JP2001330519A - Batch adiabatic type adsorption heat measuring device allowing simultaneous measurement of adsorption heat and equilibrium vapor pressure at gas adsorption time - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a batch adiabatic type adsorption heat measuring device allowing simultaneous measurement of adsorption heat and equilibrium vapor pressure at gas adsorption time. SOLUTION: A pressure sensor part is connected to a system for measuring the adsorption heat for coupling a solution reservoir for storing solution that evaporates and is adsorbed by a sample to a sample vessel for storing the sample. Thus, the batch adiabatic type adsorption heat measuring device can simultaneously measure adsorption heat and equilibrium vapor pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a batch-type adiabatic heat of adsorption measuring apparatus capable of simultaneously measuring the heat of adsorption and the equilibrium vapor pressure during gas adsorption, and particularly to the adsorption of a porous material represented by zeolite. This is an apparatus for evaluating heat and adsorption speed, evaluating heat of adsorption of cement-based materials, and evaluating heat pumps using solar heat and waste heat as heat storage materials.

[0002]

2. Description of the Related Art Heat of adsorption is generated when a substance is adsorbed, and various apparatuses have been developed to measure the heat of adsorption.

[0003] The flow method and the titration method are used to measure the heat of adsorption due to the interaction between solid and gas, and between solid and liquid. However, the amount of adsorption to a sample is small, and the amount of adsorption is measured directly. Was impossible.

Subsequently, a batch type adiabatic heat of adsorption measuring device was developed, and the amount of adsorption could be measured, and the integrated enthalpy and the adsorption speed could be obtained.

However, since the vapor pressure at the time of adsorption could not be measured, data on the vapor pressure at the time of adsorption, which is important in evaluating the heat storage material of the heat pump, at the time when the adsorption was completed, were obtained. There was a disadvantage that it could not be obtained.

Further, an apparatus has been developed which measures the equilibrium vapor pressure and obtains the differential enthalpy from the pressure-temperature relationship. However, since only the sample portion is heated, only the vapor pressure at room temperature can be measured. There was a disadvantage that it could not be done.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the fact that the conventional batch-type adiabatic adsorption heat measuring apparatus could not solve the problem, and it is intended to simultaneously measure the heat of adsorption and the equilibrium vapor pressure during gas adsorption. And a batch-type adiabatic adsorption heat measuring device that enables differential enthalpy and integral enthalpy to be measured by a single measuring device.

[0008]

According to the present invention, there is provided a system for connecting a sample container for measuring the heat of adsorption with a solution reservoir, the system comprising:
A high-sensitivity pressure sensor unit was connected to enable simultaneous measurement of adsorption heat and equilibrium vapor pressure during gas adsorption.

Further, in the equilibrium vapor pressure measurement, it is possible to measure the vapor pressure up to 45 ° C. by putting not only the sample container portion for accommodating the sample but also the entire apparatus in a thermostat.

[0010] Furthermore, the integral enthalpy and the differential enthalpy can be measured with a single measuring device by separating the solution reservoir from the measuring system so that it can be stopped with a cock and using a high-sensitivity pressure sensor unit and a sample container system. And

[0011]

BRIEF DESCRIPTION OF THE DRAWINGS The invention is explained in more detail below on the basis of the schematic diagram of the device in FIG.

The batch-type adiabatic heat of adsorption measuring apparatus comprises a measuring section 1, a heater section 2, a measurement control section (including a data processing section) 3, a vacuum sensor section 4, and a vacuum pump section 5.

The measuring section 1 comprises a sample container 8, a solution reservoir 15 and a jug bottle 7, and these measuring sections 1 are mounted in a thermostat.

A sample container 8, a solution reservoir 15 for containing a solution that is evaporated and adsorbed on the sample, and a pressure sensor 2 described later.
Numerals 3 are connected by glass tubes, and each glass tube is connected by a clamp using a spherical joint, and is designed so that a high vacuum can be maintained for a long time. Also, a cock is attached to the glass tube to be connected in the middle, so that each can be separated from the measurement system.

Further, an electromagnetic valve V6 is mounted in the middle of the glass tube connected to the sample container 8. The sample container 8 is placed in the jug bottle 7, and the jug 7 is designed so that a heater 10 and a thermistor described later can be put in addition to the stirring rod.

A stirring impeller 9 is attached to the tip of the stirring rod, and is stirred by a stirring motor so that the temperature of the water in the bottle 7 becomes uniform. The measuring unit 1 is constituted by a thermostat made by Sanyo Medica: model number MIR-153.

The heater section 2 comprises a heater 10, a constant voltage power supply 16, and a standard resistor 11 of 1Ω. Heater 10
Enclosed a manganin wire wound in a glass tube, and then filled with silicone oil. Heater 1
0 indicates that power is supplied from a 5V constant voltage power supply 16 and the voltage applied to the heater 10 is measured at both terminals of the heater 10. Obtain the current value from the measurement. The heater unit 2 is a constant voltage power supply manufactured by Yokogawa Electric Corporation: model number 768
1-PA1811, Yokogawa standard resistor: Model number 2
792.

The measuring section comprises a digital multimeter 18 and a thermistor. Digital multimeter 18
Measures the voltage of the heater section 2, the voltage applied to the 1Ω standard resistor 11, and the resistance value of the thermistor. The resistance value of the thermistor is converted into the water temperature in the jug 7, and the temperature calibration at this time is performed with a crystal thermometer. The measuring unit is a digital multimeter manufactured by Yokogawa Electric: Model No. 75
61RS232C, Toho Denshi thermistor: Model number M3-THA-30X150.

The control unit is a personal computer 1
9, consisting of personal computer software and relay board 17. The measurement by the digital multimeter 18 is the relay board 17
And the measurement is sequentially repeated. The measured result is taken into the personal computer 19. The measured data includes the outside temperature, inside temperature,
Temperature of the jug bottle 7, voltage applied to the heater 10, 1Ω
Of the standard resistor 11 of FIG. Further, the pressure (degree of vacuum) is constantly measured. The measurement is controlled from PC software and programmed so that it can be performed automatically. The control unit is composed of NEC personal computer: model number PC-MJ45JS5TMB64, Future-in PC software: model name hydration heat dedicated software, interface PC relay boat: model number PCI-2512C.

The vacuum sensor section 4 is composed of a vacuum gauge manufactured by Japan MKS: Model No. 627A, and a vacuum gauge power supply / display manufactured by Japan MKS: Model No. 113B-RS232C.

The vacuum pump section 5 is composed of a Yamato Scientific vacuum pump: Model No. PD-52 and a Yamato Scientific oil mist trap: Model No. OMT-050A.

Reference numeral 12 denotes a temperature sensor for a juwer bottle, 24 denotes a temperature sensor inside the apparatus, and 25 denotes a temperature sensor outside the apparatus.

First, the first embodiment aims at measuring the heat of adsorption.

A sample is placed in the sample container 8 and the total weight is measured.

After performing vacuum degassing while heating, the whole weight is measured again, and the weight of the air in the sample container 8 is subtracted to obtain the sample weight. In this case, the sample weight measurement
Metratoledo electronic balance: Model number AT201 was used.

After the sample container 8 into which the sample has been put and vacuum degassed is mounted on the measuring section 1, all the valves V1 to V6 are closed. The measuring unit 1 is set at the measurement temperature, and waits until the temperature is sufficiently stabilized.

After the temperature of the measuring section 1 is stabilized, the vacuum pump 20 is operated.

The valves V are sequentially arranged from the side closer to the vacuum pump 20.
1. The valve V2, the valve V3, and the electromagnetic valve V6 are opened, and the air in the glass container housed in the sample container 8 is evacuated. Finally, the valve V4 of the solution reservoir 15 is opened to sufficiently degas.

The valve V5 of the sample container 8 is kept closed during this period. Deaerate sufficiently and let the pressure rise to 0.
After the pressure becomes 1 Torr or less, the valve V of the vacuum pump 20 is
1 is closed, and the vacuum pump 20 is stopped. Thereafter, the electromagnetic valve V6 is closed and the valve V5 of the sample container 8 is opened.

The personal computer 19 inputs a measurement program and starts measurement. The procedure measured by the program is as follows.

First, a baseline is measured without any operation for 10 minutes from the start of measurement.

Next, an electric current is applied to the heater 10 for 100 seconds to generate heat, and the rise in temperature is measured by the temperature sensor 12 for the juer bottle.

Next, wait for the baseline to stabilize without doing anything for 10 minutes. After that, the electromagnetic valve V6 is opened to allow the sample to adsorb the gas evaporated from the solution reservoir 15,
The amount of heat generated at that time is measured by the temperature sensor 12 for the juwer bottle. During this time, the pressure is measured by the pressure sensor 23 of the vacuum sensor unit 4, so that the equilibrium vapor pressure during adsorption can be measured.

After the adsorption for 10 minutes, the electromagnetic valve V6 is closed.

Next, do nothing for 10 minutes and wait until the baseline is stabilized. Then, current is passed through the heater 10 for 200 seconds, and the rise in water temperature is measured by the temperature sensor 12 for the juwer bottle.

Similarly, after waiting for the baseline to stabilize for 10 minutes, finally, a current is passed through the heater 10 for 300 seconds.
The temperature rise is measured by the temperature sensor 12 for the juer bottle.

Thereafter, the measurement is completed after measuring the baseline for 10 minutes.

After the measurement, the valve V5 of the sample container 8 is closed, and the sample container 8 is removed from the measuring section 1. The weight of the entire glass container containing the gas-adsorbed sample is measured, and the amount adsorbed is determined from the weight deaerated before the measurement.

The amount of power is calculated from the voltage value and current value applied to the heater 10 each time, and a calibration curve is created from three sets of data together with the amount of temperature rise. From the result, the value of the heat of adsorption when the sample adsorbs the gas is obtained. Further, based on these results, the integral enthalpy, the adsorption speed, and the like are obtained.

The second embodiment aims at measuring the equilibrium vapor pressure.

As in the case of the heat of adsorption measurement, the weight of the sample container 8 is measured by heat dehydration treatment, and the water content is determined from the weights before and after the dehydration treatment.

After mounting the dehydrated sample container 8 on the measuring section 1, all valves V1 to V6 are closed.

The temperature of the thermostat is set to the measurement temperature, and the process waits until the temperature is sufficiently stabilized. When the temperature in the thermostat is stabilized, the vacuum pump 20 is operated.

The valves V are sequentially arranged from the side closer to the vacuum pump 20.
1. Open the valve V2, the valve V3, and the electromagnetic valve V6, and deaerate the air in the glass container housed in the sample container 8. During this time, the valve V5 of the sample container 8 and the solution reservoir 15
Valve V4 is kept closed.

After sufficient degassing and the pressure becomes 0.03 Torr or less, the valves V1 and V2 of the vacuum pump 20 are
Is closed, and the vacuum pump 20 is stopped. Then, the sample container 8
Is opened, and the equilibrium vapor pressure is measured.

After setting the temperature in the measuring unit 1 and the jug bottle 7 to each measured temperature, the above operation is performed, and the equilibrium vapor pressure for each temperature is measured by the pressure sensor 23 of the vacuum sensor unit 4. This makes it possible to obtain the pressure-temperature relationship, approximate and differentiate the graph, and obtain the differential enthalpy by applying the so-called Clausius-Clapeyron method.

[0047]

As described above in detail, the present invention relates to a system for measuring the heat of adsorption, which connects a solution reservoir for storing a solution that is evaporated and adsorbed to a sample and a sample container for storing the sample. The present invention relates to a batch-type adiabatic adsorption heat measuring apparatus which is capable of simultaneously measuring the heat of adsorption and the equilibrium vapor pressure by connecting a sensor section. Simultaneous measurement can be performed.

(2) Differential enthalpy and integral enthalpy can be measured with one device.

(3) The vapor pressure can be measured up to 45 ° C.

(4) The measurement by this apparatus is extremely useful for evaluating the heat of adsorption and the rate of adsorption of porous materials, cement-based materials, and heat pump heat storage materials utilizing solar heat and waste heat. Has the effect of

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Measurement part 2 ... Heater part 3 ... Measurement / control part 4 ... Vacuum sensor part 5 ... Vacuum part 6 ... Vacuum pump part 7 ... Dewar bottle 8 ... Sample container 9 ... Stirring impeller 10 ... Heater 11 ... Standard resistor 12 ... Temperature sensor for kettle bottle 13 ... Sensor inside the tank 14 ... Sensor outside the tank 15 ... Solution reservoir 16 ... Constant voltage power supply 17 ... Relay board 18 ... Digital multimeter 19 ... Personal computer 20 ... Vacuum pump 21 ... Pressure display unit 23 ... Pressure sensor 24: Temperature sensor inside the device 25: Temperature sensor outside the device V1, V2, V3, V4, V5: Valve V6: Electromagnetic valve

 ────────────────────────────────────────────────── ─── Continued on the front page (74) The above three agents 100080539 Patent Attorney Yoshiki Takagi (72) Inventor Tadato Mizoda 2-16-1 Tokiwadai, Ube City, Yamaguchi Prefecture Yamaguchi University Faculty of Engineering (72) Inventor Akira Maeda 3-9-22 Nishiki, Naka-ku, Nagoya-shi, Aichi Ozawa Science Co., Ltd. (72) Inventor Keiichi Inukai 2-2, 6-23 Castle North Housing, Kita-ku, Nagoya-shi, Aichi (72) Inventor Masaya Suzuki Tajimi, Gifu 4-8-212 Ichimatsusaka-cho

Claims (3)

[Claims] 1. A pressure sensor unit is connected to a system for measuring heat of adsorption, which connects a solution reservoir for storing a solution adsorbed to a sample by evaporation and a sample container for storing the sample. Batch adiabatic adsorption heat measuring device characterized in that it is possible to simultaneously measure temperature. 2. In the equilibrium vapor pressure measurement, not only the sample container part but also the entire apparatus is placed in a thermostat,
A batch-type adiabatic adsorption heat measuring apparatus characterized in that a vapor pressure measurement up to 45 ° C. is enabled. 3. A batch method wherein the solution reservoir can be stopped by a cock so that it can be separated from the measuring system, and the differential enthalpy and the integral enthalpy can be measured with one measuring device. Adiabatic adsorption heat measurement device.