JP7777488B2 - calorimeter - Google Patents
calorimeterInfo
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- JP7777488B2 JP7777488B2 JP2022065126A JP2022065126A JP7777488B2 JP 7777488 B2 JP7777488 B2 JP 7777488B2 JP 2022065126 A JP2022065126 A JP 2022065126A JP 2022065126 A JP2022065126 A JP 2022065126A JP 7777488 B2 JP7777488 B2 JP 7777488B2
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Description
本発明は、熱量計に関する。 The present invention relates to a calorimeter.
燃料ガスの熱量測定に用いられる熱量計として、燃料ガスの通路内に熱電対と触媒とを設け、通路内を通過する燃料ガスの触媒燃焼による発熱量を熱電対で測定するものが知られている（例えば、特許文献１参照）。特許文献１に記載の熱量計では、ヒーター用のニクロム線が触媒の周囲に巻回されており、メタン（ＣＨ４）等の燃料ガスが燃焼温度に加熱される。 A known calorimeter used to measure the calorific value of fuel gas is one in which a thermocouple and a catalyst are provided in a fuel gas passage, and the thermocouple measures the amount of heat generated by catalytic combustion of the fuel gas passing through the passage (see, for example, Patent Document 1). In the calorimeter described in Patent Document 1, a nichrome wire heater is wound around the catalyst, and the fuel gas, such as methane ( CH4 ), is heated to its combustion temperature.
水素（Ｈ２）を含む燃料ガスの熱量測定に、特許文献１に記載されているような従来の熱量計を用いる場合、水素とメタン等の水素以外の可燃性ガスとの燃焼温度の差を要因として測定誤差が生じることが、本願の発明者等の実験により確認された。 The inventors of the present application have confirmed through experiments that when a conventional calorimeter such as that described in Patent Document 1 is used to measure the calorific value of a fuel gas containing hydrogen (H 2 ), measurement errors occur due to the difference in combustion temperature between hydrogen and combustible gases other than hydrogen, such as methane.
本発明は、かかる事情に鑑みてなされたものであり、水素を含む燃料ガスの熱量を高精度に測定できる熱量計を提供することを目的とする。 The present invention was made in consideration of these circumstances, and aims to provide a calorimeter that can measure the calorific value of fuel gas containing hydrogen with high accuracy.
本発明に係る熱量計は、水素を含む燃料ガスの熱量を測定する熱量計であって、前記水素を常温で燃焼させるための第１触媒と、前記第１触媒における常温での燃焼による前記水素の上昇温度を測定する第１測温体と、前記燃料ガスに含まれる前記水素以外の可燃性ガスを加熱下で燃焼させるための第２触媒と、前記第２触媒を加熱する加熱部と、前記第２触媒における加熱下での燃焼による前記可燃性ガスの上昇温度を測定する第２測温体とを備える。 The calorimeter of the present invention is a calorimeter that measures the calorific value of fuel gas containing hydrogen, and includes a first catalyst for burning the hydrogen at room temperature, a first temperature measuring element that measures the temperature rise of the hydrogen due to combustion at room temperature in the first catalyst, a second catalyst for burning flammable gases other than hydrogen contained in the fuel gas under heating, a heating unit that heats the second catalyst, and a second temperature measuring element that measures the temperature rise of the flammable gas due to combustion under heating in the second catalyst.
本発明の熱量計によれば、第１触媒における常温での燃焼による水素の上昇温度を第１測温体で測定し、第２触媒における加熱下での燃焼による水素以外の可燃性ガスの上昇温度を第２測温体で測定することにより、水素を含む燃料ガスの熱量を高精度に測定できる。 The calorimeter of the present invention measures the temperature rise of hydrogen due to combustion at room temperature in the first catalyst using the first temperature measuring element, and measures the temperature rise of combustible gases other than hydrogen due to combustion under heating in the second catalyst using the second temperature measuring element, thereby enabling the calorific value of fuel gas containing hydrogen to be measured with high accuracy.
以下、本発明を好適な実施形態に沿って説明する。なお、本発明は、以下に示す実施形態に限られるものではなく、本発明の趣旨を逸脱しない範囲において適宜変更可能である。また、以下に示す実施形態においては、一部構成の図示や説明を省略している箇所があるが、省略された技術の詳細については、以下に説明する内容と矛盾が発生しない範囲内において、適宜公知又は周知の技術が適用される。 The present invention will be described below in accordance with preferred embodiments. However, the present invention is not limited to the embodiments described below, and modifications can be made as appropriate without departing from the spirit of the present invention. Furthermore, in the embodiments described below, some components are not shown or described, but for the details of the omitted technologies, publicly known or well-known technologies can be applied as appropriate, provided that they do not conflict with the content described below.
図１は、本発明の一実施形態に係る熱量計１００を備える測定システム１の概略を示すブロック図である。この図に示すように、測定システム１は、ガス混合装置１０と、熱量計１００とを備える。ガス混合装置１０は、可燃性ガスと空気とを混合することにより混合ガスを燃料ガスとして熱量計１００に供給する。熱量計１００は、ガス混合装置１０から供給された燃料ガスを燃焼させて発熱量を測定する。 Figure 1 is a block diagram showing an outline of a measurement system 1 equipped with a calorimeter 100 according to one embodiment of the present invention. As shown in this figure, the measurement system 1 includes a gas mixing device 10 and a calorimeter 100. The gas mixing device 10 mixes a combustible gas with air and supplies the mixed gas as a fuel gas to the calorimeter 100. The calorimeter 100 combusts the fuel gas supplied from the gas mixing device 10 to measure the calorific value.
ガス混合装置１０は、第１配管１１と、第２配管１２と、第３配管１３と、第１流量計１４Ａと、第２流量計１４Ｂと、第１バルブ１５Ａと、第２バルブ１５Ｂと、混合器１６と、第１レギュレーターＲ１と、第２レギュレーターＲ２とを備える。 The gas mixing device 10 includes a first pipe 11, a second pipe 12, a third pipe 13, a first flow meter 14A, a second flow meter 14B, a first valve 15A, a second valve 15B, a mixer 16, a first regulator R1, and a second regulator R2.
第１配管１１は、第１レギュレーターＲ１と混合器１６とを接続し、第１レギュレーターＲ１を通して供給される可燃性ガスを混合器１６まで導く。第１流量計１４Ａは、第１配管１１に設けられ、第１配管１１を流れる可燃性ガスの流量を測定する。第１バルブ１５Ａは、第１配管１１における第１流量計１４Ａより下流側に設けられ、混合器１６に供給される可燃性ガスの流量を調整するニードルバルブ等の流量調整バルブである。 The first pipe 11 connects the first regulator R1 and the mixer 16, and guides the flammable gas supplied through the first regulator R1 to the mixer 16. The first flow meter 14A is provided on the first pipe 11 and measures the flow rate of the flammable gas flowing through the first pipe 11. The first valve 15A is provided on the first pipe 11 downstream of the first flow meter 14A and is a flow rate adjustment valve such as a needle valve that adjusts the flow rate of the flammable gas supplied to the mixer 16.
第２配管１２は、第２レギュレーターＲ２と混合器１６とを接続し、第２レギュレーターＲ２を通して供給される空気を混合器１６まで導く。第２流量計１４Ｂは、第２配管１２に設けられ、第２配管１２を流れる空気の流量を測定する。第２バルブ１５Ｂは、第２配管１２における第２流量計１４Ｂより下流側に設けられ、混合器１６に供給される空気の流量を調整するニードルバルブ等の流量調整バルブである。 The second pipe 12 connects the second regulator R2 to the mixer 16 and guides the air supplied through the second regulator R2 to the mixer 16. The second flow meter 14B is provided in the second pipe 12 and measures the flow rate of air flowing through the second pipe 12. The second valve 15B is provided in the second pipe 12 downstream of the second flow meter 14B and is a flow rate control valve such as a needle valve that adjusts the flow rate of air supplied to the mixer 16.
混合器１６は、第１配管１１から供給された可燃性ガスと第２配管１２から供給された空気とを混合する。この混合器１６には、第３配管１３が接続されている。この第３配管１３は、混合器１６において混合された混合ガスを燃料ガスとして熱量計１００に供給する。 The mixer 16 mixes the flammable gas supplied from the first pipe 11 with the air supplied from the second pipe 12. The mixer 16 is connected to the third pipe 13. The third pipe 13 supplies the mixed gas mixed in the mixer 16 to the calorimeter 100 as fuel gas.
熱量計１００は、燃焼測温部１１０と、定電圧源（電圧源）１０２と、データロガー１０３と、演算装置１０４とを備える。燃焼測温部１１０には、第３配管１３から燃料ガスが供給される。定電圧源１０２は、燃焼測温部１１０に電力を供給する。燃焼測温部１１０は、定電圧源１０２から供給される電力により駆動され、第３配管１３から供給された燃料ガスを燃焼させて燃焼による燃料ガスの上昇温度を測定する。 The calorimeter 100 comprises a combustion temperature measuring unit 110, a constant voltage source (voltage source) 102, a data logger 103, and a computing device 104. Fuel gas is supplied to the combustion temperature measuring unit 110 from the third pipe 13. The constant voltage source 102 supplies power to the combustion temperature measuring unit 110. The combustion temperature measuring unit 110 is driven by the power supplied from the constant voltage source 102, combusts the fuel gas supplied from the third pipe 13, and measures the temperature rise of the fuel gas due to combustion.
図２は、図１に示す熱量計１００の構成を示す断面図である。この図に示す熱量計１００は、第１燃焼測温部１２０と第２燃焼測温部１３０とを備え、水素を含む燃料ガスの熱量測定に対応する。 Figure 2 is a cross-sectional view showing the configuration of the calorimeter 100 shown in Figure 1. The calorimeter 100 shown in this figure includes a first combustion temperature measuring unit 120 and a second combustion temperature measuring unit 130, and is capable of measuring the calorific value of fuel gas containing hydrogen.
第１燃焼測温部１２０は、燃料ガスに含まれる水素を常温で燃焼させその燃焼による水素の上昇温度ΔＴＨ［℃］を測定する。他方で、第２燃焼測温部１３０は、燃料ガスに含まれるメタン等の水素以外の可燃性ガスを加熱下で燃焼させその燃焼による当該可燃性ガスの上昇温度ΔＴＥ［℃］を測定する。 The first combustion temperature measuring unit 120 burns hydrogen contained in the fuel gas at room temperature and measures the temperature rise ΔT H [°C] of the hydrogen caused by the combustion, while the second combustion temperature measuring unit 130 burns flammable gases other than hydrogen, such as methane contained in the fuel gas, under heating and measures the temperature rise ΔT E [°C] of the flammable gas caused by the combustion.
燃焼測温部１１０は、管材１１１を備える。管材１１１は縦向きに配されており、管材１１１の上端に第３配管１３が接続されている。管材１１１は、燃料ガスの燃焼時の温度に対する耐熱性と、燃焼時の燃料ガスの管材１１１外への放熱を抑える低い伝熱性とを有する管材である。本実施形態の管材１１１は、内径が４ｍｍの円筒状のセラミックチューブである。なお、管材１１１の内径は、２ｍｍ以上１０ｍｍ以下が好ましい。また、管材１１１はステンレスチューブでもよい。 The combustion temperature measuring unit 110 includes a pipe 111. The pipe 111 is arranged vertically, and the third pipe 13 is connected to the upper end of the pipe 111. The pipe 111 is heat resistant to the temperature during combustion of the fuel gas and has low thermal conductivity to prevent the heat of the fuel gas from radiating outside the pipe 111 during combustion. In this embodiment, the pipe 111 is a cylindrical ceramic tube with an inner diameter of 4 mm. The inner diameter of the pipe 111 is preferably 2 mm or more and 10 mm or less. The pipe 111 may also be a stainless steel tube.
管材１１１には、第１燃焼測温部１２０と第２燃焼測温部１３０とが設けられている。第１燃焼測温部１２０と第２燃焼測温部１３０とは、燃料ガスの流れ方向に第１燃焼測温部１２０、第２燃焼測温部１３０の順で直列に配されている。このため、第３配管１３から管材１１１に供給された燃料ガスは、まず、第１燃焼測温部１２０を通過する。この際、燃料ガスに含まれる水素が常温で燃焼されその燃焼による水素の上昇温度ΔＴＨ［℃］が測定される。そして、第１燃焼測温部１２０を通過した燃料ガスが、第２燃焼測温部１３０を通過する。この際、燃料ガスに含まれるメタン等の水素以外の可燃性ガスが、加熱下で燃焼されその燃焼による当該可燃性ガスの上昇温度ΔＴＥ［℃］が測定される。 The tubular material 111 is provided with a first combustion temperature measuring unit 120 and a second combustion temperature measuring unit 130. The first combustion temperature measuring unit 120 and the second combustion temperature measuring unit 130 are arranged in series in the flow direction of the fuel gas, with the first combustion temperature measuring unit 120 first and the second combustion temperature measuring unit 130 first. Therefore, the fuel gas supplied to the tubular material 111 from the third piping 13 first passes through the first combustion temperature measuring unit 120. At this time, hydrogen contained in the fuel gas is combusted at room temperature, and the temperature rise ΔT H [°C] of the hydrogen due to the combustion is measured. Next, the fuel gas that has passed through the first combustion temperature measuring unit 120 passes through the second combustion temperature measuring unit 130. At this time, combustible gases other than hydrogen, such as methane, contained in the fuel gas are combusted under heating, and the temperature rise ΔT E [°C] of the combustible gas due to the combustion is measured.
第１燃焼測温部１２０は、熱電対１２１と、触媒１２２と、ストッパー部材１２３とを備える。熱電対１２１は、熱電対素線１２１Ａと、シース１２１Ｂとを備え、ゼーベック効果を利用して温度を測定する。熱電対素線１２１Ａは、一端（図中の上端）に測温接点Ｐが設けられている。シース１２１Ｂは、直線性の高い形状を維持する硬質で細い管材であり、熱電対素線１２１Ａを被覆している。本実施形態のシース１２１Ｂは、外径が０．５ｍｍの金属製の管材である。シース１２１Ｂ内には絶縁物が充填されている。熱電対素線１２１Ａの他端（図中の下端）には、不図示の補償導線の一端が接続されている。この補償導線は、管材１１１の中間部から引き出されており、データロガー１０３に接続されている。ここで、管材１１１の中間部には、補償導線が挿通される孔と、当該孔と補償導線との隙間を塞ぐ気密シール部とが形成されている（共に図示省略）。なお、本実施形態の熱電対１２１は、非接地型であるが、熱電対１２１を接地型や露出型に変えてもよい。 The first combustion temperature measuring unit 120 includes a thermocouple 121, a catalyst 122, and a stopper member 123. The thermocouple 121 includes a thermocouple wire 121A and a sheath 121B, and measures temperature using the Seebeck effect. The thermocouple wire 121A has a temperature measuring junction P at one end (the upper end in the figure). The sheath 121B is a hard, thin tube that maintains a highly linear shape and covers the thermocouple wire 121A. In this embodiment, the sheath 121B is a metal tube with an outer diameter of 0.5 mm. The sheath 121B is filled with an insulator. One end of a compensation wire (not shown) is connected to the other end of the thermocouple wire 121A (the lower end in the figure). This compensation wire is pulled out from the middle of the tube 111 and connected to the data logger 103. Here, a hole through which the compensation lead wire is inserted and an airtight seal portion that seals the gap between the hole and the compensation lead wire are formed in the middle of the pipe material 111 (both not shown). Note that although the thermocouple 121 in this embodiment is an ungrounded type, the thermocouple 121 may also be changed to a grounded type or an exposed type.
触媒１２２は、第１燃焼測温部１２０の燃焼室に充填された顆粒状の触媒である。触媒１２２の粒径は、粉末の粒径に比して数十倍～数百倍と大きい。触媒１２２の粒径は、１００μｍ未満に篩にかけて整粒するのは困難であり、１０００μｍより大きくすると管材１１１の内径と近くなって水素との接触が悪くなるという観点から、１００μｍ以上１０００μｍ以下が好ましく、３５５μｍ以上４２０μｍ以下がより好ましい。また、触媒１２２は、水素を常温（室温）で燃焼させることが可能なものであり、例えば、アルミナ担持白金触媒（Ｐｔ－Ａｌ２Ｏ３）等の金属酸化物担持白金触媒を例示できる。ここで、０．２質量％の白金をアルミナ担体が担持した触媒（０．２％Ｐｔ－Ａｌ２Ｏ３触媒）を用いて、１０００ｐｐｍの水素を燃焼させた場合に、燃焼開始温度が室温（ｒｏｏｍ ｔｅｍｐ）となることが知られている（貞森 博己、「特殊燃焼技術特集 触媒燃焼技術の現状 触媒燃焼バーターを中心として」、燃料協会誌 第５８巻第６２６号（１９７９） １９７９年６月発行 ４２２～４２３頁）。 The catalyst 122 is a granular catalyst filled in the combustion chamber of the first combustion temperature measuring unit 120. The particle size of the catalyst 122 is several tens to several hundreds of times larger than the particle size of powder. From the viewpoint that it is difficult to size the catalyst 122 by sieving to a particle size of less than 100 μm, and that if the particle size is larger than 1000 μm, the particle size becomes close to the inner diameter of the pipe material 111, resulting in poor contact with hydrogen, the particle size of the catalyst 122 is preferably 100 μm to 1000 μm, and more preferably 355 μm to 420 μm. The catalyst 122 is capable of burning hydrogen at normal temperature (room temperature), and an example of the catalyst 122 is a metal oxide-supported platinum catalyst such as an alumina-supported platinum catalyst (Pt—Al 2 O 3 ). It is known that when 1000 ppm of hydrogen is burned using a catalyst in which 0.2 mass % of platinum is supported on an alumina carrier (0.2% Pt-Al 2 O 3 catalyst), the combustion initiation temperature is room temperature (Sadamori, Hiroki, "Special Feature on Special Combustion Technology: Current Status of Catalytic Combustion Technology, Focusing on Catalytic Combustion Burners," Journal of the Fuel Association, Vol. 58, No. 626 (1979), published in June 1979, pp. 422-423).
第１燃焼測温部１２０の燃焼室に充填された触媒１２２の質量及び充填高さは、測温接点Ｐが触媒１２２から露出するように適宜設定すればよく、例えば、管材１１１の内径が４ｍｍの場合で０．０７５ｇ、約３ｍｍ等である。なお、測温接点Ｐが触媒１２２から露出することは必須ではなく、触媒１２２が測温接点Ｐを覆うように第１燃焼測温部１２０の燃焼室に充填されてもよい。 The mass and filling height of the catalyst 122 filled in the combustion chamber of the first combustion temperature measuring unit 120 may be set appropriately so that the temperature measurement contact point P is exposed from the catalyst 122. For example, if the inner diameter of the pipe material 111 is 4 mm, this is 0.075 g and approximately 3 mm. Note that it is not necessary for the temperature measurement contact point P to be exposed from the catalyst 122; the catalyst 122 may be filled in the combustion chamber of the first combustion temperature measuring unit 120 so that it covers the temperature measurement contact point P.
シース１２１Ｂの一端側（図中の上端側）の表面には、触媒層１２１Ｓが測温接点Ｐを覆うように形成されている。この触媒層１２１Ｓは、アルミナ担持白金触媒等の水素を常温で燃焼させる触媒により構成された塗膜である。触媒層１２１Ｓの形成方法としては、粉末状の触媒と蒸留水等とを混合した液状の触媒をシース１２１Ｂに塗布して乾燥させる方法を例示できる。 A catalyst layer 121S is formed on the surface of one end of the sheath 121B (the upper end in the figure) so as to cover the temperature measurement contact P. This catalyst layer 121S is a coating made of a catalyst that burns hydrogen at room temperature, such as an alumina-supported platinum catalyst. One method for forming the catalyst layer 121S is to apply a liquid catalyst, which is a mixture of powdered catalyst and distilled water, to the sheath 121B and then dry it.
触媒層１２１Ｓのシース１２１Ｂの一端（先端）からの長さは例えば約１ｍｍであり、触媒層１２１Ｓは、測温接点Ｐの位置を含むシース１２１Ｂの一端から約１ｍｍの範囲を覆っている。この触媒層１２１Ｓの大部分又は全体は触媒１２２から露出している。なお、触媒層１２１Ｓが触媒１２２から露出することは必須ではなく、触媒層１２１Ｓは触媒１２２に覆われるように配されてもよい。また、触媒層１２１Ｓを設けることは必須ではない。 The length of catalyst layer 121S from one end (tip) of sheath 121B is, for example, approximately 1 mm, and catalyst layer 121S covers an area of approximately 1 mm from one end of sheath 121B, including the position of temperature measurement junction P. Most or all of this catalyst layer 121S is exposed from catalyst 122. Note that it is not necessary for catalyst layer 121S to be exposed from catalyst 122; catalyst layer 121S may be arranged so as to be covered by catalyst 122. Furthermore, providing catalyst layer 121S is not essential.
ストッパー部材１２３は、第１燃焼測温部１２０の燃焼室の下側に配されている。このストッパー部材１２３は、管材１１１の内周面に嵌合したステンレス等の金属製の板であり、不図示の複数の通気孔が形成されている。この通気孔の直径は、触媒１２２の粒径（平均値）よりも小さい。これにより、燃料ガスは、通気孔は通過するが、触媒１２２は、通気孔を通過せずにストッパー部材１２３の上に堆積する。本実施形態のストッパー部材１２３は円板である。また、本実施形態のストッパー部材１２３の厚みは約１ｍｍである。さらに、本実施形態のストッパー部材１２３の通気孔の直径は０．３ｍｍである。なお、ストッパー部材１２３は、ガラスウールにより構成してもよい。 The stopper member 123 is disposed below the combustion chamber of the first combustion temperature measuring unit 120. This stopper member 123 is a metal plate, such as stainless steel, fitted to the inner surface of the pipe material 111, and has multiple ventilation holes (not shown). The diameter of these ventilation holes is smaller than the particle size (average value) of the catalyst 122. As a result, the fuel gas passes through the ventilation holes, but the catalyst 122 does not pass through the ventilation holes and accumulates on the stopper member 123. In this embodiment, the stopper member 123 is a circular plate. The thickness of the stopper member 123 in this embodiment is approximately 1 mm. The diameter of the ventilation holes in the stopper member 123 in this embodiment is 0.3 mm. The stopper member 123 may also be made of glass wool.
第２燃焼測温部１３０は、熱電対１３１と、触媒１３２と、ストッパー部材１３３と、ヒーター１３４とを備える。熱電対１３１は、熱電対１２１と同様の構成であり、熱電対素線１３１Ａと、シース１３１Ｂとを備え、ゼーベック効果を利用して温度を測定する。熱電対素線１３１Ａは、一端（図中の上端）に測温接点Ｐが設けられている。熱電対素線１３１Ａの他端（図中の下端）には、不図示の補償導線の一端が接続されている。この補償導線は、管材１１１の下流端（図中の下端）から引き出されており、データロガー１０３に接続されている。ここで、管材１１１の下流端には、補償導線が挿通される孔と、当該孔と補償導線との隙間を塞ぐ気密シール部とが形成されている（共に図示省略）。また、管材１１１の下流端には、不図示の排気孔が形成されている。なお、本実施形態の熱電対１３１は、非接地型であるが、熱電対１３１を接地型や露出型に変えてもよい。 The second combustion temperature measuring unit 130 includes a thermocouple 131, a catalyst 132, a stopper member 133, and a heater 134. The thermocouple 131 has a similar configuration to the thermocouple 121, including a thermocouple wire 131A and a sheath 131B, and measures temperature using the Seebeck effect. The thermocouple wire 131A has a temperature measuring junction P at one end (the upper end in the figure). The other end (the lower end in the figure) of the thermocouple wire 131A is connected to one end of a compensation wire (not shown). This compensation wire is pulled out from the downstream end (the lower end in the figure) of the tubular member 111 and connected to the data logger 103. The downstream end of the tubular member 111 is formed with a hole through which the compensation wire is inserted and an airtight seal (both not shown) that seals the gap between the hole and the compensation wire. The downstream end of the tubular member 111 also has an exhaust hole (not shown). In this embodiment, the thermocouple 131 is an ungrounded type, but the thermocouple 131 may be changed to a grounded type or an exposed type.
触媒１３２は、第２燃焼測温部１３０の燃焼室に充填された顆粒状の触媒である。触媒１３２の粒径は、粉末の粒径に比して数十倍～数百倍と大きい。触媒１３２の粒径は、１００μｍ未満に篩にかけて整粒するのは困難であり、１０００μｍより大きくすると管材１１１の内径と近くなって可燃性ガスとの接触が悪くなるという観点から、１００μｍ以上１０００μｍ以下が好ましく、３５５μｍ以上４２０μｍ以下がより好ましい。また、触媒１３２は、メタン等の燃料ガスに含まれる水素以外の可燃性ガスを加熱下で燃焼させることが可能な触媒であり、例えば、パラジウム（Ｐｄ）や白金（Ｐｔ）等の金属や金属酸化物が担持したもの等である。 Catalyst 132 is a granular catalyst filled into the combustion chamber of the second combustion temperature measuring unit 130. The particle size of catalyst 132 is several tens to several hundred times larger than the particle size of powder. It is difficult to sift the particle size of catalyst 132 to less than 100 μm, and a particle size larger than 1000 μm would approach the inner diameter of pipe material 111, resulting in poor contact with flammable gas. Therefore, a particle size of 100 μm to 1000 μm is preferred, with a particle size of 355 μm to 420 μm being more preferred. Furthermore, catalyst 132 is a catalyst capable of burning flammable gases other than hydrogen contained in fuel gases such as methane under heat, and is, for example, supported by a metal or metal oxide such as palladium (Pd) or platinum (Pt).
第２燃焼測温部１３０の燃焼室に充填された触媒１３２の質量及び充填高さは、測温接点Ｐが触媒１３２から露出するように適宜設定すればよく、例えば、管材１１１の内径が４ｍｍの場合で０．０７５ｇ、約３ｍｍ等である。なお、測温接点Ｐが触媒１３２から露出することは必須ではなく、触媒１３２が測温接点Ｐを覆うように第２燃焼測温部１３０の燃焼室に充填されてもよい。 The mass and filling height of the catalyst 132 filled in the combustion chamber of the second combustion temperature measuring unit 130 may be set appropriately so that the temperature measurement contact point P is exposed from the catalyst 132. For example, if the inner diameter of the pipe material 111 is 4 mm, this is 0.075 g and approximately 3 mm. Note that it is not necessary for the temperature measurement contact point P to be exposed from the catalyst 132; the catalyst 132 may be filled in the combustion chamber of the second combustion temperature measuring unit 130 so that it covers the temperature measurement contact point P.
シース１３１Ｂの一端側（図中の上端側）の表面には、触媒層１３１Ｓが測温接点Ｐを覆うように形成されている。この触媒層１３１Ｓは、パラジウムや白金等の触媒により構成された塗膜とすればよい。この触媒層１３１Ｓの形成方法としては、粉末状の触媒と蒸留水等とを混合した液状の触媒をシース１３１Ｂに塗布して乾燥させる方法を例示できる。 A catalyst layer 131S is formed on the surface of one end of the sheath 131B (the upper end in the figure) so as to cover the temperature measurement contact P. This catalyst layer 131S may be a coating made of a catalyst such as palladium or platinum. One method for forming this catalyst layer 131S is to apply a liquid catalyst, which is a mixture of powdered catalyst and distilled water, to the sheath 131B and then dry it.
この触媒層１３１Ｓのシース１３１Ｂの一端（先端）からの長さは例えば約１ｍｍとすればよく、測温接点Ｐの位置を含むシース１３１Ｂの一端から約１ｍｍの範囲を覆うようにすればよい。この触媒層１３１Ｓの大部分又は全体が触媒１３２から露出するようにしてもよく、この触媒層１３１Ｓが触媒１３２に覆われるようにしてもよい。なお、触媒層１３１Ｓを設けることは必須ではない。 The length of this catalyst layer 131S from one end (tip) of the sheath 131B may be, for example, approximately 1 mm, and it may cover an area of approximately 1 mm from one end of the sheath 131B, including the position of the temperature measurement junction P. Most or all of this catalyst layer 131S may be exposed from the catalyst 132, or this catalyst layer 131S may be covered by the catalyst 132. Note that providing a catalyst layer 131S is not essential.
ストッパー部材１３３は、第２燃焼測温部１３０の燃焼室の下側に配されている。このストッパー部材１３３は、管材１１１の内周面に嵌合したステンレス等の金属製の板であり、不図示の複数の通気孔が形成されている。この通気孔の直径は、触媒１３２の粒径（平均値）よりも小さい。これにより、燃料ガスは、通気孔は通過するが、触媒１３２は、通気孔を通過せずにストッパー部材１３３の上に堆積する。本実施形態のストッパー部材１３３は円板である。また、本実施形態のストッパー部材１３３の厚みは約１ｍｍである。さらに、本実施形態のストッパー部材１３３の通気孔の直径は０．３ｍｍである。なお、ストッパー部材１３３は、ガラスウールにより構成してもよい。 The stopper member 133 is disposed below the combustion chamber of the second combustion temperature measuring unit 130. This stopper member 133 is a metal plate, such as stainless steel, fitted to the inner surface of the pipe material 111, and has multiple ventilation holes (not shown). The diameter of these ventilation holes is smaller than the particle diameter (average value) of the catalyst 132. As a result, the fuel gas passes through the ventilation holes, but the catalyst 132 does not pass through the ventilation holes and accumulates on the stopper member 133. In this embodiment, the stopper member 133 is a circular plate. The thickness of the stopper member 133 in this embodiment is approximately 1 mm. The diameter of the ventilation holes in the stopper member 133 in this embodiment is 0.3 mm. The stopper member 133 may also be made of glass wool.
ヒーター１３４は、管材１１１が挿通されたコイル型のヒーターである。このヒーター１３４のコイル部１３４Ａは、少なくとも管材１１１の第２燃焼測温部１３０の燃焼室を含む範囲の周囲に巻回されている。コイル部１３４Ａは、リード部１３４Ｂを介して定電圧源１０２に接続されており、定電圧源１０２から電圧を印加されることにより発熱する。コイル部１３４Ａが定電圧源１０２から電圧を印加されることにより発熱すると、触媒１３２が所定の温度に加熱される。なお、コイル部１３４Ａは、管材１１１の第１燃焼測温部１２０の燃焼室から離間して配されており、第１燃焼測温部１２０の触媒１２２は、ヒーター１３４により加熱されることはなく、常温に維持される。 The heater 134 is a coil-type heater through which the tubular material 111 is inserted. The coil portion 134A of this heater 134 is wound around an area that includes at least the combustion chamber of the second combustion temperature measuring unit 130 of the tubular material 111. The coil portion 134A is connected to the constant voltage source 102 via the lead portion 134B, and generates heat when a voltage is applied from the constant voltage source 102. When the coil portion 134A generates heat as a result of the application of voltage from the constant voltage source 102, the catalyst 132 is heated to a predetermined temperature. Note that the coil portion 134A is positioned away from the combustion chamber of the first combustion temperature measuring unit 120 of the tubular material 111, and the catalyst 122 of the first combustion temperature measuring unit 120 is not heated by the heater 134 and is maintained at room temperature.
燃焼測温部１１０は、不図示の保護容器に収容されている。この保護容器は、例えば風の影響により、熱電対１２１，１３１の測定温度が変動することを抑制している。この保護容器には、燃料ガスの燃焼で発生した排ガスを保護容器外へ排出するための排気孔が設けられている。 The combustion temperature measuring unit 110 is housed in a protective container (not shown). This protective container prevents fluctuations in the temperatures measured by the thermocouples 121 and 131 due to, for example, wind. The protective container is provided with an exhaust hole for discharging exhaust gases generated by the combustion of fuel gas outside the protective container.
データロガー１０３は、熱電対１２１から出力される信号、即ち、第１燃焼測温部１２０の触媒１２２及び触媒層１２１Ｓでの水素の燃焼による上昇温度ΔＴＨ［℃］を記録する。また、データロガー１０３は、熱電対１３１から出力される信号、即ち、第２燃焼測温部１３０の触媒１３２での水素以外の可燃性ガスの燃焼による上昇温度ΔＴＥ［℃］を記録する。 The data logger 103 records the signal output from the thermocouple 121, i.e., the temperature rise ΔT H [°C] due to the combustion of hydrogen in the catalyst 122 and catalyst layer 121S of the first combustion temperature measuring unit 120. The data logger 103 also records the signal output from the thermocouple 131, i.e., the temperature rise ΔT E [°C] due to the combustion of a combustible gas other than hydrogen in the catalyst 132 of the second combustion temperature measuring unit 130.
演算装置１０４は、データロガー１０３の記録内容に基づいて燃焼測温部１１０に供給された燃料ガスの燃焼時の発熱量を演算する。発熱量を演算するに際し、演算装置１０４には、第１流量計１４Ａ及び第２流量計１４Ｂ（図１参照）の測定値も入力される。演算装置１０４としては、例えばＰＣ（Personal Computer）を用いることができる。 The calculation device 104 calculates the calorific value during combustion of the fuel gas supplied to the combustion temperature measuring unit 110 based on the contents recorded by the data logger 103. When calculating the calorific value, the calculation device 104 also receives the measured values of the first flow meter 14A and the second flow meter 14B (see Figure 1). The calculation device 104 can be, for example, a PC (Personal Computer).
以上のような構成の熱量計１００において、演算装置１０４は、熱電対１２１，１３１により測定されてデータロガー１０３に記録された上昇温度ΔＴＨ［℃］，ΔＴＥ［℃］に基づいて、燃料ガスの燃焼時の発熱量を演算する。演算装置１０４には、熱電対１２１，１３１の測定温度の変化と燃料ガスの燃焼時の発熱量との相関関係を示す相関データが記憶されており、演算装置１０４は、この相関データを利用して、燃料ガスの燃焼時の発熱量を演算する。 In the calorimeter 100 configured as described above, the arithmetic unit 104 calculates the calorific value of the fuel gas during combustion based on the temperature rises ΔT H [°C] and ΔT E [°C] measured by the thermocouples 121 and 131 and recorded in the data logger 103. The arithmetic unit 104 stores correlation data that indicates the correlation between the change in the measured temperatures of the thermocouples 121 and 131 and the calorific value of the fuel gas during combustion, and uses this correlation data to calculate the calorific value of the fuel gas during combustion.
具体的には、制御装置（図示省略）が、図１に示す第１バルブ１５Ａ、第２バルブ１５Ｂ、及び混合器１６を制御し、可燃性ガスを第１配管１１に流し、空気を第２配管１２に流し、可燃性ガスと空気とを混合器１６にて混合する。これにより、所定濃度の可燃性ガスを含む燃料ガスを生成する。この燃料ガスは、第３配管１３を通じて熱量計１００に供給される。この際、第１流量計１４Ａは、第１配管１１を流れる可燃性ガスの流量を測定して測定情報を演算装置１０４に出力し、第２流量計１４Ｂは、第２配管１２を流れる空気の流量を測定して測定情報を演算装置１０４に出力する。 Specifically, a control device (not shown) controls the first valve 15A, second valve 15B, and mixer 16 shown in FIG. 1 to flow flammable gas into the first pipe 11 and air into the second pipe 12, and mixes the flammable gas and air in the mixer 16. This generates fuel gas containing a predetermined concentration of flammable gas. This fuel gas is supplied to the calorimeter 100 through the third pipe 13. At this time, the first flow meter 14A measures the flow rate of the flammable gas flowing through the first pipe 11 and outputs the measurement information to the calculation device 104, and the second flow meter 14B measures the flow rate of the air flowing through the second pipe 12 and outputs the measurement information to the calculation device 104.
定電圧源１０２はヒーター１３４に電圧を印加しており、第２燃焼測温部１３０の熱電対１３１のベース温度は例えば２５０～４００℃程度となる。この状態において、燃料ガスに含まれる水素以外の可燃性ガスの燃焼時の発熱によって熱電対１３１の測温接点Ｐの周囲の温度が上昇する。熱電対１３１は、測温接点Ｐの周囲の温度に応じた信号をデータロガー１０３に送信し、データロガー１０３はこれを記憶する。 The constant voltage source 102 applies a voltage to the heater 134, and the base temperature of the thermocouple 131 of the second combustion temperature measuring unit 130 is, for example, approximately 250 to 400°C. In this state, the temperature around the temperature measuring junction P of the thermocouple 131 rises due to heat generated during combustion of combustible gases other than hydrogen contained in the fuel gas. The thermocouple 131 transmits a signal corresponding to the temperature around the temperature measuring junction P to the data logger 103, which stores this signal.
他方で、第１燃焼測温部１２０の熱電対１２１のベース温度は常温である。この状態において、燃料ガスに含まれる水素の燃焼時の発熱によって熱電対１２１の測温接点Ｐの周囲の温度が上昇する。熱電対１２１は、測温接点Ｐの周囲の温度に応じた信号をデータロガー１０３に送信し、データロガー１０３はこれを記憶する。 On the other hand, the base temperature of the thermocouple 121 of the first combustion temperature measuring unit 120 is room temperature. In this state, the temperature around the temperature measuring junction P of the thermocouple 121 rises due to heat generated during combustion of the hydrogen contained in the fuel gas. The thermocouple 121 transmits a signal corresponding to the temperature around the temperature measuring junction P to the data logger 103, which stores this signal.
演算装置１０４は、予め記憶している相関データと、データロガー１０３が記憶した熱電対１２１，１３１の測温情報と、第１流量計１４Ａ及び第２流量計１４Ｂの流量情報とから、燃料ガスの燃焼時の発熱量を演算する。ここで、演算装置１０４は、熱電対１２１から出力されてデータロガー１０３に記憶された水素の燃焼による上昇温度ΔＴＨ［℃］と、第１流量計１４Ａ及び第２流量計１４Ｂの流量情報とから、熱量ＱＨを算出する。また、演算装置１０４は、熱電対１３１から出力されてデータロガー１０３に記憶された水素以外の可燃性ガスの燃焼による上昇温度ΔＴＥ［℃］と、第１流量計１４Ａ及び第２流量計１４Ｂの流量情報とから、熱量ＱＥを算出する。そして、演算装置１０４は、熱量ＱＨと熱量ＱＥとを合計する。 The arithmetic device 104 calculates the amount of heat generated during combustion of the fuel gas from pre-stored correlation data, the temperature measurement information from the thermocouples 121 and 131 stored in the data logger 103, and the flow rate information from the first flow meter 14A and the second flow meter 14B. Here, the arithmetic device 104 calculates the amount of heat QH from the temperature rise ΔT H [°C] due to the combustion of hydrogen output from the thermocouple 121 and stored in the data logger 103 and the flow rate information from the first flow meter 14A and the second flow meter 14B. The arithmetic device 104 also calculates the amount of heat QE from the temperature rise ΔT E [°C] due to the combustion of a combustible gas other than hydrogen output from the thermocouple 131 and stored in the data logger 103 and the flow rate information from the first flow meter 14A and the second flow meter 14B. The arithmetic device 104 then sums the amount of heat QH and the amount of heat QE .
以下、本実施形態に係る熱量計１００の熱量測定の精度を確認するために実施された実験について説明する。本実験では、比較例に係る熱量計１００Ｃを用いた試験ガスの熱量測定と、本実施形態に係る熱量計１００を用いた試験ガスの熱量測定とを実施した。 The following describes an experiment conducted to confirm the accuracy of calorific value measurement by the calorimeter 100 according to this embodiment. In this experiment, calorific value measurement of a test gas was performed using the calorimeter 100C according to a comparative example, and calorific value measurement of a test gas was performed using the calorimeter 100 according to this embodiment.
図３は、比較例に係る熱量計１００Ｃの構成を示す断面図である。この図に示すように、比較例に係る熱量計１００Ｃの燃焼測温部１１０Ｃは、第１燃焼測温部１２０（図２参照）を備えず、第２燃焼測温部１３０を備える。即ち、比較例の燃焼測温部１１０Ｃでは、常温での水素の燃焼及びその燃焼による水素の上昇温度ΔＴＨ［℃］の測定は行われず、相対的に高温（本実験では３３０℃）での試験ガスの燃焼及びその燃焼による試験ガスの上昇温度ΔＴ［℃］の測定が行われる。 3 is a cross-sectional view showing the configuration of a calorimeter 100C according to a comparative example. As shown in this figure, the combustion temperature measuring unit 110C of the comparative example does not include the first combustion temperature measuring unit 120 (see FIG. 2), but includes a second combustion temperature measuring unit 130. That is, the combustion temperature measuring unit 110C of the comparative example does not measure the combustion of hydrogen at room temperature and the temperature rise ΔT H [°C] of the hydrogen caused by that combustion, but measures the combustion of a test gas at a relatively high temperature (330°C in this experiment) and the temperature rise ΔT [°C] of the test gas caused by that combustion.
この比較例に係る熱量計１００Ｃの燃焼測温部１１０Ｃに以下のＮｏ１．～Ｎｏ．５の５種類の試験ガスを供給して当該試験ガスの燃焼による熱量Ｑ’［Ｊ］と上昇温度ΔＴ［℃］とを測定した。
Ｎｏ．１１：単位体積当たり発熱量＝３２ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Ｎｏ．１２：単位体積当たり発熱量＝３６ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Ｎｏ．１３：単位体積当たり発熱量＝４０ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Ｎｏ．１４：単位体積当たり発熱量＝４３ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Ｎｏ．１５：単位体積当たり発熱量＝４５ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Five types of test gases, No. 1 to No. 5, were supplied to the combustion temperature measuring unit 110C of the calorimeter 100C according to this comparative example, and the calorific value Q′ [J] and the temperature rise ΔT [°C] due to the combustion of the test gases were measured.
No. 11: Calorific value per unit volume = 32 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
No. 12: Calorific value per unit volume = 36 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
No. 13: Calorific value per unit volume = 40 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
No. 14: Calorific value per unit volume = 43 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
No. 15: Calorific value per unit volume = 45 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
図４は、比較例に係る熱量計１００Ｃを用いてＮｏ．１１～Ｎｏ．１５の試験ガスの熱量Ｑ’［Ｊ］と上昇温度ΔＴ［℃］とを測定した結果を示すグラフである。このグラフに示すように、燃料ガスの熱量Ｑ’［Ｊ］と上昇温度ΔＴ［℃］との決定係数Ｒ２＝０．９９８となり、上昇温度ΔＴ［℃］の測定誤差は最大で０．４３％となった。以上により、燃料ガスが水素を含まない場合には、熱量Ｑ’［Ｊ］と上昇温度ΔＴ［℃］とを高精度に測定できることが確認された。 4 is a graph showing the results of measuring the calorific value Q' [J] and temperature rise ΔT [°C] of test gases No. 11 to No. 15 using the calorimeter 100C according to the comparative example. As shown in this graph, the coefficient of determination R2 between the calorific value Q' [J] and temperature rise ΔT [°C] of the fuel gas was 0.998, and the maximum measurement error of the temperature rise ΔT [°C] was 0.43%. From the above, it was confirmed that when the fuel gas does not contain hydrogen, the calorific value Q' [J] and temperature rise ΔT [°C] can be measured with high accuracy.
比較例に係る熱量計１００Ｃの燃焼測温部１１０Ｃに以下のＮｏ．１６～Ｎｏ．１８の３種類の試験ガスを供給して当該燃料ガスの燃焼による単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］を測定した。
Ｎｏ．１６：単位体積当たり発熱量＝３４．５ＭＪ／Ｎｍ３、Ｈ２＝２０％、ＣＨ４＝８０％
Ｎｏ．１７：単位体積当たり発熱量＝３７ＭＪ／Ｎｍ３、Ｈ２＝１０％、ＣＨ４＝９０％
Ｎｏ．１８：単位体積当たり発熱量＝４５ＭＪ／Ｎｍ３、Ｈ２＝２０％、ＣＨ４＝８０％
The following three types of test gases, No. 16 to No. 18, were supplied to the combustion temperature measuring section 110C of the calorimeter 100C according to the comparative example, and the calorific value Q [MJ/Nm 3 ] per unit volume due to the combustion of the fuel gases was measured.
No. 16: Calorific value per unit volume = 34.5 MJ/Nm 3 , H 2 = 20%, CH 4 = 80%
No. 17: Calorific value per unit volume = 37 MJ/Nm 3 , H 2 = 10%, CH 4 = 90%
No. 18: Calorific value per unit volume = 45 MJ/Nm 3 , H 2 = 20%, CH 4 = 80%
図５は、比較例に係る熱量計１００Ｃを用いてＮｏ．１６～Ｎｏ．１８の試験ガスの単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］を測定した結果を示すグラフである。このグラフに示すように、試験ガスの単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］の真値と算出値との間には、最大で１０．０％の測定誤差が生じた。具体的には、Ｎｏ．１６の試験ガスの単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］については、１０．０％の誤差の分だけ真値に対して過小に評価された。また、Ｎｏ．１７の試験ガスの単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］については、４．３％の誤差の分だけ真値に対して過小に評価された。さらに、Ｎｏ．１８の試験ガスの単位体積当たり熱量Ｑ［ＭＪ／Ｎｍ３］については、８．４％の誤差の分だけ真値に対して過小に評価された。 5 is a graph showing the results of measuring the calorific value per unit volume Q [MJ/Nm 3 ] of test gases No. 16 to No. 18 using the calorimeter 100C according to the comparative example. As shown in this graph, a measurement error of up to 10.0% occurred between the true value and the calculated value of the calorific value per unit volume Q [MJ/Nm 3 ] of the test gases. Specifically, the calorific value per unit volume Q [MJ/Nm 3 ] of test gas No. 16 was underestimated by an error of 10.0%. Furthermore, the calorific value per unit volume Q [MJ/Nm 3 ] of test gas No. 17 was underestimated by an error of 4.3%. Furthermore, the calorific value per unit volume Q [MJ/Nm 3 ] of test gas No. 18 was underestimated by an error of 8.4%.
本実施形態に係る熱量計１００に以下のＮｏ１．～Ｎｏ．４の４種類の試験ガスを連続的に供給して水素、メタンの濃度と燃焼による上昇温度ΔＴＨ［℃］，ΔＴＥ［℃］との相関を確認するための実験を実施した。本実験では、３ｍＬ／ｍｉｎの流量の試験ガスと９７ｍＬ／ｍｉｎの流量の空気とを連続的に熱量計１００に供給し、第１燃焼測温部１２０による上昇温度ΔＴＨ［℃］の測定と、第２燃焼測温部１３０による上昇温度ΔＴＥ［℃］の測定とを連続的に行った。
Ｎｏ．１：単位体積当たり発熱量＝３９．９ＭＪ／Ｎｍ３、Ｈ２＝０％、ＣＨ４＝１００％
Ｎｏ．２：単位体積当たり発熱量＝３４．７ＭＪ／Ｎｍ３、Ｈ２＝１９．２％、ＣＨ４＝８０．８％
Ｎｏ．３：単位体積当たり発熱量＝２６．３ＭＪ／Ｎｍ３、Ｈ２＝５０％、ＣＨ４＝５０％
Ｎｏ．４：単位体積当たり発熱量＝１２．８ＭＪ／Ｎｍ３、Ｈ２＝１００％、ＣＨ４＝０％
An experiment was conducted to confirm the correlation between the concentrations of hydrogen and methane and the temperature rises ΔT H [°C] and ΔT E [°C] due to combustion by continuously supplying the following four types of test gases, No. 1 to No. 4, to the calorimeter 100 according to this embodiment. In this experiment, the test gas at a flow rate of 3 mL/min and air at a flow rate of 97 mL/min were continuously supplied to the calorimeter 100, and the temperature rise ΔT H [°C] was measured by the first combustion temperature measuring unit 120 and the temperature rise ΔT E [°C] was measured by the second combustion temperature measuring unit 130 continuously.
No. 1: Calorific value per unit volume = 39.9 MJ/Nm 3 , H 2 = 0%, CH 4 = 100%
No. 2: Calorific value per unit volume = 34.7 MJ/Nm 3 , H 2 = 19.2%, CH 4 = 80.8%
No. 3: Calorific value per unit volume = 26.3 MJ/Nm 3 , H 2 = 50%, CH 4 = 50%
No. 4: Calorific value per unit volume = 12.8 MJ/Nm 3 , H 2 = 100%, CH 4 = 0%
図６は、本実施形態に係る熱量計１００にＮｏ．１～Ｎｏ．４の試験ガスを連続的に供給して水素、メタンの濃度と燃焼による上昇温度ΔＴＨ［℃］，ΔＴＥ［℃］との相関を確認した結果を示す表及びグラフである。これらの表及びグラフに示すように、水素の濃度が高くなるほど、第１燃焼測温部１２０により測定される上昇温度ΔＴＨ［℃］が高くなり、第２燃焼測温部１３０により測定される上昇温度ΔＴＥ［℃］が低くなることが確認された。他方で、メタンの濃度が高くなるほど、第２燃焼測温部１３０により測定される上昇温度ΔＴＥ［℃］が高くなり、第１燃焼測温部１２０により測定される上昇温度ΔＴＨ［℃］が低くなることが確認された。 6 is a table and graph showing the results of confirming the correlation between the concentrations of hydrogen and methane and the temperature rise ΔT H [°C] and ΔT E [°C] due to combustion when test gases No. 1 to No. 4 were continuously supplied to the calorimeter 100 according to this embodiment. As shown in these tables and graphs, it was confirmed that the higher the hydrogen concentration, the higher the temperature rise ΔT H [°C] measured by the first combustion temperature measuring unit 120, and the lower the temperature rise ΔT E [°C] measured by the second combustion temperature measuring unit 130. On the other hand, it was confirmed that the higher the methane concentration, the higher the temperature rise ΔT E [°C] measured by the second combustion temperature measuring unit 130, and the lower the temperature rise ΔT H [°C] measured by the first combustion temperature measuring unit 120.
本実施形態に係る熱量計１００に上記のＮｏ１．～Ｎｏ．４の試験ガスを間欠的に供給して水素、メタンの濃度と燃焼による上昇温度ΔＴ［℃］との相関を確認するための実験を実施した。本実験では、８５ｍＬ／ｍｉｎの流量の空気を連続的に熱量計１００に供給しながら体積が０．３６ｍＬの燃料ガスを間欠的に熱量計１００に供給し、第１燃焼測温部１２０による上昇温度ΔＴＨ［℃］の測定と、第２燃焼測温部１３０による上昇温度ΔＴＥ［℃］の測定とを間欠的に行った。 An experiment was conducted to confirm the correlation between the concentrations of hydrogen and methane and the temperature rise ΔT [°C] due to combustion by intermittently supplying the above-mentioned test gases No. 1 to No. 4 to the calorimeter 100 according to this embodiment. In this experiment, air was continuously supplied to the calorimeter 100 at a flow rate of 85 mL/min, while a fuel gas with a volume of 0.36 mL was intermittently supplied to the calorimeter 100, and the temperature rise ΔT H [°C] was measured by the first combustion temperature measuring unit 120 and the temperature rise ΔT E [°C] was measured by the second combustion temperature measuring unit 130 intermittently.
図７は、本実施形態に係る熱量計１００にＮｏ．１～Ｎｏ．４の試験ガスを間欠的に供給して水素、メタンの濃度と燃焼による上昇温度ΔＴＨ［℃］，ΔＴＥ［℃］との相関を確認した結果を示す表及びグラフである。これらの表及びグラフに示すように、水素の濃度が高くなるほど、第１燃焼測温部１２０により測定される上昇温度ΔＴＨ［℃］が高くなり、第２燃焼測温部１３０により測定される上昇温度ΔＴＥ［℃］が低くなることが確認された。他方で、メタンの濃度が高くなるほど、第２燃焼測温部１３０により測定される上昇温度ΔＴＥ［℃］が高くなり、第１燃焼測温部１２０により測定される上昇温度ΔＴＨ［℃］が低くなることが確認された。 7 is a table and graph showing the results of confirming the correlation between the concentrations of hydrogen and methane and the temperature rise ΔT H [°C] and ΔT E [°C] due to combustion when test gases No. 1 to No. 4 are intermittently supplied to the calorimeter 100 according to this embodiment. As shown in these tables and graphs, it was confirmed that the higher the hydrogen concentration, the higher the temperature rise ΔT H [°C] measured by the first combustion temperature measuring unit 120, and the lower the temperature rise ΔT E [°C] measured by the second combustion temperature measuring unit 130. On the other hand, it was confirmed that the higher the methane concentration, the higher the temperature rise ΔT E [°C] measured by the second combustion temperature measuring unit 130, and the lower the temperature rise ΔT H [°C] measured by the first combustion temperature measuring unit 120.
以上説明したように、本実施形態に係る熱量計１００の燃焼測温部１１０は、燃料ガスに含まれる水素を常温で燃焼させてその燃焼による上昇温度ΔＴＨ［℃］を測定する第１燃焼測温部１２０と、燃料ガスに含まれる水素以外の可燃性ガスを加熱下で燃焼させてその燃焼による上昇温度ΔＴＥ［℃］を測定する第２燃焼測温部１３０とを備える。これにより、水素を含む燃料ガスの熱量を、水素の燃焼による上昇温度ΔＴＨ［℃］とメタン等の水素以外の可燃性ガスの燃焼による上昇温度ΔＴＥ［℃］とに基づいて算出することが可能になる。従って、燃料ガスに水素が含まれることに起因する燃料ガスの熱量測定の精度低下を抑制でき、水素を含む燃料ガスの熱量測定の高精度化を実現できる。 As described above, the combustion temperature measuring unit 110 of the calorimeter 100 according to this embodiment includes a first combustion temperature measuring unit 120 that burns hydrogen contained in the fuel gas at room temperature and measures the temperature rise ΔT H [°C] caused by the combustion, and a second combustion temperature measuring unit 130 that burns a flammable gas other than hydrogen contained in the fuel gas under heating and measures the temperature rise ΔT E [°C] caused by the combustion. This makes it possible to calculate the calorific value of fuel gas containing hydrogen based on the temperature rise ΔT H [°C] caused by the combustion of hydrogen and the temperature rise ΔT E [°C] caused by the combustion of flammable gases other than hydrogen, such as methane. Therefore, it is possible to suppress a decrease in accuracy in calorific value measurement of fuel gas caused by the presence of hydrogen in the fuel gas, and to achieve high accuracy in calorific value measurement of fuel gas containing hydrogen.
また、本実施形態に係る熱量計１００では、演算装置１０４が、第１燃焼測温部１２０の熱電対１２１により測定された水素の燃焼による上昇温度ΔＴＨ［℃］に基づいて熱量ＱＨを算出し、第２燃焼測温部１３０により測定された水素以外の可燃性ガスの燃焼による上昇温度ΔＴＥ［℃］に基づいて熱量ＱＥを算出し、熱量の合計値（ＱＨ＋ＱＥ）［℃］を算出する。これによって、水素を含む燃料ガスの熱量を、当該熱量に相応した上昇温度ΔＴＨ［℃］，ΔＴＥ［℃］に基づいて高精度に算出することが可能になる。 Furthermore, in the calorimeter 100 according to this embodiment, the arithmetic unit 104 calculates the calorific value QH based on the temperature rise ΔT H [°C] due to the combustion of hydrogen measured by the thermocouple 121 of the first combustion temperature measuring unit 120, calculates the calorific value QE based on the temperature rise ΔT E [°C] due to the combustion of a combustible gas other than hydrogen measured by the second combustion temperature measuring unit 130 , and calculates the total value of the calorific values (Q H + Q E ) [°C]. This makes it possible to calculate the calorific value of the fuel gas containing hydrogen with high accuracy based on the temperature rises ΔT H [°C] and ΔT E [°C] corresponding to the calorific values.
また、本実施形態に係る熱量計１００では、第１燃焼測温部１２０の触媒１２２、及び第２燃焼測温部１３０の触媒１３２が、燃料ガスが第１燃焼測温部１２０の触媒１２２を通過し、この触媒１２２を通過した燃料ガスが第２燃焼測温部１３０の触媒１３２を通過するように、管材１１１に収容されている。即ち、本実施形態に係る熱量計１００では、第１燃焼測温部１２０と第２燃焼測温部１３０とが直列に接続されている。これによって、燃料ガスに含まれる水素が第１燃焼測温部１２０において常温で燃焼し、燃料ガスに含まれる水素以外の可燃性ガスが第２燃焼測温部１３０において加熱下で燃焼する。即ち、燃料ガスに含まれる水素と水素以外の可燃性ガスとが、管材１１１内の燃焼部を必ず通過する。従って、燃料ガスに含まれる水素と水素以外の可燃性ガスとが、燃焼することなく管材１１１から排気されることを防止できる。 In addition, in the calorimeter 100 according to this embodiment, the catalyst 122 of the first combustion temperature measuring unit 120 and the catalyst 132 of the second combustion temperature measuring unit 130 are housed in the tubular material 111 so that the fuel gas passes through the catalyst 122 of the first combustion temperature measuring unit 120, and the fuel gas that has passed through this catalyst 122 passes through the catalyst 132 of the second combustion temperature measuring unit 130. That is, in the calorimeter 100 according to this embodiment, the first combustion temperature measuring unit 120 and the second combustion temperature measuring unit 130 are connected in series. As a result, hydrogen contained in the fuel gas burns at room temperature in the first combustion temperature measuring unit 120, and flammable gases other than hydrogen contained in the fuel gas burn under heating in the second combustion temperature measuring unit 130. That is, the hydrogen contained in the fuel gas and flammable gases other than hydrogen always pass through the combustion section within the tubular material 111. This prevents hydrogen contained in the fuel gas and flammable gases other than hydrogen from being exhausted from the pipe material 111 without being combusted.
図８は、本発明の他の実施形態に係る熱量計２００の構成を示す断面図である。この図に示すように、本実施形態に係る熱量計２００は、第１燃焼測温部１２０と第２燃焼測温部１３０とが並列に配された燃焼測温部２１０を備える。この燃焼測温部２１０は、第１管材２１１と第２管材２１２とを備える。 Figure 8 is a cross-sectional view showing the configuration of a calorimeter 200 according to another embodiment of the present invention. As shown in this figure, the calorimeter 200 according to this embodiment includes a combustion temperature measuring unit 210 in which a first combustion temperature measuring unit 120 and a second combustion temperature measuring unit 130 are arranged in parallel. This combustion temperature measuring unit 210 includes a first pipe material 211 and a second pipe material 212.
第１管材２１１の一端には、第３配管１３が接続されている。また、第２管材２１２の一端には、第３配管１３から分岐した第４配管１４が接続されている。第１管材２１１及び第２管材２１２は、燃料ガスの燃焼時の温度に対する耐熱性と、燃焼時の燃料ガスの管外への放熱を抑える低い伝熱性とを有する管材である。本実施形態の第１管材２１１及び第２管材２１２は、内径が４ｍｍの円筒状のセラミックチューブである。なお、第１管材２１１及び第２管材２１２の内径は、２ｍｍ以上１０ｍｍ以下が好ましい。また、第１管材２１１及び第２管材２１２はステンレスチューブでもよい。 The third pipe 13 is connected to one end of the first pipe 211. Furthermore, the fourth pipe 14, which branches off from the third pipe 13, is connected to one end of the second pipe 212. The first pipe 211 and the second pipe 212 are pipes that are heat resistant to the temperature during combustion of the fuel gas and have low thermal conductivity that prevents the fuel gas from radiating heat outside the pipe during combustion. In this embodiment, the first pipe 211 and the second pipe 212 are cylindrical ceramic tubes with an inner diameter of 4 mm. The inner diameter of the first pipe 211 and the second pipe 212 is preferably 2 mm or more and 10 mm or less. The first pipe 211 and the second pipe 212 may also be stainless steel tubes.
上述したように、本実施形態の燃焼測温部２１０では、第１燃焼測温部１２０と第２燃焼測温部１３０とが燃料ガスの流れ方向に対して並列に配されている。このため、第３配管１３から第１管材２１１に供給された燃料ガスは、第１燃焼測温部１２０を通過する。この際、燃料ガスに含まれる水素が常温で燃焼されその燃焼による水素の上昇温度ΔＴＨ［℃］が測定される。他方で、第４配管１４から第２管材２１２に供給された燃料ガスは、第２燃焼測温部１３０を通過する。この際、燃料ガスに含まれるメタン等の水素以外の可燃性ガスが、加熱下で燃焼されその燃焼による当該可燃性ガスの上昇温度ΔＴＥ［℃］が測定される。 As described above, in the combustion temperature measuring unit 210 of this embodiment, the first combustion temperature measuring unit 120 and the second combustion temperature measuring unit 130 are arranged in parallel with the flow direction of the fuel gas. Therefore, the fuel gas supplied from the third pipe 13 to the first pipe 211 passes through the first combustion temperature measuring unit 120. At this time, hydrogen contained in the fuel gas is burned at room temperature, and the temperature rise ΔT H [°C] of the hydrogen due to the combustion is measured. On the other hand, the fuel gas supplied from the fourth pipe 14 to the second pipe 212 passes through the second combustion temperature measuring unit 130. At this time, combustible gases other than hydrogen, such as methane, contained in the fuel gas are burned under heating, and the temperature rise ΔT E [°C] of the combustible gas due to the combustion is measured.
以上のような構成の熱量計２００において、演算装置１０４は、熱電対１２１から出力されてデータロガー１０３に記憶された水素の燃焼による上昇温度ΔＴＨ［℃］と、第１流量計１４Ａ及び第２流量計１４Ｂの流量情報とから、熱量ＱＨを算出する。また、熱電対１３１から出力されてデータロガー１０３に記憶された水素以外の可燃性ガスの燃焼による上昇温度ΔＴＥ［℃］と、第１流量計１４Ａ及び第２流量計１４Ｂの流量情報とから、熱量ＱＥを算出する。そして、演算装置１０４は、算出した熱量ＱＨと熱量ＱＥとを合計する。 In the calorimeter 200 configured as described above, the arithmetic device 104 calculates the calorific value QH from the temperature rise ΔT H [°C] due to the combustion of hydrogen output from the thermocouple 121 and stored in the data logger 103, and the flow rate information of the first flow meter 14A and the second flow meter 14B. Also, the arithmetic device 104 calculates the calorific value QE from the temperature rise ΔT E [°C] due to the combustion of a combustible gas other than hydrogen output from the thermocouple 131 and stored in the data logger 103 , and the flow rate information of the first flow meter 14A and the second flow meter 14B. Then, the arithmetic device 104 sums the calculated calorific values QH and QE .
以上、上記実施形態に基づき本発明を説明したが、本発明は上記実施形態に限られるものではなく、本発明の趣旨を逸脱しない範囲で、変更を加えてもよいし、適宜公知や周知の技術を組み合わせてもよい。 The present invention has been described above based on the above embodiment, but the present invention is not limited to the above embodiment, and modifications may be made or publicly known or well-known technologies may be combined as appropriate without departing from the spirit of the present invention.
例えば、上記実施形態では、触媒１２２，１３２を顆粒状にしたが、触媒１２２，１３２を粉末状にしてもよい。また、管材１１１、第１管材２１１、及び第２管材２１２を縦向きとしたが、管材１１１、第１管材２１１、及び第２管材２１２を横向きにしてもよい。また、燃焼測温部１１０，２１０の構造は、上記実施形態の構成には限らず、適宜変更してもよい。 For example, in the above embodiment, the catalysts 122, 132 are granular, but the catalysts 122, 132 may also be powdered. Furthermore, while the pipe material 111, the first pipe material 211, and the second pipe material 212 are oriented vertically, the pipe material 111, the first pipe material 211, and the second pipe material 212 may also be oriented horizontally. Furthermore, the structure of the combustion temperature measuring units 110, 210 is not limited to the configuration in the above embodiment and may be modified as appropriate.
また、上記実施形態では、測温体として熱電対１２１，１３１を用いたが、測温抵抗体等の他の測温体を用いてもよい。 In addition, in the above embodiment, thermocouples 121 and 131 are used as temperature sensors, but other temperature sensors such as resistance thermometers may also be used.
１００ 熱量計
１０４ 演算装置（算出部）
１１１ 管材
１２１ 熱電対（第１測温体）
１２２ 触媒（第１触媒）
１３１ 熱電対（第２測温体）
１３２ 触媒（第２触媒）
１３４ ヒーター（加熱部）
２００ 熱量計
Ｐ 測温接点
ΔＴＨ 上昇温度
ΔＴＥ 上昇温度
ＱＨ 熱量（第１熱量）
ＱＥ 熱量（第２熱量）
100 Calorimeter 104 Arithmetic unit (calculation unit)
111 Pipe material 121 Thermocouple (first temperature measuring element)
122 catalyst (first catalyst)
131 Thermocouple (second temperature measuring element)
132 Catalyst (second catalyst)
134 heater (heating part)
200 Calorimeter P Temperature measurement junction ΔT H temperature rise ΔT E temperature rise Q H heat quantity (first heat quantity)
Q E calorie (secondary calorie)
Claims (3)
前記水素を常温で燃焼させるための第１触媒と、
前記第１触媒における常温での燃焼による前記水素の上昇温度を測定する第１測温体と、
前記燃料ガスに含まれる前記水素以外の可燃性ガスを加熱下で燃焼させるための第２触媒と、
前記第２触媒を加熱する加熱部と、
前記第２触媒における加熱下での燃焼による前記可燃性ガスの上昇温度を測定する第２測温体と
を備える熱量計。 A calorimeter for measuring the calorific value of a fuel gas containing hydrogen,
a first catalyst for burning the hydrogen at room temperature;
a first temperature measuring element for measuring a temperature rise of the hydrogen due to combustion at room temperature in the first catalyst;
a second catalyst for burning, under heating, the combustible gas other than hydrogen contained in the fuel gas;
a heating unit that heats the second catalyst;
a second temperature measuring element that measures an increase in temperature of the combustible gas due to combustion under heating in the second catalyst.
前記第１触媒、及び前記第２触媒が、前記燃料ガスが前記第１触媒を通過し、前記第１触媒を通過した前記燃料ガスが前記第２触媒を通過するように、前記管材に収容されている請求項１又は２に記載の熱量計。 a pipe member that houses the first catalyst, the temperature measuring junction of the first temperature measuring element, the second catalyst, and the temperature measuring junction of the second temperature measuring element and into which the fuel gas flows;
3. The calorimeter according to claim 1, wherein the first catalyst and the second catalyst are housed in the tubing such that the fuel gas passes through the first catalyst and the fuel gas that has passed through the first catalyst passes through the second catalyst.
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