WO2015059781A1 - Analysis sample collection device and method for using same, and collected sample analysis device and collected sample analysis method - Google Patents

Abstract

Provided are an analysis sample collection device and a method for using the analysis sample collection device that make it possible to accurately collect an analyte included in a gas using a simple device structure and a collected sample analysis device and collected sample analysis method that make it possible to accurately analyze an analyte included in a gas using a simple device structure. An analysis sample collection device includes a gas collection tube (11) that has a leading end (12) side inserted into a flue (119) and is for collecting gas that is inside the flue (119), a temperature maintaining means for keeping the gas collection tube (11) at a prescribed temperature, and a liquid supply device (65) for supplying liquid to the inside of the gas collection tube (11) or to a member connected to an outlet portion of the gas collection tube. The gas is a gas in which a portion of the compounds included in the gas precipitate when the temperature decreases, and the temperature maintaining means is a heat pipe (25).

Description

ANALYSIS SAMPLING DEVICE AND METHOD OF USING THE SAME

The present invention relates to an analytical sample collection device for collecting a sample for analysis, a method for using the same, a collected sample analysis device for analyzing a collected sample, and a collected sample analysis method.

In general thermal power plants, a denitration apparatus using a selective catalytic reduction method (SCR method) is installed in order to remove nitrogen oxides (NO _x ) contained in exhaust gas. The selective catalytic reduction method is a method in which ammonia is blown into exhaust gas, and NO _X and ammonia are reacted on a denitration catalyst to decompose NO _X into nitrogen and water. Since the performance of the denitration catalyst deteriorates with use, performance monitoring is performed by measuring the concentration of ammonia (referred to as leaked ammonia) discharged from the denitration catalyst in an unreacted state.

The ammonia concentration in the exhaust gas at the outlet of the denitration apparatus is required to be measured with high accuracy since it is greatly related to the grasp of the deterioration of the denitration catalyst and the blockage of the air heater due to acidic ammonium sulfate. However, in the case of exhaust gas at the exit of the denitration device, soot, a sulfur oxide (SO _X ), and NO _X contained in a large amount in the exhaust gas make accurate analysis of ammonia difficult. If there is a lot of dust, it may cause clogging of the sampling system and contamination. In addition, since it contains SO _X , acidic ammonium sulfate is produced when the temperature is lowered.

On the other hand, the present applicants adopted a double-structure gas sampling pipe as a method for analyzing the ammonia concentration in the exhaust gas with high accuracy, and flushed the inner pipe side to wash the inner pipe. Has also developed a method for analysis along with the absorbent. (For example, refer to Patent Document 1).

JP 2004-117271 A

In the method described in Patent Document 1, a portion where ammonia (including ammonia compound) may adhere is cleaned, and the cleaning liquid is also an analysis target. Therefore, ammonia (including ammonia compound) is completely removed by cleaning. If so, the ammonia concentration can be analyzed with high accuracy. However, in practice, ammonia (including ammonia compound) adhering to the gas sampling pipe may not be completely removed by the cleaning operation.

It is conceivable to perform washing with a large amount of washing liquid in order to perform the washing operation sufficiently. However, when washing with a large quantity of washing liquid, the ammonia concentration in the collected washing liquid is low and the analysis accuracy is lowered. It also causes an increase in waste liquid. As described above, the method described in Patent Document 1 is an excellent method, but further improvement is required to measure the ammonia concentration in the exhaust gas more stably and more accurately. Such a problem is applicable not only to the measurement of ammonia concentration in exhaust gas but also to the collection and analysis of other analytical gases.

An object of the present invention is to provide an analytical sample collection device capable of accurately collecting an analysis target component contained in a gas with a simple apparatus configuration, a method of using the analytical sample collection device, and an accurate analysis target component contained in a gas. It is an object of the present invention to provide a collected sample analysis apparatus and a collected sample analysis method that can be analyzed.

The present invention includes a gas sampling pipe for collecting the gas in the gas flow path with a distal end portion inserted into the gas flow path, temperature holding means for holding the gas sampling pipe at a predetermined temperature, and in the gas sampling pipe and / or Or a liquid supply means for supplying a liquid to a member connected to an outlet portion of the gas sampling pipe, and the gas is a gas in which a part of the compound contained in the gas is precipitated when the temperature is lowered, An analytical sample collection device characterized in that the temperature holding means is a heat pipe.

The analytical sample collection device of the present invention that can maintain the gas collection tube at a predetermined temperature via the heat pipe can limit the region where the compound is deposited. In the case of such an analytical sample collection device, the region where the compound is deposited is specified, so that cleaning with a cleaning solution is easy. Furthermore, it is possible to prevent the precipitation and / or adhesion of the compound by constantly flowing the liquid through the liquid supply means to the temperature region where the compound is precipitated, and it is possible to collect the analysis sample stably. The component to be analyzed contained in the gas can be accurately collected. In addition, the heat pipe is excellent in heat transfer property and temperature uniformity, but means for making the temperature uniform and a power source are unnecessary, so that the analytical sample collection device can be simplified.

In the present invention, it is preferable that a heating source of the working fluid of the heat pipe is a gas flowing through the gas flow passage, and a cooling source of the working fluid of the heat pipe is an atmosphere outside the gas flow passage. .

If the gas flowing in the gas flow path can be used as the heating source for the working fluid of the heat pipe and the atmosphere can be used as the cooling source for the working fluid of the heat pipe, it is not necessary to prepare a special heat source and use it immediately in the field. be able to. Such an analytical sample collection device is excellent in practicality.

In the present invention, the gas sampling tube is divided by the heat pipe into a temperature region where the compound does not precipitate and a temperature region where the compound precipitates, and the liquid deposits the compound on the gas sampling tube. It is preferable to supply only to the temperature region.

In the present invention, it is preferable that at least a portion of the gas sampling pipe straddling the wall of the gas flow passage and the front and back thereof are maintained at a temperature at which the compound is not precipitated by the heat pipe.

In the present invention, it is preferable that at least a portion of the gas sampling tube straddling the wall of the gas flow passage and the front and back thereof are maintained at a temperature at which the compound is precipitated by the heat pipe.

In the case of the gas sampling tube divided into the temperature region where the compound does not precipitate via the heat pipe as in the present invention and the temperature region where the compound precipitates, only in the temperature region where the compound precipitates against the gas sampling tube, always, If a cleaning solution or an absorbing solution is supplied, precipitation and / or adhesion of the compound can be prevented with a small amount of the cleaning solution or absorbing solution. Further, if the analysis target component in the collected gas is absorbed with a small amount of absorption liquid, the concentration of the analysis target component does not decrease, and the analysis accuracy can be maintained high. Furthermore, since no liquid is supplied to the temperature region where the compound does not precipitate, the temperature in that region does not decrease, and the compound does not precipitate in that region. This prevents the compound from precipitating in unexpected locations.

In the present invention, the heat pipe is preferably provided integrally with the gas sampling pipe on an outer wall surface of the gas sampling pipe.

Integrating the gas sampling tube and the heat pipe as in the analytical sample collecting apparatus of the present invention provides excellent heat transfer performance and further simplifies the configuration of the analytical sample collecting apparatus.

The analytical sample collection apparatus of the present invention is further supplied to a member connected to the gas collection tube and / or the outlet of the gas collection tube through the collection gas collected through the gas collection tube and the liquid supply means. Gas-liquid separating means for separating the liquid, and a conduit connecting the gas sampling pipe and the gas-liquid separating means, the inner surface of the conduit is made hydrophilic, and flows through the inner surface in the guide pipe It is preferable to form a liquid film of the liquid.

If a conduit having a hydrophilic inner surface is used as a conduit connected to the outlet of the gas sampling tube and guiding the collected gas and liquid discharged from the gas sampling tube to the gas-liquid separation means, the inner wall side of the conduit is liquidated. However, the sampling gas flows through the center side. For this reason, the contact area between the liquid and the collected gas is increased, and the analysis target component contained in the collected gas can be efficiently absorbed with a small amount of liquid, or the collected gas can be efficiently washed with a small amount of liquid.

In the present invention, the gas is a gas containing ammonia, and the component to be analyzed is ammonia.

In the present invention, the gas flow passage is a flue at the outlet of a flue gas denitration apparatus that processes boiler exhaust gas, and the gas in the gas flow passage is boiler exhaust gas in the flue.

The boiler exhaust gas flowing through the flue at the outlet of the flue gas denitration device installed in a thermal power plant etc. contains a low concentration of unconsumed ammonia, so-called leaked ammonia, among the ammonia supplied to the flue gas denitration device. . Further, the boiler exhaust gas contains sulfur oxide SO _x and a lot of soot, and an ammonia compound is deposited when the temperature is lowered. On the other hand, the analytical sample collection device of the present invention can prevent precipitation and / or adhesion of an ammonia compound by always flowing a liquid through the gas collection tube. Furthermore, since the collected gas from which dust and sulfur oxide SO _x have been removed can be obtained, it is possible to use a highly sensitive analyzer that dislikes the presence of obstructions in the analyzer, and accurately analyze low concentrations of ammonia. Can do.

In the present invention, the cleaning liquid is allowed to flow to the distal end side of the gas sampling tube through the liquid supply means, and the temperature region in which the compound does not precipitate and the temperature region in which the compound precipitates in the gas sampling tube. The method of using the analytical sample collection device is characterized in that the boundary portion is washed.

When the analytical sample collection device according to the present invention is used for a long time, the compound may adhere to the boundary portion between the temperature region where the compound does not precipitate and the temperature region where the compound precipitates in the gas sampling tube. For this reason, it is preferable to periodically wash the boundary by flowing a cleaning solution to the tip of the gas sampling tube.

The present invention further includes the analysis sample collection device and an analysis device that analyzes the analysis target component contained in the gas body, wherein the liquid in the analysis sample collection device dissolves the compound and the analysis. It is a liquid that does not absorb the target component, and the analyzer is a collected sample analyzer that analyzes the collected gas washed with the liquid.

The present invention further includes the analysis sample collection device and an analysis device for analyzing the analysis target component contained in the liquid, wherein the liquid in the analysis sample collection device dissolves the compound and the analysis target. It is an absorption liquid that absorbs a component, and the analyzer is a collected sample analyzer that analyzes an absorption liquid that has absorbed the analysis target component.

The collected sample analyzer of the present invention is practical and easy to use because the sample form may be gas or liquid.

In the collected sample analysis method of the present invention, the liquid at a constant flow is continuously collected through the liquid supply means while continuously collecting a gas at a constant flow rate through the gas sampling pipe using the collected sample analyzer. In addition, the sampled gas supplied into the gas sampling tube and cleaned with the liquid can be analyzed online.

In the sample collection analysis method of the present invention, the sample collection analyzer is used to continuously collect a constant flow rate of gas through the gas collection tube, while the liquid supply means supplies the absorption liquid at a constant flow rate. The absorption liquid that is continuously supplied into the gas sampling tube and has absorbed the analysis target component can be analyzed online.

Further, the present invention is a collected sample analysis method using the collected sample analyzer, wherein the analyzer is a liquid obtained through the absorption step, the washing step, and the mixing step described below, instead of the absorbing solution. Can be analyzed.
Absorption step: gas is collected through the gas sampling tube, the gas is passed through the absorption liquid, and the analysis target component is absorbed by the absorption liquid.
Washing step: After the absorption step, the member connected to the inside of the gas sampling tube and / or the outlet of the gas sampling tube is cleaned with the cleaning liquid supplied through the liquid supply means.
Mixing step: The absorption liquid obtained in the absorption step and the cleaning liquid obtained in the washing step are mixed.

According to the collected sample analysis method of the present invention, since it is possible to analyze the collected sample online or offline, a preferred method can be adopted depending on the application. Furthermore, since the sample may be in the form of gas or liquid, various analyzers can be used, making it easy to use.

The analysis sample collection device of the present invention has a simple device configuration, and the analysis target component contained in the gas can be collected accurately by using the analysis sample collection device of the present invention and the method of using the same. Further, the analysis target component contained in the gas can be accurately analyzed by the collected sample analyzer and the collected sample analysis method.

1 is a schematic configuration diagram of a collected sample analyzer 1 according to a first embodiment of the present invention. It is an enlarged view of the II section of FIG. It is a schematic diagram of the III section of FIG. It is a schematic block diagram of the thermal power plant 100 which is a use place of the collection sample analyzer 1 of FIG. It is a figure which shows the relationship between the sulfur oxide density | concentration in boiler exhaust gas, and acidic ammonium sulfate (ammonium hydrogen sulfate) production | generation temperature. It is a schematic block diagram of the collection sample analyzer 2 which concerns on 2nd Embodiment of this invention. It is a schematic block diagram of the collection sample analyzer 3 which concerns on 3rd Embodiment of this invention. It is a flowchart which shows the analysis procedure using the collection sample analyzer 3 which concerns on 3rd Embodiment of this invention. It is a schematic block diagram of the collection sample analyzer 4 which concerns on 4th Embodiment of this invention. It is a schematic block diagram of the collection sample analyzer 5 which concerns on 5th Embodiment of this invention. It is a schematic block diagram of the collection sample analyzer 6 which concerns on 6th Embodiment of this invention.

FIG. 1 is a schematic configuration diagram of a collected sample analyzer 1 according to the first embodiment of the present invention. 2 and 3 are enlarged views of a portion II in FIG. 1 and a schematic diagram of a portion III in FIG. FIG. 4 is a schematic configuration diagram of a thermal power plant 100 which is a usage destination of the collected sample analyzer 1 according to the first embodiment of the present invention.

The sampling sample analyzer 1 of the first embodiment of the present invention includes a gas sampling tube 11 that collects a sample gas for analysis, a heat pipe 25 that holds the gas sampling tube 11 at a constant temperature, and a gas sampling tube 11. It includes a liquid supply device 65 that supplies a cleaning liquid, a cyclone 60 that separates the collected gas and the cleaning liquid so that analysis is possible, and an analyzer 81 that analyzes the sample gas.

The collected sample analyzer 1 is suitably used for analyzing the boiler exhaust gas of the thermal power plant 100, particularly for measuring the ammonia concentration in the exhaust gas on the outlet side of the flue gas denitration device 109 for removing nitrogen oxides NOx contained in the boiler exhaust gas. be able to. Hereinafter, taking as an example the case of measuring the ammonia concentration in the exhaust gas on the outlet side of the flue gas denitration device 109 using the collected sample analyzer 1 of the first embodiment of the present invention, the configuration of the collected sample analyzer 1 is detailed. Explained. However, the collected sample analyzer 1 according to the first embodiment of the present invention can be used for purposes other than the measurement of the ammonia concentration in the exhaust gas on the outlet side of the flue gas denitration device 109. The configuration is not limited to the configuration shown below.

The thermal power plant 100 has a pulverized coal-fired boiler 101, and the combustion gas generated in the furnace 103 heats a heat transfer tube 105 such as a heater, and further heats in a coal saver 107 installed in the rear flue. It is collected and discharged from the boiler 101. The combustion gas (exhaust gas) whose temperature is discharged from the boiler 101 is sent to the flue gas denitration device 109, where nitrogen oxides NOx contained in the exhaust gas are removed.

The flue gas denitration device 109 is a selective contact reduction type flue gas denitration device, in which a denitration catalyst is housed in the denitration reactor, and ammonia is supplied into the exhaust gas upstream of the denitration reactor. Nitrogen oxide NOx contained in the exhaust gas reacts with ammonia on the denitration catalyst and is reduced to nitrogen and water.

The exhaust gas from which nitrogen oxides NOx have been removed by the flue gas denitration device 109 is sent to the air preheater 111, where the combustion air of the boiler 101 is preheated. Thereafter, the dust in the exhaust gas is gradually removed by the electric dust collector 113, and the sulfur oxide SOx in the exhaust gas is removed by the flue gas desulfurization device 115, and is diffused from the chimney 117 to the atmosphere.

The boiler 101, the flue gas denitration device 109, the air preheater 111, the electric dust collector 113, the flue gas desulfurization device 115, and the chimney 117 are connected by a flue 119. In order to measure the ammonia concentration in the exhaust gas, the gas sampling pipe 11 is installed in the flue 119 at the outlet of the flue gas denitration device 109.

The gas sampling tube 11 is a device that collects exhaust gas flowing through the flue 119, is made of a metal cylindrical pipe, and the tip 12 extends from the sampling port provided in the flue wall (duct wall) 121. The base end portion 13 is positioned outside (atmosphere side) of the flue wall 121. The exhaust gas flowing through the flue 119 has a temperature of about 300 to 400 ° C., and the exhaust gas contains a large amount of soot in addition to nitrogen oxides NOx, sulfur oxides SOx, and ammonia. It must be able to withstand it.

When the gas sampling tube 11 contains a catalyst component such as iron Fe, vanadium V, or molybdenum Mo, ammonia in the exhaust gas may be decomposed in the gas sampling tube 11. In particular, since the ammonia concentration in the exhaust gas is as low as about 0.1 to 5 ppm, it is necessary to pay careful attention to the decomposition of ammonia. Therefore, the gas sampling tube 11 is preferably a gas sampling tube in which an aluminum pipe is inserted into a stainless steel pipe, or a gas sampling tube in which aluminum is vapor-deposited on the inner surface of the stainless steel pipe.

The length and size of the gas sampling tube 11 are not particularly limited. For example, the inner diameter of the gas sampling tube 11 is about 5 to 25 mmφ.

In the gas sampling pipe 11, the part straddling the flue wall 121 and the front and rear parts thereof are maintained at a predetermined temperature via the heat pipe 25. Hereinafter, a region held at a predetermined temperature via the heat pipe 25 is referred to as a temperature holding region 15. For example, the length of the temperature holding region 15 of the gas sampling pipe 11 is about 100 to 300 mm inside the flue 119, about 100 to 300 mm outside the flue 119, and about 400 to 300 mm in total length. It is about 600 mm. In addition, the thickness of the flue wall 121 is about 200 mm. In the present embodiment, the distal end portion 12 and the proximal end portion vicinity 14 of the gas sampling tube 11 are non-temperature holding regions. The non-temperature holding area is an area that is not held at a predetermined temperature via the heat pipe 25.

In the present embodiment, the temperature holding region 15 is held at about 300 ° C. This temperature is a temperature at which the ammonia compound does not precipitate in the temperature holding region 15 of the gas sampling tube 11. In addition, the temperature of the temperature holding region 15 of the gas sampling tube 11 is not necessarily limited to 300 ° C., and may be a temperature at which the ammonia compound does not precipitate.

In the case of the exhaust gas at the outlet side of the flue gas denitration device 109, acidic ammonium sulfate (ammonium hydrogen sulfate) is generated as an ammonia compound. FIG. 5 shows the relationship between the concentration of sulfur oxide SO ₃ in boiler exhaust gas and the production temperature of acidic ammonium sulfate (ammonium hydrogen sulfate). As can be seen from FIG. 5, when the ammonia concentration in the exhaust gas is 1 ppm and the concentration of the sulfur oxide SO ₃ in the exhaust gas is 10 ppm, acidic ammonium sulfate (ammonium hydrogen sulfate) is produced at about 230 ° C. Acidic ammonium sulfate is produced at a higher temperature as the ammonia concentration and the sulfur oxide SO ₃ concentration are higher.

The heat pipe 25 is provided in the gas sampling pipe 11 so as to cover the temperature holding region 15 in the gas sampling pipe 11, straddles the flue wall 121, and is located inside the flue 119 and outside the flue 119. Yes. In the present embodiment, the gas sampling pipe 11 and the heat pipe 25 are integrated, and are fixed to the flue wall 121 via a fixing flange 41 provided on the outer peripheral wall 35 of the heat pipe 25. In addition, the fixing method with respect to the flue wall 121 of the gas sampling pipe | tube 11 and the heat pipe 25 may be another method.

The heat pipe 25 is a wick-type heat pipe, has a double pipe structure integrated with the gas sampling pipe 11, and has an airtight container called a container on the outer wall 19 of the gas sampling pipe 11. The sealed container is formed by fixing a cylindrical pipe 27 sealed at both ends to the outer wall 19 of the gas sampling tube 13 in an airtight state. A space 29 formed by the cylindrical pipe 27 and the gas sampling tube 11 has a capillary structure called a wick, and the space 29 is filled with a working fluid 31. The cylindrical pipe 27 is provided with a pressure gauge 39 for detecting the pressure in the space 29 in order to confirm the operating state of the working fluid 31.

When the heat pipe 25 and the gas sampling tube 11 are integrated, the heat transfer between the heat pipe 25 and the gas sampling tube 11 is excellent. However, the heat pipe may be separate from the gas sampling tube 11. The shape of the heat pipe may be a pipe shape provided with an insertion hole through which the gas sampling tube 11 is inserted in the center, and the gas sampling tube 11 may be inserted through the center of the heat pipe. Further, a heat pipe may be wound so as to cover the gas sampling tube 11. If it is such a structure, manufacture of a heat pipe becomes easy or it is also possible to use a commercially available heat pipe. In this case, it is necessary to prevent the heat transfer performance between the heat pipe and the gas sampling tube 11 from being lowered due to a gap between the heat pipe and the gas sampling tube 11.

Although it is possible to arrange the heat pipe in the gas sampling tube 13, since a step is generated, if there is a large amount of dust as in the present embodiment, the dust accumulates in the step portion, which is not preferable.

The working fluid used in the heat pipe 25 only needs to hold the gas sampling tube 11 at 300 ° C. Examples of the working fluid include heat transfer oil.

A heating fin 45 is attached to the outer peripheral wall 35 of the heat pipe 25 located in the flue 119 in order to promote heat transfer between the exhaust gas flowing in the flue 119 and the heat pipe 25. Although it is not necessary to provide the heating fin 45, the heat transfer between the exhaust gas flowing through the flue 119 and the heat pipe 25 is promoted by providing the heating fin 45, and as a result, the heat pipe 25 is made compact. be able to.

In the heat pipe 25, a portion located inside the flue 119 including a portion where the heating fin 45 is attached becomes a heating portion, and a portion located outside the flue 119 becomes a cooling portion.

The proximal end portion 14 of the gas sampling tube 11 is not covered with the heat pipe 25. A cooling fin 21 is attached to the outer wall near the base end portion 14 of the gas sampling tube 11 in order to cool the sampling gas (sample gas) in the gas sampling tube 11 with the atmosphere.

The gas sampling tube 11 is connected to a cyclone 60 that is a gas-liquid separator via a conduit 51. In addition, the cleaning liquid is sent to the gas sampling pipe 11 via the liquid supply device 65.

The conduit 51 is connected to the outlet of the gas sampling tube 11 via an adapter 58 and guides the sampling gas and the cleaning liquid sent from the gas sampling tube 11 to a cyclone 60 that is a gas-liquid separator. The conduit | pipe 51 consists of the cylindrical tube 52 of a tetrafluoroethylene resin, and the inner surface is hydrophilically processed. The hydrophilic treatment of the inner surface of the cylindrical tube 52 can be performed, for example, by coating the inner surface with titanium oxide and providing a hydrophilic coating layer 53. The conduit 51 may be a cylindrical tube 52 other than the tetrafluoroethylene resin, and the hydrophilic treatment of the inner surface may be a method other than the coating treatment.

The conduit 51 does not necessarily need to be a conduit having a hydrophilic inner surface. However, when a conduit having a hydrophilic inner surface is used, the cleaning liquid is contained in the conduit 51 when the sampling gas and the hydrophilic cleaning liquid are caused to flow simultaneously. A liquid film 54 is formed so as to cover the peripheral surface, and the collected gas flows through the central portion 55 of the conduit 51. Thus, when the cleaning liquid flows in the conduit 51 while forming the liquid film 54, the contact area with the sampling gas is large, and the sampling gas can be efficiently cleaned. Further, it is possible to prevent the ammonia compound from depositing and adhering to the conduit 51.

The adapter 58 is a fluororesin-based cylindrical body having rubber elasticity, and the gas sampling tube 11 and the conduit 51 are connected by inserting the gas sampling tube 11 and the conduit 51. The adapter is not limited to the adapter 58, and may be another adapter as long as the gas sampling pipe 11, the conduit 51, and the liquid supply pipe 68 can be connected in an airtight and liquidtight manner. Further, a method other than the adapter may be used as long as the gas sampling pipe 11 and the conduit 51, and further the liquid supply pipe 68 can be connected in an airtight and liquidtight manner.

The cyclone 60, which is a gas-liquid separator, separates the mixture of the sampling gas and the cleaning liquid sent from the conduit 51 into the sampling gas and the cleaning liquid. The cyclone 60 has a ball 63 inside, and a trap is formed by the cone portion 62 and the ball 63 of the cyclone. When a predetermined amount of cleaning liquid is accumulated in the cone portion 62, the ball 63 is lifted and the cleaning solution is discharged, and the cleaning solution is discharged. When discharged, the ball 63 comes into contact with the conical portion 62 to prevent the sampling gas from being discharged. As a result, the cleaning liquid can be discharged without discharging the sampling gas.

The collected gas and the cleaning liquid separated by the cyclone 60 are sent to the analyzer 81 and the liquid supply tank 66, respectively. As the gas-liquid separation device that separates the collected gas and the cleaning liquid, in addition to the cyclone 60, a collision-type gas-liquid separation device using an inertial force, a louver-type gas-liquid separation device, or the like can be used. Two or more gas-liquid separators may be arranged in series, or different types of gas-liquid separators may be arranged in series.

The liquid supply device 65 includes a liquid supply tank 66, a liquid supply pump 67, and a liquid supply pipe 68, and supplies the cleaning liquid to the non-temperature holding region on the base end portion 13 side of the gas sampling pipe 11 through the liquid supply pipe 68. . The liquid supply pipe 68 has an L-shaped pipe body 70 which is inserted into the adapter 58 and fixed. The tip 69 of the liquid supply pipe 68 is installed so as to be located at the boundary between the temperature holding area 15 of the gas sampling pipe 11 and the non-temperature holding area on the base end portion 13 side of the gas sampling pipe 11.

The cleaning liquid is circulated, and the cleaning liquid supplied to the gas sampling pipe 11 is sent to the cyclone 60 through the conduit 51 together with the sampling gas, separated from the sampling gas, and returned to the liquid supply tank 66. The liquid supply tank 66 is a sealed tank, and is connected to the cyclone 60 through a pipe 64 so as to be airtight.

As the cleaning solution, a cleaning solution that can dissolve the ammonia compound and does not absorb ammonia is used. In this embodiment, acidic ammonium sulfate (ammonium hydrogen sulfate) is mentioned as an ammonia compound, and alkaline water, for example, sodium hydroxide aqueous solution, is mentioned as a washing | cleaning liquid. The sampling gas cleaned with the cleaning liquid does not contain ammonia compounds and dust, but contains ammonia gas.

The analyzer 81 analyzes ammonia contained in the collected gas (sample gas) from which the cleaning liquid has been separated by the cyclone 60. The analyzer that can be used here is not limited to a specific analyzer as long as ammonia contained in the collected gas can be analyzed online. Of course, it is necessary to use an analyzer according to the required accuracy. Collecting gas delivered to the analyzer 81 (sample gas), soot, can be used analyzer precision for SO _x is removed.

As a usable analyzer, a known gas analyzer can be used. The gas analyzer, the laser gas analyzer for detecting concentration of ammonia from absorption strength using a laser as a light source, detecting the NH ₃ concentration by measuring the reduction of the NO _x concentration by the reduction reaction of the NO _x -NH ₃ NO _x —NH ₃ reduction differential type flue gas ammonia measurement device (for example, manufactured by Shimadzu Corporation), ammonia measurement device that measures the increased nitrogen oxide component after oxidation catalyst treatment as an ammonia concentration by a scientific effect method ( For example, HORIBA, Ltd.) is exemplified.

The analyzer 81 includes a type of analyzer that does not include a gas flow meter and a suction pump. In such an analyzer, a gas flow meter and a suction pump may be provided separately.

Next, the procedure for measuring the ammonia concentration in the exhaust gas of the collected sample analyzer 1 will be described.

The analyzer 81 is operated and exhaust gas is continuously collected at a constant flow rate through the gas sampling tube 11. At the same time, the cleaning liquid is continuously supplied to the non-temperature holding region on the base end 13 side of the gas sampling tube 11 through the liquid supply device 65 at a constant flow rate. The sampled gas collected through the gas sampling tube 11 is cleaned in contact with the cleaning liquid in the process of flowing through the gas sampling tube 11 and the conduit 51 connected to the cyclone 60. In this process, soot and SO _x are absorbed by the cleaning liquid. The collected gas from which the cleaning liquid has been separated by the cyclone 60 is measured for the ammonia concentration by the gas analyzer 81.

As described above, it is possible to analyze the ammonia gas in the exhaust gas online by collecting the collected gas at a constant flow rate and supplying the cleaning liquid at a constant flow rate using the collected sample analyzer 1. The collected gas sent to the analyzer 81 is washed with a washing liquid and the ammonia compound and dust are removed, so that it can be analyzed with high accuracy. In some cases, the dust contained in the exhaust gas adsorbs ammonia. However, since the soot dust is washed by using the sampling sample analyzer 1, the ammonia adsorbed to the dust can be analyzed.

In a conventional sampling sample analyzer, cleaning with a cleaning liquid is performed, but a conventional gas sampling tube is not divided into a temperature holding region and a non-temperature holding region, and the temperature holding region of this embodiment is used. The cleaning liquid was also supplied to the corresponding part. For this reason, in the conventional method, the same location of the gas sampling tube becomes a temperature of about 300 ° C. or a temperature of 100 ° C. or less. When heating and cooling are repeated in this manner, an ammonia compound is precipitated and easily adheres to the gas sampling tube. Furthermore, since the temperature changes greatly, cleaning with a cleaning solution is difficult, and the deposited ammonia compound cannot be sufficiently cleaned.

On the other hand, in the sampling sample analyzer 1, the gas sampling tube 11 is divided into a temperature holding region 15 and a non-temperature holding region, and the temperature holding region 15 is always held at a constant temperature. The compound does not precipitate. On the other hand, the non-temperature holding region on the base end portion 13 side is a temperature region where the ammonia compound is precipitated, but since the cleaning liquid is constantly supplied to this portion, the ammonia compound does not precipitate. Even if deposited, the ammonia compound does not adhere to the gas sampling tube 11 because it dissolves in the cleaning liquid. Thereby, the trouble by precipitation and adhesion of an ammonia compound can be solved.

Although it can be considered that the temperature holding region 15 of the gas sampling pipe 11 is replaced with the heat pipe 25 and an electric heater or a heat medium device is used, both are not preferable as the temperature holding means.

In the case of an electric heater, there is a concern about the size of the temperature distribution. When the temperature is locally lowered, an ammonia compound is precipitated. On the other hand, when the temperature is set high so that the ammonia compound does not precipitate, ammonia is decomposed when a place of 500 ° C. or higher is formed. Furthermore, since there is usually no power source near the flue 119, the electric heater is difficult to use. The heat medium device is superior in temperature uniformity as compared with the electric heater, but requires a device for heating the heat medium and a device for circulating or stirring the heat medium, which increases the size of the device and complicates the configuration.

In contrast, the heat pipe 25 has a simple structure and is compact but has excellent temperature uniformity and heat transfer. Furthermore, no power source is required, which is excellent as a temperature holding means for the gas sampling tube 11. In order to operate the heat pipe 25, a heating source and a cooling source are required. However, since the exhaust gas flowing through the flue 119 can be used as the heating source and the atmosphere can be used as the cooling source, it can be easily put into practical use. be able to.

In the sampled sample analyzer 1 as well, ammonia compounds may adhere to the boundary between the temperature holding region 15 of the gas sampling tube 11 and the non-temperature holding region on the base end 13 side of the gas sampling tube 11 with a long-term operation. There is. Accordingly, the cleaning liquid is periodically flowed to the distal end portion 12 side of the gas sampling tube 11 through the liquid supply device 65, and the temperature holding region 15 of the gas sampling tube 11 and the proximal end portion 13 side of the gas sampling tube 11 are It is preferable to clean the boundary portion with the non-temperature holding region and the temperature holding region 15. An example of the cleaning liquid is water. This cleaning operation is also applicable to a collected sample analyzer according to another embodiment described later.

FIG. 6 is a schematic configuration diagram of the collected sample analyzer 2 according to the second embodiment of the present invention. The same components as those of the collected sample analyzer 1 according to the first embodiment of the present invention are denoted by the same reference numerals and description thereof is omitted.

The collected sample analyzer 2 according to the second embodiment continuously collects exhaust gas and analyzes it online, similarly to the collected sample analyzer 1 according to the first embodiment. However, the collected sample analyzer 1 according to the first embodiment analyzes the collected gas after cleaning, whereas the collected sample analyzer 2 according to the second embodiment analyzes the absorbing solution. For this reason, in the sampling sample analyzer 1 according to the first embodiment, the cleaning liquid is supplied to the gas sampling tube 11. In the sampling sample analyzer 2 according to the second embodiment, the absorbing liquid is supplied to the gas sampling tube 11.

In the collected sample analyzer 2 according to the second embodiment, the collected gas is brought into contact with the absorbing liquid, the ammonia contained in the collected gas is absorbed by the absorbing liquid, and the absorbed liquid is analyzed by the analyzing apparatus to obtain the ammonia concentration. The absorption liquid is supplied in the same manner as the cleaning liquid of the collected sample analyzer 1 according to the first embodiment. In addition to the role of absorbing the ammonia contained in the collected gas, the supplied absorption liquid is used to wash the region so that the ammonia compound does not precipitate in the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11, Alternatively, it plays a role of dissolving the ammonia compound deposited in the region.

The absorption liquid used here needs to absorb ammonia gas contained in the sampling gas, dissolve the ammonia compound, and absorb ammonia, ammonium ions, etc. contained in the ammonia compound. Examples of such absorbing liquid include acidic aqueous solutions such as boric acid aqueous solution.

The absorption liquid is supplied to the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11 in the same manner as the sampling sample analyzer 1 according to the first embodiment, and then sent to the cyclone 61 via the conduit 51. Although it is separated from the collected gas here, the separated absorption liquid is sent to the analyzer 83 without being circulated. The cyclone 61 used here is not equipped with the ball 63, and the absorbing liquid is continuously discharged.

In the collected sample analyzer 1 according to the first embodiment shown in FIG. 1, a suction pump is basically provided to suck the collected gas using the suction pump provided in the analyzer 81. However, the second embodiment is not provided. In the collected sample analyzer 2, the suction pump 75 is installed on the downstream side of the cyclone 61, and the collected gas is sucked using the suction pump 75. Further, a gas meter 76 is installed on the downstream side of the suction pump 75 to measure the amount of suction gas.

The analysis device 83 can use a known analyzer that can analyze ammonia contained in the absorbing solution online, and may be appropriately selected and used according to the analysis accuracy and the like. An example of the analysis device 83 is a flow injection (FIA) analysis device. The FIA analyzer causes a color development (fading) reaction with a liquid sample containing a component to be analyzed, in this embodiment, an absorption liquid containing ammonia and a reagent, and measures the ammonia concentration from the absorbance of this solution.

Next, the procedure for measuring the ammonia concentration in the exhaust gas of the collected sample analyzer 2 will be described.

The suction pump 75 is operated, and the exhaust gas is continuously collected at a constant flow rate through the gas sampling pipe 11. At the same time, the absorbing liquid is continuously supplied at a constant flow rate to the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11 through the liquid supply device 65. The sampled gas collected through the gas sampling tube 11 comes into contact with the absorbing solution in the process of flowing through the gas collecting tube 11 and the conduit 51 connected to the cyclone 61, and ammonia is absorbed by the absorbing solution. The absorption liquid separated by the cyclone 61 is measured for ammonia concentration by the analyzer 83.

As described above, it is possible to analyze the ammonia gas in the exhaust gas online by collecting the collected gas at a constant flow rate and supplying the absorption liquid at a constant flow rate using the collected sample analyzer 2. The effect of the heat pipe 25 and the effect of preventing the precipitation of the ammonia compound by supplying the absorbing liquid are as described in the collected sample analyzer 1 according to the first embodiment. In addition, the action and effect of the conduit 51 having a hydrophilic inner surface is also as described in the collected sample analyzer 1 according to the first embodiment, and the amount of absorbed liquid can be reduced, so that the ammonia concentration in the liquid increases. , Analysis accuracy is improved.

FIG. 7 is a schematic configuration diagram of the collected sample analyzer 3 according to the third embodiment of the present invention. FIG. 8 is a flowchart showing the procedure for analyzing the collected gas using the collected sample analyzer 3. The same components as those of the collected sample analyzers 1 and 2 according to the first and second embodiments of the present invention are denoted by the same reference numerals and description thereof is omitted.

Unlike the sampled sample analyzers 1 and 2 according to the first and second embodiments, the sampled sample analyzer 3 according to the third embodiment collects and analyzes exhaust gas by batch operation. For this reason, the collected sample analyzer 3 according to the third embodiment has an absorption bottle 77 for absorbing the ammonia contained in the collected gas collected via the gas sampling tube 11 into the absorption liquid, and for aspirating the collected gas. A suction pump 75 and a gas meter 76 are provided. One end portion of the conduit 51 is inserted into the absorption bottle 77 so as to be immersed in the absorption liquid, and the gas phase portion of the absorption bottle 77 and the suction pump 75 are connected via the tube 78. The gas meter 76 is connected to the exhaust side of the suction pump 75.

In the sample collection analyzer 3 according to the third embodiment, the non-temperature holding region on the base end 13 side of the gas sampling tube 11 is extremely short, and a ball valve type three-way valve 79 is provided at the base end 13 of the gas sampling tube 11. Is installed. In the present embodiment, the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11 is preferably as short as possible, and should not be provided that the three-way valve 79 can be attached. A liquid supply pipe 68 and a conduit 51 are connected to the three-way valve 79.

In the collected sample analyzer 3 according to the third embodiment, a mixed liquid of an absorbing liquid that has absorbed ammonia in exhaust gas and a cleaning liquid that has cleaned the three-way valve 79 and the conduit 51 is analyzed. The absorption liquid that absorbs ammonia can be the same as the absorption liquid used in the collection sample analyzer 2 according to the second embodiment, and the absorption liquid and the cleaning liquid may be the same type of liquid.

The method for analyzing ammonia contained in the mixed solution of the absorbing solution and the cleaning solution is not limited to a specific method, and a known analyzer such as a liquid chromatograph can be used.

Next, the procedure for measuring the ammonia concentration in the exhaust gas of the collected sample analyzer 3 will be described.

The gas sampling pipe 11 and the conduit 51 communicate with each other, the three-way valve 79 is set so that the cleaning liquid cannot be supplied, the suction pump 75 is operated, a predetermined amount of exhaust gas is sucked through the gas sampling pipe 11, and the absorption liquid is obtained. The ammonia is absorbed through (step S1: absorption process). Thereafter, the three-way valve 79 is switched so that the liquid supply pipe 68 and the conduit 51 communicate with each other, and the gas sampling pipe 11 and the conduit 51 do not communicate with each other, and the suction liquid 75 is supplied and the three-way valve 79 is operated. The valve 79 and the conduit 51 are washed (step S2: washing step). The supplied cleaning liquid is sent to the absorption bottle 77 and mixed with the absorption liquid. After completion of the cleaning process, the absorption liquid in the absorption bottle 77 is sufficiently stirred (step S3: mixing process), and the absorption liquid (mixed liquid) is analyzed (step S4: analysis process).

As described above, by using the collected sample analyzer 3, a certain amount of collected gas is collected, and the three-way valve 79 and the conduit 51 are washed with a washing liquid, whereby the ammonia gas in the exhaust gas is accurately analyzed by batch operation. be able to. In this embodiment, since the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11 is very short, cleaning of this portion can be omitted. The effects of the heat pump 25 and the cleaning liquid are the same as described in the sample collection analyzers 1 and 2 according to the first and second embodiments.

In the collected sample analyzer 3 shown in FIG. 7, a three-way valve 79 is connected to the base end portion 13 of the gas sampling tube 11, and a liquid supply pipe 68 and a conduit 51 are connected to this, but the base end portion of the gas sampling tube 11 is connected. 13 may be directly connected to the liquid supply pipe 68 and the conduit 51, and each pipe may be provided with a valve for switching. Since exhaust gas contains a large amount of soot, it is preferable that the valve to be used is not easily blocked by soot, such as a ball valve.

Further, the structure on the base end portion 13 side of the gas sampling pipe 11, the connection procedure of the conduit 51 and the liquid supply pipe 68 are the same as those of the sampling sample analyzer 1 according to the first embodiment. You may make it wash | clean and supply the non-temperature holding area | region and the conduit | pipe 51 by the side of the base end part 13 of the gas sampling pipe | tube 11. FIG. Further, when supplying the cleaning liquid, the suction pump 75 may be operated.

Further, in the sample collection analyzer 3 shown in FIG. 7, the absorption liquid and the cleaning liquid absorb ammonia, and the absorption liquid (including the cleaning liquid) that has absorbed ammonia is analyzed. However, the collected gas may be analyzed. Specifically, the cleaning liquid used in the first embodiment is used as the absorption liquid and the cleaning liquid, the collected gas after passing through the cleaning liquid and the ammonia gas generated during the cleaning are collected in a gas holder or the like, and the ammonia contained in this gas is collected. You may analyze.

FIG. 9 is a schematic configuration diagram of the collected sample analyzer 4 according to the fourth embodiment of the present invention. The same components as those of the collected sample analyzers 1, 2, and 3 according to the first to third embodiments of the present invention are denoted by the same reference numerals and description thereof is omitted.

As in the sample gas analyzer 1 according to the first embodiment, the collected sample analyzer 4 according to the fourth embodiment continuously collects exhaust gas, continuously supplies a cleaning liquid, and is cleaned with the cleaning liquid. Analyze later collected gas online. Therefore, the collected sample analyzer 4 according to the fourth embodiment and the collected sample analyzer 1 according to the first embodiment have the same basic configuration. However, the temperature of the gas sampling tube 11 is greatly different between the sampling sample analyzer 4 according to the fourth embodiment and the sampling sample analyzer 1 according to the first embodiment. Accordingly, the structure of the heat pipe 26 and the tip position of the liquid supply pipe are different from those of the collected sample analyzer 1 according to the first embodiment.

In the collected sample analyzer 4 according to the fourth embodiment, the temperature of the temperature holding region of the gas sampling tube 11 is held at a temperature of 100 ° C. or lower. This is because the temperature holding region of the gas sampling tube 11 is set to a temperature at which the ammonia compound is deposited and the cleaning liquid does not become vapor, and this temperature holding region can be reliably cleaned with the cleaning liquid, thereby stably collecting and analyzing the exhaust gas. This is to improve accuracy.

In the collected sample analyzer 4 according to the fourth embodiment, the temperature holding region 15 of the gas sampling tube 11 is a portion straddling the flue wall 121 and its front and rear portions, specifically, a region covered with the heat pipe 26. It is. The total length of the temperature holding region 15 of the gas sampling tube 11 is the same as that of the gas sampling tube 11 of the sampling sample analyzer 1 according to the first embodiment, but the gas sampling tube of the sampling sample analyzer 1 according to the first embodiment. Compared to 11, the length inside the flue 119 is short, and conversely, the length outside the flue 119 is long. The distal end portion 12 and the proximal end portion vicinity 14 of the gas sampling tube 11 are non-temperature holding regions. The non-temperature holding area is an area that is not held at a predetermined temperature via the heat pipe 26.

The heat pipe 26 is integrally provided on the outer wall 19 of the gas sampling tube 11 in the same manner as the heat pipe 25 of the sampling sample analyzer 1 according to the first embodiment.

The heat pipe 26 is a wick-type heat pipe, and includes a cooling unit 30 provided so as to be orthogonal to the cylindrical unit 28 in addition to the cylindrical unit 28 covering the gas sampling tube 11. The cooling unit 30 is provided integrally with the cylindrical unit 28 so as to communicate with the cylindrical unit 28 in the cylindrical unit 28 located outside the flue 119. Cooling fins 37 for promoting heat dissipation are provided on the outer peripheral surface of the cooling unit 30.

The working fluid used in the heat pipe 26 only needs to be able to hold the gas sampling tube 11 at 100 ° C. or lower, and examples thereof include water, methanol, and acetone. Since the heat pipe 26 and the gas sampling tube 11 may be separated from each other, they are the same as the heat pipe 25 of the collected sample analyzer 1 according to the first embodiment, and thus the description thereof is omitted.

The liquid supply pipe 68 is provided so that the tip 69 is located at the end of the temperature holding area 15 of the gas sampling tube 11 on the side of the flue 119 so that the entire temperature holding area 15 of the gas sampling pipe 11 can be cleaned. . In addition, the structures and specifications of the liquid supply device 65, the conduit 51, and the cyclone 60 are the same as those of the collected sample analyzer 1 according to the first embodiment. Further, the cleaning liquid is the same as the cleaning liquid used in the collected sample analyzer 1 according to the first embodiment.

The procedure for measuring the ammonia concentration in the exhaust gas of the sampling sample analyzer 4 is the same as the procedure for measuring the ammonia concentration in the exhaust gas of the sampling sample analyzer 1 according to the first embodiment.

In the sample collection analyzer 1 according to the first embodiment, the temperature holding region 15 of the gas sampling tube 11 is set to a temperature at which the ammonia compound does not precipitate, and the gas sampling tube 11 on the base end 13 side where the ammonia compound may be deposited may be deposited. The non-temperature holding area is cleaned with a cleaning solution. On the other hand, in the collected sample analyzer 4 according to the fourth embodiment, the temperature holding region 15 of the gas sampling tube 11 is set to a temperature at which the ammonia compound is deposited and the cleaning liquid is not vaporized. Rinse thoroughly with a cleaning solution. Note that, also in the sample collection analyzer 4 according to the fourth embodiment, the non-temperature holding region on the base end portion 13 side of the gas sampling tube 11 is cleaned with the cleaning liquid.

As described above, the collected sample analyzer 1 according to the first embodiment and the collected sample analyzer 4 according to the fourth embodiment are greatly different in the temperature of the gas sampling tube 11, and accordingly, the structure of the heat pipes 25 and 26. And the position of the front-end | tip part 69 of a liquid supply pipe differs. However, by using the heat pipes 25 and 26, the specific region of the gas sampling tube 11 is always kept at a constant temperature as the temperature holding region 15, and the temperature region where the ammonia compound is deposited is washed with the cleaning liquid, thereby stabilizing the exhaust gas. The same point is achieved in improving sampling and analysis accuracy.

FIG. 10 is a schematic configuration diagram of the collected sample analyzer 5 according to the fifth embodiment of the present invention. The same components as those of the collected sample analyzers 1, 2, 3, and 4 according to the first to fourth embodiments of the present invention are denoted by the same reference numerals and description thereof is omitted.

The collected sample analyzer 5 according to the fifth embodiment uses the same apparatus as the collected sample analyzer 4 according to the fourth embodiment, and is similar to the collected sample analyzer 2 according to the second embodiment. Analyze. Therefore, the sample collection analyzer 5 according to the fifth embodiment is different from the sample sample analysis device 4 according to the fourth embodiment in the configuration around the cyclone 61, and the configuration around the cyclone 61 is the second embodiment. This is the same as the collected sample analyzer 2 according to FIG.

The absorbing liquid and cleaning liquid used in the collected sample analyzer 5 according to the fifth embodiment are the same as the absorbing liquid and cleaning liquid used in the collected sample analyzer 2 according to the second embodiment.

The procedure for measuring the ammonia concentration in the exhaust gas of the collected sample analyzer 5 according to the fifth embodiment is the same as that of the collected sample analyzer 2 according to the second embodiment. Although the temperature of the temperature holding region 15 of the gas sampling tube 11 is different from that of the sample collection analyzer 2 according to the second embodiment, the point that the exhaust gas can be stably collected and the high analysis accuracy can be realized is the same. .

FIG. 11 is a schematic configuration diagram of the collected sample analyzer 6 according to the sixth embodiment of the present invention. The same components as those of the collected sample analyzers 1, 2, 3, 4, 5 according to the first to fifth embodiments of the present invention are denoted by the same reference numerals and description thereof is omitted.

The collected sample analyzer 6 according to the sixth embodiment uses the same device as the collected sample analyzer 4 according to the fourth embodiment, and collects exhaust gas and collects the exhaust gas in the same manner as the collected sample analyzer 3 according to the third embodiment. Analyze in batch. Therefore, the sample collection analyzer 6 according to the sixth embodiment is different from the sample collection analyzer 4 according to the fourth embodiment in the structure and arrangement of the gas collection tube 11, the heat pipe 26, and the liquid supply tube 68. Although the same, the downstream side of the conduit 51 and the liquid supply tank 66 are the same as those of the collected sample analyzer 3 according to the third embodiment.

The absorbing liquid and cleaning liquid used in the collected sample analyzer 6 according to the sixth embodiment are the same as the absorbing liquid and cleaning liquid used in the collected sample analyzer 3 according to the third embodiment.

The analyzer can use a liquid chromatograph in the same manner as the collected sample analyzer 3 according to the third embodiment.

The procedure for measuring the ammonia concentration in the exhaust gas of the collected sample analyzer 6 according to the sixth embodiment is basically the same as the procedure for measuring the ammonia concentration of the collected sample analyzer 3 according to the third embodiment.

The collected sample analyzer 6 according to the sixth embodiment has a lower temperature in the temperature holding region 15 of the gas collection tube 11 than the collected sample analyzer 3 according to the third embodiment, and the outlet of the gas collection tube 11. Although the three-way valve 79 which is a switching valve is not provided in the part, it differs from the collected sample analyzer 3 according to the third embodiment, but the technical idea and the operational effect are basically the same, and the exhaust gas is stable. Higher analysis accuracy can be realized.

Further, in the collected sample analyzer 6 shown in FIG. 11, the absorption liquid and the cleaning liquid absorb ammonia, and the absorption liquid (including the cleaning liquid) that has absorbed ammonia is analyzed. These are as described in the collection sample analyzer 3 according to the third embodiment.

As described above, as described using the collected sample analyzer according to the first to sixth embodiments, the collected sample analyzer according to the present invention holds the gas sampling tube 11 at a predetermined temperature via the heat pipes 25 and 26. Therefore, the region where the compound is deposited is specified, and cleaning with the cleaning liquid becomes easy. Furthermore, it is possible to prevent the precipitation and / or adhesion of the compound by always flowing the liquid in the temperature range where the compound is precipitated, and it is possible to collect the analysis sample stably and to include the analysis target contained in the gas. Ingredients can be collected accurately.

The heat pipes 25 and 26 are excellent in heat transfer properties and temperature uniformity, but do not require a means for equalizing the temperature or a power source, and the gas flowing through the gas flow path to the heating source of the working fluid. If the atmosphere is used as a cooling source for the working fluid, there is no need to prepare a special heat source, which is excellent in practicality. In addition, although the example which uses a wick-type heat pipe was shown in the said embodiment, you may use a heat pipe of another kind, for example, a self-excited vibration heat pipe.

Further, according to the present invention, since it is possible to analyze the collected sample online or offline, a preferable method can be adopted depending on the application. Furthermore, since the sample may be in the form of gas or liquid, various analyzers can be used, which is convenient and excellent in practicality. In the above embodiment, the sampling sample analyzer according to the present invention has been described by taking the flue gas of a thermal power plant as an example. However, the analytical sample sampling device according to the present invention and the method of using the same, the sampling sample analyzer and the sampling It goes without saying that the sample analysis method is applicable to collection and analysis of other gases.

Although a preferred sample analysis apparatus and a method for using the same have been described with reference to the drawings, those skilled in the art will readily consider various changes and modifications within the obvious scope by looking at the present specification. Let's go. Therefore, such changes and modifications are interpreted as being within the scope of the invention defined by the claims.

1, 2, 3, 4, 5, 6 Sampling sample analyzer 11 Gas sampling tube 12 Gas sampling tube tip 13 Gas sampling tube proximal end 14 Gas sampling tube proximal end 15 Temperature holding region 19 Gas sampling Tube outer wall 25, 26 Heat pipe 51 Conduit 53 Coating layer 54 Liquid film 60, 61 Cyclone 65 Liquid supply device 69 Liquid supply pipe tip 77 Absorption bottle 81, 83 Analysis device 100 Thermal power plant 109 Flue gas denitration device 119 Flue 121 Flue wall

Claims (15)

1. A gas sampling tube whose tip end side is inserted into the gas flow path and collects gas in the gas flow path;
   Temperature holding means for holding the gas sampling pipe at a predetermined temperature;
   A liquid supply means for supplying a liquid to a member connected to the gas sampling pipe and / or the outlet of the gas sampling pipe;
   Including
   The gas is a gas in which a part of the compounds contained in the gas is precipitated when the temperature decreases,
   An analytical sample collecting apparatus, wherein the temperature holding means is a heat pipe.
2. The heating source of the working fluid of the heat pipe is a gas flowing in the gas flow passage, and the cooling source of the working fluid of the heat pipe is the atmosphere outside the gas flow passage. 2. The analytical sampling apparatus according to 1.
3. The gas sampling pipe is divided into a temperature region where the compound is not precipitated by the heat pipe and a temperature region where the compound is precipitated,
   The analytical sample collecting apparatus according to claim 1 or 2, wherein the liquid is supplied only to a temperature region where the compound is deposited with respect to the gas sampling tube.
4. The analytical sample collection according to claim 3, wherein the gas sampling pipe is held at a temperature at which the compound does not precipitate by the heat pipe at least at a portion straddling the wall of the gas flow passage and before and after the portion. apparatus.
5. The analytical sample collection according to claim 3, wherein at least a portion of the gas sampling tube straddling the wall of the gas flow passage and its front and back are maintained at a temperature at which the compound is precipitated by the heat pipe. apparatus.
6. The analytical sample collection device according to any one of claims 1 to 5, wherein the heat pipe is provided integrally with the gas collection tube on an outer wall surface of the gas collection tube.
7. Further, the gas / liquid that separates the collected gas collected through the gas sampling tube from the liquid supplied to the member connected to the gas sampling tube and / or the outlet of the gas sampling tube through the liquid supply means. Separating means;
   A conduit connecting the gas sampling pipe and the gas-liquid separation means,
   7. The conduit according to claim 1, wherein the conduit has a hydrophilic inner surface, and the fluid flowing through the conduit flows while forming a liquid film on the inner wall surface of the conduit. The analytical sample collection device described in 1.
8. The analytical sample collection device according to any one of claims 1 to 7, wherein the gas is a gas containing ammonia, and the component to be analyzed is ammonia.
9. The gas flow passage is a flue at an outlet of a flue gas denitration apparatus that processes boiler exhaust gas, and the gas in the gas flow passage is boiler exhaust gas in the flue. The analytical sample collection device described.
10. A cleaning liquid is allowed to flow to the tip end side of the gas sampling tube through the liquid supply means, and a boundary portion between a temperature region where the compound does not precipitate and a temperature region where the compound precipitates is included in the gas sampling tube. The method of using the analytical sample collection device according to any one of claims 3 to 9, wherein the analytical sample collection device is washed.
11. The analytical sample collection device according to any one of claims 1 to 10,
    And an analyzer for analyzing the component to be analyzed contained in the gas body,
    The liquid in the analytical sample collection device according to any one of claims 1 to 10, wherein the liquid dissolves the compound and does not absorb the analysis target component.
    The collected sample analysis apparatus, wherein the analysis apparatus analyzes the collected gas washed with the liquid.
12. The analytical sample collection device according to any one of claims 1 to 10,
    And an analyzer for analyzing an analysis target component contained in the liquid,
    The liquid in the analytical sampling device according to any one of claims 1 to 10, wherein the liquid is an absorption liquid that dissolves the compound and absorbs the analysis target component.
    The collected sample analyzer which analyzes the absorption liquid which absorbed the analysis object ingredient.
13. The sample collection analyzer according to claim 11 is used to continuously collect a constant flow rate of gas through the gas supply pipe, while continuously collecting a constant flow rate of the liquid through the liquid supply means. A method for analyzing a collected sample, wherein the collected gas supplied into the collection tube and washed with the liquid is analyzed online.
14. Using the sample collection analyzer according to claim 12, continuously collecting a constant flow rate of gas through the gas sampling tube, and continuously supplying the absorption liquid at a constant flow rate through the liquid supply means. A method for analyzing a collected sample, characterized in that an absorbing solution that has been supplied into a gas sampling tube and absorbed the component to be analyzed is analyzed online.
15. It is a collection sample analysis method using the collection sample analyzer of Claim 12, Comprising: The said analyzer replaces the said absorption liquid, The liquid obtained through the absorption process of the following, a washing | cleaning process, and a mixing process A method for analyzing a collected sample, characterized in that
    Absorption step: gas is collected through the gas sampling tube, the gas is passed through the absorption liquid, and the analysis target component is absorbed by the absorption liquid.
    Washing step: After the absorption step, the member connected to the inside of the gas sampling tube and / or the outlet of the gas sampling tube is cleaned with the cleaning liquid supplied through the liquid supply means.
    Mixing step: The absorption liquid obtained in the absorption step and the cleaning liquid obtained in the washing step are mixed.

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