JPS5923240A - Apparatus for measuring heat of reaction - Google Patents

Abstract

PURPOSE:To increase heat exchange property and to shorten heating time and also, to improve accuracy accompanied by it, by standing four heaters on the outside of a reaction tube and providing a thick cylindrical image furnace surrounding its outside. CONSTITUTION:Four heaters 10 are stood on the outside of a reaction tube 8 and an image furnace 11 consisting of a thick cylindrical aluminum block surrounding the outside of the heater 10, and provides the inner face of the aluminum block as a reflex mirror face 12. By such a constitution, heating time is shortened and measurement accuracy is improved by a decrease of the quantity of heat leakage accompanied by it, because heat exchange property can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an apparatus for measuring the heat of reaction between ash and hydrogen.

Conventionally, various types of calorific values 1 for measuring the heat of combustion of substances are commercially available, and their measurement accuracy is relatively high. Because it requires a difficult gas distribution system,
Not yet developed.

However, accurate measurement of the heat of reaction between a solid and a gas has always been of great importance in elucidating the reaction mechanism between the two, and its development is strongly desired.

The present inventor has completed the present invention as a result of extensive research to develop an apparatus for measuring the heat of reaction between a solid and a gas.

That is, according to the present invention, a cylindrical reaction tube is provided, in which a thermocouple for measuring the reaction temperature is erected through the upper end of the cylindrical measurement cell, and reaction gas flow holes are provided in the upper part of the circumference. A heater and an infrared imaging furnace with a reflective mirror surface on the inner surface are sequentially and concentrically installed on the outside of the cell, and the measuring cell is held in a cylindrical water tank. A helical tube for heat exchange of the produced gas, a stirring rod, a thermometer for measuring water temperature, etc., which open into two parts of the water tank along the inner circumferential surface, are installed, and the water tank is connected to an external side with a helical tube for heat exchange of the reactant gas. There is provided a reaction heat measuring device, characterized in that it is installed in a water tank and is provided with an external power side connected to the heater.

An embodiment of the present invention will be explained with reference to the drawings. Fig. 1 shows the main parts excluding the external water tank, where ◯ is a measurement cell, and the lower end is formed into a small diameter filter housing part 3 having fins 2. . This 11 constant cell j is suspended and held in a water tank 4 via a suitable fitting, and is connected to an external water tank (described later) via a reaction gas introduction pipe 5 provided through the lid of the water tank 4. The reaction gas adjusted to a constant temperature is fed into the reaction gas heat exchange spiral pipe 23 in the reaction gas heat exchanger 19, and the generated gas is still flowing from the bottom of the filter housing 3 through the spiral pipe 6 along the inner peripheral surface of the water tank 4. The generated gas is taken out through a discharge pipe 7 located at the top of the water tank 4.

As shown in FIG. 2, a reaction tube 8 consisting of a standpipe whose upper end is connected to its lid and whose lower end is connected to the filter accommodating section 3 is inserted into the measuring cell l, as shown in FIG. A solid sample (for example, coal) is sealed in the perforated plate 9 provided. Four heaters 1o are installed on the outer peripheral surface of the reaction tube 8, and an image furnace 11 made of a thick cylindrical aluminum block is installed on the outside of the reaction tube 8 as a reflective mirror surface 12 on the inner surface of the aluminum block. @13 is a cooling water pipe embedded in this aluminum block, and 4
As shown in FIG. 1, the water in the water tank 4 is forced to circulate through the rotating blades 14. On the upper surface of the water tank 4, in addition to the reaction gas introduction pipe 5 which passes through the lid and leads into the reaction tube 8, the generated gas discharge pipe 7, and the electrode 15 connected to the heater 10, the lower end is placed inside the sample on the perforated plate 9. A thermocouple 16 for measuring the reaction temperature, a thermometer for measuring the water temperature in the water tank 4, and a thermometer for measuring the water temperature in the water tank 4 are suspended in the water tank 4, and are rotated by connecting the upper end to an appropriate power source. Stirring rods 18 are each protruded, and relief pipes 19 (=J) are provided to release gas expansion in the measurement cell 1 during heating, and their attachment portions are made in a sealed state with the water tank 4. There is.

As shown in FIG. 1, the above-mentioned parts are further held in a heat insulating container 30, which will be described later, and as described above, are further housed in an external water tank and assembled together.

That is, in FIG. 3, reference numeral 19 denotes an external water tank, which is equipped with a heating mechanism 20, a temperature detection mechanism 21, a stirring mechanism 22, and a helical tube 23 for heat exchange of the reaction gas. It has a solenoid valve 25 and a communication pipe 26 communicating with an external water tank 19 which supplies water in the external water tank at a required water level. Spiral tube 23 for reaction gas heat exchange
is connected to the reaction gas introduction pipe 5 after exchanging heat with the reaction gas (for example, hydrogen) supplied from the outside at the same temperature as the water in the external water tank 19 . 27 is an automatic temperature controller, 28 is a temperature recorder, and 29 is an electric contact for setting the water amount. Reference numeral 30 denotes a heat insulating container, the inner surface of which is lined with a heat insulating material 31 to block heat from flowing out from the water tank 4 to the outside. 3
2 is a reaction temperature controller, and 33 is a power meter.

The present invention is constructed as described above, and the measuring cell 1 is opened, a certain amount of powdered solid, for example, coal is sealed on the perforated plate 9 in the reaction tube 8, and the measuring cell 1 is placed in the water tank 4. At the same time, the entire body is housed in a heat insulating container 30 and housed in an external water tank 19 as shown in FIG.

Next, water is poured into the external water tank 19 at a required temperature, for example, 20° C., by the action of the temperature detection mechanism 21 and the automatic temperature controller 270.
After the water is maintained at 100° C., the solenoid valve 25 is opened, and a portion of the external aquarium water is introduced into the aquarium 4 through the communication pipe 26 using a beach difference or the like. At this time, since the communication pipe 26 passes through the water in the external aquarium, there is no change in the adjusted temperature of the water. By setting the electric contacts 29 of the wooden structure inside the aquarium 4 at predetermined positions,
The water level in the water tank 4 rises to this point, and when the water level reaches the position of this electrical contact, the liquid level relay 24 is activated and the solenoid valve 2
5 will be closed. Therefore, by this operation, the temperature in the external water tank can be adjusted to a constant value, and a certain amount of water can always be automatically weighed into the water tank 4.

After completing the measurement setup as described above, electricity is passed from the electrode 15 to the heater 10 to heat the solid sample in the reaction tube 8 through the image furnace 11 and the reaction tube 8.

In this case, the amount of power supplied to the heater is recorded by the wattmeter 33. The temperature of the solid sample is measured by a thermocouple 16 and recorded on the temperature recording side.

When the sample temperature reaches a predetermined reaction temperature, the reaction gas is heated through the heat exchange spiral tube 23 in the external water tank 19 and introduced from the reaction gas introduction tube 5.

This heated reaction gas enters the inside of the reaction tube 8 and comes into contact with the solid sample to react.

The product gas obtained by the above-mentioned contact reaction passes through the filter housing part 3 from the lower part of the reaction tube, comes into contact with a "filter" filter (for example, a packed bed of quartz cotton, absorbent cotton, etc.), and is included in the product gas. The liquid component is removed here.The product gas from which the liquid component has been removed passes through the spiral pipe 6 and is cooled to the temperature of the water tank 4, and then is also discharged through the product gas discharge pipe 7.

In the apparatus, the reaction temperature (temperature of the sample) is adjusted to a predetermined temperature by a reaction temperature regulator 32 connected to the thermocouple 16 and the heater electrode 15, and the temperature is recorded over time. As the temperature of the water tank 4 rises as the reaction progresses, the automatic temperature controller 27 and the water tank 4 connected to it
The water temperature of the external water tank 19 follows the water temperature of the water tank 4 and is scooped by the cooperation of the thermocouple 17 for measuring water temperature, the thermocouple of the temperature detection mechanism 21 for water in the external water tank, and the heating mechanism 20. Through this temperature control, the water temperature in the external water tank 19 is always maintained at approximately the same temperature as the water temperature in the water tank 4, preventing heat from escaping from the water tank 4, and the reaction gas is still transferred into the water tank 19 through the heat exchange spiral pipe 23. Effective insulation of the water tank 4 is achieved by supplying the water into the water tank 4 after the water temperature is approximately equal to that of the water.

After the reaction is carried out for a predetermined period of time as described above, the reaction is stopped. That is, the introduction of the reaction gas, the discharge of the generated gas, and the heating of the heater IO are stopped. Next, aquarium 4
Measure the water temperature when no rise in water temperature is observed, and end the measurement.

When the measurement is performed as described above, the total amount of heat Q added to the water in the water tank 4 is expressed by the following formula.

Total heat i Q (Ill = (W1+W2) X△T
(1) Wl...Amount of water in tank 4 (g) W2...Equipment water equivalent (g) △T...This is the difference in water temperature in tank 4 before and after measurement. The total amount of heat Q can be expressed by the following formula.

Q cat = ql +q2+q3
(n) ql Heat of reaction q2... Joule heat q3... Difference in sensible heat between reaction gas and produced gas. Therefore,
From the above equations (11 and (b)), the reaction heat ql is expressed by the following equation.

q + = Q - (qz+q3) = (w, +W2) x△T (q2+q3) In other words, the reaction heat q1 is the amount of water in the water tank 4 W, the equipment water equivalent W2
, the temperature of the water in the water tank 4 E△T1 can be determined by measuring the dicot heat q2 and the difference q3 between the sensible heats of the reaction gas and the produced gas, respectively. In this case, tank 4
The amount of water W1 in the water tank 4 and the equipment water equivalent W2 are predetermined as equipment factors, so they are treated as constants. Since it is introduced and extracted at a temperature approximately equal to the water temperature, it can be virtually ignored. Therefore, according to the misfire morning device, the reaction heat q1 can be obtained by measuring the water temperature rise ΔT in the water tank 4 and the Joule heat q2. Incidentally, the Joule heat q2 is determined by the following formula based on the record of the above-mentioned "Electrical Calendar" 33.

q2 = J” FRdt
(mouth I) ■...
・・・・Anhair R・Heater resistance 0 L・Electrification time (seconds) As explained above, the present invention measures the temperature of a certain amount of water and measures the Joule heat using an external ammeter. The heat of reaction is known through measurement, and in particular, the reaction gas that should be pressurized is directly introduced into the reaction tube 8, and the
Since the heater 10 is heated via an infrared imaging furnace 11 that uses the inner surface of a thick-walled cylindrical aluminum block as a reflecting mirror surface 12, heat transfer due to thermal radiation is large and the sample is heated rapidly. In addition to being able to heat the image furnace 11, the water in the water tank 4 is forced to circulate in order to cool the reflecting mirror of the image furnace 11, thereby increasing the heat exchangeability. This has the advantage that measurement accuracy can be improved by reducing the amount of leakage, and the structure of the entire device can be simplified.

In this case, the escape pipe 19 for releasing the gas expansion inside the measurement cell 1 during heating is used to store the heated gas in the upper part of the water tank 4 after exchanging heat with the water in the water tank 4, and after the heating is completed. Since the sample is sucked into the cooled measurement cell 1 and the inside of the cell is maintained at normal pressure, heat leakage can be extremely reduced, which is efficient.

The present invention is applicable to the measurement of reaction heat in various reaction systems between solids and gases, such as hydrogenation reaction of coal, carbonization of coal, biomass, thermal decomposition of industrial waste, pie baking of various metal ores, etc. be advantageously applied.

[Brief explanation of drawings]

1 and 2 are vertical cross-sectional views showing essential parts of the present invention, and FIG. 3 is an overall explanatory view. Symbols in the figure: 1 is a measurement cell, 2 is a fin, 3 is a filter housing part, 4 is a water tank, 5 is a reaction gas introduction pipe, 6 is a spiral pipe, 7 is a produced gas discharge pipe, 8 is a reaction tube, 9 is the eye plate, IO
is a heater, 11 is an image furnace, 12 is a reflecting mirror surface, 13 is a cooling water pipe, 1.4 is a rotating blade, 16 is a thermocouple, 17 is a thermometer, I8 is a stirring rod, 19 is an external water tank, 23 is a reaction gas A spiral tube for heat exchange, 26 a communication tube, 27 an automatic temperature controller, 29 an electric contact, 30 a heat insulating container, 32 a reaction temperature control tube, and 33 a power meter. Patent applicant Makoto Ishizaka, Director of the Agency of Industrial Science and Technology - Figure 1 Isamu 2

Claims (1)

[Claims] (1) Inside the cylindrical measurement cell, a thermocouple for measuring the reaction temperature was erected through the upper end, and a cylindrical reaction tube with reaction gas flow holes on the second part of the circumferential surface was placed on the outside of the cell. A heater and a thick-walled cylindrical image furnace with a reflective mirror surface on the inner surface are sequentially and concentrically installed, and this measurement cell is held in a cylindrical water tank. A spiral pipe for heat exchange of the produced gas that opens along the inner circumferential surface to the top of the water tank, a stirring rod, a thermometer for measuring water temperature, a cooling water pipe that runs inside the peripheral wall of the image reactor, and a relief for discharging expanded gas from the measurement cell. 1. A reaction heat measuring device, characterized in that each pipe is provided, a water tank is provided in an external water tank, and a wattmeter connected to the heater is provided externally.