JPS5934966B2 - calorimeter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a calorimeter for measuring the calorific value of liquids and solid substances, and in particular, in a calorimeter that can directly record the rise in internal cylinder water temperature as the calorific value. The aim is to improve measurement accuracy and simplify operation.

In general, a calorimeter that measures the calorific value of liquids and solid substances consists of filling a pump with a certain amount of sample along with compressed oxygen for complete combustion, and immersing the pump in an inner cylinder containing a specified amount of water. This inner cylinder is placed in an outer tank filled with water at the same temperature as the water temperature in the inner cylinder, and a current is passed through the ignition wire of the pump to combust the sample inside the pump, and the combustion heat is absorbed by the water in the inner cylinder. It measures the amount of heat generated from the rise in temperature.

In this case, the outer tank is equipped with an outer tank water heating device, which increases the temperature of the outer tank water in accordance with the rise in the temperature of the inner tank water, so that the temperature difference between the inner tank water and the outer tank water is virtually zero. This provides a heat insulating effect, eliminates the influence of ambient temperature when measuring calorific value, and improves measurement accuracy. The calorific value in such a calorimeter is expressed by the following formula.
Calorific value (cal) ■ (inner cylinder water volume (9) + equipment water equivalent J)
)×Temperature rise of the inner tube water (C) By the way, in such a calorimeter, the calorific value is measured in proportion to the temperature rise of the inner tube water. Equivalent (
g))) is required to be constant at all times, but in reality, the water efficiency of the equipment fluctuates depending on the temperature at the time of measurement, so the measured calorific value includes this fluctuation value as an error. You will be able to do it.

Therefore, conventionally, as seen in Japanese Patent Publication No. 40-9960, after the temperature at the start of measurement is properly determined in advance, benzoic acid for calorific value standardization is actually burned in the pump and the inner cylinder is heated. The rising temperature of the water is measured and recorded, and if the value exceeds or falls short of the previously known benzoic acid calorific value, the water equivalent of the device has fluctuated. Correspondingly, compensate for (inner cylinder water volume &) equipment water equivalent (J)) in the above formula so that it is always constant, and record the measured value of the rising temperature of the inner cylinder water as it is as the measured value of calorific value. I'm starting to let them do it. However, in this type of calorimeter, the temperature at the start of measurement (outer tank water temperature) is set in relation to the indoor temperature (usually matched to the indoor temperature), and the indoor temperature is within a certain range (±
3℃), it is necessary to adjust the amount of water supplied into the inner cylinder according to the room temperature each time, and this operation is extremely complicated and becomes a major drawback in use, and also causes a reduction in measurement accuracy. It's summery. The present invention overcomes these drawbacks of conventional calorimeters, and by attaching an outer tank water temperature setting device and a device water equivalent compensating device in conjunction with each other, the measurement operation is significantly simplified. This provides a calorimeter with significantly improved measurement accuracy. That is, according to the present invention, in a calorimeter that is capable of directly recording an increase in inner cylinder water temperature as a calorific value, an outer tank water temperature setting device that sets the temperature of outer tank water to several predetermined specific temperatures is provided. And, a calorimeter is provided which is attached with a device water equivalent compensating device which works in conjunction with this outer tank water temperature setting device and compensates the device water equivalent in accordance with the temperature set by this outer tank water temperature setting device. . Next, the present invention will be explained with reference to the drawings.

Reference numeral 1 denotes an outer tank, and the outer tank includes a heating device 2 for heating the outer tank water 19, a temperature detector for detecting the temperature of the outer tank water 19, an agitator 4 for stirring the outer tank water, and a space layer 6. A double-walled inner cylinder 5 is inserted.

7 is a lid of the inner cylinder 5.

Also, inside the inner cylinder 5, a support 8 fixed to the lid 7,
8, a pump 9 supported by the inner cylinder water 20, an electric contact 10 for setting the amount of water in the inner cylinder 20, temperature detectors 11 and 12 for detecting the temperature of the inner cylinder water 20, and stirring the inner cylinder water 20. A stirrer 13 for stirring the inner cylinder water is inserted. Further, a motor 15 for driving an inner tube water stirrer is directly connected to the shaft 14 of the stirrer 13. A driving motor 16 is connected to the agitator 4 for agitating the outer tank water. Reference numeral 17 denotes a communication pipe provided at the bottom of the inner cylinder 5 for guiding the outer tank water into the inner cylinder, and a solenoid valve 18 is provided in the middle.

Reference numeral 21 denotes a liquid level relay to which a terminal of an electric contact 10 for setting a water amount provided in the inner cylinder 5 is connected, and its output side is connected to a solenoid valve 18 .

Reference numeral 22 denotes an automatic temperature control device, which is connected to the inner cylinder water temperature detector 11, the outer tank water temperature detector 3, and the outer tank water temperature heating device 2.

23 is an inner cylinder water temperature automatic stagnation device, and an inner cylinder water temperature detector 1
2, and its output is connected via a device water equivalent compensator 24 to a recorder 25 that records the temperature rise of the inner cylinder water.

26 is an outer tank water temperature setting device, which is connected to the outer tank water temperature detector 3 and the outer tank water heating device 2.

In the present invention, the outer tank water temperature setting device 26 is used to set the temperature of the outer tank water at several predetermined temperatures at the start of measurement, and may be configured with a conventional bridge circuit.

In other words, one of the four resistance sides that make up the bridge circuit (resistance thermometer, such as a platinum resistance thermometer or thermistor) is placed in the water in the outer tank, and the other one is placed into several divided resistance sides. Set the resistance value for each in accordance with a pre-specified temperature, for example, at 5°C intervals,
Then, at the start of measurement, one of the divided resistance sides is selected to form a bridge circuit. By using such a bridge circuit, the outer tank water temperature can be set at a predetermined specific temperature at certain temperature intervals. The outer tank water temperature setting device 26 is preferably configured to be able to set the outer tank water temperature at temperature intervals of 3 to 10°C in a temperature range of 10 to 40°C, depending on the heat insulation properties of the calorimeter. The temperature interval can be made wider as the thermal insulation of the calorimeter increases. Further, since the automatic temperature adjustment device 22 includes a bridge circuit, the outer tank water temperature setting device 26 can also be used as the bridge circuit by using a changeover switch or the like. In the present invention, the device water equivalent compensation device 24 is for compensating the device water equivalent based on the temperature of the measured water at the start of measurement, and converting the rise in the inner cylinder water temperature into an accurate calorific value.

As mentioned above, in order to directly measure the temperature rise of the inner tube water as the calorific value, {inner tube water amount (2) + equipment water equivalent (7
)} is constant, but even if the internal cylinder water volume is constant, the equipment water equivalent will actually vary depending on the water temperature at the start of measurement, and this variation will be included in the measured value as an error. You will be able to do it. According to the research of the present inventor, it has been found that there is a certain relationship between the water temperature change during measurement and the amount of change in the device water equivalent. The amount of variation in the device water equivalent corresponding to each temperature specified by the water temperature setting device 26 is determined, and a circuit for compensating for this amount of variation is housed in the device water equivalent compensating device 24 in relation to the set temperature of the outer tank water. Then, ζ, the output from the temperature measuring device is input to this compensator 24, and the compensated output is input to the recorder 2.
5 and record it as the calorific value. Note that the device water equivalent in the present invention is defined to include all heat absorption factors including the inner cylinder water in the device system.

Next, the principle of device water equivalent compensation in the present invention will be explained in detail.

In a calorimeter, the calorific value of a substance obtained when measurement is started at the reference temperature (TO) is expressed by the following formula.

Q=[W(TO)]ΔTO Q: Calorific value W(TO): Reference temperature T.

Equipment water equivalent ΔTO at: reference temperature T. On the other hand, for the same substance, the calorific value of the substance obtained when measurement is started at the measurement temperature (Tx) is expressed by the following formula.

Q=[W(Tx)]ΔTx Q: Calorific value W(Tx): Apparatus water equivalent at temperature Tx ΔTx: Increased temperature from measurement start temperature Tx As mentioned above, the apparatus water equivalent changes depending on the temperature. Therefore, even if the amount of water in the inner cylinder is the same, if measurement starts from temperature Tx, the temperature will rise ΔT.
x varies depending on the amount of change in the water equivalent of the device.

That is, the device water equivalent is T at the measured temperature. If the temperature is changed by ΔW by changing from ΔW to Tx, the temperature increase ΔTx at that time is expressed by the following equation. In the present invention, the device water equivalent compensator 24 converts the electrical signal corresponding to the actual temperature increase ΔTx taken out from the temperature measuring device 23 to the reference temperature T. Calorific value Q obtained when measurement starts at
The temperature increase ΔTO is directly related to the temperature increase ΔTO. This conversion circuit is connected to the voltage Vx=α(Tx)ΔTx set by the temperature measuring device 23, VO=d(T
x) Any suitable arithmetic circuit that converts into ΔTO may be used. In the present invention, the specific value of such compensation coefficient α' (Tx) determined by the measurement start temperature is determined in advance by burning a standard substance in relation to each set temperature of the outer tank water. However, these values are incorporated into the arithmetic circuit of the compensator 24 so that they can be selected in accordance with the set temperature of the outer tank water.

Then, these compensating device 24 and outer tank water temperature setting device 2
6 is operationally linked, it is possible to set the temperature setting device 26 to a specific temperature for the water in the outer tank and at the same time operate the compensation device 24 in accordance with the set temperature. In some cases, this compensation device may
One is divided according to each set temperature of the outer tank water temperature setting device, and the resistance value of each resistance side is compensated for by a voltage V. It can also be configured by appropriately setting so that =α'(Tx)ΔTO occurs. The calorimeter of the present invention has the above configuration, and in order to operate this calorimeter, after installing the pump 9, the outer tank water 19 is poured. next,
Select an appropriate switch from among the set temperature switches attached to the outer tank water temperature setting device 26 and turn it on.
As a result, the outer tank water temperature is set to that specific temperature.
In this case, the outer tank water temperature is set to the temperature closest to room temperature. Further, since this outer tank water temperature setting device 26 is linked with the device water equivalent compensating device 24, the compensating device 24 is also set to operate in accordance with the set temperature. Next, the solenoid valve 18 is opened and a portion of the outer tank water 19 is introduced into the inner cylinder 5 through the communication pipe 17 using the head.

At this time, the communication pipe 17 passes through the outer tank water 19, so there is no fluctuation in the temperature of the water.The electric contact 10 for setting the water volume in the inner cylinder 5 is set at the position of the specified water volume, so the temperature of the water does not change. A specified amount of water is always collected in the cylinder 5 by the action of the liquid level relay 21. Next, an electric current is passed through the ignition wire (not shown) of the pump 9 to cause the sample to burn in the compressed oxygen within the pump 9.
This combustion heat causes the temperature of the inner cylinder water 20 to rise, but due to the action of the automatic temperature adjustment device 22, the temperature of the outer tank water 19 changes to follow the temperature of the inner cylinder water 20, and the inner cylinder 5 is effectively insulated. action takes place. The temperature rise of the inner cylinder water at this time is recorded on the recorder 25. In this case, the increased temperature recorded on the recorder 25 is a value that has been compensated and converted into the reference temperature (TO) by the compensator 24, so the increased temperature is added to the reference temperature (TO).
The calorific value of the sample can be directly determined by multiplying by the conversion coefficient W(TO). Also, recorder 2
5 is provided with a scale according to the amount of heat generated, so that the amount of heat generated can be directly read. As described above, the calorimeter of the present invention is easy to operate and allows the recorder to directly record the calorific value compensated for the water equivalent of the device, and has great industrial significance.

[Brief explanation of drawings]

The drawing is an explanatory cross-sectional view of the calorimeter of the present invention. 1...Outer tank, 2...Outer tank water heating device,
3... Outer tank water temperature detector, 9... Pump, 10... Electric contact for setting inner cylinder water amount, 11,
12... Inner cylinder water temperature detector, 17...
Communication pipe, 18...Solenoid valve, 19...Outer tank water, 20...Inner tank water, 21...Liquid level relay, 22... ...Hakudo temperature control device, 23...
... Inner cylinder water temperature automatic measuring device, 24 ... Device water equivalent compensation device, 25 ... Recorder, 26 ...
...Outer tank water temperature setting device.

Claims (1)

[Claims] 1 Among calorimeters that measure the calorific value of a sample by adiabatically burning it, water in the outer tank adjusted to a predetermined temperature is automatically supplied from the outer tank to the inner cylinder via an inlet pipe and a solenoid valve. death,
A calorimeter that can directly record the rise in inner cylinder water temperature as a calorific value includes an outer tank water temperature setting device that sets the outer tank water to several predetermined specific temperatures, and this outer tank water temperature setting device. A calorimeter characterized in that it is equipped with a water equivalent compensating device which is interlocked with the device and compensates the device water equivalent with respect to the temperature set by the outer tank water temperature setting device.