JPH0510869A - Device and method for measuring amount to be adsorbed/ desorbed - Google Patents

Abstract

PURPOSE:To obtain an accurate adsorption/desorption isotherm by determining a flow value of a gas by obtaining an amount of adsorption of a solid sample based on a calculated flow rate to a sample container and a pressure within the sample container and a volume of the sample container which are measured. CONSTITUTION:A desired sample is placed into a sample container 10, a gas is introduced from a gas cylinder 13 to a gas reservoir 12, and the gas is allowed to flow out of the gas reservoir 12 into the container 10 through a control valve 11 in actuation. A pressure of the gas reservoir 12 and that of the container 10 are measured by manometers 16 and 14 at a lapse of time starting from its initial flow. The amount of gas which is discharged from the gas reservoir 12 to the container 10 is calculated accurately and constantly at an arbitrary time based on a pressure value within the gas reservoir 12 and the amount of adsorption of the sample is calculated based on pressure, etc., within the container 10 according to the amount of discharge and the manometer 14. An amount of desorption of the sample is measured by switching the measurement system oppositely, thus obtaining an absorption/desorption isotherm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorption / desorption amount measuring device used to accurately measure the amount of gas adsorbed or desorbed on a solid sample, and a method for measuring adsorption / desorption amount using this device. Specifically, the adsorption / desorption amount measuring device used for measuring the gas adsorption / desorption amount of the solid sample required for calculating the surface area, pore size distribution, pore volume, etc. of the solid sample, and adsorption / desorption using this device. Regarding quantity measurement method.

[0002]

2. Description of the Related Art For example, various solid catalysts, adsorbents, ion exchangers, ceramics, and other powders and granules are widely used as industrial materials. Physical properties such as specific surface area, pore volume, and pore size distribution vary depending on the conditions. Therefore, since the performance when used as an industrial material often greatly changes due to changes in this physical property value, in using as an industrial material, the specific surface area pore volume and pore diameter distribution, etc. should be accurately understood. This is very important.

Conventionally, as a method of measuring these physical property values, for example, an inert gas such as nitrogen gas is used to detect a pressure change or a volume change of a gas phase adsorbate caused by physical adsorption of a sample to be measured. The so-called gas phase gas adsorption method, which measures the adsorption / desorption amount of a sample, is generally adopted. This measurement method is the relationship between the adsorption pressure at several points and the amount of adsorbed gas,
In short, it is a method of obtaining adsorption / desorption isotherms.

This measuring method is basically composed of a conventional batch type apparatus, that is, a quantitative unit capable of measuring gas volume and pressure and a sample container connected to the quantitative unit through a valve. This is performed by a device provided with a valve for supplying the adsorbed gas and a valve for discharging the adsorbed gas.

When performing measurement with this apparatus, a quantity M of gas is introduced into the quantification part, and then the quantification part and the sample container are communicated with each other, and when the pressures inside them are in equilibrium (ie, A series of cycles for obtaining the pressure value when the adsorption equilibrium of the sample is established is repeated (the above M is increased in each cycle), and the adsorption amount is calculated from the obtained pressure values and the volume of the fixed quantity part. It was calculated. Conversely, when measuring the desorption amount, vacuum the quantification part, then connect the quantification part and the sample container and repeat a series of cycles to obtain the pressure value when the pressure inside them becomes equilibrium (each cycle The desorption gas accumulated in the fixed quantity part is discharged every time), and the desorption amount is calculated from the obtained pressure values and the volume of the fixed quantity part.

However, it takes time to equilibrate the pressure in each cycle, and it takes 8 to 1 to measure one sample.
It takes a long time of 5 hours or more, and during that time, the measurer needs to judge the introduction pressure of the adsorbed gas or discharge the accumulated desorption gas and open / close each valve based on it, which is a great labor for the measurer. Met. In addition, a considerable skill is required to accurately determine the introduction pressure and adjust the opening of the valve, but still, some degree of individual difference depending on the measurer cannot be avoided.

Japanese Unexamined Patent Publication No. 61-102538 discloses a method for measuring adsorption / desorption amount using a mass flow controller. This method is different from the method using the above batch type apparatus, in which the gas is continuously flowed in small amounts into the vacuum sample container by the mass flow controller while keeping the flow rate substantially constant, This is a method of calculating the gas adsorption / desorption amount of the sample based on the gas flow rate inside and the measured pressure change in the sample container, and thereby obtaining the adsorption / desorption isotherm. In this method, while the gas in the sample container is being introduced, it is assumed that the sample in the sample container continues to hold the adsorption equilibrium state, and therefore some pressures are obtained from the start of gas introduction to the end of introduction. The adsorption / desorption isotherm can be obtained in a relatively short time without requiring time to obtain the pressure.

[0008]

However, in the method disclosed in the above publication, the adsorption amount of the sample is calculated by a predetermined equation using the gas flow rate value which is substantially constant value (target value) by the mass flow controller. It Therefore, maintaining the accuracy of the calculated value is of the utmost importance, and it has been necessary to adjust the flow rate by adjusting the mass flow controller quite frequently so that the gas flow rate value does not deviate from the target value. Even so, it is difficult to make the actual flow rate of the gas constant, and since it often deviates from the target value, there is a problem that an accurate adsorption amount cannot be obtained. Further, since the thermal conductivity detector is used in the flow rate detecting portion of the mass flow controller, there is a problem that the structure of the adsorption / desorption amount measuring device becomes complicated and expensive.

The present invention solves the above-mentioned problems, and an accurate flow rate of gas can be easily determined, so that an accurate adsorption / desorption isotherm can be obtained. It is an object to provide a method for measuring adsorption / desorption amount using this device.

[0010]

A device for measuring adsorption / desorption amount of the present invention is a device for measuring adsorption / desorption amount used for measuring adsorption amount or desorption amount of gas by a solid sample, comprising: A sample container of known volume that can introduce a solid sample, a gas reservoir of known volume that can store gas,
A gas discharge means for discharging gas from the sample container or the gas reservoir, and a pressure change in the gas reservoir at a predetermined change rate from the gas reservoir to the sample container or from the sample container to the gas reservoir. A gas delivery means for continuously delivering gas by adjusting the valve opening degree, a pressure gauge for measuring the pressure in the sample container, and a pressure gauge for measuring the pressure in the gas reservoir. Device for measuring adsorption and desorption amount.

The adsorption amount measuring method of the present invention for measuring the adsorption amount of a solid sample using the adsorption / desorption amount measuring device is as follows. While introducing a solid sample into the sample container,
The gas is discharged from the sample container by a gas discharging means, and thereafter, the gas is continuously sent out from the gas reservoir that is maintained at the predetermined temperature and contains the gas into the sample container that is maintained at the predetermined temperature. Sending out by means, during the sending out, by each pressure gauge, the pressure in the sample container and the pressure in the gas reservoir, respectively measured over time, and the measured pressure in the gas reservoir, Calculate the flow rate of the gas to the sample container based on the volume of the gas reservoir, based on the calculated flow rate, the pressure in the measured sample container, and the volume of the sample container,
Adsorption amount of the solid sample (adsorption amount of the solid sample at each time point)
Ask for.

The desorption amount measuring method of the present invention for measuring the desorption amount of a solid sample using the above adsorption / desorption amount measuring device is
It is done as follows. While introducing the solid sample into the sample container, the gas is discharged from the gas reservoir by the gas discharging means, and thereafter, from the sample container maintained at the predetermined temperature, the gas is stored in the gas reservoir maintained at the predetermined temperature. Is continuously sent out by the gas sending means, during the sending out, by each pressure gauge, the pressure in the sample container and the pressure in the gas reservoir are respectively measured with the passage of time, the measured gas The pressure inside the dam,
Calculate the flow rate of the gas to the gas reservoir based on the volume of the gas reservoir, based on the calculated flow rate, the pressure in the measured sample container, and the volume of the sample container of the solid sample The desorption amount (the desorption amount of the solid sample at each time point) is calculated.

Therefore, even if the flow rate is not directly and accurately adjusted, the flow rate state can be accurately determined by observing only the pressure in the gas reservoir. Also, the state of the amount of gas not adsorbed in the sample container can be found by observing the pressure in the sample container. Therefore, the adsorption amount state is easily found from the difference between the flow rate state and the non-adsorbed gas amount state in the sample container. That is, the state of the adsorption amount can be accurately obtained even if the flow rate changes. This also applies to the case of obtaining the desorption amount. That is, the gas is previously removed from the gas reservoir, and when the gas adsorbed to the solid sample in the sample container is continuously delivered to the gas reservoir side by the gas delivery means, only the pressure in the gas reservoir is changed. By observing, the flow rate from the sample container to the gas reservoir can be accurately determined. Similarly, the amount of gas not adsorbed in the sample container is also found by observing the pressure in the sample container. Therefore, the state of the desorption amount can be easily found from the difference between the flow rate state and the state of the amount of gas not adsorbed in the sample container. The flow rate control during desorption may be as follows. That is, the gas reservoir is constantly evacuated by the vacuum pump, and the flow rate of the gas delivery means is adjusted so that the gas reservoir pressure at that time is constant, and the gas reservoir is desorbed. In the above method, it was necessary to remove the gas in the gas reservoir again each time the pressure in the gas reservoir increased, but this method does not require this and the operation is simpler than that in the above method. However, in this method, the desorption amount cannot be calculated from the internal pressure of the gas sump, so the desorption amount is calculated as follows. That is, depending on how long the adsorbed gas is emptied,
The flow rate is calculated, and the desorption amount is calculated based on it. Or
Introduce the gas without putting the sample in the sample container in advance,
The same operation as the desorption step is performed, the flow rate is calculated from the pressure drop change in the sample container at that time and the dead volume of the sample container, and a conversion table of the gas reservoir internal pressure and the flow rate measured at the same time is prepared. The desorption amount may be calculated based on the flow rate at the time of desorption based on this conversion table.

Further, in the gas feeding means of the adsorption / desorption amount measuring apparatus of the present invention, the gas flow rate is measured by measuring the pressure change inside the gas reservoir, and the measurement result is fed back to obtain a constant flow rate. The opening of the valve is adjusted so as to be obtained. The pressure change in the gas sump is influenced only by the flow rate of the gas in the gas discharge means because the temperature of the gas sump is kept constant. for that reason,
An accurate flow rate control is possible by feeding back the pressure change in the gas reservoir. Further, it is not necessary to provide a thermal conductivity detector for detecting the gas flow rate. The pressure gauge for detecting the pressure change in the gas reservoir and controlling the flow rate may also be used as the pressure gauge for measuring the pressure in the gas reservoir, or near the gas intake from the gas reservoir of the gas delivery means. Another pressure gauge may be provided.

Since the adsorption / desorption amount is accurately determined as described above, the adsorption / desorption isotherm can be obtained by plotting the pressure at each time point and the adsorption / desorption amount of the solid sample corresponding thereto. Also, since the amount of gas fed out is adjusted based on the pressure change in the gas reservoir, it is not necessary to provide a thermal conductivity detector to detect the flow rate of gas, and the device configuration is simplified. .

[0016]

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The present invention is not limited to these examples and can be carried out in various modes without departing from the gist.

FIG. 1 is a block diagram showing an embodiment of the adsorption / desorption amount measuring device of the present invention. As shown in this figure, the adsorption / desorption amount measuring device of the present embodiment has a sample container 10 into which a solid sample for which surface area, pore size distribution, pore volume, etc. are to be obtained, is introduced. A control valve 11, a gas sump 12, a gas cylinder 13, two pressure gauges and a vacuum pump capable of continuously sending out a substantially constant amount of gas are mainly constituted.

The sample container 10 includes a control valve 1
1. A pipe H1 is connected to a gas cylinder 13 via a gas sump 12. Pressure gauge 14, vacuum pump 15
To the respective points A and C of the pipe H1 connecting the sample container 10 and the control valve 11 to the pipes H2 and H3, respectively.
Connected by.

The pressure gauge 16 is connected to the gas sump 12 by a pipe H4. The vacuum pump 15 is also connected to a pipe H5 that communicates with the atmosphere. The pipe H5
And the pipe H4 are connected at an intersection B. Further, a pipe H6 is connected to the sample container 10 from an intermediate portion between the control valve 11 and the gas sump 12.

Three valves V1, are provided in the pipe H1 at the portion connecting the sample container 10 and the control valve 11.
V2 and V3 are provided. Further, a valve V4 is connected to the pipe H1 connecting the control valve 11 and the gas sump 12, a valve V5 is further connected to the pipe H1 connecting the gas sump 12 and the gas cylinder 13, and the control valve 11 and the gas sump 12 are added. A valve V6 is provided in a pipe H6 connecting the space between the space and the sample container 10. Furthermore,
Pipe H between point A of pipe H1 and vacuum pump 15
3, the valves V7 and V10 are vacuum pumps 15 of the pipe H5.
The valve V8 is connected between the point B and the point B. Pipe H
A valve V9 is provided in the atmosphere communicating portion 5 of FIG.

In the apparatus having the above structure, the sample container 10
Is preferably kept at a constant temperature by being immersed in the coolant tank 17 as shown in the figure. In that case, the liquid level of the refrigerant tank 17 is kept constant and adjusted so that the volume in the sample container 10 does not change.

The control valve 11 comprises a control part, a valve part and an actuator, and a pressure gauge 16
The pressure in the gas reservoir 12 measured by is received as information, and the opening / closing of the valve is controlled so that the change in the pressure becomes constant. With this, the flow rate of the gas in the control valve 11 can be maintained at a certain set constant value.

The gas reservoir 12 for accumulating the gas from the gas cylinder 13 can be maintained at a known constant temperature, and the temperature is usually around room temperature (25 ° C.). The pressure gauge 16
The absolute pressure in the gas reservoir 12 and the absolute pressure in the sample container 10 are for measuring the absolute pressure continuously or intermittently. As these pressure gauges 14 and 16,
It is preferable to use a semiconductor type pressure transducer or the like to read the absolute pressure using a computer and record it in a recorder.

The vacuum pump 15 is used to exhaust the inside of the sample container 10 in preparation for measuring the amount of adsorption of the sample. In addition, it is used together with the valves V8, V9, etc. when calibrating the pressure gauges 14, 16 by the method described below. The valves V1, V2, V3 and V6 are used when switching the apparatus of the present embodiment from a system for measuring the adsorption amount of the sample to a system for measuring the desorption amount of the sample, or vice versa.

Next, a method for measuring the adsorption amount of a solid sample using the above apparatus will be described below. As a preparation for carrying out this measuring method, first, the pressure gauge is calibrated, the gas reservoir capacity is measured, and the dead volume is measured in order. These will be described. Calibration of Pressure Gauge First, the pressure gauges 14 and 16 are calibrated. for that reason,
The valves V1, V3, V4, V5, V6 and V9 are closed, and the valves V2, V7, V8 and V10 are opened, and the vacuum pump 1
Degas to the maximum at 5 (about 0 kg / cm ² A), and in that state, set the 0 points of the pressure gauges 14, 16 to zero. Next, the vacuum pump 15 is stopped, the valve V9 is opened to open the atmosphere, and the readings of the pressure gauges 14 and 16 at that time are set to atmospheric pressure values accurately measured by a mercury barometer or an aneroid type barometer. Then, the calibration of the pressure gauges 14 and 16 is completed.

With respect to the atmosphere on the pressure gauge 14 side, atmospheric pressure may be measured by removing the sample container 10. The capacity of the gas reservoir 12 (accurately, the sum of the capacity of the gas reservoir 12 and the capacity of the pipe from the gas reservoir 12 to the control valve 11) The measuring valve V9 of the V0 has a known capacity sample container (not shown: gas as much as possible). It is preferable that the capacity is about the same as that of the dead 12. The temperature is kept at a predetermined value when measuring the capacity, and it is preferably 25 ° C. like other parts.
8 and V9 are opened, valves V5, V6 and V7 are closed, and the control valve 11 is closed, and the sample container of known capacity and the gas reservoir 12 are evacuated by the vacuum pump 15. After that, the valves V8 and V9 are closed and the valve V5 is opened,
A gas (normally nitrogen gas) is introduced into the gas sump 12. After the pressure is stabilized, the pressure P0 in the gas reservoir 12 is measured by the pressure gauge 16, then the valve V9 is opened to introduce the gas into the sample container, and after the pressure is stabilized, the pressure P1 is read by the pressure gauge 16.
Based on the pressures P0 and P1 and the sample container volume Vs of known volume, the gas reservoir volume V0 is calculated from the following equation.

P0V0 = P1 (V0 + Vs) V0 = (P1Vs) / (P0-P1) During this time, each gas reservoir, pressure gauge 16, pipe H1, etc.
In order to maintain a constant temperature, it is necessary to provide sufficient ventilation around them. After connecting the sample container 10 for measuring the dead volume Vt to the valve V1, the sample container is immersed in the refrigerant tank 17, and then the same operation as described above is performed to obtain the pressures corresponding to the pressures P11, P12, P21 and P22. Find P31, P32, P41, P42. Based on these pressures and the values of Vs and V0 already obtained, the dead volume Vt in the standard state is obtained from the above equation. Of course, the pressure P
Pressure P33, P34, P4 corresponding to 13, P14, P23, P24
3, P44 may be obtained and Vt may be obtained from the above equation.

After the above preparation is completed, the adsorption amount of the solid sample is measured. For that purpose, first, a desired sample is put in the sample container 10, and gas is first introduced into the gas reservoir 12 and stored therein by the same operation as in the measurement of the dead volume Vt, and thereafter,
From the gas sump 12 to the activated control valve 11
Gas is caused to flow out to the sample container 10 via the pressure gauge, and the pressure of the gas sump 12 and the pressure of the sample container 10 are measured by the pressure gauges 16 and 14 with the lapse of time from the beginning of the flow.

The relationship between the pressure of the gas reservoir 12 and the pressure of the sample container 10 and time is preferably continuously and automatically recorded by a recorder using a microcomputer connected to the pressure gauges 16 and 14. In this measurement, the inner dead volume of the measurement changes depending on the volume of the sample, but in order to avoid an error accompanying it, after the sample is put in the sample container 10, for example, a non-inspiratory gas (such as helium gas) ( Instead of the method used in the above dead volume measurement process, an appropriately selected method, such as a method of measuring the dead volume by a gas that is not adsorbed to the sample) or a method of measuring the dead volume by calculating the refrigerant temperature and the true specific gravity of the sample , Should be adopted.

Gas sump 12 obtained as described above
Based on the internal pressure value, the discharge mass Qc of the gas discharged from the gas reservoir 12 to the sample container 10 is always accurately calculated at an arbitrary time t by the following formula, and the discharge mass Qc and the pressure gauge 14 are calculated. The adsorption amount Qs of the sample is calculated based on the pressure value in the sample container 10 and the like. -Discharged mass Qc Qc [mol] = (Ps-Pt1) V0 / RT1 Ps [mmHg]: Release start pressure Pt1 [mmHg] of gas sump 12: Pressure V0 [ml] of gas sump 12 at time t: Gas sump 12 Volume T1 [K]: temperature inside gas sump 12 (almost constant) -adsorption amount Qs Qs [mol / g] = [Qc- (Pt2Vt / RT2)] / W Pt2 [mmHg]: sample container measurement pressure (time t Vt [ml]: dead volume during sample measurement T2 [K]: 〃 conversion time temperature R: gas constant W [g]: sample weight Incidentally, when the pressure at each time is obtained, it is shown in FIG. A graph is obtained as shown. The adsorption end point amount can be clearly discriminated from the intersection of the saturation pressure extension line and the adsorption rise curve in the graph of FIG.

In the above method, since the flow rate of the gas released into the sample container 10 at each time is accurately obtained based on the value of the pressure gauge 16, the adsorption amount of the sample at each time is also accurately calculated. It As a result, an accurate adsorption isotherm is obtained. The desorption amount of the sample can be calculated by using the device of the above-mentioned embodiment or the device of which design is changed. Next, an example will be shown in which the above-mentioned apparatus after measuring the adsorption amount is used.

The inside of the gas sump 12 is evacuated by the vacuum pump 15 with the valves V8, V10 of the apparatus after the adsorption amount measurement shown in FIG. 1 opened and the valves V7, V4, V5, V9 closed. To do. Next, open the valves V7, V3, V6 and V1,
The valves V4 and V2 are closed and the control valve 11 is operated to record the values of both pressure gauges 14 and 16.

Next, the valve V10 is closed to start desorption. Since it is already in the saturated pressure state, the pressure gauge 14 remains at a constant pressure for a while after the start of desorption and does not decrease. The starting point of the desorption isotherm is when the pressure gauge 14 starts to fall. At this time, the gas desorption mass Qd flowing out of the sample container 10 and the actual desorption mass Qt from the sample are calculated from the amount of increase of the pressure gauge 16 of the gas reservoir 12 as follows.

Qd = (Ppt ₁ -Pps) V ₃ / RT ₁ Qt = [Qd- (Ppt ₂ Vt / RT ₂ )] / W where Ppt ₁ [mmHg]: measurement of gas sump 12 at time t ₁ . Pressure Pps [mmHg]: Measurement start pressure V ₃ [ml] of gas reservoir 12: Desorption volume T ₁ [K] of gas reservoir 12: Temperature of gas reservoir 12 (almost constant) Ppt ₂ [mmHg]: Time t ₂ Measured pressure Vt [ml] of the sample container 10 at: Sample dead volume T2 [K] at measurement: Temperature R at the time of measurement R: Gas constant W [g]: Sample weight and saturation pressure obtained by the above adsorption measurement A value obtained by subtracting the desorption amount Qt at the time t ₁ from the adsorption amount Qso (Qso−Qt: the adsorption amount on the desorption isotherm) and the pressure gauge 14 at the time t _1.
The desorption isotherm can be obtained by plotting the value P pt _{2 of}

During the desorption measurement, if the pressure in the gas reservoir 12 approaches the pressure of the sample container 10, the gas will not flow. At this time, the valve V3 is closed and the valve V10 is opened, and the vacuum pump 15 brings the gas reservoir 12 into a vacuum state again. Then, the valves V3 and V10 may be returned to the original state and the desorption measurement may be started. Thus, the desorption isotherm is obtained over the entire pressure range.

The volume V ₃ of the gas reservoir 12 during desorption is the same as the volume V 0 of the gas reservoir 12, and a sample container of known capacity and a glass rod of zero capacity are attached to the valve V1, respectively.
It is calculated from the pressure change when the gas reservoir 12 is connected from the valve V1 side via the control valve 11. <Measurement Example> Measurement data using the apparatus of the above embodiment will be described.

Silica gel was used as the sample, nitrogen gas was used as the adsorption gas, and the flow rate of the control valve was 1.
The measurement was performed after adjusting to 00 (SCCM). The specific surface area / pore volume was calculated based on the results. The specific surface area is based on the adsorption isotherm B. E. The pore volume was calculated from the T theory, and the pore volume was obtained from the adsorption amount corresponding to a relative pressure of 1.0 (P / P00). The above values are for specific surface area 685-699m ² / g
And the pore volume is 0.383 to 0.394.
It is within ml / g and stable measurement is possible. Further, it is not necessary to provide a thermal conductivity detector or the like for controlling the gas flow rate.

The results obtained by using nitrogen as an adsorbed gas by the gas phase gas adsorption method which has been conventionally used are as follows: specific surface area (m ^{2 /} g): 706.3 ± 4.6 pore volume (ml / g): 0.40.

[0039]

As described in detail above, according to the present invention,
The actual flow rate of the gas sent into the sample container or the gas reservoir in which the solid sample is introduced can be accurately read at a desired time by the pressure change of the gas reservoir serving as the outflow source or the inflow destination, and the read value can be read. Since the gas adsorption / desorption amount of the solid sample at each time point is calculated by using it, the accurate adsorption / desorption isotherm of the solid sample can be obtained at all times. It is possible to calculate distribution, pore volume, etc.

Moreover, in order to achieve the above, the troublesomeness of frequently calibrating the flow rate of the mass flow controller is unnecessary. Further, a mass flow controller using a thermal conductivity detector is not needed, and the device configuration is simplified.

[Brief description of drawings]

FIG. 1 is a block diagram showing an embodiment of a device for measuring adsorption / desorption amount of the present invention.

FIG. 2 is a graph showing an example of a time change of pressure when measuring an adsorption amount.

[Explanation of symbols]

10 ... Sample container 11 ... Control valve 12 ... No gas 15 ... Vacuum pump 14, 16 ... Pressure gauge

Claims (3)

[Claims] 1. A device for measuring an adsorption / desorption amount used for measuring an adsorption amount or a desorption amount of a gas by a solid sample, comprising a sample container of a known volume into which the solid sample can be introduced, and storing a gas. A gas reservoir of known volume capable of, a gas discharge means for discharging gas from the sample container or the gas reservoir, and from the gas reservoir to the sample container or from the sample container to the gas reservoir, in the gas reservoir The valve opening is adjusted so that the pressure change becomes a predetermined rate of change, a gas delivery means for continuously delivering gas, a pressure gauge for measuring the pressure in the sample container, and the pressure in the gas reservoir. An adsorption / desorption amount measurement device comprising a pressure gauge for measurement. 2. A method for measuring an adsorption amount of a solid sample by using the adsorption / desorption amount measuring device according to claim 1, wherein the solid sample is introduced into the sample container and gas is discharged from the sample container. Discharged by means, then from the gas reservoir containing a gas maintained at a predetermined temperature, into the sample container maintained at a predetermined temperature,
The gas is continuously sent out by the gas sending means, and during the sending out, the pressure inside the sample container and the pressure inside the gas reservoir are respectively measured by the respective pressure gauges with the passage of time, and the measured Calculating the flow rate of the gas to the sample container based on the pressure in the gas reservoir and the volume of the gas reservoir, the calculated flow rate, and the measured pressure in the sample container,
A method for measuring an adsorption amount of a solid sample, wherein an adsorption amount of the solid sample is obtained based on the volume of the sample container. 3. A method for measuring the desorption amount of a solid sample by using the adsorption / desorption amount measuring device according to claim 1, wherein the solid sample is introduced into a sample container and gas is discharged from a gas reservoir. And then from the sample container maintained at a predetermined temperature,
Gas is continuously fed into the gas reservoir maintained at a predetermined temperature by the gas delivery means, and during the delivery, the pressure in the sample container and the pressure in the gas reservoir are adjusted by each pressure gauge. Each is measured over time, and the flow rate of the gas to the gas reservoir is calculated based on the measured pressure in the gas reservoir and the volume of the gas reservoir, and the calculated flow rate and the measured value. The pressure inside the sample container,
A method for measuring the amount of desorption of a solid sample, wherein the amount of desorption of the solid sample is obtained based on the volume of the sample container.