JP3327866B2 - Calorimetric measuring method, calorimetric measuring device, drainage measuring method, and drainage measuring device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calorific value measuring method, a calorimetric measuring device, a drainage measuring method, and a drainage measuring device for measuring the heat of solidification or the heat of fusion of a heat storage material applied to a heat storage system.

[0002]

2. Description of the Related Art As a heat storage method in a conventional heat storage system, there are a water heat storage method in which heat is stored using only sensible heat of water and an ice heat storage method in which water is used as a heat storage material and the latent heat of melting of the water is used. Are known. In this ice heat storage method, brine (antifreeze) cooled to 0 ° C. or less during heat storage
The water is cooled by using water to store cold heat as ice, and the heat is extracted by directly using cold water or indirectly melting the ice via brine during heat radiation.

In the heat storage system using the conventional ice latent heat method, when storing heat, it is necessary to cool the brine to about -5.degree. C. with a refrigerator, so that it is necessary to lower the refrigerant evaporation temperature of the refrigerator. The ratio of the amount of stored heat to the input of the refrigerator, that is, the coefficient of performance, is reduced. In addition, it is necessary to use brine when cooling ice, and care must be taken in its management.

As another example of a latent heat storage system, a latent heat storage material that changes phase at room temperature is utilized, and the latent heat storage material is encapsulated in a capsule or container as a core material to form cold water or water. Cooling as a solid by cooling using brine, or storing heat as a liquid by heating using warm water, and indirectly melting the cold heat by indirectly melting the latent heat storage material during heat radiation, taking out the heat by solidifying Methods are known. When using the latent heat storage material that changes phase at normal temperature, it is necessary to enclose the latent heat storage material in a capsule or container in terms of handling when the latent heat storage material has volatility or when used in a eutectic salt solution. .

On the other hand, as these capsules and containers, spherical ones having a diameter of 70 mm or rectangular or plate-like containers having a side of several tens cm are used, filled in a heat storage tank and used in a stationary state. The space between the heat storage tank and these capsules or containers is filled with water or brine.

[0006] In such a stationary capsule system and a container system, during heat storage and heat radiation, between these capsules or containers (hereinafter referred to as heat storage material containers) and a heat medium fluid such as water, or heat storage. The thermal resistance between the wall of the material container and the latent heat storage material is large. Therefore, the temperature of the latent heat storage material heated at the time of heat release or the temperature difference between the temperature of the latent heat storage material cooled at the time of heat storage and the temperature of the heat medium fluid used, such as water, must be about 5 ° C. or more in each state. The temperature of the heat transfer fluid used such as water during heat storage and heat release is 10
It is necessary to provide a temperature difference of at least ° C. That is, when trying to extract cold water of 5 ° C., it is necessary to cool with brine of −5 ° C. when storing heat. In addition, if it is attempted to store heat at a temperature level where brine is not used, the cold water discharge temperature will be 1
The temperature is 0 ° C. or higher, which is a temperature that cannot be directly used for general air conditioning and the like.

In order to solve the problem of the system using such a latent heat storage method, a microcapsule formed by encapsulating a latent heat storage material as a core material in a microcapsule is mixed with water to form a slurry to form a fluid. (Below,
This slurry is called a microcapsule slurry), and a system with improved heat transfer performance is known. In this system, during heat storage, the microcapsule slurry is directly cooled by exchanging heat with cold water or brine by a heat exchanger, thereby storing cold heat in the latent heat storage material in the microcapsules. Also, at the time of heat release, the microcapsule slurry is returned to the heat exchanger and exchanged heat with cold water or brine to directly heat, thereby extracting cold from the latent heat storage material in the microcapsules.

As described above, the heat storage characteristics of the microcapsule slurry are good, but for practical use, it is necessary to associate an arbitrary temperature with a heat quantity.

(1) First Prior Art A differential scanning calorimeter (DSC: Differen) is a device for measuring the relationship between the temperature and the amount of heat of a medium having a latent heat substance.
tial scanning calorimeter
The method using y) is generally used.

[0010] In the DSC apparatus, the specimen is left standing on the heating and cooling surfaces, and the relationship between the heat of fusion and the temperature of the heating surface during heating is measured.
By measuring the relationship between the heat of solidification and the temperature of the cooling surface during cooling, the phase change heat in each temperature range can be determined. The apparatus is quite expensive and the specimen is in a stationary state, so it is not suitable for calorimetric measurement of the microcapsule slurry.

(2) Second Prior Art Next, FIG. 7 shows an example of a method for measuring the calorific value of the microcapsule slurry. A slurry circulation pump is provided between a high temperature heat exchanger 61, a heating pump 63, a microcapsule heating system having a high temperature side calorimeter 64, and a low temperature heat exchanger 62, a cooling pump 65, and a cooling system having a low temperature side calorimeter 66. 69, a slurry flow rate controller 70 and an outlet slurry temperature control 67 and a low-temperature heat exchanger 62 of the high-temperature heat exchanger 61 for the microcapsule slurry.
The slurry system is composed of a microcapsule slurry system consisting of a slurry temperature control 68 at the outlet, and the slurry system has a slurry expansion tank 71 because it is a closed system.

In this method, the calorific value of each calorimeter 6 depends on the temperature difference between the slurry outlet temperature of the high-temperature heat exchanger 61 and the slurry outlet temperature of the low-temperature heat exchanger 62 and the slurry flow rate.
6, 64 can be measured.

[0013]

[Problems to be Solved by the First Prior Art] The amount of heat stored in the microcapsule slurry can be reduced by the heat of solidification and heat of fusion in the first prior art using the latent heat storage material in the microcapsules. And the specific heat of the entire microcapsule slurry. Conventionally, when measuring the amount of heat stored in a microcapsule, the microcapsule in a dry state or a slurry state is cooled and heated, and a DSC method using a differential scanning calorimeter (DSC: Differential S) is used.
The measurement is performed by using a scanning calorimetry.

However, since the state of the microcapsules in this measuring method is measured in a stationary state in the DSC test section, the microcapsules in a slurry state, which is a practical condition, and in a flow condition are actually used as heat exchangers in a heat storage system. Cooling through,
Different from heated state. Therefore, the heat of solidification and heat of fusion in the microcapsules obtained by the DSC measurement method are as follows:
Unlike the amount of heat of solidification and the amount of heat of fusion in a microcapsule in a slurry state, which is a practical condition, there is a problem that the accuracy is low and the cost of the measuring device is high.

(Problem of the second conventional technique) In the method of the second conventional technique shown in FIG. 7, the measurement accuracy is improved as the slurry flow rate is increased, but the heat source equipment capacity on the high temperature side and the low temperature side is increased. And the volume of the microcapsule slurry, which is the test sample, needs to be considerable.Therefore, there is a problem in economy, and it takes a considerable amount of time to reach heat balance and temperature stabilization. Become. In addition, since many microcapsule slurries are required, verification at the prototype stage becomes difficult.

It is an object of the present invention to provide a calorific value measuring method and a calorific value measuring device capable of obtaining a heat of solidification and a heat of fusion with high accuracy by a simple structure.

It is another object of the present invention to provide a method and an apparatus for measuring a drainage liquid, which improve the accuracy of calorimetric measurement.

[0018]

Means for Solving the Problems In order to solve the above-mentioned problems and achieve the object, a calorific value measuring method of the present invention is configured as follows.

(1) The calorie measuring method according to the present invention provides a heat storage material comprising a microcapsule made of an organic film material in which a core material mainly containing a latent heat storage material with a phase change is enclosed, and a liquid. A predetermined amount of the slurry is maintained at a predetermined temperature,
Mix the slurry and a predetermined amount, a cooling medium or a heating medium of known physical properties at a predetermined temperature, measure the temperature of the slurry after mixing, and at least the heat of solidification and the heat of fusion of the core material based on the temperature. One is measured according to the cooling or heating process.

(2) The calorimeter according to the present invention comprises a microcapsule slurry tank containing the slurry, a slurry heat exchanger, a slurry temperature control system, a mass control system, and a piping system connecting them. A known physical medium system consisting of a known physical medium tank for storing known physical media and a medium heat exchanger, a known medium temperature control system, a medium flow control system, and a piping system connecting them is connected by a mixer to measure the equilibrium temperature after mixing. At least one thermometer is installed, and the melting, solidification heat and sensible heat of the optional temperature range of the microcapsule slurry are measured by the mixing method described in (1) above. The heat exchanger of each system can be switched to a separately prepared cooling system and heating system, and can be adjusted to an arbitrary temperature.

That is, in the calorimetric method using the cooling and heating medium of known physical properties, a temperature control system composed of a microcapsule slurry tank, a medium tank of known physical properties, respective supply pumps and a heat exchanger is used. The mixing is performed at predetermined temperatures and flow rates in a mixer, and the calorific value is measured according to the cooling or heating process from the measurement result of the temperature after mixing.

(3) The calorimeter according to the present invention has the above-mentioned (2).
And a drain line is provided in a line after mixing the known physical medium as fresh water, and a conduit for returning the diluted microcapsule slurry to the microcapsule slurry tank is provided, and the diluted microcapsule slurry is provided. Also constitutes an auxiliary means characterized in that the calorific value can be easily measured.
The return line may be driven by gravity depending on the height of the drainage tank or may be provided with a pump.

When the medium having a known physical property is water, it is a component of the microcapsule slurry and is diluted after mixing. However, it is returned from the drainage receiving tank to the microcapsule slurry tank via a transfer pump. It is possible to re-measure the dilution state.

(4) The calorimeter of the present invention employs the calorimetric method for slurry by mixing with a known physical medium described in (1) above, and has a microcapsule slurry stirring section, a slurry temperature control section, and a weighing scale. A microcapsule slurry system consisting of a microcapsule slurry tank and a slurry mass flow rate control system, a known physical property medium tank having a known physical property medium stirring unit, a medium temperature control system, a weighing scale, and a known medium system consisting of a medium flow rate control system are mixed. At least one thermometer for measuring the equilibrium temperature after mixing is installed, and the melting, solidification heat, and sensible heat of the microcapsule slurry in an arbitrary temperature range are measured by the mixing method (1).

That is, a mixer, a cooling / heating device, and a weighing meter are respectively provided in the microcapsule slurry tank and the known physical medium tank, and a mass flowmeter and a flow rate control system are provided in the microcapsule take-out line. A flow meter and a flow control system are provided in the medium take-out line, and after mixing by a mixer, the mixing temperature is measured to measure the calorific value at the predetermined temperature difference.

(5) The drainage measuring device of the present invention uses the calorie measuring device of the above (4), is provided with a drainage valve in the line after mixing, and is provided with a branch and a drainage measuring valve. The lower mixed slurry is taken into a drainage measuring tank having a drainage stirring section, a weighing meter, and a drainage thermometer.

That is, in order to improve the measurement accuracy, the drainage tank after mixing is composed of two tanks, one of which is a drainage receiver until the temperature is settled, and the other is a drainage receiver for the main measurement after the temperature is settled. In addition, a stirrer, a weighing meter, and a drainage thermometer are provided in the main measurement tank to enable correction of unmixed components, non-equilibrium, and the like.

(6) In the drainage measuring method of the present invention, the drainage is measured by the drainage measuring device of (5).

(7) The calorific value measuring apparatus of the present invention is the above (2)
The apparatus according to any one of (1) to (4), wherein a function of simultaneously measuring a volume flow rate in the microcapsule slurry system is added, and a specific gravity measurement can be performed together with a calorie measurement and a sensible heat measurement at an arbitrary temperature width of the microcapsule slurry. It is configured so that: As a function of measuring the volume flow rate, an electromagnetic flow meter or the like may be interposed in the volume flow meter, or a volume flow signal of the mass flow meter may be used.

That is, by installing a volume flow meter in the microcapsule slurry take-out line and simultaneously measuring it with the mass flow rate, it is possible to measure the specific gravity under a predetermined temperature condition, and also perform the specific gravity measurement simultaneously with the calorimetric measurement at a predetermined temperature difference. To make things possible.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (First Embodiment) FIG. 1 is a diagram showing a configuration of a test apparatus for carrying out a calorific value measuring method according to a first embodiment of the present invention. In the first embodiment, a test is performed by mixing the microcapsule slurry with cold or hot water, the amount of heat of solidification and the amount of heat of fusion in the latent heat storage material in the microcapsule are calculated, and the heat storage density of the microcapsule slurry is obtained. .

In the test apparatus shown in FIG. 1, a beaker 2 and a stirrer (magnetic stirrer) 3 are installed in a constant temperature chamber 1, and a microcapsule slurry 21 is contained in the beaker 2. A propeller 32 is attached to the stirrer 3 via a shaft 31, and the propeller 32 is provided in the beaker 2. A data logger 4 is installed outside the constant temperature chamber 1, and a thermocouple 41 of the data logger 4 is inserted into the beaker 2.

Hereinafter, tests are performed on two types of microcapsule slurries, Type A and Type B, for the purpose of confirming the dependence of the amount of heat storage and heat release on the slurry temperature on both the solidification side and the melting side.

First, at the time of the solidification side test, the latent heat storage material (comprising a mixture of paraffinic hydrocarbons such as pentadecane and tetradecane) in a microcapsule heated to a predetermined temperature or higher at a melting temperature or higher is in a liquid phase state. A capsule slurry is prepared and placed in the beaker 2. Thereafter, the mass of the slurry in the beaker 2 is measured. Then, a predetermined amount of small crushed ice, which has sufficiently removed water from the surface of the ice, is put into the beaker 2, the stirrer 3 is operated, and the propeller 32 is rotated through the shaft 31 to be instantaneously mixed with the slurry. Measure the temperature of the entire slurry after mixing.

At the time of the melting side test, a microcapsule slurry is prepared at a predetermined temperature in which the latent heat storage material in the microcapsules is cooled to a solidification temperature or lower and is in a solid state.
Put in. Thereafter, the mass of the slurry in the beaker 2 is measured. Then, water at a predetermined temperature sufficiently higher than the coagulation temperature is supplied into the beaker 2, the stirrer 3 is operated, and the propeller 32 is rotated through the shaft 31 to be instantaneously mixed with the slurry. Measure the temperature of. The heat of solidification and the heat of fusion of the microcapsule slurry, that is, the heat storage and heat release, are measured from the temperatures and masses measured during the coagulation side test and the melting side test.

Next, during the coagulation test, the total temperature after mixing is
At the time of the melting test, the initial temperature of the slurry and the initial temperature of the supply water are changed as follows to derive the heat storage amount and the heat release amount before and after the change. The temperature of the slurry is measured by inserting a thermocouple 41 into the slurry, and the temperature is recorded on the data logger 4.

Tables 1 and 2 below show the conditions of the microcapsule slurries of types A and B in the above test.

Table 1: Mixing test conditions (Type A) Slurry concentration Slurry Slurry Feed water After mixing (stock solution) Weight Initial temperature Initial temperature Total temperature (%) (g) (° C) (° C) (° C) 44.8 100 9 ~ 12 0 ~ 1 2 ~ 5 44.8 100 2 ~ 5 22 ~ 23 9 ~ 12 Table 2: Mixing test conditions (Type B) Slurry concentration Slurry Slurry Feed water After mixing (stock solution) Weight Initial temperature Initial temperature Overall temperature (%) (G) (° C) (° C) (° C) 46.8 100 9 to 120 to 12 to 5 46.8 100 2 to 5 22 to 23 9 to 12 Heat of solidification and heat of fusion of the microcapsule slurry Is obtained by a computer (not shown) based on the following equations (1) and (2).

(1) Coagulation calorific value calculation formula Gp · Cp · (Tp−T) + Gp · L = Gice · Cw (T-Tice) + Gice · Lice + Q (1) L: Coagulation heat of microcapsule slurry (kcal /
kg) Rice: Heat of melting of ice (79.4 kcal / kg) T: Total temperature after mixing of microcapsule slurry (° C) Tp: Initial temperature of microcapsule slurry (° C) Tice: Ice temperature (° C) Gp: Fine Gice: Weight of ice (g) Cp: Specific heat of microcapsule slurry (0.8 kca)
1 / kg ° C.) Cw: Specific heat of water (1.0 kcal / kg ° C.) Q: Heat input correction value (kcal) (2) Heat of fusion calculation formula Gp · Cp · (T−Tp) + Gp · L = Gw · Cw (T
wT) L: heat of fusion of microcapsule slurry (kcal /
kg) T: Overall temperature after mixing of the microcapsule slurry (° C) Tp: Initial temperature of the microcapsule slurry (° C) Tw: Initial temperature of the supply water (° C) Gp: Weight of the microcapsule slurry (g) Gw: Supply water Weight (g) Cp: Specific heat of the microcapsule slurry (0.8 kca
1 / kg ° C.) Cw: Specific heat of water (1.0 kcal / kg ° C.) FIGS. 2A and 2B are diagrams showing the heat of solidification and the heat of fusion obtained by the test described above. From this result,
Looking at the solidification side, both types A and B fall out of the phase change region and settle down to the same amount of heat as the solidification end temperature decreases, but in the 3-5 ° C region, type B has a relatively higher heat of solidification. It can be seen that there is a tendency. Also, when plotting against the melting end temperature on the melting side, type B also tends to have a higher heat of fusion. This is presumably because the type B slurry concentration is higher than the type A and the type B phase change region is higher than the type A, so that such a tendency is relatively observed.

(Second Embodiment) FIG. 3 shows a second embodiment. In the second embodiment, a microcapsule adjusting system including a microcapsule slurry tank 301, a slurry heat exchanger 303, a slurry temperature control system 310, a slurry mass flow control system 320 and a slurry thermometer 330, and a known physical medium tank 351, a known medium heat exchanger 353, a known medium temperature control system 360, a medium flow rate control system 370, a slurry and a medium obtained from a known medium control system including a medium thermometer 380 are continuously mixed by a mixer 390, The temperature after the mixing is measured by a mixing thermometer 391, and the calorific value is measured by the mixing method described in the first embodiment.

Further, the slurry heat exchanger 303 and the known medium heat exchanger 353 include a cooling system 395 or a heating system 3.
The heat exchanger is connected to the heat exchanger 96 by heating or cooling, and any mode can be selected by switching the pipe.

The illustrated pipeline is simplified and only the outward route is shown. The device control and calorific value calculation of the second embodiment are as follows:
It is controlled by the control / arithmetic unit 393. The drainage after mixing is
It is stored in the drainage tank 392. At this time, the known physical property medium may be water, brine, oil, or the like. In the case of water, the medium has the same composition as the microcapsule slurry, and can be reused for measuring the physical properties of the diluted microcapsule slurry. In this case, the liquid is returned to the empty microcapsule slurry tank 301 via the drainage return pump 394 and the return valve 398 shown in the figure, and can be used for the next calorie measurement of the diluted microcapsule slurry.

In the second embodiment, ice cannot be used in the measurement of the heat of solidification as in the first embodiment. However, since the measurement is continuous, the measurement is performed by increasing the flow rate of the known physical medium. It becomes possible.

Next, the form at the time of measuring the heat of solidification will be described.
The temperature of the microcapsule slurry system needs to be raised to a predetermined temperature, and the slurry heat exchanger 303 is connected to the heating system 396 by selecting a pipeline. The slurry pump 302 is started and heated to a predetermined temperature by the slurry heat exchanger 303 by the slurry temperature control system 310. At this time, in the slurry temperature control system 310,
The slurry supply valve 312 is closed, the slurry circulation valve 311 is opened, and the temperature is raised to a predetermined temperature while circulating back to the microcapsule slurry tank 301.

On the other hand, in the known physical medium system, the known medium heat exchanger 353 is similarly connected to the cooling system 395 by selecting a pipeline, starts the known medium pump 352, and starts the known medium temperature control system 36.
According to 0, the known medium heat exchanger 353 cools down to a predetermined temperature (a signal from the control / arithmetic unit 393). At this time, in the known medium temperature control system 360, the medium supply valve 362 is closed, the medium circulation valve 361 is opened, and the medium is cooled to a predetermined temperature while circulating back to the known physical medium tank 351. In this manner, the temperature is maintained by the control / arithmetic unit 393 until the respective temperatures reach the predetermined temperatures.
2 is opened and measurement starts.

The control / arithmetic unit 393 controls the slurry mass flow control system 3 according to a preset program.
The operation is performed at predetermined time intervals while changing the combination of the set flow rate of the medium flow control system 370 and the set flow rate of the medium flow control system 370.

The state of each flow rate combination was measured by a slurry thermometer 330, a medium thermometer 380, and a mixing thermometer 39.
The temperature monitor of Step 1 and the PV value of the slurry mass flow system 320 are monitored, and the PV value of the medium flow control system 370 is monitored. From this combination data, it is possible to determine the change in total enthalpy of the heat of solidification and the sensible heat in a predetermined temperature range from an arbitrary temperature of the microcapsule slurry.

Here, the reason why the flow rate adjusting system 320 of the microcapsule slurry system is a mass flow meter is that the specific volume change accompanying the phase change in the microcapsule is large and it is often unknown at first. A commercially available Coriolis force type mass flow meter or the like is used. In addition, the known physical property medium system is a volume flow meter (such as an electromagnetic flow meter) to improve the economic efficiency.

Next, when measuring the heat of fusion, the microcapsule slurry-based slurry heat exchanger 303 is connected to the cooling system 395 by selecting a pipe line, and the known medium heat exchanger 35 of the known physical medium system is used.
3 is connected to a heating system 396, and the heat of fusion is measured by raising the temperature of the microcapsule slurry from a predetermined low temperature by mixing a known temperature medium in the same manner as the above-described measurement at the time of solidification.

As described above, in the second embodiment, the temperature-controlled microcapsule slurry and the known physical property medium are continuously mixed in a predetermined flow rate combination, regardless of the heat capacity problem and the heat balance matching. Automatic sequential measurement can be performed, and the temperature and specific enthalpy correlation can be obtained efficiently. In addition, since the method is a continuous mixing method, a test at a small flow rate can be performed, the test can be performed with a small amount of microcapsule sample, and problems at the prototype stage can be reduced.

(Third Embodiment) Next, a third embodiment is shown in FIG. In the second embodiment, a slurry pump, a known medium pump, a cooling system, and a heating system are still large-scaled. Therefore, in the third embodiment, cooling and heating are performed by a mixing method using a position head of a tank. An example in which the system is simplified and the measurement accuracy is increased by adding a weighing function will be described.

In the third embodiment, a microcapsule slurry tank 401, a slurry mass flow control system 420, a slurry thermometer 430 and a known physical medium tank 451, a medium flow control system 470, a medium thermometer 480, and a mixer 490 are used. , A mixing thermometer 491 and a control / arithmetic unit 493. Also,
The microcapsule slurry tank 401 has a slurry temperature control system 4
As 10, a heating / cooling jacket 412 and a temperature controller 411 are provided, and a stirrer 413 and a weighing scale 414 are provided. Similarly, the known physical medium tank 451 includes the heating / cooling jacket 462 and the temperature control controller 461 as the known medium temperature control system 460, and the stirring device 4
63 and a scale 464 are provided. The waste liquid after mixing flows into the drain tank 492. In addition, each tank is arranged according to the vertical relationship shown in the figure, and mixing is performed at a position difference. Pumps are not provided. However, a pump may be provided in order to expand the test range.

In the microcapsule slurry tank 401, the slurry is constantly stirred by a stirring device 413 such as a stirrer and kept uniformly. Heating and cooling according to each test of melting and solidification are arranged and wired so that the thermoelectric element (using the Peltier effect) installed in the wall jacket of the slurry tank 401 satisfies both the heating surface side and the cooling surface side. , A heating / cooling jacket 412. Further, the jacket may be a coil jacket of cooling water and heating water.

The heating / cooling jacket 412 is provided with a temperature controller 411 which operates by sensing the temperature in the slurry.
Thus, the microcapsule slurry is heated or cooled so as to maintain the set temperature of the control / calculation device 493 according to the test conditions. The weight of the microcapsule slurry filled in the slurry tank 401 is measured by a weighing meter 414. The slurry tank is designed so that external force from the slurry pipeline system is not applied, and in such a case, consideration is given so that correction can be made. This weighing machine 414
In the figure, the load cell is shown below the holding handle of the tank, but any of a balance method, a spring method, and the like may be used. Similarly, in the known physical medium tank 451, the medium is temperature-controlled and weighed by the stirrer 463, the known medium temperature control system 460, and the scale 464.

As described above, in the third embodiment, the calorimetric measurement is performed by the mixing and controlling method using a control / arithmetic apparatus, except that the temperature holding function of the microcapsule slurry and the known physical medium is different from that of the second embodiment. 493, slurry mass flow control system 420, slurry thermometer 430, medium flow control system 4
70, a medium thermometer 480, and a mixer 490.

The major feature of the third embodiment is that the weighing scales 414 and 464 are provided, and the time difference between the actually mixed microcapsule slurry and the medium is obtained from the weighing difference between measurement timings under stable conditions. The integral weight can be obtained, and the measurement accuracy can be improved. The slurry mass flow control system 420 and the medium flow control system 4
The indicated value calibration of 70 can be easily performed. In addition, although there is a flow rate variation corresponding to the outflow amount at the position head, correction when the flow rate is out of the control range of the flow rate adjustment system is facilitated by performing the mass measurement.

As described above, in the third embodiment, a calorie measuring device which is more compact and has higher measurement accuracy than the second embodiment is obtained by using the heating / cooling of the jacket, the weighing device, and the use of the position head by the vertical arrangement. be able to.

(Fourth Embodiment) FIG. 5 shows a fourth embodiment. In the fourth embodiment, the drainage system of the third embodiment is improved, and a drainage valve 444 and a drainage measurement valve 44 are provided between the mixing thermometer 491 and the drainage tank 492.
5. A drainage measuring tank 440 is provided. Further, a stirrer 441, a drain thermometer 442,
A weigh scale 443 is provided.

The fourth embodiment is to cope with a case where the equilibrium time constant is long after the mixing of the microcapsule slurry, and to complement the accuracy by common measurement of each measurement system of the microcapsule system and the known medium system. It is.

The functions at the time of calorie measurement are as follows. Third
During the period up to the temperature stabilization of the pipe immediately after the start of mixing according to the embodiment, the drain control valve 445 is closed and the drain valve 444 is open, and the non-stabilized mixed slurry is discharged to the drain tank 492. Is done. The control / arithmetic unit determines the temperature stabilization state of the mixing thermometer 491, and opens the drainage measuring valve 445 and closes the drainage valve 444. Immediately before the end of the predetermined time measurement, the drainage valve 444 is opened and the drainage measurement valve 445 is closed, and the drainage within the measurement time period is taken into the drainage measurement tank 440.

In the drainage measuring tank 440, the wastewater taken in by the stirring device 441 is mixed uniformly, and the temperature transition after the non-equilibrium degree is released is monitored by monitoring the temperature transition by the wastewater thermometer 442. At 443, the inflow amount within the measurement time is measured, and is used for correction of the weighed value and the like of the microcapsule slurry system and the known medium system. The drainage measuring tank does not need to be emptied each time, and is used for cumulative evaluation under arbitrary conditions.

The calibration can be performed by using the drainage measuring tank 440 system when calibrating the instrument system of the slurry system and the known medium system other than the calorimetric measurement.

As described above, in the fourth embodiment, the accuracy of calorie measurement of the microcapsule slurry having a high degree of non-equilibrium is improved as compared with the third embodiment, and the mixing method is a transient measurement. Accuracy can be checked for the measurement error caused by the cumulative measurement of the drainage measuring system, and the calibration of the slurry system and the known medium system is facilitated, so that the accuracy can be further improved.

(Fifth Embodiment) FIG. 6 shows a fifth embodiment. In the fifth embodiment, as a function enhancement of the fourth embodiment, a method is shown in which the specific gravity of the microcapsule slurry can be measured simultaneously with the calorific value measurement. This method can be applied commonly to the second, third, and fourth embodiments. In the fifth embodiment, a volumetric flowmeter 4 is added to the microcapsule slurry system of the fourth embodiment.
95 is interposed in addition to the mass flow control system 420.

Under the same conditions as the mass flow rate of the microcapsule slurry at a predetermined temperature prepared for calorie measurement, the volume flow meter 4 was used.
95 (electromagnetic flow meter, orifice flow meter, etc.) is also provided, and the specific gravity of the microcapsule slurry can be measured from the data obtained at the same time, so that the calorific value and the specific gravity can be measured industrially in a short period of time.

The present invention is not limited to the above-described embodiments, and can be modified as needed without departing from the scope of the invention.

(Summary of Embodiment) The configuration, operation and effect shown in the embodiment are summarized as follows.

[1] The calorimetric method described in the first embodiment is a calorimetric method for microcapsule slurry.
A predetermined amount of slurry is maintained at a predetermined temperature, and a predetermined amount of liquid having a known specific heat such as hot water or cold water maintained at a predetermined temperature as a heating medium or a cooling medium is instantaneously mixed to obtain an equilibrium temperature. The amount of heat of solidification and the amount of heat of fusion generated between the predetermined temperature and the temperature after equilibrium are specified.

Therefore, according to the above calorimetric method, since a small number of specimens are used and the slurry is mixed with a substance having known physical properties, a simple structure can be used at low cost, in a short time, with high accuracy, It becomes possible to measure the heat of solidification and the heat of fusion for the microcapsule slurry in the temperature range.

[2] The second embodiment provides a specific device capable of continuously measuring data of a microcapsule slurry and a medium having known physical properties at a predetermined temperature and a predetermined flow rate. It consists of a microcapsule system consisting of a microcapsule slurry tank, a slurry heat exchanger, a slurry temperature control system, and a mass flow control system, a known physical medium tank and a medium heat exchanger, a known medium temperature control system, and a medium flow control system. A known medium system is connected with a mixer, and the calorie measurement is continuously performed by measuring the equilibrium temperature after mixing.Each system has a switching function, a control system that controls the cooling system, heating system device, and the entire device. It is composed of an apparatus, and it is possible to automatically and continuously measure the heat of solidification and the heat of fusion with a relatively small amount of slurry of the microcapsules.

When the known physical medium is water, a return line from the drainage tank to the microcapsule slurry tank can be provided to enable re-measurement with the diluted slurry.

[3] The third embodiment provides an apparatus for improving accuracy with a more compact apparatus configuration, and includes a stirring apparatus, a slurry temperature control system, a microcapsule slurry tank having a weighing scale, a slurry mass As with the microcapsule slurry system consisting of a flow rate control system, a stirring device, a known medium temperature control system,
A calorie measurement is continuously performed by connecting a known medium medium tank having a weighing meter and a known medium system including a medium flow rate temperature control system with a mixer and measuring an equilibrium temperature after mixing. Also,
Each system is controlled by a control and arithmetic unit.

In the third embodiment, the measurement of the mixing amount is multiplexed by the weighing in each tank, so that the accuracy can be improved, and the calibration of the flow rate control system becomes easy.
This is also advantageous in maintaining accuracy.

[4] The fourth embodiment is a further extension of the third embodiment, and is intended to cope with microcapsule slurries having a high degree of non-equilibrium and further improve accuracy. In addition to the configuration of the embodiment, a drain valve and a drain measuring valve by branching are provided in the line after mixing, and the liquid is guided to the drain measuring tank. Also,
Equipped with a stirrer, weighing meter, and drainage thermometer in the drainage measuring tank, collect only the mixed wastewater during calorimetric measurement, and improve the measurement accuracy by feedback from the equilibrium temperature measurement and accumulated state quantity measurement data. be able to.

Further, since the drainage measuring tank system is provided in the common system of the microcapsule system and the known medium system, the respective calibrations become easier than in the third embodiment, and the accuracy can be further improved.

[5] The fifth embodiment is common to the second to fourth embodiments, and a specific gravity can be measured by adding a volume flow meter to the microcapsule slurry line and simultaneously measuring the mass flow rate. It is intended to provide a function-up method that makes it possible.

[0077]

(1) According to the calorific value measuring method of the present invention,
With a simple structure, the heat of solidification and heat of fusion can be obtained with high accuracy.

(2) According to the calorimeter of the present invention, the heat of solidification and the heat of fusion can be obtained with a simple configuration and with high accuracy.

(3) According to the calorimeter of the present invention, when the known physical medium is water, it is possible to return the microcapsule slurry from the drainage tank and to re-measure the diluted slurry.

(4) According to the calorimeter of the present invention, the amount of heat of fusion, the amount of heat of solidification, and the amount of sensible heat of the microcapsule slurry in an arbitrary temperature range can be measured.

(5) According to the drainage measuring device of the present invention, the accuracy of calorie measurement can be improved.

(6) According to the drainage measuring method of the present invention, the accuracy of calorific value measurement can be improved.

(7) According to the calorimeter of the present invention, specific gravity measurement can be performed simultaneously with calorimetry at an arbitrary temperature difference.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration of a test apparatus for performing a calorific value measuring method according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a heat of solidification and a heat of fusion obtained by a test according to the first embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a test apparatus for performing a calorific value measuring method according to a second embodiment of the present invention.

FIG. 4 is a diagram showing a configuration of a test apparatus for performing a calorific value measuring method according to a third embodiment of the present invention.

FIG. 5 is a diagram showing a configuration of a test apparatus for performing a calorific value measuring method according to a fourth embodiment of the present invention.

FIG. 6 is a diagram showing a configuration of a test apparatus for performing a calorific value measuring method according to a fifth embodiment of the present invention.

FIG. 7 is a diagram showing an example of a calorimetric measurement method for a microcapsule slurry according to a conventional example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Constant temperature bath, 2 ... Beaker, 21 ... Microcapsule slurry, 3 ... Starter, 31 ... Shaft, 32 ... Propeller, 4 ... Data logger, 41 ... Thermocouple 301, 401 ... Microcapsule slurry tank 302 ... Slurry pump 303 ... Slurry heat exchangers 310, 410 ... Slurry temperature control system 311 ... Slurry circulation valve 312 ... Slurry supply valve 320,420 ... Slurry mass flow rate control system 330,430 ... Slurry thermometer 351,451 ... Known physical medium tank 352 ... Known medium Pump 353 ... known medium heat exchanger 360,460 ... known medium temperature control system 361 ... medium circulation valve 362 ... medium supply valve 370,470 ... medium flow control system 380,480 ... medium thermometer 390,490 ... mixer 391, 491: Mixing thermometer 392, 492 Drainage tank 393, 493 Control / calculation equipment 394 Drain return pump 395 Cooling system 396 Heating system 398 Return valve 411 Temperature controller 412 Heating / cooling jacket 413,463 Stirring device 414,464 Weighing meter 440 Drainage measuring tank 441 Stirring Device 442: drainage thermometer 443: weighing meter 444: drainage valve 445: drainage measuring valve 461: temperature controller 462: heating / cooling jacket 495: volume flow meter

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshio Tashiro 24, Kinone Jindai, Narita City, Chiba Prefecture Inside the Tokyo International Airport Corporation (72) Inventor Takao Yokose 24, Kinone Jindai, Kinoki, Narita City, Chiba Prefecture Inside the Airport Authority (72) Inventor Seiji Shibuya 2-1-1 Shinama, Araimachi, Takasago City, Hyogo Prefecture Inside the Takasago Works, Mitsubishi Heavy Industries, Ltd. Inside Takasago Machinery Co., Ltd. No. Takasago Research Laboratory, Mitsubishi Heavy Industries, Ltd. (56) References JP-A-2-265642 (JP, A) JP-A-7-98290 (JP, A JP-A-11-30599 (JP, A) JP-A-8-50063 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 25/20 F28D 20/00 G01K 17 / 00

Claims (7)

(57) [Claims] 1. A predetermined amount of a slurry, which is a heat storage material composed of a microcapsule made of an organic film material in which a core material mainly containing a latent heat storage material accompanied by a phase change is sealed and a liquid, and a predetermined temperature. The slurry is mixed with a predetermined amount, a cooling medium or a heating medium having known physical properties at a predetermined temperature, and the temperature of the slurry after mixing is measured. Based on the temperature, the heat of solidification of the core material and A calorimetric method comprising measuring at least one of the heats of fusion. 2. A microcapsule slurry tank for storing the slurry, a microcapsule slurry system comprising a slurry heat exchanger, a slurry temperature control system, a mass control system and a piping system connecting them, and a known physical medium tank for storing a known physical medium. Medium heat exchanger,
The at least one thermometer for measuring the equilibrium temperature after mixing by connecting a known physical medium system consisting of a known medium temperature control system, a medium flow control system and a piping system connecting them with a mixer, is provided, according to claim 1. Calorimeter characterized by measuring the melting, coagulating calorie and sensible calorie of the microcapsule slurry at an arbitrary temperature range by the mixing method of (1). 3. The method according to claim 2, wherein a drainage tank is provided in a line after mixing the known physical medium as fresh water, and a conduit for returning the diluted microcapsule slurry to the microcapsule slurry tank is provided. A calorimetric device as described. 4. A microcapsule slurry tank having a microcapsule slurry stirring section, a slurry temperature control section, a weighing scale, and a slurry mass flow rate control system using the slurry calorimetric method by mixing with the known physical medium of claim 1. A microcapsule slurry system consisting of a known physical medium stirrer, a medium temperature control system, a known physical medium tank having a weighing scale, and a known medium system consisting of a medium flow rate control system are connected by a mixer, and the equilibrium temperature after mixing is adjusted. A calorie measuring device, comprising at least one thermometer for measuring, and measuring the melting, coagulating heat and sensible heat of the microcapsule slurry in an arbitrary temperature range by the mixing method according to claim 1. 5. An apparatus according to claim 4, wherein a drain valve is provided in the line after mixing, and a branch and a drain measuring valve are provided.
A drainage measuring device characterized in that the slurry after mixing under calorimetric conditions is taken into a drainage measuring tank having a drainage stirring section, a weighing meter, and a drainage thermometer. 6. A drainage measuring method, comprising measuring drainage by the drainage measuring device according to claim 5. 7. The microcapsule slurry system is provided with a function of simultaneously measuring a volume flow rate, so that a specific gravity measurement can be performed together with a calorie measurement and a sensible heat measurement at an arbitrary temperature range of the microcapsule slurry. Item 5. A calorimetric device according to any one of Items 2 to 4.