JP5422493B2 - Gas calorific value measuring device and gas calorific value measuring method - Google Patents

Description

  The present invention relates to a gas calorific value measuring device and a gas calorific value measuring method for measuring the calorific value of a gas flowing in a pipeline.

  For example, a gas discharged from a combustion engine such as an internal combustion engine or an incinerator or a fuel gas obtained by vaporizing fuel is a mixed gas in which various gaseous substances are mixed. Such exhaust gas and fuel gas are flowed through the pipe and supplied (exhausted) to a predetermined device or the atmosphere. Here, as a method of measuring the calorific value of gas, there is a method of measuring using laser Raman scattering spectroscopy. For example, in Patent Document 1 filed by the present applicant, a pipe through which a coal gasification gas having a pressure higher than the normal pressure generated by the coal gasification apparatus and a flow path of the coal gasification gas in the middle of the pipe are narrowed. A measurement unit provided at a location immediately after the exit of the throttle member, a laser unit that irradiates laser light having a wavelength of 400 nm or more to the coal gasification gas that has not undergone pretreatment that passes through the measurement unit, and laser light A spectroscopic unit that measures the intensity for each wavelength of scattered light generated from the coal gasification gas by irradiation of the gas, and a calculation unit that calculates the calorific value of the coal gasification gas from the measurement results. It is provided between the window through which the light passes and the area through which the coal gasification gas passes in the measurement part, protects the window from the coal gasification gas, and opens when the laser gas is irradiated to the coal gasification gas. A gas calorific value measuring device comprising a valve, It has been mounting.

  In addition, as a method for measuring the concentration of a specific substance contained in a mixed gas (mainly circulating gas) flowing in a pipeline, a laser beam is passed through a predetermined path of the pipeline, and the specific substance to be measured is measured from its input and output. There is a method for measuring the concentration. For example, Patent Document 2 filed by the present applicant discloses that a light source that oscillates a laser beam having an absorption wavelength specific to a gaseous substance to be measured, and at least two oscillation wavelengths of the laser beam oscillated from this light source. Means for modulating at two different frequencies, means for directing the laser light modulated by the modulating means to a measurement region where gaseous substances are present, and light receiving means for receiving laser light transmitted, reflected or scattered in the measurement region There is described a gas concentration measuring apparatus comprising a plurality of phase sensitive detectors that sequentially demodulate a signal modulated from signals received by the light receiving means for each frequency.

Japanese Patent No. 38422982 Japanese Patent No. 3342446

  Here, the measurement by laser Raman scattering spectroscopy described in Patent Document 1 has a problem that it is difficult to realize measurement accuracy at about 1 vol% at atmospheric pressure. In addition, since the Raman scattering cross section is small, there is also a problem that it is easily affected by stray light due to excitation light, scattered light, and fluorescent lamp noise. Therefore, the environment that can be measured is limited.

  Moreover, the apparatus described in Patent Document 2 can measure a substance to be measured with high responsiveness. However, as in the apparatus described in Patent Document 2, hydrogen cannot be measured by a measurement method that irradiates laser light in the near-infrared wavelength region and measures absorption by a measurement target. Since hydrogen cannot be measured in this way, the amount of hydrogen contained in the circulating gas cannot be detected, and it is difficult to calculate the calorific value of the gas with high accuracy.

  The present invention has been made in view of the above, and is a gas calorific value measuring device and a gas calorific value measurement capable of measuring the calorific value of circulation gas with high responsiveness, simply and with high accuracy. It is an object to provide a method.

In order to solve the above-described problems and achieve the object, the present invention provides a gas calorific value measuring device for measuring a hydrogen concentration of a measurement target contained in a circulation gas, the piping unit through which the circulation gas flows, A conversion unit that is arranged in the piping unit and converts hydrogen contained in the flowing gas passing through the piping unit into H ₂ O, and a first of the flowing gas flowing through the piping unit that flows through the piping path passing through the converting unit. A first measured value including measured values of H ₂ O concentration, CH ₄ concentration, CO concentration, CO ₂ concentration contained in the circulating gas, and a second circulating gas that has flowed through the piping path that does not pass through the conversion means Control means for measuring the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, the second measurement value including the measurement value of the CO ₂ concentration, and the operation of the piping unit and the measurement means And the first measurement Control means for calculating the calorific value of the flow gas based on the calculated hydrogen concentration and combustion component concentration from the difference between the value and the second measured value, The measurement means includes an absorption wavelength of H ₂ O, and includes a laser beam in the near infrared wavelength region, an absorption wavelength of CH ₄ , and includes a laser beam in the near infrared wavelength region, an absorption wavelength of CO, and the laser beam of near-infrared wavelength region, wherein the absorption wavelength of CO _2, and near-infrared light-emitting section and outputs the laser light of the wavelength range, the gas measuring cell the flowing gas flows, the gas measuring cell An optical system for allowing laser light to enter, at least one measurement unit including a light receiving unit that receives the laser light that has been incident from the light emitting unit and passed through the gas measurement cell, and the intensity of the laser light output from the light emitting unit, The laser beam received by the light receiving unit And a calculation unit that calculates the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ of the flow gas flowing through the gas measurement cell based on the strength.

  According to the gas calorific value measuring device, the calorific value of the circulation gas can be detected with high responsiveness and high accuracy.

Further, a first flow meter that is arranged on the upstream side of the conversion means and measures the flow rate of the flow gas flowing into the conversion means, and is arranged on the downstream side of the conversion means and is discharged from the conversion means. A second flow meter for measuring the flow rate of the flow gas, and the control means determines the H of the flow gas based on the measurement result of the first flow meter and the measurement result of the second flow meter. It is preferable to calculate by correcting measured values of ₂ O concentration, CH ₄ concentration, CO concentration, and CO ₂ concentration. Thereby, the calorific value of circulation gas can be measured with higher accuracy.

Further, the conversion unit preferably has a temperature adjusting unit for adjusting the temperature of the atmosphere in the region for converting hydrogen into H _{2 O.} Thereby, hydrogen of circulation gas and hydrocarbons other than methane can be suitably converted into hydrogen and carbon dioxide.

  Moreover, it is preferable that the said temperature adjustment part sets the temperature of the said atmosphere to 100 degreeC or more and 200 degrees C or less. Thereby, hydrogen of circulation gas and hydrocarbons other than methane can be more suitably converted into hydrogen and carbon dioxide.

Further, the measuring means further outputs laser light in the near-infrared wavelength region including the absorption wavelength of O ₂ from the light emitting part, and the concentration of O ₂ contained in the first flow gas and the second The concentration of O ₂ contained in the circulation gas is measured, and the control means includes the H ₂ O concentration, the CH ₄ concentration, the CO concentration, the CO ₂ concentration, the O ₂ concentration, 2. Calculate the composition ratio of hydrocarbons and hydrogen based on the change in mass balance between H ₂ O concentration, CH ₄ concentration, CO concentration, CO ₂ concentration, and O ₂ concentration in the distribution gas It is preferable to calculate the calorific value of the circulation gas from the calculation result. Thereby, the calorific value of circulation gas can be measured with higher accuracy.

  The pipe unit is connected to an inflow pipe into which the flow gas flows in, a downstream end of the inflow pipe in the flow direction of the flow gas, and the first pipe in which the conversion means is disposed; A second pipe that is connected to the downstream end of the inflow pipe in the flow direction of the flow gas together with the first pipe, and in which the conversion means is not disposed; an end on the downstream side of the first pipe; A three-way valve that connects an end on the downstream side of the second pipe and an end on the upstream side in the flow direction of the gas flow of the gas measurement cell, and the control means uses the three-way valve to An end on the downstream side of the first pipe and an end on the upstream side in the flow direction of the flow gas of the gas measurement cell are connected, and the first flow gas is caused to flow into the measurement means, so that the first measurement is performed. Value is measured, and the end of the second pipe on the downstream side is measured by the three-way valve. Serial and said upstream end of the flow direction of the flowing gas in the gas measuring cell is connected, said allowed to flow into the second circulation gas in the measurement unit, it is preferable to measure the second measured value. Thereby, it can measure with one measuring unit.

  The pipe unit is connected to an inflow pipe into which the flow gas flows in, a downstream end of the inflow pipe in the flow direction of the flow gas, and the first pipe in which the conversion means is disposed; A second pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas together with the first pipe and not having the conversion means disposed thereon, and the measuring means includes two measuring units. One of the measurement units is disposed downstream of the conversion means in the flow direction of the flow gas in the first pipe, and the other measurement unit is disposed in the first pipe. preferable. Thereby, hydrogen can be measured continuously.

  The pipe unit includes an inflow pipe into which the flow gas flows, and a holding pipe that is connected to an end of the inflow pipe on the downstream side in the flow direction of the flow gas and in which the conversion unit is disposed. The measuring means includes two measuring units, and one of the measuring units is arranged downstream of the converting means in the flow direction of the circulating gas in the holding pipe, and the other measuring unit is It is preferable that the holding pipe is disposed upstream of the conversion means in the flow direction of the circulating gas. Thereby, hydrogen can be measured continuously.

Moreover, it is preferable that the conversion means is an oxidation catalyst that causes hydrogen to undergo an oxidation reaction to form H ₂ O. Thereby, hydrogen can be converted into a measurable substance with a simple configuration.

Moreover, it is preferable to further include an oxidant supply unit that is disposed upstream of the conversion unit in the flow direction of the circulation gas and supplies an oxidant that oxidizes the hydrogen to the piping unit. Thereby, hydrogen can be more reliably converted into H ₂ O.

In the flow direction of the flow gas, the pipe unit further includes an oxidant supply unit that supplies an oxidant that oxidizes the hydrogen to the pipe unit, and the pipe unit includes the flow unit. An inflow pipe into which gas flows in, and a holding pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, in which the conversion means is disposed, and the measurement means includes the measurement unit Is disposed downstream of the conversion means in the flow direction of the circulating gas in the holding pipe, the conversion means is an oxidation catalyst that oxidizes hydrogen to H ₂ O, and the control means includes: Switching between a state where the oxidant is supplied from the oxidant supply means to the piping unit and a state where the oxidant is not supplied from the oxidant supply means to the piping unit, A measurement unit, a state in which the first flowing gas is flowing, it is preferable to switch between a state in which the second flowing gas is flowing. Thereby, it can measure with one measuring unit.

Further, the converting means preferably having an aqueous reverse shift catalyst to shift the carbon dioxide and hydrogen contained in the circulation gas to the carbon monoxide and H _{2 O.} Thereby, hydrogen can be converted into H ₂ O without using oxygen.

Moreover, it is preferable to further include a carbon dioxide supply means that is disposed upstream of the conversion means in the flow direction of the circulating gas and supplies the carbon dioxide to the piping unit. Thereby, hydrogen can be more reliably converted into H ₂ O, and the measurement accuracy can be increased.

The flow direction of the flow gas further includes a carbon dioxide supply unit that is disposed upstream of the conversion unit and supplies carbon dioxide to the pipe unit, and the pipe unit is configured to receive the flow gas. An inflow pipe, and a holding pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, and in which the conversion means is disposed, and the measurement means includes the measurement unit, An aqueous reverse shift is arranged downstream of the conversion means in the flow direction of the flow gas in the holding pipe, and the conversion means shifts carbon dioxide and hydrogen contained in the flow gas to carbon monoxide and H ₂ O. A catalyst, wherein the control means supplies the carbon dioxide from the carbon dioxide supply means to the piping unit; It is preferable to switch the state in which the carbon dioxide is not supplied to the unit, and to switch the state in which the first circulation gas flows into the measurement unit and the state in which the second circulation gas flows into the measurement unit. . Thereby, it is possible to perform measurement with one measurement unit.

The conversion means is formed on the downstream side of the ozone supply means of the piping unit in the flow direction of the circulation gas, the ozone supply means for supplying ozone to the piping unit, and hydrogen contained in the circulation gas And a reaction region in which ozone supplied by the ozone supply means reacts.

  The pipe unit includes an inflow pipe into which the circulation gas flows, and a pipe connected to the downstream end of the inflow pipe in the flow direction of the circulation gas, and through which the circulation gas flows. The means is configured to supply ozone to the piping unit, ozone supply means for supplying ozone, and the supply of hydrogen and ozone contained in the circulation gas, which is formed downstream of the ozone supply means of the piping in the flow direction of the circulation gas. A reaction region in which ozone supplied by the device reacts, and the measurement unit includes the measurement unit disposed downstream of the reaction region in the flow direction of the circulating gas, and the control unit includes: A state in which the ozone is supplied from the ozone supply means to the piping unit, and the ozone is not supplied from the ozone supply means to the piping unit. Switching deliberately, to the measuring unit, and a state in which the first flowing gas is flowing, it is preferable to switch between a state in which the second flowing gas is flowing. Thereby, it is possible to perform measurement with one measurement unit.

Further, the conversion means further includes ultraviolet irradiation means for irradiating the reaction area with ultraviolet rays, and the control means irradiates the reaction area with the ultraviolet rays from the ultraviolet irradiation means, and the ultraviolet irradiation. The state is switched from the state where the reaction region is not irradiated with the ultraviolet light, and the state where the first flow gas is flowing into the measurement unit and the state where the second flow gas is flowing into the measurement unit are switched. It is preferable. Thereby, hydrogen can be more reliably converted to H ₂ O.

Moreover, it is preferable that the conversion means further includes a reaction promoting member that promotes a reaction between the ozone and the hydrogen in the reaction region. Thereby, hydrogen can be more reliably converted to H ₂ O.

  Moreover, it is preferable that the said measurement unit passes the inside of the piping which hold | maintains the said conversion means for a laser beam. Thereby, a part of measurement cell can be used as piping, and circulation gas can be measured more directly.

  Moreover, it is preferable that the said piping unit flows the whole quantity of the said circulation gas discharged | emitted from the apparatus of a measuring object. Thereby, circulation gas can be measured with higher precision.

  Moreover, it is preferable that the said piping unit is collecting a part of said circulation gas from the measurement object piping through which the whole quantity of the said circulation gas discharged | emitted from the apparatus of a measuring object flows. Thus, the measurement unit can be appropriately sized by performing measurement by sampling.

Further, a dehumidifying device for recovering H ₂ O contained in the circulating gas and a dust removing device for recovering dust contained in the circulating gas, arranged upstream of the conversion means in the flow direction of the circulating gas. It is preferable to have at least one. Thereby, generation | occurrence | production of a measurement error can be suppressed.

In order to solve the above-described problems and achieve the object, the present invention is a gas calorific value measuring method for measuring the hydrogen concentration of a circulating gas flowing through a pipe, and hydrogen is extracted from the flowing gas flowing through the pipe. The first circulating gas that has passed through the region where the conversion means for converting to ₂ O is disposed includes the absorption wavelength of H ₂ O, the laser light in the near infrared wavelength region, and the absorption wavelength of CH ₄ Including near-infrared wavelength region laser light, CO absorption wavelength, near-infrared wavelength region laser light, CO ₂ absorption wavelength, and near-infrared wavelength region laser light Based on the intensity of the output laser beam and the intensity of the laser beam received by the light receiving unit, the laser beam that has been output and received through the pipeline through which the first circulation gas flows is received. _{H 2} O concentration, the concentration of CH _4, the concentration of CO contained in A first step of measuring the concentration of CO ₂ as a first measurement value, among the circulation gas flowing through the pipe, a second that has not passed through the region where the conversion means for converting the hydrogen in H _{2 O} is located For the flowing gas, the absorption wavelength of H ₂ O, the laser light in the near infrared wavelength region, the absorption wavelength of CH ₄ , the laser light in the near infrared wavelength region, the absorption wavelength of CO Including the near-infrared wavelength region laser light, the CO ₂ absorption wavelength, outputting the near-infrared wavelength region laser light, and passing through the pipe through which the second flow gas flows. The concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, the concentration of CO ₂ contained in the flow gas based on the intensity of the laser beam received and output and the intensity of the laser beam received by the light receiving unit A second measurement step of measuring the concentration of the second measurement value as a second measurement value; Calculating a hydrogen concentration from a difference between the first measurement value and the second measurement value, and calculating a calorific value of the flow gas based on the calculated hydrogen concentration and combustion component concentration. It is characterized by that.

  According to the gas calorific value measuring device, the calorific value of the circulation gas can be measured with high responsiveness and high accuracy.

  The gas calorific value measuring device and the gas calorific value measuring method according to the present invention have an effect that the calorific value of the circulation gas can be measured with high accuracy and high responsiveness.

FIG. 1 is a schematic diagram showing a schematic configuration of an embodiment of a gas calorific value measuring device. FIG. 2 is a block diagram showing a schematic configuration of a measuring means main body of the gas calorific value measuring device shown in FIG. FIG. 3 is a flowchart for explaining the operation of the gas calorific value measuring device. FIG. 4A is a graph for explaining the substance conversion operation by the conversion means. FIG. 4B is a graph for explaining the substance conversion operation by the conversion means. FIG. 5 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 6 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 7 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 8 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 9 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. 10-1 is explanatory drawing for demonstrating operation | movement of a gas calorific value measuring apparatus. FIG. 10-2 is an explanatory diagram for explaining the operation of the gas calorific value measurement device. FIG. 11 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 12 is an explanatory diagram for explaining the operation of the gas calorific value measurement device. FIG. 13 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 14 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 15 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 16 is a schematic diagram showing a schematic configuration of the preprocessing means.

  Hereinafter, an embodiment of a gas calorific value measuring device and a gas calorific value measuring method according to the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by this embodiment. Here, the gas calorific value measuring device and the gas calorific value measuring method can measure the calorific value of the target gas for various gases flowing through the pipeline. For example, the calorific value of the combustion gas may be measured by attaching a gas calorific value measuring device and a gas calorific value measuring method to a pipeline through which the fuel gas flows. Examples of the apparatus having a pipeline through which fuel gas flows include various combustion engines such as vehicles, ships, generators, incinerators and the like. Moreover, as a material which produces | generates gaseous fuel gas, gasoline, light oil, heavy oil, natural gas, biofuel (bioethanol), etc. are illustrated. It can also be used as a device for measuring the calorific value of the gas supplied to the fuel cell. Moreover, you may measure to the emitted-heat amount (circulation gas) exhausted from a diesel engine, attached to a diesel engine, and the circulation gas discharged | emitted from a garbage incinerator. Thereby, the combustion component remaining in the exhaust gas can be detected. In the present embodiment, the calorific value due to hydrogen and hydrocarbons present as gaseous substances in the flowing gas (mixed gas) flowing in the pipe is a measurement target.

[Embodiment 1]
FIG. 1 is a schematic diagram showing a schematic configuration of an embodiment of a gas calorific value measuring device of the present invention. The gas calorific value measuring device 10 is a measuring device that collects (samples) a part of the circulating gas flowing through the measurement target pipe 8 and measures the calorific value of the circulating gas. As shown in FIG. 1, the gas calorific value measurement device 10 includes a piping unit 12, a conversion unit 14, a measurement unit 16, and a control unit 18. The gas calorific value measuring device 10 includes flow meters 36 and 38.

  The piping unit 12 is connected to the measurement target piping 8 and constitutes a route for guiding the circulating gas. The piping unit 12 includes a sampling pipe (inflow pipe) 20, a first pipe 22, a second pipe 24, branch pipes 26 and 28, a three-way valve 30, a pump 31, and on-off valves 32 and 34. Have.

  The sampling pipe (inflow pipe) 20 is a pipe that is connected to the measurement target pipe 8 and collects part of the circulating gas flowing through the measurement target pipe 8. The sampling pipe 20 has one end (upstream end in the flowing gas flow direction) arranged inside the measurement target pipe 8 and the other end (downstream end in the flowing gas flow direction). Are disposed outside the measurement target pipe 8. Further, since the sampling pipe 20 can reduce dust contained in the collected flow gas, the opening surface of one end is orthogonal to the flow direction of the flow gas or downstream from the orthogonal direction. It is arranged in the direction toward the side. The other end of the sampling pipe 20 is connected to two pipes, a first pipe 22 and a second pipe 24. In the present embodiment, the position where the measurement target pipe 8 flows into the sampling pipe 20 is the most upstream in the flow direction of the circulating gas. Further, the flow gas flowing into the piping unit 12 flows from one end portion of the sampling piping 20 toward the other end portion. The direction in which the flow gas flowing in from the measurement target pipe 8 flows is the flow direction of the flow gas.

  The first pipe 22 has one end connected to the sampling pipe 20 and the other end connected to the three-way valve 30. Moreover, the conversion means 14 mentioned later is arrange | positioned in the 1st piping 22 in the pipe line. Moreover, the area | region where the conversion means 14 of the 1st piping 22 is arrange | positioned has the diameter of the pipe line larger than another area | region. In the present embodiment, the diameter of the pipeline in the region where the conversion means 14 is arranged is increased, but the diameter of the pipeline may be constant.

  Further, the first pipe 22 is provided with a branch pipe 26 downstream of the conversion means 14 in the flow direction of the circulating gas. The branch pipe 26 is provided with an on-off valve 32. The downstream side of the branch pipe 26 in the flow direction of the flow gas may be opened to the outside air. However, if the flow gas contains a toxic component or the like, it is connected to a processing device for processing the flow gas. It is preferable to connect to the downstream of the measurement target pipe 8.

  The second pipe 24 is basically a pipe formed in parallel with the first pipe 22 and has one end connected to the sampling pipe 20 and the other end connected to the three-way valve 30. Further, the second piping 24 is not provided with a conversion means 14 to be described later in the pipeline.

  The second pipe 24 is also provided with a branch pipe 28. The branch pipe 28 is preferably provided at a position corresponding to the branch pipe 26 in the flow direction of the circulating gas. The branch pipe 28 is provided with an on-off valve 34. Note that the downstream side of the branch pipe 28 in the flow direction of the flow gas may be opened to the outside air, but if the flow gas contains a toxic component or the like, it is connected to a processing device for processing the flow gas. It is preferable to connect to the downstream of the measurement target pipe 8.

  The three-way valve 30 connects the downstream end of the first pipe 22, the downstream end of the second pipe 24, and the upstream end of the measuring means 16. The three-way valve 30 switches between a state in which the first pipe 22 and the measuring unit 16 are connected and a state in which the second pipe 24 and the measuring unit 16 are connected. In the three-way valve 30, when the first pipe 22 and the measuring unit 16 are connected, the flow gas that has passed through the first pipe 22 from the sampling pipe 20 flows to the measuring unit 16. Further, in the three-way valve 30, when the second pipe 24 and the measurement unit 16 are connected, the flow gas that has passed through the second pipe 24 from the sampling pipe 20 flows to the measurement unit 16. Thus, the three-way valve 30 switches the flow gas flowing through the measuring means 16.

  The pump 31 is disposed on the downstream side of the measuring means 16 in the flow direction of the circulating gas. The pump 31 sucks air in the direction in which the flow gas flows from the sampling pipe 20 toward the measuring means 16.

The conversion means 14 is a mechanism for converting hydrogen, which is one of the measurement target substances contained in the circulation gas, into H ₂ O (gaseous water, water vapor), and is disposed in the pipe line of the first pipe 22. . The conversion means 14 includes an oxidation catalyst 39 disposed in the pipe line of the first pipe 22 and a temperature adjusting unit 40 that controls the temperature of the region where the oxidation catalyst 39 is disposed. The oxidation catalyst 39 oxidizes hydrogen contained in the flowing gas that passes through it, that is, reacts hydrogen and oxygen to convert them into H ₂ O. As the oxidation catalyst 39, various catalysts that oxidize hydrogen can be used. Further, the oxidation catalyst 39 burns hydrocarbons according to the temperature and converts them into water (H ₂ O) and carbon dioxide (CO ₂ ). Here, as the oxidation catalyst 39, a general combustion catalyst containing platinum or the like can be used. The temperature adjustment unit 40 is a mechanism that adjusts the temperature of the oxidation catalyst 39 and includes an electric furnace, a blower, and the like. The temperature adjustment unit 40 performs heating and cooling so that the temperature in the vicinity of the oxidation catalyst 39, that is, the atmosphere in the reaction region becomes a predetermined temperature. The temperature adjustment unit 40 may be provided with only a heating mechanism when the oxidation catalyst 39 is naturally cooled, and may be provided with only a cooling mechanism when it is naturally heated.

The measuring means 16 is a measuring means for measuring the concentration of H ₂ O contained in the flowing gas flowing in the pipe line (flowed from the three-way valve 30), and flows the flowing gas through a predetermined pipe line and passes the laser beam. A measuring unit 42 for supplying the laser beam to the measuring unit 42 and calculating a measurement value (concentration) from the intensity of the received laser beam.

  The measurement unit 42 includes a measurement cell 45, an optical fiber 46, a light incident part 48, and a light receiving part 50.

  The measurement cell 45 basically includes a main pipe 52, an inflow pipe 54, and a discharge pipe 56. The main pipe 52 is a cylindrical member, and the flow gas flows inside. A window 58 is disposed at one end (upper surface) of the cylindrical shape of the main pipe 52, and a window 59 is disposed at the other end (lower surface). In other words, the main pipe 52 has a cylindrical upper and lower surfaces closed by the window 58 and the window 59, respectively. The windows 58 and 59 are made of a light transmitting member, such as transparent glass or resin. Thereby, the main pipe 52 is in a state in which both ends where the windows 58 and 59 are provided are in a state where no air flows and light can pass therethrough. That is, light can be incident from the outside of the main tube 52 to the inside, and light can be emitted from the inside of the main tube 52 to the outside.

  One end of the inflow pipe 54 is connected to the three-way valve 30, and the other end is connected to the window 58 side of the side surface (circumferential surface) of the main pipe 52. One end of the discharge pipe 56 is connected to the window 59 side of the side surface (circumferential surface) of the main pipe 52, and the other end is connected to a more downstream pipe (pipe on which the pump 31 is disposed). Has been. The measurement cell 45 supplies the flow gas supplied from the first pipe 22 or the second pipe 24 through the three-way valve 30 to the main pipe 52 from the inflow pipe 54. Further, the measurement cell 45 discharges the circulating gas flowing through the main pipe 52 from the discharge pipe 56 to the outside.

  Next, the optical fiber 46 guides the laser light output from the measuring means main body 44 to the light incident portion 48. That is, the laser light output from the measuring means main body 44 is incident on the light incident portion 48. The light incident portion 48 is an optical system (mirror, lens, etc.) disposed in the window 58 and makes the laser light guided by the optical fiber 46 enter the inside of the main tube 52 from the window 58.

  The light receiving unit 50 is a light receiving unit that receives the laser light that passes through the main pipe 52 of the measurement cell 45 and is output from the window 59. The light receiving unit 50 includes, for example, a photo detector such as a photodiode (PD), receives the laser beam by the photo detector, and detects the intensity of the light. The light receiving unit 50 sends the intensity of the received laser light as a light reception signal to the measuring means main body 44.

  Next, the measuring means main body 44 will be described with reference to FIGS. Here, FIG. 2 is a block diagram showing a schematic configuration of the measuring means main body of the gas calorific value measuring device shown in FIG. The measuring means body 44 includes a light emitting unit 62, a light source driver 64, and a calculating unit 66.

Emitting unit 62 includes a light emitting element for emitting a laser beam of near-infrared wavelength region H 2 _O absorbs a light emitting element for emitting a laser beam of near-infrared wavelength region H 2 _O absorbs, CO absorption A light emitting element that emits laser light in the near infrared wavelength region, a light emitting element that emits laser light in the near infrared wavelength region absorbed by CO ₂ , and a laser beam in the near infrared wavelength region that CH ₄ absorbs. A light emitting element that emits light. As the light emitting element, for example, a laser diode (LD) can be used. The light emitting unit 62 causes the light emitted from each light emitting element to enter the optical fiber 46.

  The light source driver 64 has a function of controlling the driving of the light emitting unit 62 and adjusts the wavelength and intensity of the laser light output from the light emitting unit 62 by adjusting the current and voltage supplied to the light emitting unit 62.

The calculation unit 66 calculates the concentration of each substance to be measured based on the intensity signal of each laser beam received by the light receiving unit 50 and the condition for driving the light source driver 64. Specifically, the calculation unit 66 calculates the intensity of the laser light output from the light emitting unit 62 and incident on the main tube 52 based on the conditions for driving the light source driver 64, and the laser received by the light receiving unit 50. Compared with the light intensity, the concentration of each substance to be measured contained in the flowing gas flowing through the main pipe 52, that is, the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ are calculated.

  The measuring means 16 is configured as described above, and laser light in the near-infrared wavelength region output from the light emitting unit 62 is a predetermined path from the optical fiber 46 to the measuring cell 45, specifically, a window 58, a main tube. 52, after passing through the window 59, reaches the light receiving unit 50. At this time, if the gas to be measured is contained in the flowing gas in the measurement cell 45, the laser light passing through the measurement cell 45 is absorbed. For this reason, the output of the laser light reaching the light receiving unit 50 varies depending on the concentration of the substance to be measured in the flowing gas. The light receiving unit 50 converts the received laser light into a light reception signal and outputs it to the calculation unit 66. Further, the light source driver 64 outputs the intensity of the laser beam output from the light emitting unit 62 to the calculating unit 66. The calculation unit 66 compares the intensity of the light output from the light emitting unit 62 with the intensity calculated from the light reception signal, and calculates the concentration of the substance to be measured of the flowing gas flowing in the measurement cell 45 from the decrease rate. . In this way, the measuring means 16 uses a so-called TDLAS method (Tunable Diode Laser Absorption Spectroscopy), and based on the intensity of the output laser light and the received light signal detected by the light receiving unit 50. The concentration of the substance to be measured in the circulating gas passing through the predetermined position, that is, the measurement position is calculated and / or measured. Moreover, the measurement means 16 can calculate and / or measure the concentration of the substance to be measured continuously.

  In the present embodiment, one set of the optical fiber 46, the light incident part 48, and the light receiving part 50 is provided and four laser beams are received by one light receiving part. However, the present invention is not limited to this. In the measuring means 16, the optical fiber 46, the light incident part 48, and the light receiving part 50 may be arranged corresponding to each of the light emitting elements. That is, when measuring the concentration of four substances as in the present embodiment, a set including a light emitting unit 62 (light emitting element thereof), an optical fiber 46, a light incident unit 48, and a light receiving unit 50 is formed. Four sets may be provided according to the substance to be measured.

  Here, the flow meter 36 is arranged on the upstream side of the conversion means 14 of the first pipe 22 and measures the flow rate of the flowing gas flowing through the first pipe 22. The flow meter 36 measures the flow rate of the flow gas before passing through the conversion means 14 (oxidation catalyst 39), that is, the flow gas before hydrogen is oxidized among the first flow gas flowing through the first pipe 22. . The flow meter 38 is disposed downstream of the conversion means 14 of the first pipe 22 and measures the flow rate of the flowing gas flowing through the first pipe 22. The flow meter 38 measures the flow rate of the flow gas that has passed through the conversion means 14 (oxidation catalyst 39), that is, the flow gas after hydrogen has been oxidized, among the first flow gas flowing through the first pipe 22. The flow meters 36 and 38 send the measured flow rate to the control means 18.

  The control unit 18 has a control function for controlling the operations of the piping unit 12, the conversion unit 14, the measurement unit 16, and the flow meters 36 and 38, and controls the operation of each unit as necessary. Specifically, the measurement conditions (driving conditions of the light source driver 64, the light receiving operation of the light receiving unit 50), the path selection operation of the three-way valve 30 of the piping unit 12, and the opening / closing operations of the on / off valves 32 and 34 are controlled. . Further, the control means 18 has a gas heating value calculation unit 68. The gas calorific value calculation unit 68 calculates the calorific value of the circulation gas based on the measurement results measured by the measuring means 16, the conditions set and detected by each unit, and the flow rates measured by the flow meters 36 and 38. / Or measure.

  Next, operation | movement of the gas calorific value measuring apparatus 10 is demonstrated. Here, FIG. 3 is a flowchart for explaining the operation of the gas calorific value measuring device. The control means 18 of the gas calorific value measuring device 10 drives the pump 31 and flows to the measurement target pipe 8 when an instruction to start measurement is input in a state where the flowing gas is flowing into the measurement target pipe 8. The flowing gas is sucked from the sampling pipe 20. At this time, the on-off valves 32 and 34 are preferably left open. The three-way valve 30 may be connected to any pipe line, but is connected to the measurement unit 42 and the pipe connected to the measurement unit 42 and the first pipe 22. It is preferable to alternately switch the connected pipe and the state where the second pipe 24 is connected.

  After that, when the circulating gas is flowing into the piping unit 12 and the circulating gas is filled in the piping unit 12, the control means 18 uses the three-way valve 30 to connect the first piping 22 and the measuring unit 42 as step S12. The flow gas that is connected and flows through the first pipe 22, that is, the flow gas that has passed through the conversion means 14 (flow gas converted from hydrogen, hereinafter also referred to as “first flow gas”) flows into the measurement unit 42. . At this time, the on-off valve 32 is in a closed state, and the flow gas flowing through the first pipe 22 is in a state where the entire amount is supplied to the measurement unit 42. Moreover, the on-off valve 34 may be in any state of opening and closing. The flow meters 36 and 38 measure the flow rate of the first flow gas flowing through the measurement position of the first pipe 22.

When the first circulation gas is in a state of flowing through the measurement cell 45, the control means 18 performs H ₂ O contained in the first circulation gas flowing in the main pipe 52 of the measurement cell 45 of the measurement unit 42 by the measurement means 16 as step S 14. Concentration, CH ₄ concentration, CO concentration, CO ₂ concentration (hereinafter also referred to as “first measurement value”). Thereby, the conversion means 14 can measure the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ contained in the first flow gas. Note that the first flow gas includes H ₂ O obtained by converting (oxidizing) hydrogen to be measured by the conversion means 14 and H ₂ O (coexistence gas) contained before oxidation. Thus, H _{2 O} concentration in the first measurement value, the hydrogen of H _{2 O} oxidized in the oxidation catalyst 39 to be measured (H _{2 O} derived from hydrogen to be measured contained in the flowing gas), before oxidation The total concentration of H ₂ O (coexisting gas) contained in the gas is measured.

  After measuring the concentration of the first flow gas, the control means 18 connects the second pipe 24 and the measurement unit 42 by the three-way valve 30 and connects the flow gas flowing through the second pipe 24 (converting hydrogen) as step S16. No flow gas (hereinafter also referred to as “second flow gas”) flows into the measurement unit 42. At this time, the on-off valve 34 is in a closed state, and the flow gas flowing through the second pipe 24 is in a state where the entire amount is supplied to the measurement unit 42. The on-off valve 32 may be in any state of opening and closing.

When the second flowing gas is in a state of flowing through the measurement cell 45, the control unit 18, as step S < _b > 18, includes H ₂ O contained in the second flowing gas flowing in the main pipe 52 of the measurement cell 45 of the measurement unit 42 by the measuring unit 16. Concentration, CH ₄ concentration, CO concentration, CO ₂ concentration (hereinafter also referred to as “second measurement value”). Thereby, the conversion means 14 can measure the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ contained in the second circulation gas. The second circulating gas contains H ₂ O (coexistence gas) that has been contained before oxidation. Therefore, the second measurement, the concentration of H _{2 O} contained before oxidation (coexisting gas) is measured.

After measuring the concentration of each substance in the second flow gas, the control means 18 calculates the heat generation amount of the flow gas by the gas heat generation amount calculation unit 68 in step S20. Specifically, first, the gas calorific value calculation unit 68, the concentration of of H _{2 O} first measurement value measured in step S14, the difference between the second measured value of H _{2 O} concentration measured in step S18 The concentration of hydrogen contained in the circulation gas is calculated. That is, by subtracting the concentration of the coexisting gas from the total concentration of H ₂ O derived from the measurement target hydrogen contained in the flow gas and the coexistence gas, the H ₂ O derived from the hydrogen contained in the flow gas is subtracted. The concentration can be calculated. The gas heating value calculation unit 68 measures the concentration of hydrogen contained in the circulation gas based on the concentration of H ₂ O derived from hydrogen contained in the circulation gas. Furthermore, the control means 18 determines the relationship between the flow rate of the H ₂ O derived from hydrogen contained in the flow gas and the flow gas based on the information supplied from the flow meters 36, 38, etc. By adding (correcting) the increase / decrease of each component in the reaction process, the concentration of hydrogen to be measured contained in the flow gas can be calculated.

Next, the gas calorific value calculation unit 68 measures the concentration of CH ₄ contained in the flow gas based on the first measurement value and the second measurement value. Incidentally, CH _4, since not changed on passing through the converting means 14, basically, the concentration of CH ₄ calculated by the first measurement value is the concentration of CH _4. Next, the gas calorific value calculation unit 68 measures the concentration of CO contained in the circulation gas based on the first measurement value and the second measurement value. The CO concentration is basically the CO concentration calculated by the first measurement value.

Thereafter, the gas calorific value calculation unit 68 measures a component that generates heat by combustion among substances contained in the circulation gas, based on the calculated H ₂ concentration, the calculated CO concentration, and the CH ₄ concentration. The calorific value is calculated based on the measurement result. Here, the calorific value of the circulation gas can be calculated by a flow rate × (H ₂ concentration × 3.026 kcal / L + CO concentration × 3.018 kcal / L + CH ₄ concentration × 9,465 kcal / L). When the control means 18 calculates the calorific value of the circulation gas, this process is terminated. The control means 18 may continuously measure the heat generation amount of the circulation gas by repeating the above process. Here, in this embodiment, the calorific value can be measured without using the measurement result of the CO ₂ concentration. In this case as well, the concentration of each substance may be corrected using the measurement result of the CO ₂ concentration.

As described above, the gas calorific value measurement device 10 measures the concentration of H ₂ O contained in the first flow gas obtained by oxidizing the measurement target hydrogen by the conversion means 14 by the measurement means 16, and further measures the hydrogen to be measured. The concentration of hydrogen to be measured can be calculated by measuring the concentration of H ₂ O contained in the second flow gas that is not oxidized by the measuring means 16 and taking the difference. Further, by measuring the concentration of CH ₄ (methane), the combustion component contained in the circulation gas can be measured, and the calorific value of the circulation gas can be measured based on the measurement result.

Moreover, the gas calorific value measuring device 10 irradiates a laser beam in the near-infrared wavelength region of the absorption wavelength region of H ₂ O converted from hydrogen as the measuring means 16 and detects the intensity absorbed by the H ₂ O. Thus, the hydrogen concentration can be measured in a short time and with high accuracy. In addition to hydrogen, the concentration of various combustion components can be measured in a short time and with high accuracy. As described above, since each concentration component can be measured with high accuracy, the calorific value of the circulation gas can be measured with high accuracy.

  Further, the concentration of hydrogen having no absorption wavelength in the near-infrared wavelength region can be measured using the semiconductor laser absorption spectroscopy shown in the measuring means 16 by oxidizing the measurement target hydrogen and measuring it as an oxide. It becomes possible. In addition, as in the present embodiment, measurement using light having a wavelength in the near-infrared region of the substance to be measured can be performed with high accuracy.

  Furthermore, in measurement using laser light in the near-infrared wavelength region, the concentration of the measurement target can be measured appropriately even when components other than the measurement target are mixed. That is, it is possible to make it difficult for components other than the measurement target to become noise. Thereby, a filter and a dehumidification process can be eliminated or reduced, and the time from when the flow gas is sucked from the measurement target pipe 8 to when the measurement is performed and the measurement result is calculated can be shortened. it can. That is, the measurement time delay can be reduced. Thereby, responsiveness can be made high.

Further, the gas calorific value measuring device 10 calculates the flow rate before and after the conversion means 14, and corrects the influence of the change in mass balance due to the oxidation reaction and the change in the number of moles based on the change in the flow rate. The calorific value of the gas can be calculated more appropriately. Note that, since the hydrogen concentration can be corrected more appropriately, it is preferable to measure a change in the flow rate before and after the conversion unit 14 as in the present embodiment, but the present invention is not limited to this, and correction is not performed. It may be. Further, the amount of change in the flow rate may be estimated from the relationship between the first measurement value and the second measurement value, and correction may be performed based on the estimated value. In the above-described embodiment, the concentration correction, specifically the H ₂ O concentration correction, and the H ₂ concentration correction are performed based on the flow rate. However, the CH ₄ concentration and the measured value are used to determine the concentration. May be corrected. That is, the density can also be corrected by using CH ₄ whose amount does not change by passing through the conversion means 14.

  Further, by providing the pump 31, the flow gas flowing through the measurement target pipe 8 can be appropriately sucked from the sampling pipe 20. Although the pump 31 is preferably provided, the pump 31 is provided when a flow gas of a certain flow rate or more flows through the pipe unit 12 due to the configuration of the pipe unit 12 or the pressure of the flow gas flowing through the measurement target pipe 8. It does not have to be.

In the above embodiment, the calorific value of the circulation gas is measured only from the methane concentration, the carbon monoxide concentration, and the hydrogen concentration, but the present invention is not limited to this. The gas calorific value measuring device 10 measures hydrocarbon components other than methane (CH ₄ ) using the measurement results of the H ₂ O concentration, CH ₄ concentration, CO concentration, and CO ₂ concentration, It is preferable to measure the calorific value of the circulation gas also using the measurement result. Here, when the distribution gas contains hydrocarbons other than CH ₄ , hydrocarbons other than methane (CH ₄ ) react with oxygen (O ₂ ) by the conversion means 14 and are converted into carbon dioxide and water. ing. Note that hydrocarbons other than methane (CH ₄ ) can be reacted (combusted) at a temperature higher than that of methane.

Here, FIGS. 4A and 4B are graphs for explaining the substance conversion operation by the conversion unit. Fig. 4-1 is a graph showing the relationship between the temperature of CH ₄ and the conversion rate (ratio of carbon dioxide and water), and Fig. 4-2 shows the relationship between the temperature of various substances and the conversion rate. It is a graph to show. As shown in FIG. 4A, the reaction of methane starts when the catalyst temperature is about 250 ° C. or higher. In contrast, as shown in FIG. 4B, hydrogen reacts at 50 ° C. or lower. Carbon monoxide and methyl alcohol react at 100 ° C. or lower, and ethylene also reacts at 200 ° C. or lower. Thus, the concentration of of _{H 2} O first flowing gas, the concentration of CH _4, the concentration of CO, and the concentration of CO _2, the concentration of of _{H 2} O second flowing gas, the concentration of CH _4, the concentration of CO, CO by comparing the change in concentration of each substance between the _second concentration, it can also be calculated percentage of reacted hydrocarbon. As a result, the calorific value of the circulating gas can be calculated in consideration of hydrocarbons other than methane, and the calorific value of the circulating gas can be calculated with higher accuracy.

For this reason, it is preferable that the temperature adjustment part 40 sets the temperature in the atmosphere of the oxidation catalyst 39, that is, the temperature in the reaction region of the flowing gas to 100 ° C. or more and 200 ° C. or less. Thereby, hydrogen, carbon monoxide, and hydrocarbon can be reacted without reacting methane. Accordingly, the concentration of each combustion component can be appropriately measured using the measurement results of the H ₂ O concentration, the CH ₄ concentration, the CO concentration, and the CO ₂ concentration, and the calorific value of the circulation gas is suitable. Can be calculated. Here, the calorific value of the circulating gas can be calculated by a flow rate × (H ₂ concentration × 3.026 kcal / L + CO concentration × 3.018 kcal / L + CH ₄ concentration × 9,465 kcal / L + hydrocarbon calorific value).

The measuring means 16 preferably further measures the O ₂ concentration. In this case, the light emitting unit includes a light emitting element that emits laser light in the near-infrared wavelength region that is absorbed by O ₂ , and the light receiving unit receives the laser light incident on the measurement cell, so that the first distribution is achieved. The concentration of O ₂ in each of the gas and the second circulation gas can be measured. Further, the concentration can be corrected based on the detection result of the flow meter and the like as described above. By measuring the concentration of O ₂ in addition to the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, the concentration of CO ₂ , C and H between the first circulation gas and the second circulation gas Changes in the mass balance of O can be measured. Thereby, the structure of the hydrocarbon can be calculated with higher accuracy, and the calorific value of the circulation gas can be calculated with higher accuracy.

In addition to the difference between the H ₂ O concentration of the first measurement value and the H ₂ O concentration of the second measurement value, the hydrogen concentration also takes into account the concentration of H ₂ O generated by the hydrocarbon reaction. It is preferable. That is, the concentration of of H _{2 O} first measurement value, from the difference between the of H _{2 O} concentration in the second measurement value, further pulling the concentration of H _{2 O} produced by the reaction of hydrocarbons (except for ) It is preferable to calculate. Thereby, the concentration of hydrogen can be calculated more accurately.

  Here, the gas calorific value measuring device is not limited to the above embodiment, and can be various embodiments. Hereinafter, other embodiments will be described with reference to FIGS. 5 to 16.

[Embodiment 2]
FIG. 5 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. The gas calorific value measuring device 100 shown in FIG. 5 includes a piping unit 112, a conversion unit 14, a measuring unit 116, a control unit 118, and flow meters 36 and 38. Here, the gas calorific value measurement device 100 is provided with two measurement units, and the measurement units are arranged in the first pipe 122 and the second pipe 124, respectively. The conversion means 14 and the flow meters 36 and 38 have the same configuration as the conversion means 14 and the flow meters 36 and 38 shown in FIG. In the present embodiment, the pump 31 is not provided, but may be provided. The pump 31 is the same in any of the following embodiments. Moreover, in the following embodiment, although the dotted line which shows the connection of a control means and a control object is partially omitted, it is connected with each part.

  The piping unit 112 includes a sampling piping 20, a first piping 122, and a second piping 124. Since the sampling pipe 20 has the same configuration as each part of the pipe unit 12, the description thereof is omitted.

  The first pipe 122 has one end connected to the sampling pipe 20 and the other end connected to the first measurement unit 130 of the measuring means 116. Moreover, the conversion means 14 mentioned later is arrange | positioned in the 1st piping 122 in the pipe line. Moreover, the area | region where the conversion means 14 of the 1st piping 122 is arrange | positioned has the diameter of the pipe line larger than another area | region.

  The second pipe 124 is basically a pipe formed in parallel with the first pipe 122, one end is connected to the sampling pipe 20, and the other end is connected to the second measurement unit 132 of the measuring means 116. It is connected. Further, the second piping 124 is not provided with a conversion means 14 to be described later in the pipeline. Thus, the piping unit 112 is not provided with a three-way valve that connects the other end of the first piping 122 and the other end of the second piping 124, and is connected to separate measurement units. .

  The measuring unit 116 includes a first measuring unit 130, a second measuring unit 132, and measuring unit main bodies 134 and 136. The first measurement unit 130 is connected to the other end of the first pipe 122 and supplied with a flow gas flowing through the first pipe 122, that is, a flow gas (first flow gas) that has passed through the conversion means 14. Is done. In addition, since the structure of each part of the 1st measurement unit 130 is the same as that of the measurement unit 42 mentioned above, detailed description is abbreviate | omitted.

  The second measurement unit 132 is connected to the other end of the second pipe 124, and the flow gas flowing through the second pipe 124, that is, the flow gas not passing through the conversion means 14 (second flow gas). Is supplied. In addition, since the structure of each part of the 2nd measurement unit 132 is the same as that of the measurement unit 42 mentioned above, detailed description is abbreviate | omitted.

  The measurement means main body 134 has basically the same configuration as the measurement means main body 44, outputs laser light to the first measurement unit 130, and receives a light reception signal from the first measurement unit 130. The measuring means main body 136 has basically the same configuration as the measuring means main body 44, outputs a laser beam to the second measuring unit 132, and receives a light reception signal from the second measuring unit 132.

Based on the intensity of the laser beam output to the first measurement unit 130 and the received light signal sent from the first measurement unit 130, the measurement means main body 134 has a concentration of H ₂ O and a concentration of CH ₄ contained in the first flow gas. , CO concentration and CO ₂ concentration are measured. Further, the measuring means main body 136 determines the concentration of H ₂ O contained in the second flow gas, CH ₄ based on the intensity of the laser beam output to the second measuring unit 132 and the received light signal sent from the second measuring unit 132. Concentration, CO concentration, and CO ₂ concentration are measured. The measuring means main bodies 134 and 136 send the measurement results to the control means 118, respectively.

  The control means 118 controls the operation of each part of the piping unit 112, the conversion means 14, and the measurement means 116, similarly to the control means 18. Further, the control means 118 has a gas heat generation amount calculation unit 68, and the gas heat generation amount calculation unit 68 measures (calculates) the heat generation amount of the circulation gas based on the measurement result sent from the measurement unit 116. The calculation method is the same as the calculation method of the control means 18 described above.

The gas calorific value measuring device 100 can measure the calorific value of the circulation gas with the above configuration. Similarly to the gas calorific value measuring apparatus 10 described above, a so-called TDLAS type measuring means is used as the measuring means, and the concentration (H ₂ O) of oxide obtained by oxidizing hydrogen is measured by the measuring means. Thus, the same effect as described above can be obtained.

The gas calorific value measurement device 100 can measure the first flow gas and the second flow gas separately by providing two measurement units, the first measurement unit 130 and the second measurement unit 132. As a result, the concentration of the substance to be measured (concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, the concentration of CO ₂ , etc.) contained in the first circulation gas and the measurement object contained in the second circulation gas The substance concentration can be measured simultaneously. Thereby, it becomes unnecessary to switch the flow path, and the concentration of the substance to be measured contained in the circulation gas can be measured more continuously. Thereby, the calorific value of circulation gas can also be measured continuously. Moreover, since measurement can be performed without switching the flow path, the responsiveness of measurement can be further increased.

  In addition, the gas calorific value measurement device 100 also obtains various effects by increasing or decreasing the gas to be measured or changing the calculation method, similarly to the gas calorific value measurement device 10. Can do. The gas calorific value measuring device 100 may also correct the hydrogen concentration and the like based on the measurement results of the flow meter 36 and the flow meter 38 in the same manner as described above. Similar to the gas calorific value measurement device 10, various effects can be obtained by increasing or decreasing the gas to be measured or changing the calculation method. The form is also the same.

[Embodiment 3]
FIG. 6 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. The gas calorific value measuring device 200 shown in FIG. 6 includes a piping unit 212, conversion means 14, measuring means 216, control means 218, and flow meters 224 and 226. Here, in the gas calorific value measuring device 200, the piping unit is provided by one piping, and two measuring units are provided. The conversion unit 14 has the same configuration as the conversion unit 14 shown in FIG.

  The piping unit 212 includes a sampling piping 220, a piping 222, and a flow meter 224. The sampling pipe 220 is a pipe that is connected to the measurement target pipe 8 and collects a part of the circulating gas flowing through the measurement target pipe 8, and has one end disposed inside the measurement target pipe 8 and the other side. Is connected to the upstream measuring unit 230 of the measuring means 216.

  One end of the pipe 222 is connected to the upstream measurement unit 230, and the other end is connected to the downstream measurement unit 232 of the measurement unit 216. The piping 222 is provided with a conversion means 14 to be described later in the pipeline. Moreover, the area | region where the conversion means 14 of the piping 222 is arrange | positioned has the diameter of the pipe line larger than another area | region.

  The measurement means 216 includes an upstream measurement unit 230, a downstream measurement unit 232, and measurement means main bodies 234 and 236. The upstream measurement unit 230 has an upstream end connected to the other end of the sampling pipe 220 and a downstream end connected to one end (upstream end) of the pipe 222. The flow gas (second flow gas) before flowing through the sampling pipe 220 and passing through the conversion means 14 is supplied. The upstream measurement unit 230 is the same as the measurement unit 42 described above, and a detailed description thereof will be omitted.

  The downstream measurement unit 232 has an upstream end connected to one end (downstream end) of the pipe 222, and a downstream end connected to a further downstream pipe (exhaust pipe or the like). The flow gas (first flow gas) that has flowed through the pipe 222 and passed through the conversion means 14 is supplied. The downstream measurement unit 232 is also the same as the measurement unit 42 described above, and a detailed description thereof will be omitted.

  The measuring means main body 234 basically has the same configuration as the measuring means main body 44, outputs a laser beam to the upstream measuring unit 230, and receives a light reception signal from the upstream measuring unit 230. The measuring means body 236 basically has the same configuration as the measuring means body 44, outputs a laser beam to the downstream measuring unit 232, and receives a light reception signal from the downstream measuring unit 232.

The measuring means main body 236 measures the concentration of H ₂ O contained in the first flow gas based on the intensity of the laser beam output to the downstream measuring unit 232 and the received light signal sent from the downstream measuring unit 232. Further, the measuring means main body 234 measures the concentration of H ₂ O contained in the second flow gas based on the intensity of the laser beam output to the upstream measuring unit 230 and the received light signal sent from the upstream measuring unit 230. . The measuring means main bodies 234 and 236 send the measurement results to the control means 218.

  The flow meter 224 is arranged on the path of the sampling pipe 220 and measures the flow rate of the flow gas flowing through the sampling pipe 220, that is, the flow rate of the flow gas (second flow gas) before passing through the conversion means 14. . The flow meter 226 is disposed between the conversion unit 14 of the pipe 222 and the downstream measurement unit 232, and measures the flow rate of the flow gas (first flow gas) after passing through the conversion unit 14.

  The control unit 218 controls the operation of each part of the piping unit 212, the conversion unit 14, and the measurement unit 216, similarly to the control unit 18. Further, the control means 218 has a gas heating value calculation unit 68, and the gas heating value calculation unit 68 measures the concentration of hydrogen to be measured contained in the circulation gas based on the measurement result sent from the measurement means 216. (Calculate) and measure the calorific value of the circulating gas. The calculation method is the same as the calculation method of the control means 18 described above.

  The gas calorific value measuring device 200 has the above-described configuration, and the measurement unit included in the circulation gas can be provided by providing measurement units on the upstream side and the downstream side of the region where the oxidation catalyst 39 is disposed. The concentration of hydrogen can be measured. Similar to the gas calorific value measuring apparatus 10 described above, the so-called TDLAS type measuring means is used as the measuring means, and the same effect as described above is obtained by using an oxide obtained by oxidizing the hydrogen to be measured. be able to.

  The gas calorific value measuring device 200 is provided with two measuring units 230 and 232 on the upstream side and the downstream side of the region where the oxidation catalyst is arranged, so that two pipes for guiding the circulation gas are provided. The first circulation gas and the second circulation gas can be measured separately without separating them into one. Also in this case, the concentration of the substance to be measured contained in the first circulation gas and the concentration of the substance to be measured contained in the second circulation gas can be measured simultaneously. Thereby, it becomes unnecessary to switch the flow path, and the calorific value of the circulation gas can be measured more continuously. Moreover, since measurement can be performed without switching the flow path, the responsiveness of measurement can be further increased. Further, the gas to be measured can be the same circulating gas. That is, the downstream measurement unit 232 can measure the flow gas measured by the upstream measurement unit 230 after being oxidized. Further, the flow meter 224 and the flow meter 226 are used to balance the number of moles of the circulation gas (second circulation gas) before passing through the conversion means 14 and the circulation gas (first circulation gas) after passing through the conversion means 14. Changes can be detected. Thereby, the calculated value of the concentration of hydrogen in the flow gas can be corrected from the calculated number of moles, and a more accurate calorific value can be measured.

[Embodiment 4]
FIG. 7 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. 7 includes a piping unit 312, a conversion unit 14, a measurement unit 316, a control unit 318, and flow meters 322 and 324. Here, the gas calorific value measuring device 300 is the same as the gas calorific value measuring device 200 except for the configuration of the piping unit 312 and the arrangement position and configuration of the measuring unit. Moreover, since the conversion means 14 is the structure similar to the conversion means 14 shown in FIG. 1, description is abbreviate | omitted.

  The piping unit 312 has a sampling piping 320 and a flow meter 322. The sampling pipe 320 is a pipe that is connected to the measurement target pipe and collects a part of the circulating gas flowing through the measurement target pipe 8, and has one end arranged inside the measurement target pipe and the other end. The portion is connected to a downstream pipe (exhaust pipe). A flow meter 322 for measuring the flow rate of the flowing gas flowing through the sampling pipe 320 is disposed on the path of the sampling pipe 320. In the sampling pipe 320, the conversion means 14 is disposed in the pipe line. Moreover, the area | region where the conversion means 14 of the sampling piping 320 is arrange | positioned has the diameter of the pipe line larger than another area | region. That is, the piping unit of the present embodiment is composed of a single pipe.

  The measurement means 316 includes an upstream measurement unit 330, a downstream measurement unit 332, and measurement means main bodies 334 and 336. The upstream measurement unit 330 is provided on the upstream side of the arrangement position of the conversion means 14 of the sampling pipe 320, and flows through the sampling pipe 320 and passes through the conversion means 14 (second flow gas) before passing through the conversion means 14. Measure the concentration of the substance to be measured. The upstream measurement unit 330 measures the gas concentration by causing the laser light, which is measurement light, to enter the sampling pipe 320 and receiving the laser light that has passed through the sampling pipe 320.

  The upstream measurement unit 330 includes an incident tube 342a, an output tube 344a, windows 346a and 348a, an optical fiber 350a, a light incident portion 352a, and a light receiving portion 354a.

  The incident tube 342a is a tubular member, and one end thereof is connected to the sampling pipe 320. Further, in the sampling pipe 320, the connection portion with the incident tube 342a is an opening having substantially the same shape as the opening (end opening) of the incident tube 342a. That is, the incident tube 342a is connected to the sampling pipe 320 in a state where air can flow. A window 346a is provided at the other end of the incident tube 342a and is sealed by the window 346a. The window 346a is made of a light transmitting member such as transparent glass or resin. As a result, the incident tube 342a is in a state in which the end portion where the window 346a is provided is in a state in which no air flows and light can pass therethrough.

  As shown in FIG. 7, the incident tube 342a has an area of an opening at the end of the window 346a (that is, an opening closed by the window 346a) and an end of the sampling pipe 320 (that is, the sampling pipe 320). And the area of the opening of the portion connected to the cylindrical shape is substantially the same. Note that the shape of the incident tube 342a is not limited to a cylindrical shape, and may be any cylindrical shape as long as it allows air and light to pass therethrough. For example, the cross section may be a square, a polygon, an ellipse, or an asymmetric curved surface. Moreover, the shape of the cross section of a cylindrical shape and the shape where a diameter changes with positions may be sufficient.

  The exit tube 344a is a tubular member having substantially the same shape as the entrance tube 342a. One end of the exit tube 344a is connected to the sampling pipe 320, and a window 348a is provided at the other end of the exit tube 344a. The exit tube 344a is also in a state where air can flow through the sampling pipe 320, and an end portion where the window 348a is provided is in a state where air does not flow and light can pass therethrough. In addition, the exit tube 344a is disposed at a position where the central axis is substantially the same as the central axis of the incident tube 342a. That is, the entrance tube 342a and the exit tube 344a are disposed at positions where the sampling tube 320 is opposed to each other.

  The exit tube 344a is also connected to the area of the opening at the end on the window 348a side (that is, the opening closed by the window 348a) and the end on the sampling pipe 320 side (that is, the sampling pipe 320). The area of the partial opening) is substantially the same cylindrical shape. Note that the shape of the emission tube 344a is not limited to a cylindrical shape, and may be any shape as long as it has a cylindrical shape that allows air and light to pass therethrough. For example, the cross section may be a square, a polygon, an ellipse, or an asymmetric curved surface. Moreover, the shape of the cross section of a cylindrical shape and the shape where a diameter changes with positions may be sufficient.

  Next, the optical fiber 350a guides the laser beam output from the measuring means main body 334 to the light incident portion 352a. That is, the laser beam output from the measuring means main body 334 is incident on the light incident portion 352a. The light incident part 352a is an optical system (mirror, lens, etc.) disposed in the window 346a, and makes the laser light guided by the optical fiber 350a enter the inside of the incident tube 342a from the window 346a. The laser light incident on the incident tube 342a passes through the sampling pipe 320 from the incident tube 342a and reaches the output tube 344a.

  The light receiving unit 354a is a light receiving unit that receives the laser light that passes through the sampling pipe 320 and is output from the window 348a. The light receiving unit 354a sends the intensity of the received laser light as a light reception signal to the measuring means main body 334.

  The upstream side measurement unit 330 passes the laser light supplied from the measurement means main body 334 to the optical fiber 350a through the light incident part 352a, the window 346a, the incident pipe 342a, the sampling pipe 320, the output pipe 344a, and the window 348a. It enters the light receiving part 354a. Thereby, the upstream measurement unit 330 can detect the output of the laser beam that has passed through the region where the flow gas (second flow gas) before passing through the conversion means 14 flows. Thereby, the upstream side measurement unit 330 can measure the second measurement value in the same manner as the upstream side measurement unit 230.

The downstream side measurement unit 332 is provided on the downstream side of the arrangement position of the conversion means 14 of the sampling pipe 320, and flows through the sampling pipe 320 and passes through the conversion means 14 (first flow gas). The concentration of H ₂ O is measured. The downstream measurement unit 332 also measures the gas concentration by causing the laser light, which is measurement light, to enter the sampling pipe 320 and receiving the laser light that has passed through the sampling pipe 320. The downstream measurement unit 332 includes an incident tube 342b, an emission tube 344b, windows 346b and 348b, an optical fiber 350b, a light incident portion 352b, and a light receiving portion 354b. The downstream measurement unit 332 is the same as the upstream measurement unit 232 except for the arrangement position of the measurement unit, and a description thereof will be omitted.

  The downstream measurement unit 332 receives the laser light supplied from the measurement means main body 334 to the optical fiber 350b through the incident portion 352b, the window 346b, the incident tube 342b, the sampling pipe 320, the emission pipe 344b, and the window 348b. Incident on the portion 354b. As a result, the downstream measurement unit 332 can detect the output of the laser beam that has passed through the region where the flow gas (first flow gas) that has passed through the conversion means 14 flows. As a result, the upstream measurement unit 330 can measure the first measurement value in the same manner as the downstream measurement unit 232.

  The measuring means main body 334 basically has the same configuration as the measuring means main body 44, outputs a laser beam to the upstream measuring unit 330, and receives a light reception signal from the upstream measuring unit 330. The measuring means main body 336 basically has the same configuration as the measuring means main body 44, outputs a laser beam to the downstream measuring unit 332, and receives a light reception signal from the downstream measuring unit 332.

  The measuring means main body 336 measures the concentration of the substance to be measured contained in the first flow gas based on the intensity of the laser beam output to the downstream measuring unit 332 and the light reception signal sent from the downstream measuring unit 332. Further, the measuring means main body 334 measures the concentration of the substance to be measured included in the second circulation gas based on the intensity of the laser beam output to the upstream measuring unit 330 and the light reception signal sent from the upstream measuring unit 330. To do. The measuring means main bodies 334 and 336 send the measurement results to the control means 318.

  Further, the flow meter 322 is disposed between the upstream measurement unit 330 and the conversion means 14 on the path of the sampling pipe 320, and the flow rate of the flow gas (second flow gas) before passing through the conversion means 14 is measured. measure. The flow meter 324 is disposed between the conversion unit 14 and the downstream measurement unit 332 on the path of the sampling pipe 320, and measures the flow rate of the flow gas (first flow gas) after passing through the conversion unit 14. To do. The flow meter 332 and the flow meter 334 send the flow rate measurement result to the control means 318.

  Similar to the control means 18, the control means 318 controls the operation of each part of the piping unit 312, the conversion means 14, the measurement means 316, and the flow meters 322 and 324. The control unit 318 includes a gas heat generation amount calculation unit 68, and the gas heat generation amount calculation unit 68 measures (calculates) the heat generation amount of the flow gas based on the measurement result sent from the measurement unit 316. The calculation method is the same as the calculation method of the control means 18 described above.

The gas calorific value measuring device 300 can be used as a circulating gas by providing measuring units on the upstream side and the downstream side of the region where the conversion means 14 (oxidation catalyst 39) is arranged. The concentration of hydrogen to be measured can be measured. Similarly to the gas calorific value measuring apparatus 10 described above, a so-called TDLAS type measuring means is used as the measuring means, and the concentration of H ₂ O in the circulating gas is measured by the measuring means, as described above. The effect of can be obtained. Further, the gas calorific value measurement device 300 can also correct the calculated value of the calorific value of the flow gas based on the measurement results of the flow meters 322 and 324, and can calculate with higher accuracy.

  In addition, the gas calorific value measurement device 300 also guides the circulation gas by providing two measurement units 330 and 332 on the upstream side and the downstream side of the region where the oxidation catalyst 39 is disposed. The first circulation gas and the second circulation gas can be separately measured without separating the pipe into two. Also in this case, the concentration of the substance to be measured contained in the first circulation gas and the concentration of the substance to be measured contained in the second circulation gas can be measured simultaneously. Thereby, it becomes unnecessary to switch the flow path, and the concentration of the substance to be measured contained in the circulation gas can be measured more continuously. Thereby, the emitted-heat amount of distribution | circulation gas can be measured continuously. Moreover, since measurement can be performed without switching the flow path, the responsiveness of measurement can be further increased. Further, the gas to be measured can be the same circulating gas. That is, after the flow gas measured by the upstream measurement unit 330 is converted (oxidized) into a predetermined substance, it can be measured by the downstream measurement unit 332.

  Furthermore, the gas calorific value measuring device 300 can directly measure the flow gas flowing through the sampling pipe 320. Thereby, it can install only by forming opening in the sampling piping 320, without providing a measurement cell. Moreover, although the said embodiment demonstrated as the case where it provided in the sampling piping 320, it is not limited to this, It can also be earth | grounded directly to measurement object piping. Even when the measurement target pipe is directly provided, since a dedicated measurement cell is not required, measurement can be performed without changing the flow rate and flow velocity of the flowing gas flowing through the measurement target pipe.

  Moreover, in the said embodiment, although the incident tube and the output tube were provided coaxially, it is not limited to this. For example, an optical mirror may be provided in the sampling pipe, and the laser beam incident from the window of the incident tube may be multiple-reflected by the optical mirror in the measurement cell and then reach the window of the emission tube. In this manner, multiple reflections of the laser light can pass through more regions in the sampling pipe. As a result, the influence of the distribution of the distribution gas concentration flowing in the sampling pipe (variation in flow rate and density of the distribution gas, variation in concentration distribution in the distribution gas) can be reduced, and the concentration can be accurately detected. it can.

  In the above embodiment, the incident tube and the output tube are directly provided in the sampling pipe. However, the incident tube and the output tube are installed in a tube having the same diameter as that of the sampling pipe, and the tube is inserted into a part of the sampling pipe. Anyway. That is, a part of the sampling pipe may be cut, and a pipe provided with an incident pipe and an outgoing pipe may be fitted into the cut portion.

[Embodiment 5]
FIG. 8 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. Here, the gas calorific value measuring device 400 is basically the same as the gas calorific value measuring device 200 except for the point that the oxidant supply means 450 is provided. Therefore, the same components as those of the gas calorific value measuring device 200 are denoted by the same reference numerals, description thereof is omitted, and points unique to the gas calorific value measuring device 400 will be described. Here, the gas calorific value measurement device 400 shown in FIG. 8 includes a piping unit 212, a conversion unit 14, a measurement unit 216, flow meters 224 and 226, a control unit 418, and an oxidant supply unit 450. . The piping unit 212, the conversion unit 14, the measurement unit 216, and the flow meters 224 and 226 have the same configuration as each unit of the gas calorific value measurement device 200 shown in FIG.

The oxidant supply unit 450 is disposed downstream of the measurement unit 230 of the pipe 222 and upstream of the conversion unit 14 in the flow direction of the circulating gas. That is, in the oxidant supply means 450, the measurement of the concentration is finished, and the flow gas (second flow gas) before the oxidation process (the process of reacting hydrogen and oxygen to make H ₂ O) is performed. Connected to piping. The oxidant supply unit 450 includes a pipe 452, an oxidant supply device 454, and a flow meter 456. One end of the pipe 452 is connected to the upstream side of the conversion means 14 of the pipe 222, and the other end is connected to the oxidant supply device 454. The oxidant supply device 454 is a device that inputs oxidant (O ₂ , O _3, etc.) to the pipe 222 through the pipe 452. The oxidant supply device 454 has a storage mechanism that stores the oxidant and a charging mechanism that inputs the stored oxidant to the pipe 452. In addition, as an injection | throwing-in mechanism, the mechanism in which an oxidizing agent is conveyed by air, for example, a fan (blower) can be used. The flow meter 456 is a measuring instrument that measures the flow rate of air flowing through the pipe 452, measures the amount of air that is input from the oxidizer supply device 454 to the pipe 222, and sends the measurement result to the control means 418.

  The control unit 418 controls the operation of each part of the piping unit 212, the conversion unit 14, the measurement unit 216, and the flow meters 224 and 226. The control means 418 also has a gas heating value calculation unit 68, similar to the control means 18, and the gas heating value calculation unit 68 uses the measurement result sent from the measurement means 216 to measure the distribution gas. Measure (calculate) the concentration of the target substance and measure the calorific value of the circulating gas. The calculation method is the same as the calculation method of the control means 18 described above. Further, the control means 418 controls the amount of oxidant that is introduced from the oxidant supply means 450 into the pipe 222.

  The gas calorific value measuring device 400 has the above-described configuration, and even if the measurement unit is provided on each of the upstream side and the downstream side of the region where the conversion means 14 (oxidation catalyst 39) is disposed, The calorific value can be measured. Similar to the gas calorific value measuring apparatus 10 described above, the so-called TDLAS type measuring means is used as the measuring means, and an oxide obtained by oxidizing the hydrogen to be measured provides the same effects as described above. be able to.

  Further, the gas calorific value measuring device 400 can suitably convert hydrogen into an oxide by introducing an oxidizing agent that oxidizes hydrogen (oxidation reaction) into the flow gas upstream of the conversion means 14. . As a result, the remaining amount of hydrogen to be measured in the flowing gas passing through the downstream measurement unit 232 can be reduced, the concentration of hydrogen to be measured can be calculated with higher accuracy, and the heat generated from the flowing gas The quantity can be calculated with high accuracy. In addition, even when oxygen is low in the flow gas, the reaction can be appropriately promoted by introducing an oxidizing agent. In addition, by introducing an oxidant, hydrocarbons other than methane can also be suitably converted into carbon dioxide and water. In addition, the flow rate of the oxidant supplied to the pipe 222 can be detected by the flow meter 456. Thereby, the change of the number of moles, the change of the number of moles balance, and the change of the flow rate can be corrected.

[Embodiment 6]
FIG. 9 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. The gas calorific value measuring device 500 shown in FIG. 9 includes a piping unit 512, a conversion unit 14, a measurement unit 516, a control unit 518, flow meters 522 and 524, and an oxidant supply unit 550.

In the present embodiment, a storage type oxidation catalyst (SCR catalyst) that selectively stores a gas oxide to be measured and promotes a reaction with an oxidant to form an oxide as an oxidation catalyst of the conversion means 14. It is preferable to use it. That is, it is preferable to use a catalyst that promotes a reaction in which hydrogen becomes H ₂ O by supplying an oxidizing agent. The storage-type oxidation catalyst stores hydrogen until it is saturated. Further, when the oxidant is supplied, the storage-type oxidation catalyst promotes the reaction between the adsorbed hydrogen and the oxidant, and causes H ₂ O that is reacted and generated as an oxide to flow downstream along with the flow gas. Hereinafter, Embodiment 6 demonstrates as a case where a storage type oxidation catalyst is used as a catalyst.

  The piping unit 512 includes a sampling piping 520 and a flow meter 522. The sampling pipe 520 is a pipe that is connected to the measurement target pipe 8 and collects a part of the circulating gas flowing through the measurement target pipe 8, and has one end disposed inside the measurement target pipe 8 and the other side. Is connected to the measuring unit 532 of the measuring means 516. In the sampling pipe 520, the conversion means 14 is disposed in the pipe. In the region where the conversion means 14 of the sampling arrangement 520 is arranged, the diameter of the pipe line is larger than the other regions. That is, the piping unit of the present embodiment is composed of a single pipe.

  The measuring unit 516 includes a measuring unit 532 and a measuring unit main body 534. The measurement unit 532 has an upstream end connected to one end (downstream end) of the sampling pipe 520 and a downstream end connected to a further downstream pipe (exhaust pipe or the like). It is connected. The measurement unit 532 is supplied with the circulating gas that has passed through the conversion means 14.

  The measuring means main body 534 outputs laser light to the measuring unit 532, receives a light reception signal from the measuring unit 532, and measures the concentration of the substance to be measured, and is basically the same as the measuring means main body 44. It is a configuration.

  The oxidant supply means 550 is disposed upstream of the conversion means 14 in the sampling pipe 520 in the flow direction of the circulating gas. That is, the oxidant supply unit 550 is connected to a pipe through which the circulating gas before reaching the conversion unit 14 flows.

  The oxidant supply unit 550 includes a pipe 552, an oxidant supply device 554, an on-off valve 556, and a flow meter 558. One end of the pipe 552 is connected to the upstream side of the conversion means 14 of the sampling pipe 520, and the other end is connected to the oxidant supply device 554. The oxidant supply device 554 is a device that inputs an oxidant to the sampling pipe 520 via the pipe 552. The oxidant supply device 554 has a storage mechanism that stores the oxidant and a charging mechanism that inputs the stored oxidant to the pipe 552. In addition, as an injection | throwing-in mechanism, the mechanism in which an oxidizing agent is conveyed by air, for example, a fan (blower) can be used. The on-off valve 556 is a valve that switches between a state where the oxidant supplied from the oxidant supply device 554 is supplied to the sampling pipe 520 and a state where it is not supplied. The opening / closing valve 556 is controlled to be opened / closed by the control means 518. The flow meter 558 is a measuring instrument that measures the flow rate of air flowing through the pipe 552, measures the amount of air that is input from the oxidizer supply device 554 to the sampling pipe 520, and sends the measurement result to the control means 518.

  Further, the flow meter 522 is disposed on the upstream side of the conversion unit 14 and the oxidant supply unit 550 on the path of the sampling pipe 520, and the flow rate of the flow gas (second flow gas) before passing through the conversion unit 14. Measure. The flow meter 524 is disposed between the conversion unit 14 and the measurement unit 532 on the path of the sampling pipe 520, and measures the flow rate of the flow gas (first flow gas) after passing through the conversion unit 14. The flow meter 522 and the flow meter 524 send the flow rate measurement result to the control means 518.

Similar to the control means 18, the control means 518 controls the operation of each part of the piping unit 512, the conversion means 14, the measurement means 516, and the flow meters 522 and 524. Further, the control means 518 has a gas heat generation amount calculation unit 68, and the gas heat generation amount calculation unit 68 measures (calculates) the heat generation amount of the flow gas based on the measurement result sent from the measurement means 516. Further, the control unit 518 controls the opening / closing of the on-off valve 556 of the oxidant supply unit 550 to supply the oxidant to the conversion unit 14, and the conversion unit 14 causes the oxidant to react with the hydrogen to be measured, A first state in which hydrogen is oxidized (set to H ₂ O) and a _second state in which hydrogen is stored in the conversion means 14 by storing the hydrogen in the conversion means 14 without supplying an oxidizing agent to the conversion means 14 Switch.

This will be specifically described below with reference to FIGS. 10-1 and 10-2. Here, FIGS. 10A and 10B are explanatory diagrams for explaining the operation of the gas calorific value measurement device. 10-1 and 10-2, the horizontal axis is time t, FIG. 10-1 is the open / close signal on the vertical axis, and FIG. 10-2 is the H ₂ O concentration on the vertical axis. In FIG. 10A, the open signal is 1 and the close signal is 0. Also, _{H 2} O concentration in FIG. 10-2 is a _{H 2} O concentration in the downstream side of the converter 14.

For example, the control unit 518, from the closed-off valve 556 outputs the close signal as shown in Figure 10-1, and outputs an open signal at time t _1, the switch valve 556 to the open state, a certain period of time a closed-off valve 556 again outputs close signal at time t ₂ later. Thus, Thus, the time t ₁ earlier, a state in which the oxidizing agent is not supplied to the conversion means 14, between time t ₁ to time t ₂ becomes a state where the oxidizing agent is supplied to the conversion means 14, time t ₂ later, again, the oxidant is a state of not being supplied to the conversion means 14.

Correspondingly, the conversion means 14, the time t ₁ earlier, a state that absorbs hydrogen in the conversion means 14, while from time t ₁ of time t _2, the by oxidizing hydrogen conversion means 14 a state where there, the time t ₂ later, a state that again, absorb hydrogen at conversion unit 14. Thereby, before time t ₁ and after time t ₂ , basically only H ₂ O contained in the flowing gas before oxidation (coexistence gas, H ₂ O included in the flowing gas from the time of collection) is converted. Between the time t ₁ and the time t ₂ , the hydrogen stored in the conversion means 14 reacts with the oxidant in addition to the coexisting gas, and the produced H ₂ O is also contained in the flowing gas that has passed through the means 14. It will be included. Thus, as shown in Figure 10-2, the time _{t 1} earlier, low concentration of _{H 2} O (concentration _x 1), between time _{t 1} to time _{t 2,} the higher the concentration of _{H 2} O (Concentration x ₂ ) After time t ₂ , the concentration of H ₂ O again decreases (concentration x ₁ ).

The control means 518 uses the relationship shown in FIG. 10-2 to measure the concentration of the coexisting gas, and further, the concentration of H ₂ O detected during the oxidation treatment, and the time during which the hydrogen was occluded before the oxidation treatment (For example, by averaging the concentration by the sum of the time of occlusion and the time of reaction), the calculation of H ₂ O derived from hydrogen contained in the flow gas is performed. The concentration is calculated, and from the result, the concentration of hydrogen to be measured contained in the circulation gas is measured (calculated). Further, the substance to be measured other than hydrogen contained in the circulation gas can be measured in each of the first state and the second state as in the gas calorific value measuring device 10 described above. The gas calorific value calculation unit 68 calculates the ratio of combustion components using the measurement results as described above, and measures the calorific value of the circulation gas.

  The gas calorific value measuring device 500 is configured as described above, using an occlusion-type oxidation catalyst that occludes hydrogen as an oxidation catalyst, and by adjusting the supply of the oxidant to repeatedly occlude and oxidize hydrogen, The concentration of hydrogen to be measured contained in the circulation gas can be measured, and the calorific value of the circulation gas can be measured. Also in this case, similar to the gas calorific value measuring device 10 described above, the same effect as described above can be obtained by using a so-called TDLAS measuring unit as the measuring unit and using an oxide obtained by oxidizing the hydrogen to be measured. Can be obtained.

  In addition, in this embodiment, since the time for switching is needed, it becomes an intermittent measurement similarly to the gas calorific value measuring apparatus 10, However, A density | concentration can be measured with one measurement unit.

  In the case of the present embodiment, the amount of hydrogen necessary for saturation is calculated in advance by, for example, the relationship between the concentration, the flow rate, and the circulation time, and at the time of supplying the oxidant, the oxidation catalyst 39 of the conversion means 14. It is preferable to supply the sampling pipe 520 with an amount of 1 to 10 times the saturation amount of hydrogen, that is, the maximum amount of oxidant necessary to oxidize the hydrogen stored in the oxidation catalyst 39 of the conversion means 14. . The control means 518 preferably sets the amount of hydrogen stored in the oxidation catalyst 39 of the conversion means 14 to 1/10 or more and 1/2 or less of the saturated storage amount. By performing the oxidation treatment in a state where the amount of hydrogen stored in the oxidation catalyst 39 of the conversion means 14 is not more than the above range, the hydrogen concentration can be suitably calculated.

In the sixth embodiment, a storage-type oxidation catalyst is used as the oxidation catalyst 39. However, the present invention is not limited to this, and a catalyst that does not store hydrogen can also be used. In this case, when the oxidizing agent is not supplied, the hydrogen contained in the circulation gas also passes through the conversion means 14 as it is. Further, when supplying the oxidizing agent, only hydrogen contained in the flow gas mixed with the oxidizing agent is reduced to H ₂ O. As a result, the control means 518 can measure the hydrogen concentration of the flow gas using the values at the time of detection in each state as the first measurement value and the second measurement value, respectively, and measure the calorific value of the flow gas. Can do. The gas calorific value measuring device 500 may also convert hydrocarbons into carbon dioxide and water by the oxidation catalyst 39.

[Embodiment 7]
FIG. 11 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. Here, the gas calorific value measuring device 600 is basically the same as the gas calorific value measuring device 200 except for the point that the aqueous reverse shift catalyst 650 is provided in the conversion means 614. Therefore, the same components as those of the gas calorific value measuring device 200 are denoted by the same reference numerals, description thereof is omitted, and points unique to the gas calorific value measuring device 600 will be described. Here, the gas calorific value measurement device 600 shown in FIG. 11 includes a piping unit 212, a conversion unit 614, a measurement unit 216, flow meters 224 and 226, and a control unit 618. Since the piping unit 212, the flow meters 224 and 226, and the measuring unit 216 have the same configuration as each unit of the gas calorific value measuring device 200 shown in FIG.

The conversion unit 614 includes an aqueous reverse shift catalyst 650 and a temperature adjustment unit 40. In addition, the temperature adjustment part 40 adjusts the temperature of the atmosphere of the reaction area | region of the aqueous | water-based reverse shift catalyst 650 similarly to the temperature adjustment part 40 of the conversion means 14 mentioned above. The aqueous reverse shift catalyst 650 is disposed downstream of the upstream measurement unit 230 in the piping 222 and upstream of the downstream measurement unit 232 in the flow direction of the flow gas. The aqueous reverse shift catalyst 650 reacts hydrogen (H ₂ ) and carbon dioxide (CO ₂ ) contained in the flow gas to generate carbon monoxide (CO) and water (H ₂ O). That is, the aqueous reverse shift catalyst 650 converts hydrogen into (H ₂ O) with carbon dioxide.

Thereby, the second flow gas passes through the aqueous reverse shift catalyst 650 and becomes the first flow gas, so that the molar ratio of the flow gas is converted as shown in FIG. Here, FIG. 12 is an explanatory diagram for explaining the operation of the gas calorific value measuring device. Specifically, FIG. 12 is a graph showing the relationship between the position in the pipe 222 and the gas concentration, where the vertical axis is the gas concentration and the horizontal axis is the position. As shown in FIG. 12, the state of the sampling gas, that is, the circulating gas supplied from the measurement target pipe 8 and before reaching the aqueous reverse shift catalyst 650 is carbon monoxide (CO), carbon dioxide (CO ₂ ), water vapor. (H ₂ O, water) and hydrogen (H ₂ ) are contained at a constant concentration. When the flowing gas in this state passes through the aqueous reverse shift catalyst 650, hydrogen and carbon dioxide react to generate carbon monoxide and water, that is, a reaction of “H ₂ + CO ₂ → H ₂ O + CO” occurs. The longer the time that the circulating gas is present in the aqueous reverse shift catalyst 650, that is, the more the flow gas moves downstream in the flow direction of the circulating gas, the more the reaction proceeds. As a result, as shown in FIG. 12, the amount of hydrogen and carbon dioxide decreases and the amount of carbon monoxide and water increases as the flow gas moves downstream, and at the inlet of the downstream measurement cell 232, hydrogen flows. The total amount of is converted to water. The aqueous reverse shift catalyst 650 thus converts hydrogen to water.

  The control unit 618 controls the operation of each part of the piping unit 212, the conversion unit 14, and the measurement unit 216. Similarly to the control means 218, the control means 618 includes a gas heat generation amount calculation unit 68. The gas heat generation amount calculation unit 68 determines the heat generation amount of the circulation gas based on the measurement result sent from the measurement means 216. Measure (calculate). The calculation method is the same as the calculation method of the control means 18 described above. Note that the control means 618 controls the temperature of the aqueous reverse shift catalyst 650 by the temperature adjustment unit 40, thereby adjusting the temperature so that hydrogen can be converted into water with high efficiency.

  The gas calorific value measuring device 600 can obtain the same effect as described above by providing the conversion means 614 with the aqueous reverse shift catalyst 650 with the above configuration. Further, the gas calorific value measuring device 600 can measure the hydrogen concentration of the circulating gas even when measuring the calorific value of the circulating gas containing less oxygen, and can measure the calorific value of the circulating gas. Moreover, since it can convert into water, without throwing oxygen into the distribution | circulation gas containing a combustion component, hydrogen can be converted into water more safely.

In addition, the gas calorific value measurement device 600 may supply a substance that reacts with hydrogen upstream of the conversion unit 614 as in the case of FIG. That is, a device for supplying CO ₂ to the pipe 222 may be provided. In addition, the gas calorific value measuring device 600 can be suitably used when the hydrocarbons other than methane are not included in the flow gas.

[Embodiment 8]
FIG. 13 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. 13 includes a piping unit 512, a conversion unit 614, a measurement unit 516, a control unit 718, flow meters 522 and 524, and a CO ₂ supply unit 750. A gas calorific value measuring device 700 shown in FIG. 13 is a device that combines the hydrogen concentration measuring method of the gas calorific value measuring device 500 and the conversion means of the gas calorific value measuring device 600. That is, the conversion means of the gas calorific value measuring device 500 is changed to an aqueous reverse shift catalyst, and the oxidant supply means is changed to CO ₂ supply means. The piping unit 512, the measuring unit 516, and the flow meters 522 and 524 are the same as the units of the gas calorific value measuring device 500, and the converting unit 614 is the same as the converting unit of the gas calorific value measuring device 600. Therefore, explanation is omitted. In the present embodiment, the aqueous reverse shift catalyst 650 is preferably an occlusion type catalyst. However, as described above, the catalyst may not be occluded.

The CO ₂ supply means 750 is disposed upstream of the conversion means 614 in the sampling pipe 520 in the flow direction of the circulating gas. That is, the CO ₂ supply means 750 is connected to a pipe through which the circulating gas before reaching the conversion means 614 flows.

The CO ₂ supply means 750 includes a pipe 752, a CO ₂ supply device 754, an on-off valve 756, and a flow meter 758. One end of the pipe 752 is connected to the upstream side of the conversion means 14 of the sampling pipe 520, and the other end is connected to the CO ₂ supply device 754. The CO ₂ supply device 754 is a device that inputs CO ₂ into the sampling pipe 520 via the pipe 752. CO ₂ supply device 754 has a charging mechanism to launch and storage mechanism for storing the CO _2, the CO ₂ that is stored in the pipe 752. As the input mechanism, a mechanism for pneumatically conveying CO ₂ , for example, a fan (blower) can be used. The on-off valve 756 is a valve that switches between a state where the CO ₂ supplied from the CO ₂ supply device 754 is supplied to the sampling pipe 520 and a state where it is not supplied. The opening / closing valve 756 is controlled to be opened / closed by the control means 718. The flow meter 758 is a measuring instrument that measures the flow rate of air flowing through the pipe 752, measures the amount of air that is input from the CO ₂ supply device 754 to the sampling pipe 520, and sends the measurement result to the control means 518.

Further, the flow meter 522 is disposed on the upstream side of the conversion unit 614 and the CO ₂ supply unit 750 on the path of the sampling pipe 520, and the flow rate of the flow gas (second flow gas) before passing through the conversion unit 614. Measure. The flow meter 524 is disposed between the conversion unit 614 and the measurement unit 532 on the path of the sampling pipe 520, and measures the flow rate of the flow gas (first flow gas) after passing through the conversion unit 614. The flow meter 522 and the flow meter 524 send the flow rate measurement result to the control means 718.

Similar to the control means 18, the control means 718 controls the operation of each part of the piping unit 512, the conversion means 14, the measurement means 516, and the flow meters 522 and 524. Further, the control means 718 has a gas heat generation amount calculation unit 68, and the gas heat generation amount calculation unit 68 measures (calculates) the heat generation amount of the circulation gas based on the measurement result sent from the measurement means 516. Further, the control means 718 controls the opening and closing of the on-off valve 756 of the CO ₂ supply means 750 to supply CO ₂ to the conversion means 614, and the conversion means 614 reacts CO ₂ with hydrogen to be measured, In the first state where hydrogen is converted to H ₂ O, CO ₂ is not supplied to the conversion means 614, hydrogen is stored in the conversion means 614, and hydrogen is stored in the conversion means 614, or the hydrogen is not converted into water and is aqueous The second state in which the reverse shift catalyst 650 is allowed to pass is switched. The control means 718 measures the first measurement value and the second measurement value by switching between the first state and the second state.

Like the gas calorific value measuring device 700, even when an aqueous reverse shift catalyst is used as the conversion means, by adjusting the supply of the substance (CO ₂ ) that reacts with hydrogen in the same manner as described above, with one measuring unit, The calorific value of the circulating gas can be measured. In addition, when a circulation gas containing almost no carbon dioxide is used as the circulation gas, the reaction from hydrogen to water can be controlled with high accuracy by adopting the configuration of this embodiment. It can be measured. Further, since the hydrogen concentration can be measured with high accuracy, the calorific value of the circulating gas can also be measured with high accuracy.

[Embodiment 9]
FIG. 14 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. Here, the gas calorific value measuring device 800 is basically the same as the gas calorific value measuring device 200 except for the converting means 814. Therefore, the same components as those of the gas calorific value measuring device 200 are denoted by the same reference numerals, description thereof is omitted, and points unique to the gas calorific value measuring device 800 will be described. Here, the gas calorific value measurement device 800 shown in FIG. 14 includes a piping unit 212, a conversion unit 814, a measurement unit 216, flow meters 224 and 226, and a control unit 818. Since the piping unit 212, the flow meters 224 and 226, and the measuring unit 216 have the same configuration as each unit of the gas calorific value measuring device 200 shown in FIG.

  The conversion unit 814 includes a reaction region 830, an ozone supply unit 832, an ultraviolet irradiation device 834, and a reaction promoting member 836. The reaction region 830 is disposed downstream of the upstream measurement unit 230 in the pipe 222 and upstream of the downstream measurement unit 232 in the flowing gas flow direction. The reaction region 830 is provided in a part of the pipe 222 and is a pipe through which the flow gas passes. The reaction region 830 is a pipe having a diameter larger than that of the pipe 222.

The ozone supply unit 832 includes a pipe 840, an ozone supply device 842, an on-off valve 844, and a flow meter 846. One end of the pipe 840 is connected to the reaction region 830, and the other end is connected to the ozone supply device 842. Note that the pipe 840 is disposed on the upstream side in the flow direction of the flowing gas in the reaction region 830. The ozone supply device 842 is a device that inputs ozone (O ₃ ) into the reaction region 830 via the pipe 840. The ozone supply device 842 has a storage mechanism for storing ozone and a charging mechanism for charging the stored ozone into the reaction region 830. In addition, as an injection | throwing-in mechanism, the mechanism in which ozone is conveyed by air, for example, a fan (blower), can be used. The on-off valve 844 is a valve that switches between a state in which ozone supplied from the ozone supply device 842 is supplied to the reaction region 830 and a state in which ozone is not supplied. The opening / closing valve 844 is controlled to be opened / closed by the control means 818. The flow meter 846 is a measuring instrument that measures the flow rate of air flowing through the pipe 840, measures the amount of air that is introduced into the reaction region 830 from the ozone supply device 842, and sends the measurement result to the control means 818.

  The ultraviolet irradiation device 834 is a device that irradiates the reaction region 830 with ultraviolet rays. In addition, the ultraviolet irradiation device 834 irradiates ultraviolet rays downstream from the position where the ozone supply device 842 supplies ozone to the reaction region 830.

  The reaction promoting member 836 is disposed in the reaction region 830 and is a member that promotes the reaction between ozone and hydrogen. As the reaction promoting member 836, a member for stirring air or a member having a catalytic function for promoting a chemical reaction can be used.

The conversion unit 814 has the above-described configuration, and ozone and hydrogen are reacted by supplying ozone to the reaction region 830 by the ozone supply unit 832 to generate oxygen and water (H ₂ O). Thereby, hydrogen can be converted into water. Furthermore, the reaction between ozone and hydrogen can be promoted by irradiating the reaction region 830 with ultraviolet rays by the ultraviolet irradiation device 834. Specifically, O ₃ can be decomposed into O ₂ and O by irradiating ultraviolet rays to O ₃ , and hydrogen can be converted to H ₂ O by reacting the generated O and H ₂ . Further, the reaction can be promoted by the reaction promoting member 836.

  The control unit 818 controls the operation of each part of the piping unit 212, the conversion unit 814, and the measurement unit 216. Similarly to the control means 218, the control means 818 has a gas heat generation amount calculation unit 68, and the gas heat generation amount calculation unit 68 uses the measurement result sent from the measurement means 216 to measure the distribution gas. Measure (calculate) the concentration of the target hydrogen. The calculation method is the same as the calculation method of the control means 18 described above. Note that the control unit 818 also controls the supply of ozone from the ozone supply device 842 of the conversion unit 814 and the presence / absence of ultraviolet irradiation by the ultraviolet irradiation device 834.

  The gas calorific value measuring device 800 can obtain the same effect as described above by using a device that supplies ozone to the conversion means 814 with the above-described configuration.

  In the gas calorific value measuring device 800, the upstream measuring unit 230 is provided upstream of the conversion unit 814. However, the present invention is not limited to this. For example, similarly to the gas calorific value measuring device 700, switching between the first state and the second state by switching the supply of ozone by the ozone supply means 832 and the presence or absence of ultraviolet irradiation by the ultraviolet irradiation device 834, Only the downstream measurement unit 232 may measure each concentration, and the calorific value of the circulation gas may be measured based on the result. In addition, the gas calorific value measuring device 600 can be suitably used when the hydrocarbons other than methane are not included in the flow gas.

  Note that the ultraviolet irradiation device 834 and the reaction promoting member 836 are preferably provided in order to react in a shorter route and in a shorter time, but are not necessarily provided.

[Embodiment 10]
FIG. 15 is a schematic diagram showing a schematic configuration of another embodiment of the gas calorific value measuring device. FIG. 16 is a schematic diagram showing a schematic configuration of the preprocessing means. Here, the gas calorific value measuring device 900 is basically the same as the gas calorific value measuring device 10 except that the pre-processing means 919 is provided. Therefore, the same components as those of the gas calorific value measuring device 10 are denoted by the same reference numerals, description thereof is omitted, and points unique to the gas calorific value measuring device 900 will be described. A gas calorific value measurement device 900 shown in FIG. 15 includes a piping unit 912, a conversion unit 14, a measurement unit 16, flow meters 36 and 38, a control unit 918, and a preprocessing unit 919. The piping unit 912 has the same configuration as that of the piping unit 12 except that a pretreatment unit 919 is provided in a part of the sampling piping 20 of the piping unit 12.

  The pre-processing means 919 is arranged in the sampling pipe 20, specifically, the part before the branching of the sampling pipe 20. Further, as shown in FIG. 16, the pretreatment unit 919 includes a dehumidifying device 922 and a dust removing device 924. The pre-processing means 919 supplies the flow gas supplied from the sampling pipe 20 to the first pipe 22 and the second pipe 24 after processing with the dehumidifier 922 and the dust remover 924. Further, the pretreatment means 919 is arranged in the order of the dehumidifying device 922 and the dust removing device 924 from the upstream side in the flow direction of the circulating gas.

The dehumidifier 922 is a device that removes water (H ₂ O) contained in the circulation gas, and removes water contained in the circulation gas from the circulation gas that has passed through the sampling pipe 20. Thereby, the dehumidifier 922 removes coexisting gas contained in the circulation gas, that is, water that is not caused by hydrogen contained in the circulation gas.

  The dust removal device 924 is a device that removes dust contained in the circulation gas, and removes dust from the circulation gas from which moisture has been removed by the dehumidification device 922.

  The gas calorific value measuring device 900 is configured as described above, and supplies the flow gas to the pipes 22 and 24 by the pretreatment device 919. Thereby, the gas calorific value measuring device 900 can perform measurement after removing water and dust from the circulation gas. Thereby, various components contained in the circulation gas can be removed, the influence on the measurement can be reduced, the calorific value of the circulation gas can be measured, and the calorific value of the circulation gas can be measured more accurately. Moreover, the gas calorific value measurement measure 900 can measure the flow rate of each circulation gas by measuring the upstream and downstream flow rates of the pretreatment means 919 of the sampling pipe 20, respectively. Based on the flow rate, By correcting the measurement value of the hydrogen concentration, the calorific value of the circulation gas can be measured with higher accuracy.

  Here, the present invention is not limited to the above embodiment, and various forms can be adopted. For example, you may combine each embodiment. For example, an oxidizing agent supply unit may be added to the first embodiment. Further, in any of the piping unit paths, as the conversion means, a conversion means using an aqueous reverse shift catalyst or a conversion means using an ozone supply means can be used.

  Further, the gas calorific value measurement device may be provided with a filter (dust removal device) in the vicinity of the upstream end of the sampling pipe, as described above, when the circulation gas contains a large amount of dust. By providing the filter, dust contained in the circulation gas can be removed. Even in the case where a filter is provided, the gas calorific value measuring device has a large tolerance for dust, so that a simpler filter can be used than when other measurement methods are used. Thereby, the time delay which generate | occur | produces by arrange | positioning a filter can be decreased, and responsiveness can be maintained highly.

  Further, the measurement unit may be provided with a purge gas supply unit that injects air in a direction away from the window in the window of the measurement cell. By injecting the purge gas, it is possible to suppress foreign matter from adhering to the window and causing an error in measurement using the laser beam.

  As described above, the gas calorific value measuring device and the gas calorific value measuring method according to the present invention are useful for measuring the calorific value contained in the circulation gas flowing in the pipeline.

8 Measurement target pipe 10, 100, 200, 300, 400, 500, 600, 700, 800, 900 Gas calorific value measuring device 12 Piping unit 14 Conversion means 16 Measuring means 18 Control means 20 Sampling pipe (inflow pipe)
22 First pipe 24 Second pipe 26, 28 Branch pipe 30 Three-way valve 31 Pump 32, 34 On-off valve 36, 38 Flow meter 39 Oxidation catalyst 42 Measuring unit 44 Measuring means body 45 Measuring cell 46 Optical fiber 48 Light receiving part 50 Light receiving Section 52 Main pipe 54 Inflow pipe 56 Outlet pipe 58, 59 Window 62 Light emitting section 64 Light source driver 66 Calculation section

Claims (23)

A gas calorific value measuring device for measuring a hydrogen concentration of a measurement target contained in a circulating gas,
A piping unit through which the flow gas flows;
Conversion means arranged in the piping unit and converting hydrogen contained in the flowing gas passing therethrough into H ₂ O;
Of the circulating gas flowing through the piping unit, measurement of the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ contained in the first circulating gas flowing through the piping path passing through the conversion means. A first measured value including a value and a measured value of the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ contained in the second circulating gas that has flowed through the piping path that does not pass through the conversion means. Measuring means for measuring a second measured value including:
Controls the operation of the piping unit and the measuring means, calculates the hydrogen concentration from the difference between the first measured value and the second measured value, and distributes based on the calculated hydrogen concentration and combustion component concentration. Control means for calculating the calorific value of the gas,
The measuring means includes
Including the absorption wavelength of H ₂ O, including laser light in the near infrared wavelength region, including absorption wavelength of CH ₄ , including laser light in the near infrared wavelength region, absorption wavelength of CO, and near red A light emitting unit that includes laser light in an outer wavelength region, an absorption wavelength of CO ₂ , and outputs laser light in a near infrared wavelength region;
At least one measurement unit including a gas measurement cell through which the flow gas flows, an optical system that allows laser light to enter the gas measurement cell, and a light receiving unit that receives the laser light that has entered the gas measurement cell and has passed through the gas measurement cell. When,
Based on the intensity of the laser beam output from the light emitting unit and the intensity of the laser beam received by the light receiving unit, the concentration of H ₂ O, CH ₄ concentration, CO of the flowing gas flowing through the gas measurement cell A gas calorific value measurement device comprising: a calculation unit that calculates a concentration and a concentration of CO ₂ . Further, a first flow meter that is arranged on the upstream side of the conversion means and measures the flow rate of the flow gas flowing into the conversion means, and is arranged on the downstream side of the conversion means and is discharged from the conversion means. A second flow meter for measuring the flow rate of the circulating gas,
The control means, based on the measurement result of the first flow meter and the measurement result of the second flow meter, the H ₂ O concentration, the CH ₄ concentration, the CO concentration, and the CO ₂ concentration of the flow gas. The gas calorific value measuring device according to claim 1, wherein the measured value is corrected and calculated. And the converting means, the gas heating value measuring apparatus according to claim 1 or 2 characterized by having a temperature adjustment unit for adjusting the temperature of the atmosphere in the region for converting hydrogen into H _{2 O.}   The gas temperature measuring device according to claim 3, wherein the temperature adjustment unit sets the temperature of the atmosphere to 100 ° C. or more and 200 ° C. or less. The measuring means further outputs laser light in the near-infrared wavelength region including the absorption wavelength of O ₂ from the light emitting unit, and the concentration of O ₂ contained in the first circulation gas and the second circulation gas. Measure the concentration of O ₂ contained in
The control means includes a concentration of H ₂ O in the first circulation gas, a concentration of CH _4, a concentration of CO, a concentration of CO _2, a concentration of O _2, a concentration of H ₂ O in the second circulation gas, and a concentration of CH ₄ . Calculate the composition ratio of hydrocarbons and hydrogen based on the change in mass balance with the concentration, CO concentration, CO ₂ concentration, and O ₂ concentration, and calculate the calorific value of the circulating gas from the calculation results. The gas calorific value measuring device according to any one of claims 1 to 4, wherein: The piping unit includes an inflow piping into which the circulation gas flows,
A first pipe which is connected to an end of the inflow pipe on the downstream side in the flow direction of the circulating gas and in which the conversion means is disposed;
A second pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas together with the first pipe, and the conversion means is not disposed;
A three-way valve that connects an end on the downstream side of the first pipe, an end on the downstream side of the second pipe, and an end on the upstream side in the flow direction of the flow gas of the gas measurement cell; Have
The control means connects, by the three-way valve, an end on the downstream side of the first pipe and an end on the upstream side of the flow direction of the gas in the gas measurement cell, and the measurement means is connected to the first flow. Flow in gas, measure the first measurement value,
The three-way valve connects the downstream end of the second pipe and the upstream end of the gas measurement cell in the flow direction of the flow gas, and allows the second flow gas to flow into the measurement means. The gas calorific value measurement device according to any one of claims 1 to 5, wherein the second measurement value is measured. The piping unit includes an inflow piping into which the circulation gas flows,
A first pipe which is connected to an end of the inflow pipe on the downstream side in the flow direction of the circulating gas and in which the conversion means is disposed;
A second pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas together with the first pipe, and the conversion means is not disposed;
The measurement means includes two measurement units, and one of the measurement units is disposed on the downstream side of the conversion means in the flow direction of the circulating gas in the first pipe,
The gas calorific value measurement device according to any one of claims 1 to 5, wherein the other measurement unit is arranged in the first pipe. The piping unit includes an inflow piping into which the circulation gas flows,
A holding pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, the conversion means being disposed,
The measurement means includes two measurement units, and one of the measurement units is disposed downstream of the conversion means in the flow direction of the circulating gas in the holding pipe.
6. The gas heat generation according to claim 1, wherein the other measurement unit is arranged upstream of the conversion means in the flow direction of the circulating gas in the holding pipe. Quantity measuring device. The gas calorific value measuring device according to any one of claims 1 to 8, wherein the conversion means is an oxidation catalyst that oxidizes hydrogen to make H ₂ O.   The oxidant supply means which is arrange | positioned in the flow direction of the said distribution | circulation gas upstream from the said conversion means, and supplies the oxidant which oxidizes the said hydrogen to the said piping unit is further provided. The gas calorific value measuring device described. In the flow direction of the circulating gas, provided with an oxidant supply means that is disposed upstream of the conversion means and supplies an oxidant that oxidizes the hydrogen to the piping unit,
The piping unit includes an inflow piping into which the circulation gas flows,
A holding pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, the conversion means being disposed,
The measuring means is arranged such that the measuring unit is located downstream of the converting means in the flow direction of the circulating gas in the holding pipe.
The conversion means is an oxidation catalyst that oxidizes hydrogen to H ₂ O,
The control means switches between a state in which the oxidant is supplied from the oxidant supply means to the piping unit and a state in which the oxidant is not supplied from the oxidant supply means to the piping unit, The gas according to any one of claims 1 to 5, wherein a state in which the first circulation gas flows into the measurement unit and a state in which the second circulation gas flows in are switched. Calorific value measuring device. And the converting means, as claimed in any one of claims 1 to 11, characterized in that it comprises an aqueous reverse shift catalyst to shift the carbon dioxide and hydrogen contained in the circulation gas to the carbon monoxide and H _{2 O} Gas calorific value measuring device.   The gas heat generation according to claim 12, further comprising a carbon dioxide supply means arranged upstream of the conversion means in the flow direction of the circulation gas and supplying the carbon dioxide to the piping unit. Quantity measuring device. In the flow direction of the circulation gas, the carbon dioxide supply means is further provided upstream of the conversion means, and supplies carbon dioxide to the piping unit,
The piping unit includes an inflow piping into which the circulation gas flows,
A holding pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, the conversion means being disposed,
The measuring means is arranged such that the measuring unit is located downstream of the converting means in the flow direction of the circulating gas in the holding pipe.
The conversion means is an aqueous reverse shift catalyst that shifts carbon dioxide and hydrogen contained in the flow gas to carbon monoxide and H ₂ O.
The control means switches between a state in which the carbon dioxide is supplied from the carbon dioxide supply means to the piping unit and a state in which the carbon dioxide is not supplied from the carbon dioxide supply means to the piping unit, The gas according to any one of claims 1 to 5, wherein a state in which the first circulation gas flows into the measurement unit and a state in which the second circulation gas flows in are switched. Calorific value measuring device. The conversion means includes ozone supply means for supplying ozone to the piping unit;
A reaction region formed downstream of the ozone supply means of the piping unit in the flow direction of the circulation gas and in which hydrogen contained in the circulation gas reacts with ozone supplied by the ozone supply means; The gas calorific value measuring device according to any one of claims 1 to 14, characterized in that: The piping unit includes an inflow piping into which the circulation gas flows,
A pipe connected to the downstream end of the inflow pipe in the flow direction of the flow gas, the pipe through which the flow gas flows,
The conversion means includes ozone supply means for supplying ozone to the piping unit;
A reaction region that is formed downstream of the ozone supply means of the piping in the flow direction of the circulation gas, and in which hydrogen contained in the circulation gas and ozone supplied by the ozone supply means react;
The measurement means is arranged such that the measurement unit is located downstream of the reaction region in the flow direction of the flow gas.
The control means switches between a state in which the ozone is supplied from the ozone supply means to the piping unit and a state in which the ozone is not supplied from the ozone supply means to the piping unit, The gas calorific value measuring device according to any one of claims 1 to 5, wherein a state in which the first circulation gas flows in and a state in which the second circulation gas flows in are switched. . The conversion means further comprises ultraviolet irradiation means for irradiating the reaction area with ultraviolet rays,
The control means switches between a state in which the ultraviolet ray irradiating means irradiates the reaction region with the ultraviolet ray and a state in which the ultraviolet ray irradiating unit does not irradiate the reaction region with the ultraviolet ray. The gas calorific value measurement device according to claim 15 or 16, wherein the state in which the first circulation gas flows in and the state in which the second circulation gas flows in are switched.   18. The gas calorific value measurement device according to claim 15, wherein the conversion unit further includes a reaction promoting member that promotes a reaction between the ozone and the hydrogen in the reaction region.   The gas calorific value measurement device according to any one of claims 1 to 18, wherein the measurement unit allows laser light to pass through a pipe holding the conversion means.   The gas calorific value measuring device according to any one of claims 1 to 19, wherein the piping unit allows the entire amount of the circulation gas discharged from the device to be measured to flow.   The said piping unit is collecting the said one part circulation gas from the measurement object piping through which the whole quantity of the said circulation gas discharged | emitted from the apparatus of a measuring object flows. The gas calorific value measuring device according to item 1. At least one of a dehumidifying device for recovering H ₂ O contained in the circulating gas and a dust removing device for recovering dust contained in the circulating gas, arranged upstream of the conversion means in the flow direction of the circulating gas. The gas calorific value measuring device according to any one of claims 1 to 21, characterized by comprising: A gas calorific value measurement method for measuring the hydrogen concentration of a circulating gas flowing through a pipe,
Of the flow gas flowing through the pipe, the first flow gas that has passed through the region where the conversion means for converting hydrogen into H ₂ O is disposed, which includes the absorption wavelength of H ₂ O and near infrared Including the laser beam in the wavelength range, the absorption wavelength of CH ₄ , including the laser beam in the near infrared wavelength range, the absorption wavelength of CO, and the laser beam in the near infrared wavelength range, including the absorption wavelength of CO ₂ In addition, each laser beam in the near-infrared wavelength region is output, the laser beam that has passed through the pipeline through which the first flow gas flows is received, and the intensity of the output laser beam and the laser beam received by the light receiving unit A first measurement step of measuring the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, and the concentration of CO ₂ contained in the first flow gas as a first measurement value based on the intensity of
Of the flow gas flowing through the pipe, the second flow gas that does not pass through the region where the conversion means for converting hydrogen into H ₂ O is disposed, includes an absorption wavelength of H ₂ O, and Infrared wavelength region laser light, CH ₄ absorption wavelength, near infrared wavelength region laser light, CO absorption wavelength, near infrared wavelength region laser light, CO ₂ absorption wavelength In addition, the laser beam in the near-infrared wavelength region is output, the laser beam that has passed through the pipe through which the second flow gas flows is received, and the intensity of the output laser beam and the light receiving unit are received A second measurement step of measuring the concentration of H ₂ O, the concentration of CH ₄ , the concentration of CO, the concentration of CO ₂ contained in the flow gas as a second measurement value based on the intensity of the laser beam;
Calculating a hydrogen concentration from the difference between the first measurement value and the second measurement value, and calculating a calorific value of the flow gas based on the calculated hydrogen concentration and combustion component concentration; A gas calorific value measurement method comprising:

Images