JP2003014674A - Method for controlling calorimeter installing atmosphere - Google Patents
Method for controlling calorimeter installing atmosphereInfo
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- JP2003014674A JP2003014674A JP2001201916A JP2001201916A JP2003014674A JP 2003014674 A JP2003014674 A JP 2003014674A JP 2001201916 A JP2001201916 A JP 2001201916A JP 2001201916 A JP2001201916 A JP 2001201916A JP 2003014674 A JP2003014674 A JP 2003014674A
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- temperature
- calorimeter
- heat
- sample
- heat insulating
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、断熱熱量計、熱流
束型熱量計等の熱量計設置雰囲気の制御方法に関する。TECHNICAL FIELD The present invention relates to a method for controlling an atmosphere in which a calorimeter is installed, such as an adiabatic calorimeter or a heat flux type calorimeter.
【０００２】物質の状態変化や化学反応等に伴う熱量や
温度変化を測定し、物質の熱的性質や危険性を評価する
手段として熱量計が使用されている。熱量計としては、
例えば断熱下での熱量測定が可能な暴走反応測定装置
（断熱熱量計）やグラム単位の試料の熱量測定が可能な
混合・反応熱量計（熱流束型熱量計）等が挙げられる。
前記熱量計は、加熱部、試料容器、断熱材保温部等を備
えており、様々な熱的環境の下での熱量や温度変化等を
測定することができる。[0002] A calorimeter is used as a means for evaluating the thermal properties and dangers of a substance by measuring the amount of heat and the temperature change associated with the state change of a substance or a chemical reaction. As a calorimeter,
For example, a runaway reaction measuring device (adiabatic calorimeter) capable of measuring a calorific value under adiabatic condition, a mixing / reaction calorimeter (heat flux calorimeter) capable of measuring a calorific value of a sample in gram units, and the like can be mentioned.
The calorimeter is provided with a heating unit, a sample container, a heat insulating material heat retaining unit, and the like, and can measure the amount of heat, temperature change, and the like under various thermal environments.
【０００３】しかし、これらの熱量計を使用する際に、
熱量計設置雰囲気の気温変化や湿度変化等で生じる結露
によって前記した加熱部等で漏電トラブルが発生した
り、断熱材保温部に使用している断熱材が結露により吸
湿することによって断熱性能が低下し温度調節機能が低
下するという問題があった。However, when using these calorimeters,
The heat insulation performance deteriorates due to the occurrence of electrical leakage trouble in the above-mentioned heating part due to the condensation caused by the temperature change and humidity change of the calorimeter installation atmosphere, or the heat insulating material used in the heat insulation part absorbs moisture due to the dew condensation. However, there was a problem that the temperature control function deteriorated.
【０００４】また、化学物質の中には室温以下の温度で
も危険な発熱反応を起こす物質があり、これらの試料の
危険性を評価するためには、その試料の熱量測定温度を
室温以下に低下させなければならない。しかし、従来の
断熱熱量計や熱流束型熱量計では、試料の熱量測定温度
をヒーター等の加熱部のみで制御しているため、制御可
能な熱量測定温度は室温よりも高い温度範囲に限られて
いた。Further, some chemical substances cause a dangerous exothermic reaction even at a temperature below room temperature, and in order to evaluate the risk of these samples, the calorimetric measurement temperature of the samples is lowered to below room temperature. I have to let you. However, in conventional adiabatic calorimeters and heat flux type calorimeters, the calorific value measurement temperature of the sample is controlled only by the heating part such as a heater, so the calorific value measurement temperature that can be controlled is limited to a temperature range higher than room temperature. Was there.
【０００５】[0005]
【発明が解決しようとする課題】本発明の主たる目的
は、結露による電気系統の漏電トラブルや断熱材の断熱
性能低下が生じない熱量計設置雰囲気の制御方法を提供
することである。本発明の他の目的は、室温以下の温度
での熱量測定が可能で、かつ結露による電気系統の漏電
トラブルや断熱材の断熱性能低下が生じない熱量計設置
雰囲気の制御方法を提供することである。SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for controlling the atmosphere in which a calorimeter is installed, which does not cause electrical leakage troubles in the electric system or deterioration of the heat insulating performance of the heat insulating material due to dew condensation. Another object of the present invention is to provide a method for controlling a calorimeter installation atmosphere that is capable of measuring calorific value at a temperature of room temperature or lower, and that does not cause leakage trouble of an electric system due to dew condensation or insulation performance deterioration of a heat insulating material. is there.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意研究を重ねた結果、熱量計内の少なくと
も加熱部および断熱材保温部の表面温度を露点よりも高
い温度に保てば、熱量計の加熱部および断熱材保温部に
結露が生じないため、電気系統の漏電トラブルや断熱材
の性能低下を防止することができるという新たな事実を
見出し、本発明を完成させるに至った。As a result of intensive studies to solve the above problems, the inventors of the present invention have maintained the surface temperature of at least the heating section and the heat insulating section of the heat insulating material in the calorimeter at a temperature higher than the dew point. Therefore, since dew condensation does not occur in the heating part of the calorimeter and the heat insulating part of the heat insulating material, it is possible to prevent the leakage trouble of the electric system and the deterioration of the performance of the heat insulating material. I arrived.
【０００７】すなわち、本発明の熱量計設置雰囲気の制
御方法は、熱量計内の少なくとも加熱部および断熱材保
温部の表面温度を露点よりも高い温度に保つことを特徴
とする。特に、熱量計内に除湿された空気を導入して熱
量計内の露点を低下させ、熱量計内の少なくとも加熱部
および断熱材保温部の表面温度を露点よりも高い温度に
保つのが好ましい。That is, the method for controlling the atmosphere in which the calorimeter is installed according to the present invention is characterized in that the surface temperature of at least the heating portion and the heat insulating material heat insulating portion in the calorimeter is maintained at a temperature higher than the dew point. In particular, it is preferable to introduce dehumidified air into the calorimeter to lower the dew point in the calorimeter and to keep the surface temperature of at least the heating portion and the heat insulating material heat retaining portion in the calorimeter at a temperature higher than the dew point.
【０００８】ここで、「少なくとも加熱部および断熱材
保温部の表面温度を露点よりも高い温度に保つ」とは、
熱量計全体の表面温度を露点よりも高い温度に保つよう
にしてもよく、あるいは局所的に加熱部および断熱材保
温部の表面温度のみを露点よりも高い温度に保つように
してもよいという意味である。また、露点よりも高い温
度に保つのは、漏電防止、断熱材保温部の性能低下防止
の見地から、常時、当該温度条件下に制御しておくのが
好ましいが、熱量計の設置環境を考慮して適宜決定すれ
ばよい。例えば加熱部に通電する前の前準備として、少
なくとも加熱部および断熱材保温部の表面温度を露点よ
りも高い温度に保てばよい。Here, "at least keep the surface temperature of the heating portion and the heat insulating material heat insulating portion at a temperature higher than the dew point" means
Meaning that the surface temperature of the entire calorimeter may be maintained at a temperature higher than the dew point, or that only the surface temperature of the heating part and the heat insulating material heat retaining part may be locally maintained at a temperature higher than the dew point. Is. In addition, it is preferable to keep the temperature higher than the dew point at all times under the temperature conditions from the viewpoint of leakage prevention and performance deterioration of the heat insulation part of the heat insulating material.However, consider the environment in which the calorimeter is installed. Then, it may be appropriately determined. For example, as a preparation before energizing the heating unit, at least the surface temperature of the heating unit and the heat insulating material heat retaining unit may be maintained at a temperature higher than the dew point.
【０００９】本発明における他の熱量計設置雰囲気の制
御方法は、熱量計を恒温槽内に格納し、恒温槽内の雰囲
気温度を試料の熱量測定温度以下に制御し、かつ熱量計
内の少なくとも加熱部および断熱材保温部の表面温度を
露点よりも高い温度に保つことを特徴とする。特に、恒
温槽内に除湿された空気を導入することで、熱量計内の
少なくとも加熱部および断熱材保温部の表面温度を露点
よりも高い温度に保つのが好ましい。Another method for controlling the atmosphere in which the calorimeter is installed according to the present invention is to store the calorimeter in a thermostatic bath, control the atmospheric temperature in the thermostatic bath to be equal to or lower than the calorimetric measurement temperature of the sample, and at least in the calorimeter. It is characterized in that the surface temperature of the heating section and the heat insulation section is maintained at a temperature higher than the dew point. In particular, by introducing dehumidified air into the thermostatic chamber, it is preferable to maintain the surface temperature of at least the heating portion and the heat insulating material heat retaining portion in the calorimeter at a temperature higher than the dew point.
【００１０】恒温槽内の温度制御については、恒温槽本
体が温度調整機能を有する場合は、恒温槽内部に導入す
る除湿空気の温度制御は必須ではなく、恒温槽本体に温
度調整機能が無い場合には、温調かつ除湿された空気を
恒温槽内に導入することによって恒温槽内部の温度を制
御することが出来る。Regarding the temperature control in the constant temperature oven, when the main body of the constant temperature oven has a temperature adjusting function, the temperature control of the dehumidified air introduced into the constant temperature oven is not essential, and the main body of the constant temperature oven does not have a temperature adjusting function. In addition, the temperature inside the thermostatic chamber can be controlled by introducing temperature-controlled and dehumidified air into the thermostatic chamber.
【００１１】このように、熱量計を恒温槽内に格納し、
恒温槽内に除湿された空気を導入することで、雰囲気温
度および露点を制御することができるため、室温以下の
温度での熱量測定が可能となり、かつ熱量計内の少なく
とも加熱部および断熱材保温部の表面温度を露点よりも
高い温度に保つことができる。In this way, the calorimeter is stored in the thermostatic chamber,
By introducing dehumidified air into the thermostatic chamber, it is possible to control the ambient temperature and dew point, making it possible to measure the calorific value at a temperature below room temperature, and to keep at least the heating part and heat insulation of the calorimeter. The surface temperature of the part can be maintained at a temperature higher than the dew point.
【００１２】[0012]
【発明の実施の形態】以下、図面を参照して本発明を詳
細に説明する。図１は本発明の一実施形態である断熱熱
量計１を示している。この断熱熱量計１は、断熱型の熱
量計であり試料の自己発熱による温度および圧力の時間
変化を測定、記録し、化学物質の熱的危険性のスクリー
ニング、暴走反応条件の評価、安全な貯蔵条件の決定、
反応速度論的解析等の用途で使用できる。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below with reference to the drawings. FIG. 1 shows an adiabatic calorimeter 1 which is an embodiment of the present invention. This adiabatic calorimeter 1 is an adiabatic calorimeter that measures and records changes in temperature and pressure over time due to self-heating of the sample, and screens for thermal danger of chemical substances, evaluation of runaway reaction conditions, and safe storage. Determination of conditions,
It can be used for applications such as reaction kinetic analysis.
【００１３】断熱熱量計１は、断熱材保温部６と、断熱
材保温部６の内部に設置されている放射熱ヒーター４ａ
とジャケットヒーター４ｂ、４ｃおよび４ｄとからなる
加熱部４と、この加熱部４で囲まれた内側に設置され
た、試料２を入れるための試料容器３とを備えている。
格納容器１１は測定中の試料容器３の破裂等に備えて設
置されるが、爆発等のおそれがない場合には格納容器１
１は設置しなくても良い。The adiabatic calorimeter 1 comprises a heat insulating material heat insulating portion 6 and a radiant heat heater 4a installed inside the heat insulating material heat insulating portion 6.
And a jacket heater 4b, 4c, and 4d, and a sample container 3 for containing the sample 2 installed inside the heating unit 4 surrounded by the heating unit 4.
The storage container 11 is installed in preparation for the rupture of the sample container 3 during measurement, but when there is no risk of explosion or the like, the storage container 1
1 does not need to be installed.
【００１４】恒温槽１５には除湿された空気を恒温槽１
５内に導入するための配管１０が挿入されている。この
配管１０から導入される除湿された空気によって、恒温
槽１５内の露点を低下させることができる。配管１０か
ら導入される除湿された空気は、熱量測定に悪影響を及
ぼさない範囲内で、かつ熱量計内部もしくは恒温槽１５
内部を適正な露点に保つことが出来る範囲の一定流量
で、実験中は常に導入することが望ましい。その結果、
加熱部４および断熱材保温部６に結露が発生せず、漏電
トラブルや断熱材の断熱性能が低下しない。Dehumidified air is stored in the constant temperature bath 15 in the constant temperature bath 1.
A pipe 10 for introducing into the inside 5 is inserted. The dehumidified air introduced from the pipe 10 can lower the dew point in the constant temperature bath 15. The dehumidified air introduced from the pipe 10 is within the range that does not adversely affect the calorific value measurement, and inside the calorimeter or the thermostatic chamber 15
It is desirable to introduce it constantly during the experiment at a constant flow rate within the range where the inside can be maintained at an appropriate dew point. as a result,
Condensation does not occur in the heating portion 4 and the heat insulating material heat insulating portion 6, and there is no electric leakage trouble or deterioration of the heat insulating performance of the heat insulating material.
【００１５】また、恒温槽１５内部は、恒温槽１５本体
に備えられた恒温槽加熱ヒーター３４および恒温槽冷却
装置３５等による温度調節機能を作動させながら除湿さ
れた空気を吹き込む操作を行うか、あるいは温度調整さ
れた除湿された空気を導入することによって恒温槽１５
外部の気温未満に制御しながら恒温槽１５内の温度を露
点よりも高い温度に保つことが出来る。したがって、熱
量測定温度が室温以下の場合であっても、恒温槽１５内
の雰囲気温度を熱量測定温度以下に制御し、加熱部４に
より試料２の温度を熱量測定温度に精度良く制御できる
ため、従来の断熱熱量計では困難であった室温以下での
熱量測定をすることができる。The inside of the constant temperature bath 15 is operated by blowing dehumidified air while operating the temperature adjusting function of the constant temperature bath heater 34 and the constant temperature bath cooling device 35 provided in the main body of the constant temperature bath 15. Alternatively, by introducing dehumidified air whose temperature has been adjusted, the constant temperature bath 15
It is possible to maintain the temperature in the constant temperature bath 15 at a temperature higher than the dew point while controlling the temperature below the outside air temperature. Therefore, even if the calorific value measurement temperature is equal to or lower than room temperature, the ambient temperature in the constant temperature bath 15 can be controlled to be equal to or lower than the calorific value measurement temperature, and the heating unit 4 can accurately control the temperature of the sample 2 to the calorific value measurement temperature. It is possible to measure the calorific value at room temperature or lower, which is difficult with the conventional adiabatic calorimeter.
【００１６】加熱部４は、放射熱ヒーター４ａとジャケ
ットヒーター４ｂ、４ｃおよび４ｄとからなる。放射熱
ヒーター４ａは、試料容器３内の試料２を熱量測定時の
設定温度まで加熱するためのものであり、ジャケットヒ
ーター４ｂ、４ｃおよび４ｄは、これらのジャケットヒ
ーターで囲まれた内側の空気を加熱して試料２と試料容
器３周辺との温度差を一定範囲内（例えば０．０５℃以
内）に制御し、試料２を断熱状態に維持するためのもの
である。The heating section 4 comprises a radiant heat heater 4a and jacket heaters 4b, 4c and 4d. The radiant heat heater 4a is for heating the sample 2 in the sample container 3 to a set temperature at the time of calorific value measurement, and the jacket heaters 4b, 4c and 4d are for the air inside surrounded by these jacket heaters. This is for heating and controlling the temperature difference between the sample 2 and the periphery of the sample container 3 within a fixed range (for example, within 0.05 ° C.) to maintain the sample 2 in an adiabatic state.
【００１７】ジャケットヒーター４ｂ、４ｃおよび４ｄ
には、ヒーター温度測定用の熱電対９が埋め込まれてい
る。また、断熱材保温部６は、試料２の断熱状態を維持
するためのものである。Jacket heaters 4b, 4c and 4d
A thermocouple 9 for measuring the heater temperature is embedded in the. Further, the heat insulating material heat retaining unit 6 is for maintaining the heat insulating state of the sample 2.
【００１８】試料容器３は、チタン、ハステロイ、ステ
ンレス等の金属が使用されており、必要とされる耐圧性
や試料２との反応性に応じて使い分けられる。試料容器
３の試料投入口は、熱損失を小さくするため小口径とな
っており、試料容器３の外面には、試料温度を測定する
ための熱電対８が取り付けられている。The sample container 3 is made of a metal such as titanium, hastelloy, stainless steel, etc., and can be used depending on the required pressure resistance and reactivity with the sample 2. The sample inlet of the sample container 3 has a small diameter to reduce heat loss, and a thermocouple 8 for measuring the sample temperature is attached to the outer surface of the sample container 3.
【００１９】試料容器３内の圧力変化は、圧力センサー
７で測定される。また、圧力測定用の配管１９から分岐
した配管１２を設けることによって、試料容器３の内部
を窒素、アルゴン、酸素等のガスによって置換すること
ができる。The pressure change in the sample container 3 is measured by the pressure sensor 7. Further, by providing the pipe 12 branched from the pressure measuring pipe 19, the inside of the sample container 3 can be replaced with a gas such as nitrogen, argon, or oxygen.
【００２０】本発明の一実施形態である断熱熱量計１
は、大気圧〜１７３ｂａｒＡの圧力範囲、５〜４５０℃
の温度範囲で試料２の熱量測定が可能である。また、熱
電対８は、試料２の発熱速度を０．０１℃／分の検知精
度で測定することができる。Adiabatic calorimeter 1 according to one embodiment of the present invention
Is the pressure range from atmospheric pressure to 173 barA, 5 to 450 ° C.
The calorific value of the sample 2 can be measured in the temperature range of. Further, the thermocouple 8 can measure the heat generation rate of the sample 2 with a detection accuracy of 0.01 ° C./min.
【００２１】恒温槽１５内に除湿された空気を導入する
場合は、その導入空気は、加熱部４および断熱材保温部
６の温度を露点よりも高い温度に保つことができる程度
に除湿されたものであればよい。また、恒温槽１５内に
除湿された空気を導入するに際して、その導入空気の温
度は、恒温槽１５本体の温度調節機能を作動させる場合
は、室温程度でよく、除湿された空気で恒温槽１５内部
の温度を制御する場合には、目的に応じて−２０℃〜室
温程度の範囲内で温度調整を行った除湿された空気を吹
き込む。When dehumidified air is introduced into the constant temperature bath 15, the introduced air is dehumidified to such an extent that the temperature of the heating section 4 and the heat insulating material heat retaining section 6 can be maintained at a temperature higher than the dew point. Anything will do. Further, when the dehumidified air is introduced into the constant temperature chamber 15, the temperature of the introduced air may be about room temperature when the temperature adjusting function of the constant temperature chamber 15 is operated, and the temperature of the constant temperature chamber 15 may be adjusted by the dehumidified air. When controlling the internal temperature, dehumidified air whose temperature is adjusted within the range of -20 ° C to room temperature is blown according to the purpose.
【００２２】以下に、断熱熱量計１による熱量測定方法
の一例を示す。試料容器３の下方に設置されている放射
熱ヒーター４ａにより試料２の温度（実際には試料容器
３の温度）を初期の熱量測定温度まで加熱し、一定の待
ち時間（通常５〜１０分程度）の後に試料２の発熱の有
無を確認する探索過程に入る。その探索過程において一
定の自己発熱速度（通常０．０２℃／分程度）以上の温
度上昇が検出されないときは、さらに放射熱ヒーター４
ａにより試料２の温度（実際には試料容器３の温度）を
数℃（通常は５℃程度）上げ、同じような断熱下での操
作を繰り返す。上記した一定の自己発熱速度を越える発
熱現象が検出されると、熱電対８で測定される試料容器
３と熱電対９で測定されるジャケットヒーター４ｂ、４
ｃおよび４ｄとの温度差が例えば０．０５℃以内となる
ように制御され、試料２の温度が断熱的に上昇する。こ
のように試料２の温度が断熱的に上昇し反応熱が蓄積さ
れていくにつれて、試料２の温度が指数関数的に上昇
し、最大反応速度を経て最高温度に達する。このように
して試料２の熱的特性を断熱下で測定することができ
る。An example of a calorific value measuring method using the adiabatic calorimeter 1 will be shown below. The temperature of the sample 2 (actually the temperature of the sample container 3) is heated to the initial calorimetric measurement temperature by the radiant heat heater 4a installed below the sample container 3, and a fixed waiting time (usually about 5 to 10 minutes) After), a search process for confirming the heat generation of the sample 2 is started. When no temperature rise above a certain self-heating rate (usually about 0.02 ° C./min) is detected in the search process, the radiant heat heater 4 is further added.
By a, the temperature of the sample 2 (actually the temperature of the sample container 3) is raised by several degrees Celsius (usually about 5 degrees Celsius), and the same operation under heat insulation is repeated. When an exothermic phenomenon exceeding the above-mentioned constant self-heating rate is detected, the sample container 3 measured by the thermocouple 8 and the jacket heaters 4b, 4 measured by the thermocouple 9 are detected.
The temperature difference between c and 4d is controlled to be, for example, within 0.05 ° C., and the temperature of the sample 2 rises adiabatically. As described above, as the temperature of the sample 2 rises adiabatically and the heat of reaction is accumulated, the temperature of the sample 2 rises exponentially and reaches the maximum temperature through the maximum reaction rate. In this way, the thermal characteristics of Sample 2 can be measured under adiabatic condition.
【００２３】断熱熱量計１としては、例えば市販されて
いるＡＲＣ(Accelerating Rate Calorimeter)等の熱量
計に、恒温槽を取り付けて、加熱部および断熱材保温部
等をこの恒温槽で格納したものを使用することができ
る。As the adiabatic calorimeter 1, for example, a commercially available calorimeter such as ARC (Accelerating Rate Calorimeter) is attached with a constant temperature bath, and the heating part and the heat insulating material keeping part are stored in this constant temperature bath. Can be used.
【００２４】なお、図１に示す本発明の一実施形態で
は、恒温槽１５の内部には加熱部４および断熱材保温部
６の他に格納容器１１も格納した形態を示したが、爆発
等のおそれがない場合には格納容器１１を用いずに、試
料容器３、加熱部４および断熱材保温部６を恒温槽１５
の内部に格納してもよい。In the embodiment of the present invention shown in FIG. 1, a storage container 11 is stored in the constant temperature bath 15 in addition to the heating portion 4 and the heat insulating material heat insulating portion 6, but an explosion or the like may occur. If there is no fear of the above, the sample container 3, the heating unit 4, and the heat insulating material heat retaining unit 6 are not used in the storage container 11 and the constant temperature tank 15 is used.
May be stored inside.
【００２５】図２は本発明の他の実施形態である熱流束
型熱量計２１を示している。この熱流束型熱量計２１
は、試料２４と標準試料２２とを同時に加熱し、熱流束
の変化の差を測定するものであって、グラム単位の試料
の熱量測定が可能な高感度の熱量計である。この熱流束
型熱量計２１は、固体と液体あるいは液体と液体の混合
・反応危険性評価、固体と気体との混合・反応危険性評
価、液体の比熱測定、溶解、希釈、中和、吸着等の混合
系の熱物性評価、蒸発潜熱の測定、熱伝導率の測定等に
使用できる。FIG. 2 shows a heat flux type calorimeter 21 which is another embodiment of the present invention. This heat flux type calorimeter 21
Is a high-sensitivity calorimeter capable of simultaneously heating the sample 24 and the standard sample 22 to measure the difference in heat flux change and capable of measuring the calorific value of the sample in grams. The heat flux calorimeter 21 is a solid / liquid or liquid / liquid mixture / reaction risk evaluation, a solid / gas mixture / reaction risk evaluation, a liquid specific heat measurement, dissolution, dilution, neutralization, adsorption, etc. It can be used for evaluation of thermophysical properties of mixed system, measurement of latent heat of vaporization, measurement of thermal conductivity, and the like.
【００２６】熱流束型熱量計２１は、アルミナなどの熱
的に安定な物質である標準試料２２を入れるための標準
容器２３と、評価対象である試料２４を入れるための試
料容器２５と、標準試料２２および試料２４の熱流束を
検知する熱流束検知部２６と、測定温度を制御するため
のサーモスタットブロック２９および温度センター２８
と、加熱ヒーター２７（加熱部）と、これらを収納する
断熱材保温部３０とを備えている。The heat flux calorimeter 21 comprises a standard container 23 for containing a standard sample 22 which is a thermally stable substance such as alumina, a sample container 25 for containing a sample 24 to be evaluated, and a standard container. A heat flux detection unit 26 for detecting the heat flux of the sample 22 and the sample 24, a thermostat block 29 and a temperature center 28 for controlling the measured temperature.
And a heating heater 27 (heating unit) and a heat insulating material heat retaining unit 30 for housing them.
【００２７】標準容器２３、試料容器２５、加熱ヒータ
ー２７および断熱材保温部３０は恒温槽１５の内部に格
納されている。恒温槽１５内部には除湿された空気を恒
温槽１５内に導入するための配管１０が挿入されてい
る。この配管１０から導入される除湿された空気によっ
て、恒温槽１５内の露点を低下させることができる。配
管１０から導入される除湿された空気は、熱量測定に悪
影響を及ぼさない範囲内で、かつ熱量計内部もしくは恒
温槽１５内部を適正な露点に保つことが出来る範囲の一
定流量で、実験中は常に導入することが望ましい。その
結果、加熱ヒーター２７および断熱材保温部３０に結露
が発生せず、漏電トラブルや断熱材の断熱性能が低下し
ない。The standard container 23, the sample container 25, the heater 27, and the heat insulating material heat retaining section 30 are housed inside the thermostatic chamber 15. A pipe 10 for introducing dehumidified air into the constant temperature bath 15 is inserted inside the constant temperature bath 15. The dehumidified air introduced from the pipe 10 can lower the dew point in the constant temperature bath 15. The dehumidified air introduced from the pipe 10 has a constant flow rate within a range that does not adversely affect the calorific value measurement and that can maintain an appropriate dew point inside the calorimeter or the thermostat 15, and during the experiment. It is desirable to always introduce it. As a result, dew condensation does not occur in the heater 27 and the heat insulating material heat retaining part 30, and the leakage trouble and the heat insulating performance of the heat insulating material do not deteriorate.
【００２８】また、恒温槽１５内部は、恒温槽１５本体
に備えられた恒温槽加熱ヒーター３４および恒温槽冷却
装置３５等による温度調節機能を作動させながら除湿さ
れた空気を吹き込む操作を行うか、あるいは温度調整さ
れた除湿された空気を導入することによって恒温槽１５
外部の気温未満に制御しながら恒温槽１５内の温度を露
点よりも高い温度に保つことが出来る。したがって、熱
量測定温度が室温以下の場合であっても、恒温槽１５内
の雰囲気温度を熱量測定温度以下に制御し、加熱ヒータ
ー２７により標準試料２２および試料２４の温度を熱量
測定温度に精度良く制御できるため、従来の熱流束型熱
量計では困難であった室温以下での熱量測定をすること
ができる。The inside of the constant temperature bath 15 is operated by blowing dehumidified air while operating the temperature adjusting function of the constant temperature bath heater 34 and the constant temperature bath cooling device 35 provided in the main body of the constant temperature bath 15. Alternatively, by introducing dehumidified air whose temperature has been adjusted, the constant temperature bath 15
It is possible to maintain the temperature in the constant temperature bath 15 at a temperature higher than the dew point while controlling the temperature below the outside air temperature. Therefore, even when the calorific value measuring temperature is equal to or lower than room temperature, the atmospheric temperature in the constant temperature bath 15 is controlled to be equal to or lower than the calorific value measuring temperature, and the heating heater 27 accurately adjusts the temperature of the standard sample 22 and the sample 24 to the calorific value measuring temperature. Since it can be controlled, it is possible to measure the calorific value at room temperature or lower, which was difficult with the conventional heat flux calorimeter.
【００２９】標準容器２３および試料容器２５は、ハス
テロイ、ステンレス等からなる高圧条件あるいは高真空
条件用の容器やガラス製の容器等が使用できる。また、
容器の下部が２重構造になっており、２種類の試料を各
々が混ざらないように仕込むことができる混合用容器も
使用できる。この容器は、反転機構３３により容器を反
転させることによって容器中の２種類の試料を混合し、
そのとき発生する発熱量を測定するためのものである。
標準容器２３および試料容器２５には、数グラムの固体
または液体の標準試料２２および試料２４がそれぞれ仕
込まれ、熱流束検知部２６の内部に設置される。As the standard container 23 and the sample container 25, a container made of Hastelloy, stainless steel or the like under high pressure conditions or high vacuum conditions, a glass container or the like can be used. Also,
A lower part of the container has a double structure, and a mixing container in which two kinds of samples can be charged so as not to mix with each other can be used. This container mixes two kinds of samples in the container by inverting the container by the inversion mechanism 33,
This is for measuring the amount of heat generated at that time.
The standard container 23 and the sample container 25 are charged with several grams of the solid or liquid standard sample 22 and the sample 24, respectively, and are installed inside the heat flux detection unit 26.
【００３０】加熱ヒーター２７は、標準容器２３および
試料容器２５内の標準試料２２および試料２４を同時に
加熱し、熱流束検知部２６において相対的な熱流束の変
化を測定する。温度センサー２８は、サーモスタットブ
ロック２９の内部温度を測定するためのものである。モ
ーター３２で駆動しているファン３１は、主に測定後の
冷却時に使用するために設けられている。The heating heater 27 simultaneously heats the standard sample 22 and the sample 24 in the standard container 23 and the sample container 25, and measures the relative change in heat flux in the heat flux detector 26. The temperature sensor 28 is for measuring the internal temperature of the thermostat block 29. The fan 31 driven by the motor 32 is provided mainly for use during cooling after measurement.
【００３１】本発明の一実施形態である熱流束型熱量計
２１は、真空〜３５０ｂａｒＡの圧力範囲、５〜３００
℃の温度範囲で試料の熱量測定が可能である。また、試
料の昇温速度を０．０１〜２℃／分の範囲内で制御する
ことができる。The heat flux type calorimeter 21 which is an embodiment of the present invention has a vacuum to a pressure range of 350 barA and a pressure of 5 to 300.
The calorific value of the sample can be measured in the temperature range of ° C. Further, the temperature rising rate of the sample can be controlled within the range of 0.01 to 2 ° C./minute.
【００３２】熱流束型熱量計２１としては、例えば市販
されているSetaram社製「Ｃ−８０Ｄ」等の熱量計に、
恒温槽を取り付けて、加熱ヒーター２７および断熱材保
温部３０をこの恒温槽１５で格納したものを使用するこ
とができる。As the heat flux type calorimeter 21, for example, a commercially available calorimeter such as "C-80D" manufactured by Setaram,
It is possible to use one in which a constant temperature tank is attached and the heater 27 and the heat insulating material heat retaining section 30 are stored in the constant temperature tank 15.
【００３３】なお、熱量計内の少なくとも加熱部および
断熱材保温部の表面温度を露点よりも高い温度に保つた
めの他の手段として、前記加熱部および断熱材保温部の
周辺に乾燥剤（塩化カルシウム、シリカゲル等）を設置
する方法や恒温槽１５自体に除湿能力を持たせる方法等
が挙げられる。As another means for maintaining the surface temperature of at least the heating portion and the heat insulating material heat retaining portion in the calorimeter at a temperature higher than the dew point, a desiccant (chlorinated material) is provided around the heating portion and the heat insulating material heat retaining portion. Examples of the method include a method of installing calcium, silica gel, etc., a method of imparting dehumidifying ability to the constant temperature bath 15 itself, and the like.
【００３４】[0034]
【実施例】以下、実施例を挙げて本発明を詳細に説明す
るが、本発明は以下の実施例のみに限定されるものでは
ない。The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
【００３５】実施例
２０℃の室内に設置された図１に示す断熱熱量計１の恒
温槽１５内に除湿された空気を導入することによって、
恒温槽１５内を温度約６℃、湿度約１９％に保持した
（このときの露点は約−１４℃）。この雰囲気中では、
漏電等の異常は発生せず、断熱材保温部６の断熱性能も
良好な状態であった。また、恒温槽１５内部の雰囲気温
度を約６℃に制御したため、試料２の温度を熱量測定温
度に精度良く調節することができ、その後、一連の測定
を完了することができた。
比較例
温度および湿度管理していない室内（室温２０℃、湿度
８０％）に設置された図１に示す断熱熱量計１の恒温槽
１５内に除湿された空気を導入せずに、恒温槽１５内を
温度約６℃に保持して試料の熱量測定を試みたが、この
とき加熱部４および断熱材保温部６の温度は露点（約１
７℃）よりも低い温度であったため結露が発生してい
た。この設置雰囲気で、測定を開始したところ、グラン
ドフォルトエラー（漏電が原因のエラー）が発生し、測
定を継続することができなかった。Example 3 By introducing dehumidified air into the thermostat 15 of the adiabatic calorimeter 1 shown in FIG.
The temperature inside the constant temperature bath 15 was kept at about 6 ° C. and the humidity at about 19% (the dew point at this time was about −14 ° C.). In this atmosphere,
No abnormality such as electric leakage occurred, and the heat insulating property of the heat insulating material heat insulating portion 6 was in a good state. Further, since the atmospheric temperature inside the constant temperature bath 15 was controlled to about 6 ° C., the temperature of the sample 2 could be adjusted to the calorific value measurement temperature with high accuracy, and then the series of measurements could be completed. Comparative Example Temperature and humidity were not controlled in a room (room temperature 20 ° C., humidity 80%) installed in the thermostatic chamber 15 of the adiabatic calorimeter 1 shown in FIG. 1 without introducing dehumidified air into the thermostatic chamber 15. An attempt was made to measure the calorific value of the sample while maintaining the inside at a temperature of about 6 ° C.
Since the temperature was lower than (7 ° C), dew condensation occurred. When the measurement was started in this installation atmosphere, a ground fault error (error caused by electric leakage) occurred and the measurement could not be continued.
【００３６】[0036]
【発明の効果】本発明によれば、熱量計の少なくとも加
熱部および断熱材保温部の表面温度を露点よりも高い温
度に保つことにより、熱量計の加熱部および断熱材保温
部に結露が生じないようにしたため、電気系統の漏電ト
ラブルや断熱材の性能低下を防止することができ、熱量
測定を安定的にかつ精度良く行うことができるという効
果がある。According to the present invention, by maintaining the surface temperature of at least the heating portion and the heat insulating material heat retaining portion of the calorimeter at a temperature higher than the dew point, dew condensation occurs in the heating portion and the heat insulating material heat retaining portion of the calorimeter. Since this is not done, there is an effect that it is possible to prevent leakage trouble of the electric system and deterioration of the performance of the heat insulating material, and it is possible to stably and accurately measure the heat quantity.
【００３７】また、熱量計を恒温槽に格納し、恒温槽内
部の雰囲気温度を試料の熱量測定温度以下に制御するこ
とにより、室温以下の温度での熱量測定ができ、かつ熱
量計の少なくとも加熱部および断熱材保温部の表面温度
を露点よりも高い温度に保つことにより熱量計の加熱部
および断熱材保温部に結露が生じないようにしたため、
電気系統の漏電トラブルや断熱材の性能低下を防止する
ことができ、熱量測定を安定的にかつ精度良く行うこと
ができるという効果がある。Further, by storing the calorimeter in a thermostat and controlling the atmospheric temperature inside the thermostat below the calorie measurement temperature of the sample, the calorimeter can be measured at a temperature below room temperature and at least the calorimeter can be heated. By keeping the surface temperature of the heat insulation part and the heat insulation part at a temperature higher than the dew point, it is possible to prevent dew condensation on the heating part and heat insulation part of the calorimeter.
It is possible to prevent the leakage trouble of the electric system and the performance deterioration of the heat insulating material, and it is possible to stably and accurately measure the calorific value.
【図１】本発明の一実施形態である熱量計設置雰囲気の
制御方法に使用する断熱熱量計を示す構成図である。FIG. 1 is a configuration diagram showing an adiabatic calorimeter used in a method for controlling a calorimeter installation atmosphere according to an embodiment of the present invention.
【図２】本発明の他の実施形態である熱量計設置雰囲気
の制御方法に使用する熱流束型熱量計を示す構成図であ
る。FIG. 2 is a configuration diagram showing a heat flux type calorimeter used in a method of controlling a calorimeter installation atmosphere according to another embodiment of the present invention.
１…断熱熱量計、２…試料、３…試料容器、４…加熱
部、４ａ…放射熱ヒーター、４ｂ、４ｃおよび４ｄ…ジ
ャケットヒーター、６…断熱材保温部、７…圧力センサ
ー、８…熱電対、９…熱電対、１０…配管、１１…格納
容器、１２…配管、１５…恒温槽、１９…圧力測定用の
配管、２１…熱流束型熱量計、２２…標準試料、２３…
標準容器、２４…試料、２５…試料容器、２６熱流束検
知部、２７…加熱ヒーター、２８…温度センサー、２９
…サーモスタットブロック、３０…断熱材保温部、３１
…ファン、３２…モーター、３３…反転機構、３４…恒
温槽加熱ヒーター、３５…恒温槽冷却装置DESCRIPTION OF SYMBOLS 1 ... Adiabatic calorimeter, 2 ... Sample, 3 ... Sample container, 4 ... Heating part, 4a ... Radiant heat heater, 4b, 4c and 4d ... Jacket heater, 6 ... Insulator heat insulation part, 7 ... Pressure sensor, 8 ... Thermoelectric Pair, 9 ... Thermocouple, 10 ... Piping, 11 ... Containment vessel, 12 ... Piping, 15 ... Constant temperature bath, 19 ... Pressure measuring piping, 21 ... Heat flux calorimeter, 22 ... Standard sample, 23 ...
Standard container, 24 ... Sample, 25 ... Sample container, 26 Heat flux detection unit, 27 ... Heater, 28 ... Temperature sensor, 29
… Thermostat block, 30… Insulation insulation, 31
... fan, 32 ... motor, 33 ... reversing mechanism, 34 ... constant temperature bath heater, 35 ... constant temperature bath cooling device
フロントページの続き Ｆターム(参考） 2G040 EB01 EB06 EC01 EC06 GA03 5H323 AA29 AA38 BB07 BB20 CA02 CB02 CB25 DA01 QQ05 RR06Continued front page F-term (reference) 2G040 EB01 EB06 EC01 EC06 GA03 5H323 AA29 AA38 BB07 BB20 CA02 CB02 CB25 DA01 QQ05 RR06
Claims (4)
保温部の表面温度を露点よりも高い温度に保つことを特
徴とする熱量計設置雰囲気の制御方法。1. A method for controlling an atmosphere in which a calorimeter is installed, characterized in that the surface temperature of at least the heating portion and the heat insulating material heat retaining portion in the calorimeter is maintained at a temperature higher than the dew point.
計内の露点を低下させる請求項１記載の熱量計設置雰囲
気の制御方法。2. A method for controlling a calorimeter installation atmosphere according to claim 1, wherein dehumidified air in the calorimeter is lowered by introducing dehumidified air into the calorimeter.
囲気温度を試料の熱量測定温度以下に制御し、かつ熱量
計内の少なくとも加熱部および断熱材保温部の表面温度
を露点よりも高い温度に保つことを特徴とする熱量計設
置雰囲気の制御方法。3. A calorimeter is stored in a thermostatic chamber, the atmospheric temperature in the thermostatic chamber is controlled to be below the calorific value measurement temperature of the sample, and the surface temperature of at least the heating part and the heat insulating material heat retaining part in the calorimeter is the dew point. A method for controlling the atmosphere in which a calorimeter is installed, which is characterized by maintaining a higher temperature than
項３記載の熱量計設置雰囲気の制御方法。4. A method for controlling a calorimeter installation atmosphere according to claim 3, wherein dehumidified air is introduced into the constant temperature bath.
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|---|---|---|---|
| JP2001201916A JP2003014674A (en) | 2001-07-03 | 2001-07-03 | Method for controlling calorimeter installing atmosphere |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001201916A JP2003014674A (en) | 2001-07-03 | 2001-07-03 | Method for controlling calorimeter installing atmosphere |
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|---|---|
| JP2003014674A true JP2003014674A (en) | 2003-01-15 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009097882A (en) * | 2007-10-12 | 2009-05-07 | Tokyo Riko:Kk | Device for measuring amount of insulated heat |
| JP2010181408A (en) * | 2009-02-03 | 2010-08-19 | Mettler-Toledo Ag | Thermo-analytical instrument |
| CN102109478A (en) * | 2011-02-24 | 2011-06-29 | 长沙开元仪器股份有限公司 | Method for testing heat of calorimeter |
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| CN106153676A (en) * | 2016-06-21 | 2016-11-23 | 桂林市淦隆环保科技有限公司 | A kind of assay method of alcohol radical liquid fuel calorific value |
| CN109974902A (en) * | 2019-03-29 | 2019-07-05 | 中国计量大学 | A kind of insulation accelerating calorimeter with dynamic thermal inertia amendment feature |
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| CN106153676A (en) * | 2016-06-21 | 2016-11-23 | 桂林市淦隆环保科技有限公司 | A kind of assay method of alcohol radical liquid fuel calorific value |
| CN109974902A (en) * | 2019-03-29 | 2019-07-05 | 中国计量大学 | A kind of insulation accelerating calorimeter with dynamic thermal inertia amendment feature |
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