JPH05346379A - Ionic gas analyzer - Google Patents

Abstract

PURPOSE:To analyze a thin ionic gas in an intake gas with high sensitivity and high precision. CONSTITUTION:An intake system 1 and an exhaust system 4 for a gas containing an ionic gas, a steam mixing system 2 which mixes steam in the aforesaid gas containing the ionic gas and taken in, in the middle between the intake system and the exhaust system, a condenser 3 which cools down the steam together with the gas containing the ionic gas and produces a condensate, a condensate collector 6 provided with a level gage 7, an ion detecting system 14, a liquid supply system 11 which supplies the condensate to a detector, a demineralized water introducing system 17 which introduces demineralized water into a steam mixer and the cooling condenser, and a disposal system, are provided. According to this constitution, an analysis of each object gas and a precision analysis having responsiveness improved can be executed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ionic gas analyzer for analyzing trace ionic mixed gas components in a gas.

[0002]

2. Description of the Related Art Recently, it has become important to analyze and manage harmful gases such as chimneys and other exhaust gases, and it is increasingly necessary to analyze pollutant gases in the atmosphere as environmental measurement targets. In addition, it is important to measure and control the environment of the room atmosphere in the production line of semiconductor parts, which is a special environment, and in other parts production lines where the atmosphere is a problem.

Conventionally, the analysis technique disclosed in Japanese Patent Application Laid-Open No. 56-109050 has been put into practical use as a halogen ion gas analyzer mixed in the atmosphere, and substantially similar devices have been manufactured by various manufacturers. It is on sale. FIG. 3 is a block diagram illustrating the configuration of an ionic gas analyzer that incorporates the flow of the technology disclosed in the above publication, in which 201 is an intake system,
202 is a steam mixing system, 203 is a steam separator, 204 is an exhaust system, 205 is a pipe, 206 is a condensate recovery reservoir, 20
7 is a liquid sending pipe, 208 is a liquid sending pump, 209 is an ion detector, and 210 is a data processing system.

FIG. 4 is a schematic diagram for explaining the configuration around the ion electrode detector in FIG. 3, and the same reference numerals as those in FIG. 3 correspond to the same parts, 211-1, 211-2, 2
11-3 is an ion electrode, 212 is a pocket, and 220 is a waste liquid treatment system. 5 is a schematic diagram for explaining the configuration of the steam separator in FIG. 3, the same reference numerals as those in FIGS. 3 and 4 correspond to the same portions, and 240 and 241 are cooling plates and 2
42 and 243 are cooling water.

In FIG. 3, in this type of ionic gas analyzer, an intake system 201, a steam mixing system 202, a steam separator 203, and an exhaust system 204 are connected by a pipe 205, and a condensate recovery reservoir is provided. 206 is steam separator 2
It is configured to be installed directly below 03. The ionic gas component in the sucked gas is taken into the condensate in a condensed form in the process of cooling and condensing the vapor in the steam separator 203, and is stored downstream in the condensate recovery reservoir 206.

A liquid delivery pipe 207 is provided in the coagulation liquid recovery reservoir 206.
Is attached as a branch pipe system, and the collected condensate (sample) is sent by the liquid sending pump 208 to the ion detector 209 that constitutes the ion detecting unit, and the ion electrode 20
9 is a system for detecting target ions contained therein. When the number of target ions is large, a plurality of pockets 212 are provided in series in the detection system flow path as shown in FIG.
Detection is performed by installing 1, 211-2 and 211-3 for each target ion.

The ion electrode 211- of the ion detector 209
There is a correlation between the outputs of 1, 211-2 and 211-3 and the ion content in the intake gas, and when a calibration curve or the like is created and placed under predetermined conditions, it is possible to measure The data processing system 210 can determine the content of the ionic gas in the intake gas from the obtained detection output value. The steam separator has a diameter of about 70 mm as shown in the schematic sectional view of FIG.
hole (orifice) 233,2 of about 1 mm in the center of the portion corresponding to the drum surface of the drum-shaped hollow containers 231 and 232 of mm.
34 is perforated, and the opposite surface of the surface where the holes are formed is the cooling water 2
The cooling plates 240 and 241 are water-cooled by 42, and the gap between both surfaces is set to about 10 mm. An intake pipe 2051 having a diameter of about 10 mm, which is connected to the intake system and the steam mixing system, is formed in the perforated portion (holes 233 and 234).
At the bottom of the body, the diameter of about 10
mm recovery pipes 2052, and exhaust pipes 2053 having a diameter of about 10 mm connected to the exhaust system are attached to the upper part of the body.

In the structure shown in FIG. 5, two drum-shaped hollow containers of the above structure are connected to each other in order to improve the cooling capacity. However, an exhaust pipe is not attached to the upper part of the body of the container 231 corresponding to the upstream part in the connection.
The operation of the steam separator 203 will be described. First, the gas sent from the intake pipe 2051 collides against the cooling plates 240 and 241 because the flow velocity of the gas is extremely increased at the orifices (holes 233 and 234). become. As a result, the gas is efficiently cooled, and the water vapor containing the ionic gas component becomes a dew condensation liquid (condensate) in a state in which the ionic gas component is contained on the cooling plates 240 and 241, and when it becomes a certain amount, it is condensed. It flows down to the liquid recovery reservoir 206 and is stored therein.

On the other hand, the intake gas carrying the ionic gas and separated from the ionic gas is discharged to the exhaust pipe 2053 provided at the upper part of the drum-shaped container 232. That is, the condensable component and the non-condensable component are separated in the steam separator.

[0010]

The above-mentioned conventional ionic gas analyzer has the following major drawbacks. A considerably large amount of analysis liquid (condensate) is required to sufficiently immerse the tip of the ion electrode, and the time required to collect and secure the necessary amount of condensate, so-called analysis time, becomes long.

In the analysis using the ion electrode, it is necessary to consider interfering ions in which coexisting ions interfere with the analysis. Occasionally, interfering ions cause significant interference, resulting in a large decrease in measurement accuracy. In ion electrode analysis, the ions emitted by the ion electrode itself often interfere with the measurement. In particular, when chlorine ions, potassium ions, etc. are to be measured, the same type of ions emitted by the ion electrode itself mix with the measurement liquid and give a large error to the measured value.

When there are many kinds of ions to be analyzed, the above-mentioned influence becomes extremely serious and influences each other so that analysis cannot be performed or the analysis time does not end within a practical time. Analytical sensitivity basically depends on the concentration of ionic gas in the condensate. The concentration rate is determined by the mixing ratio of the amount of intake gas and the amount of water vapor that plays the role of absorbing liquid (called gas-liquid ratio). Since a large amount of analysis liquid is required for analysis using an ion electrode, System or steam mixing system becomes too large,
That is, since the apparatus is physically too large, it is difficult to increase the above mixing ratio, and it is difficult to increase the concentration of the analysis liquid to significantly improve the analysis sensitivity.

The linearity range of detection of the ion electrode is 1
Many of them are in the order of ppm, which causes a problem of lack of sensitivity in the detector. That is, in the present environmental analysis, the gas concentration in the atmosphere is about 0.01 ng / 1, which is the target level, and the conventional device cannot concentrate to a detectable concentration. The above are the drawbacks of the detection system, such as insufficient sensitivity and large measurement error, or long measurement time,
Therefore, the problems of the prior art such as the loss of the real-time property of measurement have been described.

In addition to the above problems, there were the following problems with the entire measuring system. In the analysis of the analysis principle of the prior art, the fluctuation of the water content in the intake gas causes the fluctuation of the condensate amount and the ion concentration in the condensate, which in turn gives an error in the analysis value. It is important to always consider the fluctuation of humidity when measuring the general atmosphere, but the conventional device does not consider the influence of the fluctuation of humidity on the analysis accuracy. Was lacking in generality. That is, it was an apparatus that can be used only for gases under specific conditions.

In the prior art, there was a serious defect that the responsiveness of analysis was poor. That is, there is a serious drawback that the response of the analysis is extremely lowered when the gas-liquid ratio is increased to increase the concentration rate to increase the sensitivity. Poor responsiveness means that when a predetermined concentration of gas and pure gas containing no ionic gas are alternately inhaled and the increase or decrease in the detection output is observed, the output does not become "0" when the pure gas is output. This is a phenomenon in which a considerably large output is observed under the influence of intake gas immediately before measurement. On the contrary, the negative effect that the output at the time of measuring the gas containing the ionic gas was decreased due to the influence at the time of measuring the pure gas was also observed. That is, when pure gas is continuously inhaled many times to thoroughly purify the system, and then gas containing a predetermined concentration of ionic gas is inhaled, the detection output increases as the number of times of inspiration continues. A phenomenon that does not give a so-called true analysis value was observed.

These phenomena mean that correct analysis cannot be performed if the concentration rate is increased to improve the analysis sensitivity. As described above, the conventional technique has many serious drawbacks and deficiencies and cannot meet the current analysis requirements. It is an object of the present invention to provide an ionic gas analyzer capable of solving the above-mentioned problems of the prior art and performing accurate, continuous and real-time analysis.

[0017]

In order to solve the above-mentioned problems, the present invention relates to the apparatus shown in FIG. 1, that is, an intake system 1 and an exhaust system 4 for a gas containing an ionic gas, and the intake system and the exhaust system. A steam mixing system 2 that mixes steam with a gas containing the ionic gas that has been sucked in, and a cooling condensing system 3 that cools the steam together with the gas containing the ionic gas to generate a condensate (sample). A condensate recovery reservoir 6 for receiving the condensate, and an ion detection system 14 for detecting ions
And a liquid delivery system 11 for delivering the condensate to the ion detection system 14, an ionic gas analyzer is provided with a level gauge 7 in the condensate recovery reservoir 6, and the condensate recovery reservoir is provided. 6, a condensate disposal system 15 is provided.

Further, the present invention is characterized in that an ion separation column 12 is provided before the ion detection system 14. Furthermore, the present invention is characterized in that a volatile gas permeable tube 10 is installed between the condensate liquid collecting reservoir 6 and the liquid sending system 11. That is, according to the present invention, (1) a conductivity cell is used as a detector, and an ion separation column is inserted in the front part of the introduction path to the cell.

(2) Between the detector and the ion separation column,
Anion exchange tubes or columns that pass or remove only cations are used in the system for anions.
The system for cations is provided with an ion exchange tube or column for passing or removing only anions. (3) A volatile gas permeable tube is interposed in the front part of the liquid feed pump arranged between the collection reservoir and the detection system. The permeable tube is held under reduced pressure around its circumference.

(4) If the volatile gas permeable tube is not interposed or the effect of the intervention is insufficient, an ultrasonic oscillator is attached to the recovery reservoir. (5) Attach two or more solution sending tubes to the bottom of the collection reservoir. One is a liquid transfer pipe to the detection system, the other one
The book is a liquid delivery pipe that discharges excess recovery liquid.

(6) Two liquid level detectors are attached to the recovery reservoir. (7) An ultrasonic oscillator is attached to the condensate recovery reservoir, or the bottom of the condensate recovery reservoir is immersed in the ultrasonic oscillator tank. (8) A pipe for supplying water is attached directly below the steam mixing system or at the top of the steam separator.

(9) A pipe attached to the bottom of the condensate recovery reservoir is connected directly below the steam mixing system or to the top of the steam separator, and the recovered liquid is directly below the steam mixing system or to the top of the steam separator. Provide a recovery liquid circulation pipe to pump up. The discharge and circulation pipes can be shared. Further, the water supply pipe and the mounting pipe of the recovered liquid circulation system can be shared.

(10) Immediately below the steam mixing section, the inner surfaces of the steam separator and the recovery reservoir section are mirror-polished. (11) Immediately below the steam mixing section, the inner surfaces of the steam separator and the recovery reservoir section are finished with gold or platinum plating or fluororesin coating. (12) The role of the steam-water separator is divided into the role of the inner cooling condenser and the role of the gas-liquid separation, and the role of the gas-liquid separation is assigned to the condensate recovery reservoir. That is, the upper space of the recovery reservoir is taken large, and the pipe from the cooling condenser and the exhaust pipe connected to the exhaust system are attached to the upper space of the recovery reservoir, and the cooling condenser is a fine straight pipe or a corrugated pipe. Use a cooling structure.

[0024]

In the above configuration of the present invention, (a) by inserting the ion separation column immediately before the detector cell, it becomes possible to separate the ions to be analyzed and then introduce them into the detector cell. It is possible to prevent interference with the analysis of target ions in the reactor cell.

A conductivity cell or the like is suitable for the detector cell, and an optimum stationary phase is selected for the ion separation column according to the ions to be analyzed. In the analysis performed by using the ion separation column in combination with the conductivity cell, there is an advantage that the amount of the analysis liquid may be extremely small and therefore the amount of the condensate to be analyzed may be small. That is, there is an advantage that the amount of supplied steam can be suppressed to increase the ion concentration rate and the sensitivity of the entire analysis system can be increased. In addition, the separated ions can be successively guided to the conductivity cell, various types of ions can be detected in time series, and an electric output proportional to the existing concentration can be output. At this time, it is not necessary to increase the supply of the condensate for each ion, and an extremely small amount of the condensate may be supplied even when analyzing various kinds of ions.

Incidentally, the analysis itself using the conductivity cell is extremely sensitive in itself, and the attachment of the trace ionic gas analysis system to the detector is effective for achieving ultra-high sensitivity.
Compared with the ion electrode, the linearity range of the detector extends to the low concentration range by about three digits, that is, the sensitivity can be increased by about three digits by its attachment. (B) A developing solution is used for introducing and developing the condensate sample into the ion separation column. The developing solution may be referred to as an eluent. The developing solution is also called a mobile phase with respect to the stationary phase in the column.

An electrolytic solution is suitable as the developing solution. For example, when anions are to be analyzed, a mixed solution of sodium carbonate and sodium hydrogen carbonate is suitable.
It is necessary to select a developing solution according to the ions to be analyzed. Ion separation is performed by utilizing the difference in the adhesion property of each ion to the stationary phase. For example, the release of anions from the stationary phase (referred to as elution) is carried out by replacing carbonate ions at the attachment sites of the ions when the developing solution is carbonate, and the stronger the adhesion, the more carbonate. It is difficult to replace the ion. Therefore, separation from various ions is carried out by the difference in the strength of adhesion. Ions having weak adhesion move faster and conversely, stronger ions move slower and separate in the column.

In the anion analysis, the electrolyte such as sodium carbonate used as the developing solution causes the electric conductivity to become excessive, so that it has a function of making it difficult to capture the change in the electric conductivity of the target ion, and the ion is passed through the ion exchange tube there. The sodium ions are exchanged for hydrogen ions inside, and the carbon dioxide is converted into inactive carbon dioxide having a low electric conductivity to improve the detection sensitivity of the target ions. The same procedure is performed in the cation analysis.

(C) The ion separation and detection cell, etc. are set to have a small dead volume so that a minute amount of analysis can be carried out. When air bubbles are injected or generated in the system, the flow of the analysis liquid is disturbed and the analysis becomes unstable. Or it becomes impossible to analyze. In particular, in long-term continuous analysis, the generation of bubbles in the system is fatal. When the condensate was injected into the system for ion separation and analysis, a large amount of bubbles were generated, and the trouble that injection of the condensate by the pump was impossible frequently occurred. This is due to the method of generating the condensate to be analyzed, and in the process of mixing and condensing a large amount of gas and a small amount of water vapor, the base gas in the condensate and the ionic gas component to be analyzed are relatively It depends on melting in a large amount.

It is considered that this was caused by the fact that the gas such as dissolved oxygen in the condensate became extremely large because water and gas were brought into good contact with each other. In addition, since the amount of dissolved gas increases as the temperature decreases, when the condensate is injected into the ion separation system and gradually warmed at room temperature, the dissolved gas is released, that is, foaming occurs, corresponding to the decrease in the solubility. Therefore, a system for applying ultrasonic waves was added between the condensate generation system and the ion separation detection system to remove the dissolved gas prior to injection. The collection reservoir was suitable for the position of addition. That is, there is a space in the upper part of the collection reservoir, and the foaming gas released by being aided by cavitation can escape to the upper space, which is the optimum mounting position.

When the atmospheric gas to be analyzed is introduced into the analysis system by the suction pump, the recovery reservoir is in a slightly negative pressure state, and the foaming gas is discharged to the outside of the system relatively quickly. We were able to. A method of inserting a gas permeable tube immediately before the liquid delivery pump to the ion separation detection system as a countermeasure against bubbles that are generated due to insufficient degassing after ultrasonic degassing or due to spontaneous temperature rise in the condensate detection system Proved to be effective. By depressurizing the outside of the gas permeable tube to about a vacuum, the dissolved gas in the liquid permeates the tube wall while the condensate is passing through the tube, and is relatively quickly removed.

The degassing operation will be more complete if both methods are carried out, but generally if one is carried out, most troubles can be prevented. A method with a small increase in dead volume is particularly advantageous because these measures are accompanied by an obstacle to increase in dead volume in the treatment system and lead to an increase in the dose of the analytical sample. The ultrasonic wave application method has a complicated structure when attached to the collection reservoir,
This causes problems such as an increase in dead volume and unevenness in the collection reservoir, making it difficult to discharge and wash the analysis solution. In the tube addition method, the dead volume of the tube itself increases.

That is, in implementing these countermeasures, it is important to devise so as not to increase the dead volume as much as possible. It should be noted that the dissolved ionic gas that is the analysis target in the condensate is hardly degassed by these measures and is not substantially affected, so it can be confirmed by carrying out the invention that it can be analyzed with confidence. It was

(D) Two or more liquid feed pipes were attached to the bottom of the recovery reservoir. When liquid is sent from the recovery reservoir to the ion separation / detection system, if all the liquid in the reservoir is sent out, gas will be sent to the ion separation / detection system, which causes a problem that the countermeasure against bubbles is invalid. Therefore, an extra condensate is generated and only the required amount is sent to the ion separation detection system to prevent gas from entering the solution sending system. Since the excess condensate hinders the next analysis, it was constructed to be discharged from the system through the pipe connected to the waste container.

The backflow from the liquid delivery pipe system causes an analysis error for each measurement, but the effect of this error is such that the response of the whole analysis deteriorates, and the ratio of the error to the whole is relatively small. Generally acceptable. (E) The ionic gas analyzer is a device that calculates the dissolved ion amount of the recovered condensate to determine the ionic component in the gas. The conversion formula is as follows.

G = (C · M) / (k · S) or G = (C / k) / (S / M) where G is the ion concentration in the gas, C is the ion concentration of the condensate, M is the amount of condensate, S is the amount of intake gas, and k is the transfer coefficient (referred to as absorption coefficient) of ions from the gas to the condensate. S / M is a gas-liquid ratio.

In the analysis method of the conventional apparatus, the measurement conditions are set to be very narrow such that the amount of condensed liquid is approximately the amount of mixed vapor. That is, it is assumed that the amount of water vapor that does not condense and scatters outside the system is negligible, and that the amount of water in the intake gas is negligible compared to the amount of water vapor mixed, and the amount of water vapor supplied is immediately condensed. It was considered as the liquid volume. When the amount of vapor is reduced in order to greatly improve the sensitivity and the amount of intake air is increased significantly as in the configuration of the present invention, the water contained in the inspired gas from the beginning cannot be ignored. That is, in the situation where the water content in the intake gas cannot be ignored, such as the phenomenon that the water content in the intake air is condensed and the concentration of the condensate is reduced, the mixing ratio of gas and water vapor The ratio should be the ratio of the intake gas amount and the condensed liquid amount, which is an effective gas-liquid ratio, assuming that the amount of condensed liquid is increased by mixing extra steam.

Therefore, the present invention is devised so that the amount of condensate can be measured and the ion concentration in the gas can be accurately calculated. As a method for measuring the amount of condensate, the method of measuring the rise of the liquid level in the recovery reservoir during the falling reservoir is the most suitable. In particular, the method of indirectly observing the liquid surface without touching the liquid surface and measuring the liquid surface rising speed is optimal. The method of touching the liquid surface is
Since the detection sensor is installed in the collection reservoir, there are disadvantages that the sensor itself is liable to be contaminated and a measurement error is likely to occur, and the structure of the collection reservoir is complicated to increase the collection dead volume.

Therefore, in the present invention, a method in which the collection reservoir is constituted by a transparent tubular container having a known inner diameter and uniform and the liquid surface is detected by a photocoupler (a light emitting / receiving pair) is optimally used. When the liquid surface passes the optical axis of the photocoupler, a signal is emitted, so that the liquid surface can be detected. Liquid level detection is performed at two locations, upper and lower, the signal generation time difference is calculated, and if the ratio to the dead volume of the container calculated from the height difference of the detection position of the container is calculated, the amount of condensed liquid (condensate generation rate) is calculated. Be done. This method is optimal as it does not increase the dead volume of the recovery reservoir and does not contaminate the condensation.

(F) When a very high concentration of gas is sucked into the condenser and the recovery reservoir system, the effect thereof remains for a long time in the subsequent analysis,
It becomes polluted. It is necessary to clean the inside of the system to remove contaminants when an inadvertent analysis is performed or during initial setting. Although cleaning can be replaced by continuous running, forced cleaning can bring the measurement state into a faster state. Due to the forced cleaning, an injection pipe was attached just below the steam mixing section (top of the condenser) so that a relatively large amount of cleaning water could be injected so that the area below the upper side of the condenser, where strong contamination is likely to adhere, could be washed. Since the inside of the system can be washed with a large amount of washing liquid, decontamination can be completed easily.

(G) As described above, the conventional apparatus has a problem that the response of the analysis is extremely poor. When a small amount of pure water was additionally supplied from the cleaning water injection pipe described above during the analysis, the responsiveness of the analysis was remarkably improved. The cause of poor responsiveness in the conventional method is the phenomenon that the ion concentration in the condensate gradually decreases in the process of condensate generation from the upstream part to the downstream part in the condensing system, and the condensate has a certain amount of liquid. It is presumed that this is because the phenomenon of flowing down by its own weight and accumulating in the recovery reservoir only occurs at the same time when it reaches.

That is, when the high-concentration condensate at the top of the condenser grows to a size necessary for flowing down and is stored, the analysis liquid becomes a high-concentration liquid, and when not stored, the analysis liquid becomes a low concentration. .. That is, the analysis becomes very unstable. at the same time,
If the condensate remaining without flowing down grows as droplets in the next analysis and is recovered as the analysis liquid, the influence that the analysis value does not give a correct value appears. On the other hand, if low-concentration gas is continuously analyzed, the low-concentration condensate will adhere to the top of the condenser. And the detection value becomes low.

It is presumed that the responsiveness was remarkably deteriorated because the above phenomenon occurred in the condenser.
It is presumed that the injection of a small amount of pure water resulted in a significant improvement in the responsiveness of the analysis due to the effect of helping the flow of the adhered water to flow and not collecting and not collecting. (H) When the condenser and the inner surface of the collecting reservoir were mirror-finished, the response of the analysis could be improved considerably. If microscopic unevenness is present, a large amount of condensate will adhere to the concave parts, resulting in recovery leakage, and the responsiveness of analysis will deteriorate. The mirror surface finish improved the responsiveness because the adhesion amount was small.

(I) When the inner surface of the condenser was plated with gold or platinum or coated with a resin, particularly a fluororesin-based resin, the responsiveness of analysis was remarkably improved. As described above, it is important to devise the responsiveness of this analysis system so that the condensate does not leak or remain unread. Therefore, in order to reduce the adherence of the condensate to the tube wall, a fluororesin that serves as a water repellent surface was applied.

(J) In order to improve the response of the analysis, it is necessary to avoid the uncollected condensate from the above (g) and (h).
As described in (i), it is very important, and it is very important to devise a way to improve the flow of the condensate in the steam / water separator. Further, it is also important to devise a method of making the inner surface area of the steam separator as small as possible to reduce the amount of the condensed liquid itself.

In the steam-water separator of the conventional method, a gas containing water vapor is sprayed from the through hole to the center of a circular cooling plate to cause dew condensation, and the dew condensation liquid that naturally flows down is collected at the downstream collecting reservoir. It is a method of receiving. In the conventional method, in order to keep the cooling capacity at a predetermined level, dew condensation is performed by a two-stage cooling plate, and the non-condensed gas is discharged from an exhaust pipe provided above the lower cooler.

That is, in the steam separator of the conventional method,
The structure was very complicated, the inner surface area was very large, and the condensate was likely to adhere and remain, and the condensate was difficult to collect due to the fact that the flow direction of the dew condensation liquid and the flow of the air flow were opposite. In addition, in the method of spraying and cooling to condense dew condensation, the dew condensation liquid spreads and adheres to the cooling plate, making it difficult to collect, and the flow of the air flow around the cooling plate is very slow, so the adhered liquid forms in the air flow. It is assumed that they cannot be helped and are left behind without being washed away.

Therefore, in the present invention, the role of the vapor-water separator is divided into the role of the cooling condenser and the role of vapor-liquid separation, and the role of vapor-liquid separation is assigned to the condensate recovery reservoir. did. A straight pipe or a corrugated pipe was used as the condenser, and the end of the condensation pipe and the exhaust pipe were attached to the upper space of the collection reservoir. In the case of the structure of the present invention, the flow of the air flow and the downward direction of the condensate to the collecting reservoir coincide with each other, and the flow of the air flow is uniform in the pipe and no stagnation occurs, so that the condensate can be recovered smoothly. Done. Since the airflow acts uniformly so as to push the condensate toward the collection reservoir in the leeward direction, the structure of the present invention was able to substantially prevent the leakage of the condensate recovery. Further, since the inner surface of the condenser is also small, recovery leakage due to simple adhesion can be reduced. In the upper space part of the recovery reservoir, the flow of the air flow is remarkably relaxed due to the space expansion effect, and the condensed liquid separates from the non-condensed gas and falls to the bottom of the reservoir part.

(K) The above-mentioned method of supplying a small amount of pure water is very effective in improving the responsiveness of the analysis, but has a side effect that the analytical solution becomes thin and the system becomes insensitive. Therefore,
The present invention is equipped with a circulation system that circulates the recovery liquid so that the analysis liquid does not become thin and promotes the flow of the high-concentration condensate by the recovery liquid itself. After detecting the flow-down speed of the condensate flowing down into the recovery reservoir with a liquid level detector, the recovered liquid is pumped up through a pipe attached to the bottom of the reservoir and re-constituted from the top of the condenser or directly below the vapor mixing section. Injected and circulated.

The production of the condensate was continued during the circulation, and the circulation was facilitated by the aid of the air flow. The effect of this circulation was the same as the effect described above. The attachment pipe used for the circulation system can also be used as the discharge pipe attached to the collection reservoir by using the flow path switching valve and the cleaning pipe attached to the top of the condenser system. (L) An ultrasonic oscillator is attached to the condensate recovery reservoir, or the bottom of the condensate recovery reservoir is immersed in an ultrasonic oscillator tank to remove the volatile dissolved gas remaining in the condensate by ultrasonic vibration, and further condense A volatile gas permeable tube is provided between the liquid recovery reservoir and the liquid sending system to remove the volatile dissolved gas that could not be removed by the ultrasonic vibration.

[0051]

Embodiments of the present invention will now be described in detail with reference to the drawings. FIG. 1 is a configuration diagram for explaining the configuration of a first embodiment of an ionic gas analyzer according to the present invention, in which 1 is an intake system, 2 is a steam mixing system, 3 is a condenser, 4 is an exhaust system, and 5 is Cooling water, 6 a condensate recovery reservoir, 7 a photo level detector unit, 8 an ultrasonic oscillator, 9 a waste liquid system, 10 a volatile gas permeable tube, 11 a liquid sending system, 12 ion separation Column, 13 is an ion exchange tube, 14 is an ion detection system,
Reference numeral 15 is a waste tank, 16 is a circulator system, and 17 is a pure water supply system.

In the figure, an air filter (not shown) is provided at the intake port of the intake system 1 for removing dust and the like which is not the subject of analysis.
Is attached. First, the water vapor mixing system 2, the pure water supply system 17 for cleaning the condenser, and the condensate recovery reservoir 6 are stored in front of the condenser 3 (here, a condenser whose outside is water-cooled with a spiral condenser). A circulator system 16 for returning the ion-containing liquid to the condenser 3 is installed.

The water vapor mixing system 2 comprises a pure water supply pump 21, a steam generator 22 (heating container), a pure water tank 23, etc., and is attached to the intake path. The pure water supply system 17 for cleaning includes a liquid feed pump 171 and a pure water tank 172. The circulation system 16 is an extremely thin tube, and a liquid feed pump 161 is attached midway. The lower end of the thin tube of the circulation system 16 is attached to the bottom of the condensate recovery reservoir 6 for piping.

The condenser 3 is composed of a flexible tube, and the outer peripheral portion thereof is cooled by the circulation of the cooling water 5. The lower end of the condenser 3 is connected and inserted into the upper space of the condensed liquid recovery reservoir 6. An exhaust pipe is inserted and connected to the upper space of the condensate recovery reservoir 6 and is connected to the exhaust system 4. A suction pump 41 is connected to the exhaust system 4, and the measurement gas taken into the device is discharged by the operation of this suction pump.

The lower part of the condensate recovery reservoir 6 is narrowed down to serve as a condensate (sample) reservoir. Condensate recovery reservoir 6
Is a transparent container made of acrylic resin. Two sets of light liquid level detector units 7 (light emitting / light receiving pairs) are attached to the reservoir. The liquid level detector unit 7 detects the liquid level of the condensate at two points, and the volume between the two points is measured in advance, and the flow rate of the condensate is obtained as a ratio with the detection time difference between the two points.

An ultrasonic oscillator 8 is attached to the reservoir and oscillates before the liquid is sent to the ion detection system 14 to remove the volatile dissolved gas. A waste liquid system (a liquid feed pump 151 and a waste liquid tank 152) 15 is connected to the bottom of the condensate liquid collection reservoir 6 to discharge the cleaning liquid in the system and the condensate liquid that is no longer needed after the analysis. Even if all the condensate in the condensate recovery reservoir 6 is discharged, the condensate in the pipe connected to the ion detection system 14 is not discharged, so that no gas enters the detection system.

At the bottom of the condensate recovery reservoir 6, an ion detection system 1 is provided.
4 is attached to the ion separation column 12, and the condensate is transferred to the ion detection system 14 to form a condensate.
Will be introduced to. The condensate (usually 0.1 to 20 ml) is developed in the ion separation column 12 with an electrolyte developing solution called an eluent, and then is passed through the ion exchange tube 13. This treatment converts the coexisting electrolyte into an inactive component having a low electric conductivity. Then, it is sent to the ion detector system 14 and the detection target ions are output in time series.

On the way to the ion detection system 14, the liquid feed pump 1
The volatile gas permeable tube 10 is inserted before 1, and the gas around the volatile gas permeable tube 10 is placed in a vacuum state to remove the gas dissolved in the condensate. The unnecessary analysis liquid that has left the detection system is discharged to the waste tank 152 of the waste system 15. With the above configuration and operation, the ionic gas component contained in the intake air is analyzed and processed by the data processing system (not shown) to obtain the necessary analysis data.

FIG. 2 is a constitutional view for explaining the constitution of the second embodiment of the ionic gas analyzer according to the present invention. The same symbols as in FIG. 1 correspond to the same parts, and 18 is an ultrasonic wave oscillating tank. .. In this embodiment, instead of the ultrasonic oscillator in the first embodiment, an ultrasonic oscillating tank 18 is installed so that the bottom of the condensate collecting reservoir 6 is immersed. Then, ultrasonic waves are indirectly applied to the condensate through the water filled in the ultrasonic wave oscillation tank 18.

With this configuration, the condensate recovery reservoir 6 can avoid the complication of the configuration due to the direct attachment of the ultrasonic oscillator in the above-mentioned embodiment, and the structure can be made smaller, that is, the dead volume is not increased. it can. By forming at least the bottom of the condensate recovery reservoir 6 with a container made of quartz, it is possible to avoid attenuation of ultrasonic transmission by the container.

With the above configuration and operation, the ionic gas component contained in the intake air is analyzed and processed by the data processing system (not shown), and the necessary analysis data can be obtained.

[0062]

As described above, according to the present invention, the liquid level gauge attached to the condensate recovery reservoir and the waste system attached to the recovery system cause disposal and storage for each analysis. To provide an ionic gas analyzer that can accurately, continuously, and in real time analyze the ionic gas in the intake air by measuring the amount of each time to obtain the condensate generation rate and incorporating it into the gas concentration conversion. You can

Since the details of the effects of the present invention have been described in the section of the operation of the present invention, the secondary effects which have not been described above will be described below throughout.
In a system using an ion separation column, a condensed sample solution is developed with a developing solution.Therefore, it is possible to adopt a method in which the sample solution is once concentrated and then introduced into the ion separation column using the developing solution, and the sample solution can be developed as it is. it can. In other words, even if the concentration is too low to be detected, it can be detected by increasing the amount of the sample solution and introducing it after concentrating it. It can be measured if a large amount is generated.

Although the real-time property of the analysis is considerably impaired, in the conventional method, a new means (a means of increasing the sensitivity by about 2 digits) is added to the method of increasing the sensitivity of the analysis which relies only on increasing the gas-liquid ratio. The ionic gas analyzer equipped with the ion separation column of the present invention is a very excellent analyzer. It is convenient and reliable to use cation and anion exchange columns for ion concentration.

Further, the circulation system piping and pump described in the above embodiment can share the waste liquid system attached to the bottom of the condensate collecting reservoir and its route and pump, thereby making the apparatus compact and reducing the cost. Can be planned. Similarly, the circulation system can share the same path and pump as the pure water supply system attached to the top of the condenser. By making the system common, it is possible to avoid complication of the system structure.

It is not always necessary to incorporate all of the above-mentioned methods and structures into an analyzer, and it is sufficient to adopt them at a cost ratio according to the sensitivity and responsiveness that the analyzer requires, and each effect will be achieved according to the adoption. Needless to say that you can get

[Brief description of drawings]

FIG. 1 is a configuration diagram illustrating a configuration of a first embodiment of an ionic gas analyzer according to the present invention.

FIG. 2 is a configuration diagram illustrating a configuration of a second embodiment of an ionic gas analyzer according to the present invention.

FIG. 3 is a block diagram illustrating a configuration of an ionic gas analyzer according to a conventional technique.

FIG. 4 is a schematic diagram illustrating a configuration diagram around an ion electrode detection unit in the ionic gas analyzer according to the related art shown in FIG.

5 is a schematic diagram illustrating the configuration of a steam separator in the conventional ionic gas analyzer shown in FIG.

[Explanation of symbols]

 1 Intake System 2 Steam Mixing System 3 Condenser 4 Exhaust System 5 Cooling Water 6 Condensate Recovery Reservoir 7 Optical Liquid Level Detector Unit 8 Ultrasonic Oscillator 9 Waste Liquid System 10 Volatile Gas Permeable Tube 11 Liquid Delivery System 12 Ion Separation Column 13 Ion exchange tube 14 Ion detection system 15 Waste tank 16 Circulator system 17 Pure water supply system 18 Ultrasonic oscillator tank

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location G01N 27/416 30/00 E 8310-2J (72) Inventor Osamu Yamamoto 3681 Hayano, Mobara, Chiba Hitachi Device Engineering Co., Ltd. (72) Inventor Toshiba Shiru, 3681 Hayano, Mobara, Chiba Prefecture Hitachi Device Engineering Co., Ltd. (72) Inventor, Kawasaki, Hiroshi 3681 Hayano, Mobara City, Chiba Hitachi Device Engineering Co., Ltd. ( 72) Inventor Naoyuki Okawa 3681 Hayano, Mobara-shi, Chiba Hitachi Device Engineering Co., Ltd. (72) Inventor Yukihide Ode 3681 Hayano, Mobara-shi, Chiba Hitachi Device Engineering Co., Ltd. (72) Inventor Toshiaki Kuramochi Mobara, Chiba 3681 Hayano, Hitachi Device En Engineering within Co., Ltd. (72) inventor Emiko Maki Mobara City, Chiba Prefecture Hayano 3681 address Hitachi Device Engineering Co., Ltd. in

Claims (3)

[Claims] 1. An intake system and an exhaust system for a gas containing an ionic gas, and a steam mixing system for mixing water vapor with the gas containing the inhaled ionic gas in the middle of the intake system and the exhaust system,
A cooling condenser that cools the water vapor together with the gas containing the ionic gas to generate a condensate, a condensate recovery reservoir that receives the condensate, an ion detection system that detects ions, and the condensate to the ions. In an ionic gas analyzer provided with a liquid sending system for sending liquid to a detection system, a liquid level gauge is provided in the condensate recovery reservoir, and a condensate discard system is provided in the condensate recovery reservoir. Ionic gas analyzer. 2. The ionic gas analyzer according to claim 1, wherein an ion separation column is provided before the ion detection system. 3. The ionic gas analyzer according to claim 1, wherein a volatile gas permeable tube is installed between the condensate liquid collecting reservoir and the liquid sending system.