlet I3 of the coil tube 3 and a cleaning water introduction path connecting the cleaning water supply unit and the three-way cock. The recovery unit includes, for example, a three-way cock provided in the middle of the flow path connecting the outlet O3 of the coil pipe 3 and the inlet I5 of the coagulated water collecting means 5, and a cleaning liquid recovery path connected to the three-way cock. And so on.
The washing water introduction part and the recovery part are washed from a three-way cock provided in the middle of the flow path connecting the outlet O3 of the coil tube 3 and the inlet I5 of the coagulated water collecting means 5 in the reverse manner of the above case. It is also possible to introduce water into the coil tube 3 and collect the cleaning liquid from the three-way cock provided near the inlet I3.

(Hydrophilic substance detection means)
The hydrophilic substance detecting means is not particularly limited as long as it is an apparatus capable of detecting the hydrophilic substance to be detected dissolved in the cleaning liquid. An apparatus capable of easily, quickly, accurately and accurately quantifying the concentration of a hydrophilic substance in water is preferable, and examples thereof include liquid chromatography, a spectroscopic analyzer, and a mass spectrometer.
Further, if a hydrophilic substance detecting means capable of detecting and quantifying online is used and connected to the cleaning liquid recovery unit of the cleaning means 4, detection and quantification can be continuously and automatically performed, and the cleaning liquid can be continuously and automatically performed. It is preferable because it is possible to suppress an increase in the blank value due to an operation between the collection unit and the detection and quantification and the device, and more accurate detection and quantification can be performed.

(Other configurations)
The device for collecting / detecting a hydrophilic substance in a gas of the present invention may be provided with other configurations, if necessary, in addition to the above-mentioned essential configurations. For example, a water-imparting means for imparting water to the gas to be collected / detected of the hydrophilic substance can be provided in front of the gas inlet of the coil tube (direction in which the gas flows in). As described above, when the inner wall of the coil tube is moistened, the collection efficiency of hydrophilic substances may be improved. In order to moisten the inner wall of the coil tube, it is preferable that the amount of water contained in the gas is large. Therefore, when the humidity in the target gas is low, the water addition means is used in the front stage of the collecting / detecting device ( It is preferable to provide the device at a position (position before the gas flows into the device) to add water to the target gas.
Examples of the water-imparting means include a U-shaped tube and an impinger.

(Target of detection)
The target to be collected / detected by the collecting / detecting device for the hydrophilic substance in the gas and the collecting / detecting method of the present invention is a gas that may contain a gaseous or particulate hydrophilic substance. Examples of this gas include a gas after removing harmful substances from exhaust gas from waste combustion treatment, factory exhaust gas, polluted air, etc., for the purpose of evaluating the efficiency of the removal treatment of harmful substances. The device and method of the present invention can be used.
Here, the hydrophilic substance is a substance that is soluble in water and can exist in a gas in the form of a gas or particles. For example, metal halides, hydrogen halides, halogen molecules, sulfurous acid, sulfuric acid and the like contained in exhaust gas can be mentioned.

Further, the hydrophilic virus in the atmosphere is also considered to be a hydrophilic substance collected / detected by the hydrophilic substance collecting / detecting device in the gas of the present invention. Examples of the hydrophilic virus include enterovirus and the like.
As a method for examining the amount of virus in the air, a method of increasing wetness, centrifuging and collecting, and retaining condensed water using a cooling coil tube, and a method using a filter are known. According to these methods, It is believed that there is a problem that damages the virus. However, according to the device for collecting / detecting a hydrophilic substance in a gas of the present invention, it is considered that the hydrophilic virus can be collected / detected without being damaged.

(Experimental outline of Examples and Comparative Examples)
The hydrophilic substance to be collected was ammonium chloride, and the collection efficiency was evaluated. First, the apparatus shown in FIG. 3 is used to react hydrochloric acid with ammonia to generate ammonium chloride, and the generated fine particles of ammonium chloride or the atmosphere containing the fine particles and gas (hereinafter referred to as “detected gas”) is shown in FIG. The impinger (gas-like hydrophilic substance collecting means: water-imparting means) shown in No. 4, the glass coil tube shown in FIG. 5, the cleaning means, and the coagulated water collecting means are passed through an apparatus configured by the combination shown in Table 1. Ammonium chloride was collected by an impinger, a glass coil tube, and a coagulated water collecting means. After collection, the glass coil tube is cleaned by the cleaning means shown in FIG. 5, and the concentration of the cleaning liquid collected from the outlet of the cleaning means and the concentration of ammonium chloride in the collected water collected by the coagulated water collecting means is charged. The total amount of collected ammonium chloride was determined from the amount of collected washing liquid and collected water and the concentration obtained by the measurement, which was measured by a conductivity meter. The collection efficiency was evaluated by the ratio of the total amount obtained to the amount of ammonium chloride generated.

(Equipment used in Examples and Comparative Examples)
1) Detected gas generator FIG. 3 shows a device for generating ammonium chloride fume (fine particles) and a device for heating the generated ammonium chloride fume (fine particles) to gasify. These devices include a closed bottle 101 in which hydrochloric acid and aqueous ammonia are mixed, a vacuum suction bin 102 directly connected to the outlet of the closed bottle 101 (the side where gas is sucked), and an alumina tube 103 directly connected to the outlet of the vacuum suction bin 102. It is composed of a glass tube 104 (diameter 25 mm, length 700 mm) and directly connected to the outlet side of the alumina tube 103, and the gas to be detected in the device, that is, the atmosphere containing ammonium chloride is sucked into the outlet side of the glass tube 104. .. The alumina tube 103 is provided with a tubular electric furnace (heating means) 105.

12M hydrochloric acid in 30 μL bottle A and ammonia water in 30 μL bottle B were added to the closed bottle 101 and mixed to generate ammonium chloride fume (fine particles). The generated ammonium chloride fine particles are sucked into the vacuum suction bin 102 and then further sucked into the alumina tube 103. When "Yes" is indicated in the column of presence or absence of heating in Table 1 below, the gas to be detected sucked into the alumina tube 103 is heated to about 900 ° C. by the tubular electric furnace 105, and is fine particles of ammonium chloride. Gasifies.

The gas to be detected flowing out of the alumina tube 103 is introduced into the glass tube 104. In the example of FIG. 3, the joint portion between the alumina tube 103 and the glass tube 104 is sealed by an O-ring made of an elastic body. When the gas to be detected is heated to about 900 ° C. and gasified, the gas to be detected is cooled to about 220 ° C. in the glass tube 104, and a part of the gasified ammonium chloride becomes fine particles. That is, when the gas to be detected is heated to about 900 ° C., the gas to be detected containing both gaseous and fine particle ammonium chloride flows out from the outlet O1 of the glass tube 104, and if it is not heated, The gas to be detected containing only fine particles of ammonium chloride (because it is not gasified) flows out.

2) Moisture-imparting means (gas-like hydrophilic substance collecting means)
FIG. 4 shows a device in which two gas impingeres 201 and 202 used in the experiment are connected in series. Each of the gas impinger 201 and 202 contains 10 ml of purified water. The gas to be detected flowing out from the outlet O1 of the glass tube 104 flows in from the inlet I2 of the gas impinger 201, comes into contact with the water in the gas impinger 201, 202, and then flows out from the outlet O2 of the gas impinger 202. By contact between the gas to be detected and water, ammonium chloride (hydrophilic substance) in the gas to be detected, especially gaseous ammonium chloride, is collected in water, and water evaporates into the gas to be detected to add water. Will be done. That is, the gas impingers 201 and 202 function not only as a means for imparting water, but also as a means for collecting gaseous hydrophilic substances.

3) Coil tube FIG. 5 shows the coil tube used in the experiment and a device for cleaning the inside of the coil tube to obtain a cleaning liquid. The coil tube is composed of two glass coil tubes 301 and 302 connected in series. Each glass coil tube is formed by winding a glass tube having an inner diameter of 1.8 mm and an outer diameter of 3 mm in seven layers with a winding diameter of 68 mm. During the experiment, the glass coil tubes 301 and 302 were kept at 5 to 10 ° C.
The gas to be detected flowing out from the outlet O1 of the glass tube 104 or the outlet O2 of the gas impinger 202 flows into the coil tube from the inlet I3 of the glass coil tube 301, and ammonium chloride (hydrophilic substance) is collected in the coil tube. After that, it flows out from the outlet O3 of the glass coil tube 302.

4) Aggregated water collecting means 501 in FIG. 5 represents a syringe in which a glass frit 502 is installed at the bottom. The gas to be detected flowing out from the outlet O3 of the glass coil tube 302 is sucked into the syringe 501 from the inlet I5. Water droplets and water that aggregate in the glass coil tube 302 and dissolve ammonium chloride flow out from the glass coil tube 302 together with the gas to be detected. These water droplets and water are captured by the glass frit 502 and are captured by the glass frit 502, and the syringe 501 It is stored inside and becomes water collection. That is, the syringe 501 functions as a coagulated water collecting means.
A suction port 503 is provided on the upper part of the syringe 501. The suction port 503 is connected to a means (not shown) for sucking gas such as a suction pump, and the gas to be detected is sucked from the suction port 503.
After collecting the ammonium chloride, the collected water is taken out from the syringe 501 and used for measuring the concentration of ammonium chloride (by the hydrophilic substance detecting means 6). The collected water can be taken out from the suction port 503, but even if the syringe 501 is provided with a separate outlet (not shown) for taking out the collected water and the collected water is taken out from the outlet. Good.

5) Washing means 401 and 402 in FIG. 5 represent syringes containing 10 mL each of purified water (washing water), and 403 represents a syringe for sucking water. Reference numerals 404, 405, and 406 in FIG. 5 are three-way cocks, and in the apparatus shown in FIG. 5, the cleaning means 4 is configured by these. By changing the direction of the three-way cock and sucking the washing water stored in the syringes 401 and 402 into the syringe 403, the washing water passes through the glass coil tubes 301 and 302 to wash the ammonium chloride in the tubes. Dissolves in water.

6) Detection of hydrophilic substances In the following experiments 1 to 8, ammonium chloride, impinger 201, 202 and syringes contained in the cleaning liquid sucked into the syringe 403 were used as the hydrophilic substance detecting means 6 using an electric conductivity meter. Ammonium chloride contained in the water (collected water, etc.) in 501 was detected and quantified.

Experiments 1-8
(Collection process)
In the gas generator to be detected shown in FIG. 3, 12M hydrochloric acid in bottle A and aqueous ammonia in bottle B are added to the closed bottle 101 and mixed to generate ammonium chloride fume (fine particles), and the generated ammonium chloride is generated. After being sucked into the vacuum suction bin 102, the fine particles were discharged from O1 through the alumina tube 103 and the glass tube 104.
As for the total amount of ammonium chloride generated, ammonium chloride is generated under the same conditions (same amount, concentration of hydrochloric acid, aqueous ammonia), sucked into the vacuum suction bin 102, and then a predetermined amount of purified water is added to the vacuum suction bin 102. Then, the fine particles of ammonium chloride were dissolved, and then the concentration of ammonium chloride in the obtained aqueous solution was measured with an electric conductivity meter, and the concentration was determined from the amount of purified water used and the concentration obtained by the measurement. The measurement was performed 3 to 5 times, and the average value was taken as the total amount.

In Experiments 2, 4, 6 and 8 (the column of "heating" in Table 1 is "Yes"), the alumina tube 103 was heated to about 900 ° C. to gasify the fine particles of ammonium chloride, and then the glass tube 104 was used. It was cooled to about 220 ° C. to form a part of the gas to be detected, which contained both gaseous and fine particles of ammonium chloride, and was discharged from the gas generator to be detected shown in FIG. In Experiments 1, 3, 5 and 7 (the "heating" column in Table 1 is "none"), the alumina tube 103 was not heated (ie, not gasified) and contained only particulate ammonium chloride. The gas to be detected was discharged from the gas generator to be detected.

The gas to be detected containing ammonium chloride that has flowed out of the gas generator to be detected is the gas impinger 201, 202 (moisture imparting means (gaseous hydrophilic substance collecting means)) shown in FIG. 4, and the coil tube 301 shown in FIG. , 302, Syringe 501 (aggregated water collecting means) shown in FIG. 5 was introduced into the combined apparatus as shown in Table 1 below in the order described in this manner, and ammonium chloride was collected in the apparatus.

(Cleaning of coil tube and detection of ammonium chloride)
After collecting ammonium chloride in the apparatus, the three-way cocks 404, 405 and 406 shown in FIG. 5 were turned and the washing water in the syringe 401 or 402 was sucked by the syringe 403. By this suction, the washing water in the syringe 401 passes through the coil tube 301, cleans the ammonium chloride collected in the tube, and flows into the syringe 403. Further, the washing water in the syringe 402 passes through the coil tube 302 by suction, cleans the ammonium chloride collected in the tube, and flows into the syringe 403.
After cleaning the coil tubes 301 or 302 as described above, the concentration of ammonium chloride in the cleaning solution (washing water containing ammonium chloride) flowing into the syringe 403 is measured and measured by an electric conductivity meter. The amount of ammonium chloride collected in the coil tube 301 and the coil tube 302 was calculated from the concentration and the amount of the cleaning liquid in the syringe 403, and the calculated value was 1.

In the example using the syringe 501 (cohesive water collecting means) and the gas impingers 201 and 202, after collecting ammonium chloride in each device, the concentration of ammonium chloride in the water stored in the device is determined by the electric conductivity. The amount of ammonium chloride collected in each device was calculated from the measured concentration and the amount of water in each device, and the calculated value was 2. The calculated value 1 + calculated value 2 are shown in Table 1 as the collected amount.

In Experiments 5 to 8, the same operation as the operation of passing the washing water through the coil tube was performed before collecting the ammonium chloride, and the amount of ammonium chloride in the washing liquid flowing into the syringe 403 was measured. It was calculated and a blank value of 1 was obtained. Further, in Experiments 5 to 6, the amount of ammonium chloride in the water stored in the gas impingeres 201 and 202 when the ammonium chloride was not collected was measured and calculated in the same manner as described above to obtain a blank value 2. .. In Experiments 5 to 8, the value obtained by subtracting the blank value 1 + the blank value 2 from the calculated value 1 + the calculated value 2 is shown in Table 1 as the collected amount. The blank value 1 was 2.0 to 3.0 μg, and the blank value 2 was 12 to 18 μg. It is considered that the glass coil tube is easier to suppress the blank value than the gas impinger.

As shown in Table 1, in Experiments 1 to 4 (comparative example) in which the collecting means consists of a gas impinger and a glass coil tube, or only a glass coil tube, the collection rate is low. On the other hand, in Experiments 5 to 8 (Example: Example of the present invention) in which the coagulated water collecting means was provided in the subsequent stage of the glass coil tube, the collection rate was high, and the gaseous hydrophilic substance and the particulate hydrophilic substance were obtained. Excellent collection efficiency has been obtained for all of the above. In particular, in Example 7, which was composed of a glass coil tube and a means for collecting aggregated water and did not gasify the ammonium chloride fine particles (that is, in the case of collecting fine particles), the collection rate was 100%. It is considered that the water droplets generated by condensing inside the glass coil tube could be collected by the agglomerated water collecting means, and the collecting efficiency of ammonium chloride could be significantly improved.
That is, from the above results, it is shown that according to the present invention, gaseous and fine particle hydrophilic substances can be efficiently collected at the same time. Further, according to the present invention, since the collection of hydrophilic substances can be performed by a method other than the filter, in the present invention, as compared with the conventional method in which both the method of treating the exhaust gas and the method of evaluating the exhaust gas are the filter method. Since gas and fine particles are collected by a completely different principle, it is considered that the reliability of evaluation can be significantly improved.

Further, according to the present invention using the coil tube, the coil tube can be washed with purified water at the site until just before the sample is introduced, and further, it is possible to analyze online immediately after passing through the gas to be detected. It is considered that the "blank value" can be easily lowered and the detection accuracy can be greatly improved.

3 Coil tube 4 Cleaning means 5 Aggregated water collecting means 6 Hydrophilic substance detecting means 7 Gas 101 Sealed bottle 102 Vacuum suction bottle 103 Alumina tube 104 Glass tube 105 Tubular electric furnace (heating means)
201, 202 Gas Impinger 301, 302 Glass Coil Tube 401, 402, 403 Syringe 404, 405, 406 Three-way Cock 501 Syringe (Coagulated Water Collection Means)
502 Glass frit 503 Suction port

Claims (7)

A device that collects and detects gaseous hydrophilic substances and particulate hydrophilic substances contained in a gas, and is a coil tube that allows the gas to pass through, a coagulated water collecting means connected to the outlet of the coil tube, and the like. A device for collecting / detecting a hydrophilic substance in a gas, comprising a cleaning means for passing cleaning water through the coil tube to clean the inside of the coil tube, and a hydrophilic substance detecting means. The apparatus for collecting / detecting a hydrophilic substance in a gas according to claim 1, wherein the coil tube is a glass coil tube. The device for collecting / detecting a hydrophilic substance in a gas according to claim 1 or 2, wherein the hydrophilic substance detecting means is connected to an outlet of the coagulated water collecting means. The device for collecting and detecting a hydrophilic substance in a gas according to any one of claims 1 to 3, wherein a water-imparting means for imparting water to the gas is provided in front of the gas inlet of the coil tube. A method for collecting and detecting a gaseous hydrophilic substance and a particulate hydrophilic substance contained in a gas, in which the gas is passed through a coil tube, and the gas flowing out from the coil tube is collected by agglomerated water. It is included in the collected water and the cleaning liquid, a step of collecting water droplets flowing out from the coil tube to obtain the collected water, a cleaning step of passing the cleaning water through the coil tube to obtain a cleaning liquid, and the collected water and the cleaning liquid. A method for collecting and detecting a hydrophilic substance in a gas, which comprises a hydrophilic substance detecting step of detecting a gaseous hydrophilic substance and a particulate hydrophilic substance by a hydrophilic substance detecting means. The method for collecting and detecting a hydrophilic substance in a gas according to claim 5, further comprising a step of passing washing water through the coil tube to wash the coil tube before the step of passing the gas through the coil tube. The gas according to claim 5 or 6, wherein the hydrophilic substance detecting means is a means for detecting a gaseous hydrophilic substance and a particulate hydrophilic substance contained in the collected water and the cleaning liquid online. A method for collecting and detecting medium-hydrophilic substances.

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