JP2007024649A - Pore diameter distribution measuring method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a measuring method capable of measuring accurate distribution of each pore diameter of pores in a porous body, and to provide a device that uses the method. <P>SOLUTION: This method has an adsorption potential formation process S1 for determining the adsorption potential of the first liquid relative to a sample porous body, having only pores having each size of known pore diameters, a sample equilibrium concentration ratio relation formating process S2 for determining the relation between each pore diameter of the sample porous body and the sample equilibrium concentration ratio, an equilibrium concentration ratio calculating process S3 for calculating the equilibrium concentration ratio for each known concentration, a remaining quantity calculation process S4 for calculating the remaining quantity of the first liquid remaining in the pores in the porous body relative to each concentration in the equilibrium state, and a pore evaluation process S5 for evaluating each pore diameter of the pores in the porous body and its distribution. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a measurement method for measuring the pore diameter and distribution of pores of a porous body such as a filter, a membrane, a hollow fiber, and coal.

  In order to effectively use a porous body such as an adsorbent or a filter, it is necessary to obtain information on the pore diameter and distribution of the pores on the surface of the porous body. As a method for obtaining such information, a nitrogen adsorption method, a mercury intrusion method, a bubble point method, a dry-wet flow method and the like have been widely used.

  However, in the nitrogen adsorption method, since the porous body needs to be dried, there has been a problem that the pore size distribution of the porous body made of a substance that shrinks when dried cannot be measured. Further, the mercury intrusion method requires the use of mercury that is harmful to the human body, and there is a problem that the cost for its management and disposal treatment increases.

  Furthermore, in the bubble point method and the dry-wet flow method, there is a problem that the limit of measurable pore diameter is about 50 nm, and the pore diameter and the distribution of pores having a pore diameter of 50 nm or less cannot be measured. there were.

  On the other hand, although a method for eliminating the above-described drawback of the mercury intrusion method has been proposed (see, for example, Patent Document 1), it is necessary to perform surface treatment on the porous body, and the pore diameter and distribution thereof are measured. There is a problem that the process becomes complicated.

Japanese Patent Laid-Open No. 2005-69961

  An object of this invention is to provide the measuring method which can measure the exact distribution of the pore diameter of the pore of a porous body in a comparatively simple process in view of the situation mentioned above.

The present inventor constructed a thermodynamic equation related to capillary phase separation in consideration of the adsorption potential of the liquid adsorbed on the porous body through research on the capillary phase separation phenomenon. Then, by using the thermodynamic equations, the porous body first liquid adheres to the pores, the first saturation concentration second is a C _S of the liquid the liquid to the first liquid of known Based on the residual amount of the first liquid remaining in the pores of the porous body without being dissolved in the second liquid due to the capillary phase separation phenomenon when immersed in a reference solution dissolved at a concentration and brought into equilibrium. Thus, the inventors have found that the pore diameter and distribution of the pores of the porous body can be measured, and have completed the present invention.

To solve the above problem first aspect of the present invention, the porous body first liquid adheres to the pores, the first to the second liquid wherein the first saturation concentration of the liquid is C _S When the liquid is immersed in a reference solution E1- _z dissolved at a known concentration D1- _z and brought into an equilibrium state, the porous solution does not dissolve in the reference solution E1- _z due to a capillary phase separation phenomenon. A pore diameter distribution measuring method for measuring the pore diameter w and the distribution of the pores of the porous body based on the residual amount of the first liquid remaining in the pores of the body, the same composition as the porous body or made similar composition, the first adsorption potential [Delta] [Psi] _{1 to y (W. 1 to} the liquid to the sample porous _{O 1 to y} having only pores of the respective dimensions of known pore size _{W 1 to y} It shows _y, x) (where, x is the central pore radial position as the origin of the pores of the sample porous material ) And the adsorption potential creation step of determining for each of the sample porous material _{O 1 to y,} and erasing the adsorption potential ΔΨ _{1~y (W 1~y, x 0} by substituting x) by the following formula 1 and formula 2 Thus, Equation 1 and Equation 2 are solved simultaneously, and the pore diameters W 1 _-y and the specimen equilibrium concentration ratio (C 1 _-y / C _S ) of the specimen porous bodies O 1 _-y (where C _{1 -Y} represents the equilibrium concentration of the first liquid in the second liquid in the sample porous body _O1-y having only the respective sizes of the pore diameters W1- _y . specimens equilibrium concentration ratio and the relation generation step, the first in the known concentration D the reference solution at the time of the equilibrium state by immersing the porous body in the reference solution E _{1 to Z} of _{1 to Z} E _{1 to Z} each of the equilibrium concentration _{a 1 to Z} of liquid reference solutions _{E 1 to Z} of the known concentration _{D 1 to Z} And the equilibrium concentration ratio calculating step of calculating the equilibrium concentration ratio _(A 1~z / _{C S)} of each reference solution _{E 1 to Z} of the known concentration _{D 1 to Z} measured by the dry weight of the porous body based on the weight of the porous material at equilibrium for each reference solution _{E 1 to Z} of known concentration _{D 1 to Z,} or a concentration _{D 1 to Z} of the reference solution _{E 1 to Z,} the reference solution _{E 1 -Z} and the _residual concentration in the pores of the porous body in an equilibrium state with respect to each of the reference solutions E1- _z of the known concentrations D1- _z based on the respective amounts of the equilibrium concentrations A1- _z. A residual amount calculating step of calculating a residual amount of the first liquid, and the first remaining in the pores of the porous body in an equilibrium state with respect to each of the reference solutions E 1 to _{z having} the known concentrations D 1 to _z remaining amount and the known concentration D _{1 to Z} groups of the liquid And a pore evaluation step of evaluating the distribution of the pore diameter w and the pore diameter w of the pores of the porous body based on the equilibrium concentration ratio of each solution _{E 1~z (A 1~z / C S} ) A method for measuring pore size distribution.

  In the first aspect, the pore distribution of the porous body having various shapes and compositions can be accurately and easily measured.

According to a second aspect of the present invention, in the first aspect, the adsorption potential creating step includes adsorption of the vapor of the first liquid to a non-porous body having the same or similar composition as the specimen porous body _O1-y. An adsorption isotherm measuring step for measuring an isotherm and a thickness t of the adsorption film of the first liquid corresponding to the adsorption isotherm; and vapor pressures P 1 to _z of the first liquid on the adsorption isotherm. adsorption of those the evaporated air pressure P _{1 to Z} the first liquid on the surface of the non-porous body and the thickness t _{1 to Z} of the first adsorption layer of the liquid the corresponding substituted into the following formula 3, respectively Using the relationship between the thickness t of the first liquid adsorption film and Δφ (t) and the relationship between the thickness t of the first liquid and Δφ (t), the adsorption is calculated from the following formula 4. A pore diameter distribution measurement comprising: a ΔΨ calculation step for calculating a potential ΔΨ (W, x) It lies in the way.

In the second aspect, the known pore size _W adsorption potential of the first liquid to the sample porous _{O 1 to y} having only pores of each size of _{1~y ΔΨ 1-y (W 1- y} , x) can be easily obtained.

According to a third aspect of the present invention, in the first or second aspect, in the first or second aspect, the pore evaluation step includes the step of _{measuring the} porous body for each of the equilibrium concentration ratios (A 1 _-z / C _S ). From the residual amount of the first liquid remaining in the pores, the volume of the first liquid remaining in the pores of the porous body for each of the equilibrium concentration ratios (A 1 _-z / C _S ) is calculated. Based on the volume calculation step and the relationship between the pore diameters W ₁ to _y of the specimen porous bodies O ₁ to _y and the specimen equilibrium concentration ratio (C 1 to _y / C _S ), the equilibrium concentration ratio (A 1 to _z / and pore diameter calculation step of calculating the pore diameter _{B 1 to Z} of the pores of the porous body is determined in correspondence to the C _S), two adjacent said equilibrium concentration ratio _(a 1~z _{/ C} S) Difference in volume of the first liquid remaining in the pores of the porous body and the two adjacent equilibrium concentrations Pore size distribution for calculating the distribution of the pore diameter w of the pores of the porous body from the ratio (A _{1~z / C S)} to the pores having a pore diameter of B _{1 to Z} of the porous body is determined in correspondence And a pore diameter distribution measuring method characterized by comprising a calculation step.

  In the third aspect, the pore distribution of the porous body having various shapes and compositions can be measured more easily.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the pore diameter distribution measuring method is characterized in that the pore diameter of the porous body is in the range of 1 to 50 nm.

  In the fourth aspect, the distribution of the pores of the porous body having various shapes and compositions can be measured more accurately.

A fifth aspect of the present invention, in the first to fourth one aspect, the porous body in which the first liquid is deposited in the pores, the first saturation concentration of the liquid is a C _S equilibrium when immersed in the first liquid reference was dissolved in a known concentration D _{1 to Z} solution E _{1 to Z} in the second liquid, and filled with the porous material to the column, the column the continuously supplied each reference solution _{E 1 to Z} of known concentration _{D 1 to Z,} the corresponding to each reference solution _{E 1 to Z} of concentration _{D 1 to Z} and the reference solution _{E 1 to Z} The pore diameter distribution measuring method is characterized in that the concentration of the first liquid in the solutions F 1 to _Z discharged from the column is the same.

  In the fifth aspect, an equilibrium state can be formed easily and in a short time when the porous body having the first liquid attached in the pores is immersed in the reference solution.

According to a sixth aspect of the present invention, in the fifth aspect, the solutions F 1 to _z discharged from the column are supplied to the column again as the reference solutions E 1 to _{z having} the concentrations D 1 to _z. In the method for measuring the pore size distribution characterized by

  In the sixth aspect, it is possible to more easily form an equilibrium state when the porous body having the first liquid attached in the pores is immersed in the reference solution.

  According to a seventh aspect of the present invention, in any one of the first to sixth aspects, the second liquid has a higher saturated vapor pressure than the first liquid, and the residual amount calculating step After reaching the state, the weight of the porous body when only the second liquid of the first liquid and the second liquid attached to the pores of the porous body is evaporated is measured, The pore diameter distribution measuring method is characterized in that the residual amount of the first liquid remaining in the pores of the porous body is calculated by subtracting the dry weight of the porous body from the weight of the porous body.

In the seventh aspect, the weight of the porous body in an equilibrium state with respect to each of the reference solutions E 1 to _{z having} the known concentrations D 1 to _z can be easily measured.

  According to the pore diameter distribution measuring method according to the present invention, the pore distribution of the porous body having various shapes and compositions can be accurately measured in a relatively simple process, so that the porous body can be more easily and accurately. Can be analyzed.

  Hereinafter, the best mode for carrying out the present invention will be described. Note that the description used in the present embodiment is an exemplification, and the present invention is not limited to the following description.

(Embodiment 1)
FIG. 1 is a schematic view showing a porous body having pores according to Embodiment 1 of the present invention. FIG. 2 is a schematic view showing a state in which the first liquid is attached in the pores of the porous body used in the present embodiment. Furthermore, FIG. 3 is a schematic view showing a state in which, in this embodiment, a porous body having a first liquid attached in the pores is immersed in a tank filled with a reference solution having a known concentration. And FIG. 4 is a figure which shows the sequence of the pore diameter distribution measuring method which concerns on this embodiment.

As shown in FIGS. 1 to 3, the pore diameter distribution measuring method used in the present embodiment uses a porous body 10 in which the first liquid 20 is adhered in the pores 11, and the saturation concentration of the first liquid 20 is C _S. When the first liquid 20 is immersed in a reference solution 30 in which the first liquid 20 is dissolved at a known concentration D and brought into an equilibrium state, the porous body does not dissolve in the reference solution 30 due to the capillary phase separation phenomenon. This is a method of measuring the pore diameter w and the distribution of the pores 11 of the porous body 10 based on the residual amount of the first liquid 20 remaining in the 10 pores 11. Note that the pore size distribution measuring method used in the present embodiment is performed at the same or substantially the same temperature in all the steps described below.

  The porous body 10 used in the present embodiment is not particularly limited as long as it has pores 11, but those having pores 11 having a pore diameter in the range of 1 to 50 nm are preferable, and in the range of 2 to 50 nm. Those are more preferred. Specifically, coal etc. are mentioned as the porous body 10, for example. Note that the pores 11 may penetrate the porous body 10.

Moreover, the 1st liquid 20 and 2nd liquid used for this embodiment will not be specifically limited if mutual solubility has an upper limit. Specifically, for example, water or the like is used as the first liquid 20, and dimethyl ether (DME: CH ₃ OCH ₃ ) or the like is used as the second liquid with respect to water.

Furthermore, the reference solution 30 used in the present embodiment is a pure second liquid in which the first liquid 20 is not dissolved at all, and the concentration of the first liquid 20 in the second liquid is a saturated concentration C _S. either solution in the range of up to a, i.e. refers to any solution in which the concentration of the second of the first liquid 20 in the liquid is in the range of up to 0% to a saturated concentration C _S. 1 to 3, the reference solution is described with the reference numeral “30”. _However, the same reference numeral “30” is _{applied to the} reference solutions E 1 to _z having different concentrations of the first liquid 20 to be dissolved. Will be attached.

Hereinafter, the pore size distribution measuring method used in the present embodiment will be specifically described. The pore size distribution measuring method used in the present embodiment includes steps as shown in FIG. Specifically, the pore diameter distribution measuring method used in the present embodiment has the same composition or similar composition as the porous body 10 in the coordinates within the pores 11 of the porous body 10 shown in FIG. adsorption potential [Delta] [Psi] _{1 to y} of the first liquid 20 with respect to the sample porous _{O 1 to y} having only pores of each size of _{1~y (W 1~y,} x) (where, x is the sample An adsorption potential creation step (S1) for _obtaining the position in the pore diameter direction with respect to the center of the pores of the porous body for each specimen porous body O 1 _-y , and an adsorption potential ΔΨ _{1 -y} (W _1- Substituting _{y 1} , x) into the following formulas 1 and 2 and solving the formulas 1 and 2 simultaneously so as to eliminate x ₀ , the respective pore diameters W _{1 to y} of the sample porous bodies O _{1 to y} a specimen equilibrium concentration ratio _{(C 1~y} / _{C S)} determining the relationship between the sample equilibrium concentration ratio function A generation step (S2), the time of the first liquid 20 is immersed reference solution E _{1 to Z 30} porous body 10 in which is dissolved in a known concentration D _{1 to Z} in an equilibrium state to a second liquid by measuring the equilibrium concentration _{a 1 to Z} of the first liquid 20 in the reference solution _{E 1 to Z} 30 each reference solution _{E 1 to Z} 30 of known concentration _{D 1 to Z} of known concentration _{D 1 to Z} Equilibrium concentration ratio calculation step (S3) for calculating the equilibrium concentration ratio (A 1 _-z / C _S ) for each of the reference solutions E 1 to _z 30, and the standard for the dry weight of the porous body 10 and the known concentrations D 1 to _z based on the weight of the porous body 10 in the equilibrium state for the solution _{E 1 to Z} 30 each, or a concentration _{D 1 to Z} of the reference solution _{E 1 to Z} 30, and the reference solution _{E 1 to Z} 30 each amount, the equilibrium based on the concentration _{a 1 to Z,} the reference of a known concentration _{D 1 to Z} solution _{E 1 to Z} 30 that A residual amount calculation step of calculating a remaining amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium state (S4) for Les, the reference of a known concentration D _{1 to Z} solution E _{1 to Z} The remaining amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in an equilibrium state with respect to each of the 30 and the equilibrium concentration ratio (A _{1 to} A 30) with respect to each of the reference solutions E 1 to _z 30 having known concentrations D 1 to _{z z} / C _S ), and a pore evaluation step (S5) for evaluating the pore diameter w of the pores 11 and the distribution of the pore diameters w of the porous body 10.

  By using this method, it is possible to accurately and easily measure the pore diameter and distribution of the pores of the porous body having various shapes and compositions. Hereinafter, each step will be described more specifically.

The adsorption potential creation step (S1) has the same or similar composition as that of the porous body 10 at the coordinates shown in FIG. 5, and the sample porous body O has only pores having the respective sizes of the known pore diameters W 1 to _y. 1 to _y , the adsorption potential ΔΨ 1 to _y (W 1 to _y , x) of the first liquid 20 (where x is the position in the pore diameter direction with the center of the pore of the specimen porous body as the origin) If it can obtain _{| require} for every sample porous body _O1-y , it will not specifically limit. However, as the adsorption potential creation step (S1), an adsorption potential creation step using an adsorption isotherm described below is preferable. Here, the specimen porous bodies O 1 to _y are not particularly limited as long as they have the same composition or similar composition as the porous body 10 and have only pores having the respective known pore diameters W 1 to _y. Needless to say, those having the same shape and composition as the porous body 10 are preferred. The specimen porous bodies O 1 to _y having a similar composition of the porous body 10 have an adsorption potential similar to the adsorption potential of the porous body 10 that can be used when obtaining the adsorption potential of the porous body 10. What you have. Hereinafter, as a preferable adsorption potential creation step (S1), an adsorption potential creation step using an adsorption isotherm will be specifically described.

Specifically, the adsorption potential creation step using the adsorption isotherm is performed as shown in FIG. 6 in which the vapor of the first liquid 20 is applied to a non-porous body having the same or similar composition as the specimen porous body O 1 _-y . An adsorption isotherm measurement step (S1-1) for measuring the adsorption isotherm and the thickness t 1 _-z of the adsorption film of the first liquid 20 corresponding to the adsorption isotherm, and the first liquid on the adsorption isotherm The vapor pressure P 1 _{-z of} 20 and the thickness t 1 _-z of the adsorption film of the first liquid 20 corresponding to each of the vapor pressures P 1 _-z are substituted into the following equation 3 to obtain Δφ calculating step (S1-2) for calculating the relationship between the thickness t of the first liquid 20 adsorbing film and Δφ (t), and the thickness t and Δφ (t of the first liquid 20 adsorbing film ) And a ΔΨ calculation step (S1-3) for calculating the adsorption potential ΔΨ (W, x) from the following formula 4 using the relationship with Yes.

Here, the non-porous body is particularly limited as long as it has the same or similar composition as the specimen porous body _O1-y , _i.e. , has the same or similar composition as the porous body 10, and does not have pores. Not. However, it is needless to say that a non-porous body having the same shape and composition as the porous body 10 is preferable. Note that a non-porous body _having a similar composition to the specimen porous body O 1 _-y , that is, a non-porous body having a similar composition to the porous body 10 can be used when obtaining the adsorption potential of the porous body 10. , Which has an adsorption potential similar to that of the porous body 10.

According to this method, the adsorption potential [Delta] [Psi] _1-y of the first liquid 20 with respect to the sample porous _{O 1 to y} having only pores of the respective dimensions of known pore size _{W 1~y (W 1-y} , X) can be easily obtained. Hereinafter, each process of the adsorption potential creation process using the adsorption isotherm will be described more specifically.

The adsorption isotherm measurement step (S1-1) corresponds to the adsorption isotherm of the vapor of the first liquid 20 on the non-porous body having the same or similar composition as the specimen porous bodies O 1 to _y and the adsorption isotherm. There is no particular limitation as long as the thicknesses t1 to _z of the adsorption film of the first liquid 20 can be measured. For example, using the measuring method and measuring apparatus described on pages 146 to 166 of “Science of adsorption” (co-authored by Seiichi Kondo, Tatsuo Ishikawa, Ikuo Abe, Maruzen Co., Ltd. issued on July 30, 1991) The adsorption isotherm and the thickness t 1 _-z of the adsorption film of the first liquid 20 corresponding to the adsorption isotherm can be measured.

In the Δφ calculation step (S1-2), the vapor pressures P 1 to _z of the first liquid 20 on the adsorption isotherm obtained by the adsorption isotherm measurement step (S1-1) and the vapor pressures P 1 to _{z thereof} are respectively determined. The thicknesses t1 to _{z of the} corresponding first liquid 20 adsorption film are substituted into Equation 3, respectively, and the first liquid 20 adsorption film thickness t and Δφ (t ) Is not particularly limited as long as it can be calculated. For example, a method for calculating Δφ (x) using Equation 3 is described in “H. Kanda, et. Al, Langmuir, Vol 16, p 6622-6627 (2000)”.

In the ΔΨ calculation step (S1-3), the adsorption potential is obtained from Equation 4 using the relationship between the thickness t of the adsorption film of the first liquid 20 obtained in the Δφ calculation step (S1-2) and Δφ (t). There is no particular limitation as long as ΔΨ (W, x) can be calculated. For example, the pore diameter W is first set. Then, the thickness t of the adsorption layer of the first liquid 20 corresponding to the adsorption isotherm of the vapor of the first liquid 20 to the non-porous body made of the same or similar composition as the sample porous material O _{1 to y,} FIG. Since W / 2−x at the position x in the pore as shown in FIG. 5 is a distance from the solid or the pore wall, the value of Δφ (t) for a certain t is set to W / Applicable to Δφ (W / 2−x) at 2-x. Therefore, by substituting the relationship between the thickness t of the adsorption film of the first liquid 20 obtained in the Δφ calculating step (S1-2) and Δφ (t) into Equation 4, the adsorption potential ΔΨ with respect to the pore diameter W is obtained. (W, x) can be calculated. Here, as shown in FIG. 5, the first liquid 20 adhered in the pores of the porous body is sandwiched between the two pore walls 15a and 15b. _Therefore , the adsorption potential ΔΨ 1 _-y (W 1 _-y , x) is calculated using Equation 4.

Using this method, the adsorption potential [Delta] [Psi] _{1 to y} of the first liquid 20 with respect to the sample porous _{O 1 to y} having only pores of the respective dimensions of known pore size _{W 1 to y (W. 1 to y} , x) can be easily obtained.

As has been explained above, the adsorption potential [Delta] [Psi] _{1 to y} of the first liquid 20 with respect to the sample porous _{O 1 to y} having only pores of the respective dimensions of known pore size _{W 1 to y (W 1 ~ Y} , x) can be easily obtained.

Next, the sample equilibrium concentration ratio relationship creating step (S2) will be specifically described. In the sample equilibrium concentration ratio relationship creation step (S2), the adsorption potentials ΔΨ 1 _-y (W 1 _-y , x) obtained in the adsorption potential creation step (S1) are substituted into Equations 1 and 2, and x ₀ is substituted. Equations 1 and 2 are solved simultaneously so as to be erased, and the relationship between the respective pore diameters W ₁ to _y of the sample porous bodies O _{1 to y} and the sample equilibrium concentration ratio (C 1 to _y / C _S ) is obtained. There is no particular limitation as long as it can be used. Here, Formula 1 and Formula 2 is in a non-linear simultaneous equation with respect to x _0. Therefore, for example, numerical calculation is performed so that each pore diameter W 1 _-y and the corresponding adsorption potential ΔΨ 1 _-y (W 1 _-y , x) are substituted into Equation 1 and Equation 2, respectively, and x ₀ is eliminated. By using them to solve the simultaneous equations consisting of Equations 1 and 2, the relationship between the pore diameters W 1 _-y and the sample equilibrium concentration ratio (C 1 _-y / C _S ) can be obtained. Incidentally, x ₀ is the first value obtained by subtracting the thickness t of the liquid 20 adhered to the film form on the surface of the pores of the porous body from the half of the pore diameter W, the coordinates shown in FIG. 5, x ₀ = W / 2−t.

The following assumptions can be made using the relationship between the pore diameters W 1 to _y thus obtained and the sample equilibrium concentration ratio (C 1 to _y / C _S ). For example, let us consider a case where the porous body 10 having the first liquid 20 attached in the pores 11 is immersed in a certain reference solution 30 and an equilibrium state is achieved so as to satisfy a certain equilibrium concentration ratio. First, based on the relationship between the above-described pore diameters W 1 to _y and the sample equilibrium concentration ratio (C 1 to _y / C _S ), the pore diameter determined in accordance with the equilibrium concentration ratio is obtained. And in the pore 11 whose pore diameter is smaller than the pore diameter determined corresponding to the equilibrium concentration ratio, the first liquid 20 is not dissolved in the reference solution 30, so that all the inside of the pore 11 is the first. It can be assumed that the liquid 20 is filled. On the other hand, in the pore 11 having the same or larger pore diameter than the pore diameter determined corresponding to the equilibrium concentration ratio, the first liquid 20 is dissolved in the reference solution 30, so that the inside of the pore 11 is the first. It can be assumed that the liquid 11 is not filled with one liquid 20, that is, its pores 11 are filled with the reference solution 30 except for the surface covered with the first liquid 20.

  It should be noted that Equations 1 and 2 used in the sample equilibrium concentration ratio relationship creating step (S2) used in the present embodiment are derived as follows.

  First, at the coordinates shown in FIG. 5, the following equation 5 is used as a basic equation that considers the ease of adsorption of the porous body as an equation representing the capillary phase separation phenomenon. In the following, in order to simplify the explanation, not the capillary phase separation phenomenon between the first liquid 20 and the reference solution 30, but the capillary phase separation phenomenon between the first liquid and the second liquid. Will be described.

  By substituting the following formula 6, which is a definition formula for the radius of curvature, into ρ (x) of formula 5, the following formula 7 is obtained.

Here, since the interface between the first liquid 20 and the reference solutions E 1 to _z 30 satisfies the following boundary condition from FIG.
When x = x ₀ , θ = 0
When x = 0 θ = π / 2
By substituting this boundary condition into Equation 7 and integrating x in the range of 0 ≦ x ≦ x ₀ , Equation 1 is obtained.

Further, since the in ρ (x) = ∞ when x = x ₀ than 5, by substituting the boundary conditions to equation 5, so that the equation 2 is obtained. As described above, Equations 1 and 2 used in the sample equilibrium concentration ratio relationship creating step (S2) used in this embodiment are derived.

Next, the equilibrium concentration ratio calculation step (S3) will be specifically described. In the equilibrium concentration ratio calculation step (S3), as shown in FIG. 3, the porous body 10 is _added to a reference solution E 1 _-z 30 in which the first liquid 20 is dissolved in the second liquid at a known concentration D 1 _-z. the by immersing measured every standard solution _{E 1 to Z} 30 the equilibrium concentration _{a 1 to Z} of known concentration _{D 1 to Z} of the first liquid 20 in the reference solution _{E 1 to Z} 30 upon formation of the equilibrium It not particularly limited as long as it can calculate the equilibrium concentration ratio of each reference solution _{E 1 to Z} 30 of known concentration _{D 1~z (a 1~z / C S} ) and. That is, the reference solution _E to a method of measuring the equilibrium concentration _{A 1 to Z} of _{1 to Z} 30 first liquid 20 in is not particularly limited, the equilibrium from the equilibrium concentration _{A 1 to Z} density ratio _{(A 1~z} / C _The method for calculating _S ) is not particularly limited. The reference solution _{E 1 to Z} 30 of known concentration _{D 1 to Z} used in this embodiment may be used in any order with respect to the porous body 10, but the reference solution _E 1 to Z 30 The order in which the concentration of the first liquid 20 in the reference solution E 1 _-z 30 gradually increases from low to high, or the first liquid 20 in the reference solutions E 1 to _z 30 has a high concentration to a low concentration. It is preferable to use them in the order in which the concentration gradually decreases. When the reference solutions E 1 to _z 30 having known concentrations D 1 to _z are used in this order, the equilibrium concentrations A ₁ to _z can be measured more easily.

Next, the residual amount calculation step (S4) will be specifically described. The residual amount calculation step (S4) is performed based on the dry weight of the porous body 10 and the weight of the porous body 10 in an equilibrium state with respect to each of the reference solutions E 1 to _z 30 having known concentrations D 1 to _z , or the reference solution E _{Based on} the concentrations D 1 _{-z of 1} to _z 30, the _amounts of the reference solutions E 1 to _z 30, and the equilibrium concentrations A ₁ to _z , the reference solutions E 1 to _z 30 of known concentrations D ₁ to _z 30 are used. There is no particular limitation as long as the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium state with respect to each can be calculated. For example, as described below, the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 can be calculated. The residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 may be the weight of the first liquid 20 remaining in the pores 11 of the porous body 10, or may be porous. It may be the volume of the first liquid 20 remaining in the pores 11 of the body 10.

First, using a second liquid having a higher saturated vapor pressure than that of the first liquid 20, the porous body 10 having the first liquid 20 attached in the pores 11 has a known concentration D 1 to _z . It is immersed in the tank 50 filled with the reference solutions E 1 to _z 30 to obtain an equilibrium state. When the porous body 10 is taken out from the tank 50 and dried, the second liquid has a higher saturated vapor pressure than the first liquid 20, so that the second liquid is ahead of the first liquid 20. Evaporates. Then, after the second liquid has completely evaporated, the weight of the porous body 10 is measured, and by subtracting the dry weight of the porous body 10 from the weight, the reference solutions E 1 to _z 30 _having a known concentration D ₁ to _z 30 are obtained. The residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium state with respect to each can be easily calculated. Here, the second liquid is not particularly limited as long as it has a saturated vapor pressure higher than that of the first liquid 20. However, the second liquid is preferably a substance that becomes a gas at normal temperature and pressure. The use of such materials as the second liquid, from the tank 50 filled with a reference solution E _{1 to Z 30} in which the first liquid 20 is dissolved in a known concentration D _{1 to Z} takes out the porous body 10, Since the second liquid in the reference solutions E 1 to _z 30 is easily evaporated simply by leaving it as it is, the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium state is more easily obtained. Can be calculated.

  Further, the method for measuring the dry weight of the porous body 10 is not particularly limited. For example, the dry weight may be measured before the first liquid 20 is attached to the porous body 10, or the dry weight of the porous body 10 may be measured after the equilibrium concentration ratio calculating step (S3) is completed. Good. The dry weight of the porous body 10 refers to the weight of the porous body 10 when the first liquid 20 and the second liquid are not present on the surface of the porous body 10 and in the pores 11.

Next, the pore evaluation step (S5) will be specifically described. In the pore evaluation step (S5), the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 in an equilibrium state with respect to each of the reference solutions E 1 to _z 30 _having a known concentration D 1 to _z is known. Distribution of pore diameter w and pore diameter w of pores 11 of porous body 10 based on the equilibrium concentration ratio (A 1 _-z / C _S ) with respect to each of reference solutions E 1 _-z 30 of concentrations D 1 _-z of If it can evaluate, it will not specifically limit. However, the pore evaluation step (S5) is preferably a pore evaluation step using a change amount of the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 described below. Hereinafter, the pore evaluation process using the change amount of the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 will be specifically described.

As shown in FIG. 7, the pore evaluation process using the amount of change in the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10 includes the equilibrium concentration ratio (A 1− _z / C _S ). From the residual amount of the first liquid 20 remaining in the pores 11 of each porous body 10, the first residual in the pores 11 of the porous body 10 for each equilibrium concentration ratio (A 1 _-z / C _S ). a volume calculation step of calculating the volume of liquid 20 (S5-1), based on the relationship between the pore diameter _{W 1 to y} and the specimen equilibrium concentration ratio of the sample porous _{O 1~y (C 1~y / C S} ) A pore diameter calculation step (S5-2) for calculating the pore diameter B of the pores 11 of the porous body 10 respectively determined in accordance with the equilibrium concentration ratio (A 1 _-z / C _S ), and two adjacent two The difference in volume of the first liquid 20 remaining in the pores 11 of the porous body 10 at the equilibrium concentration ratio (A 1 _-z / C _S ) and From the pore diameters B 1 _-z of the pores 11 of the porous body 10 respectively determined in accordance with the two adjacent equilibrium concentration ratios (A 1 _-z / C _S ), the pore diameters of the pores 11 of the porous body 10 It comprises a pore diameter distribution calculation step (S5-3) for calculating the distribution of w. Hereinafter, each step will be described more specifically.

  First, the volume calculation step (S5-1) will be specifically described. In the volume calculation step (S5-1), the volume of the first liquid 20 remaining in the pores 11 of the porous body 10 is calculated from the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10. If it can do, it will not specifically limit. For example, the weight of the first liquid 20 remaining in the pores 11 of the porous body 10 obtained in the residual amount calculation step (S4) is divided by the density of the first liquid 20 to thereby reduce the pores 11 of the porous body 10. The volume of the first liquid 20 remaining inside can be calculated.

Next, the pore diameter calculation step (S5-2) will be specifically described. Pore diameter calculating step (S5-2) the equilibrium concentration ratio on the basis of the relationship between the pore diameter _{W 1 to y} and the specimen equilibrium concentration ratio of the sample porous _{O 1~y (C 1~y / C S} ) (A _{1 to z} / C _S ) is not particularly limited as long as the pore diameters B ₁ to _y of the pores 11 of the porous body 10 respectively determined can be calculated. For example, taking the pore diameter of the pores of the sample porous body on the horizontal axis and the sample equilibrium concentration ratio on the vertical axis, the pore diameters W 1 _-y of the pores of the sample porous body and the sample porous bodies O 1 _-y A plurality of points indicating the relationship with the sample equilibrium concentration ratio (C 1 _-y / C _S ) are plotted, and an approximate curve is created so as to pass through all the points. Then, the pore diameters B ₁ to _y of the pores 11 of the porous body 10 corresponding to the respective equilibrium concentration ratios (A 1 to _y / C _S ) can be calculated based on the approximate curve.

Further, the pore diameter distribution calculating step (S5-3) will be specifically described. In the pore diameter distribution calculation step (S5-3), the difference in volume of the first liquid 20 remaining in the pores 11 of the porous body 10 at two adjacent equilibrium concentration ratios (A 1 _-y / C _S ) and From the pore diameters B ₁ to _y of the pores of the porous body 10 respectively determined corresponding to the two adjacent equilibrium concentration ratios (A 1 to _y / C _S ), the pore diameter w of the pores of the porous body 10 The distribution is not particularly limited as long as it can calculate the distribution. For example, the distribution of the pore diameter w of the pores 11 of the porous body 10 can be calculated as described below.

First, consider the first liquid 20 remaining in the pores 11 of the porous body 10 at the equilibrium concentration ratio (A _n / C _S ). Corresponding to this equilibrium concentration ratio (A _n / C _S ), the pore diameter of the pores 11 of the porous body 10 determined by the pore diameter calculation step (S5-2) is B _n . Then, in the equilibrium state in which this equilibrium concentration ratio (A _n / C _S ) is obtained, as described above, the pores whose pore diameter is smaller than B _n are all filled with the first liquid 20. Can be assumed. On the other hand, it is assumed that pores having the same or larger pore diameter than _Bn are filled with the reference solution used at that time except for the surface of the pores covered with the first liquid 20. can do. The volume V _n of the first liquid 20 remaining in the pores 11 of the porous body 10 at this equilibrium concentration ratio (A _n / C _S ) can be calculated by the volume calculation step (S5-1). .

Next, considering the pore diameter B _n−1 of the pores 11 of the porous body 10 at the equilibrium concentration ratio (A _n−1 / C _S ) (A _n > A _n−1 ), the fineness is similarly reduced. For pores having a pore diameter smaller than B _n-1 (B _n > B _n-1 ), it can be assumed that the inside of the pore 11 is filled with the first liquid 20. In the case of a pore 11 having the same or larger pore diameter than B _n-1, it is assumed that the pore 11 is filled with the second liquid except for the surface covered with the first liquid 20. Can do. Similarly, the volume V _n-1 of the first liquid 20 remaining in the pores 11 of the porous body 10 at this equilibrium concentration ratio (A _n-1 / C _S ) is the volume calculation step (S5- 1).

Considering the above, the pore diameters B _n and B _n−1 of the pores 11 of the porous body 10 at the adjacent equilibrium concentration ratios (A _n / C _S , A _n−1 / C _S ), and the adjacent equilibrium Consider the difference in volume (V _n −V _n−1 ) of the first liquid 20 remaining in the pores 11 of the porous body 10 at the concentration ratios (A _n / C _S , A _n−1 / C _S ). And the volume difference (V _n −V _n−1 ) of the first liquid 20 remaining in the pores 11 of the porous body 10 has a pore diameter in the range between B _n−1 and B _n. This is considered to be caused by the amount of change in the volume of the first liquid 20 adhering in the pores 11. That is, in the equilibrium state at the equilibrium concentration ratio (A _n / C _S ), all the pores 11 having a pore diameter less than B _n were filled with the first liquid 20, but the equilibrium concentration ratio (A _n-1 / In the equilibrium state in C _S ), only the pores 11 having a pore diameter of less than B _n−1 are filled with the first liquid 20. Therefore, the first liquid 20 that has adhered to the pore 11 having a pore diameter in the range between B _n-1 and B _n is a portion that is uniformly adhered to the surface of the pore 11. The volume difference (V _n −V _n−1 ) of the first liquid 20 remaining in the pores 11 of the porous body 10 is the pore diameter. Is considered to be caused by the amount of change in the volume of the first liquid 20 adhering in the pores 11 in the range between B _n-1 and B _n . Then, from the relationship between the volume difference (V _n −V _n−1 ) of the first liquid 20 remaining in the pores 11 of the porous body 10 and the pore diameters B _n−1 and B _n , the following formula 8 And Equation 9 can be derived. Here, (V _n −V _n−1 ) is preferably closer to 0, and if (V _n −V _n−1 ) is sufficiently small, the evaluation results of the pore size distributions that are almost the same as Expression 8 and Expression 9 are obtained. Will give.

In the equation 8 or 9, the volume of the first liquid 20 remaining in the pores 11 of the porous body 10 at two adjacent equilibrium concentration ratios (A _n / C _S , A _n−1 / C _S ) ( _{V n,} V _n-1) and their equilibrium concentration ratio _{(a n} / _{C S,} pore diameter _(B n of the pores 11 of the porous body 10 corresponding to _{a n-1 / C S)} , B n- ₁ ) and the thickness of the first liquid 20 attached to the surface of the pores 11 of the porous body 10 corresponding to the equilibrium concentration ratios (A _n / C _S , A _n-1 / C _S ) ( t _n, by substituting _{t n-1)} and can calculate the _{S n.} Then, by performing the same operation on all adjacent two equilibrium concentration ratios (A 1 _-y / C _S ), it corresponds to all the pore diameters B 1 _-y and the respective pore diameters B 1 _-y . It is possible to _measure the relationship between the surface _areas S 1 to _y , that is, the pore size distribution of the pores 11 of the porous body 10. Here, the above-described (V _n , V _n-1 ) can be obtained by the volume calculation step (S5-1), and the above-described (B _n , B _n-1 ) is the pore diameter calculation step (S5-2). Can be obtained. In addition, (t _n , t _n-1 ) described above substitutes the equilibrium concentration ratio (A 1 _-y / C _S ) in place of the sample equilibrium concentration ratio (C 1 _-y / C _S ) in Equation 2, Formula so as to satisfy the relationship between the pore diameters W ₁ to _Y of the specimen porous bodies O 1 to _y obtained in the specimen equilibrium concentration ratio relation creating step (S 2) and the specimen equilibrium concentration ratio (C 1 to _y / C _S ). It is obtained by solving 2.

  In the pore diameter evaluation step (S5) described above, the steps are performed in the order of the volume calculation step (S5-1), the pore diameter calculation step (S5-2), and the pore diameter distribution calculation step (S5-3). However, the order of performing each step is not particularly limited as long as the pore size distribution can be measured.

  As described above, according to the pore diameter distribution measuring method used in the present embodiment, the pore diameter and the distribution of the pores of the porous body having various shapes and compositions can be measured accurately and easily. In the pore size distribution measuring method used in this embodiment, as described above, the adsorption potential creation step (S1), the sample equilibrium concentration ratio relationship creation step (S2), the equilibrium concentration ratio calculation step (S3), and the residual amount calculation step. Although the respective steps are performed in the order of (S4) and the pore evaluation step (S5), the order of performing the steps is not particularly limited as long as the pore diameter distribution can be measured.

Here, in the pore diameter distribution measuring method used in the present embodiment, for example, the porous body 10 having the first liquid 20 attached in the pores is immersed in the reference solutions E 1 to _z 30 having a known concentration D 1 to _z. Must be in equilibrium. However, in this case, it depends on the distribution state of the pore diameters of the pores 11 of the porous body 10, the combination of the first liquid 20 and the second liquid, the concentrations D1- _z of the reference solutions E1- _z30 , and the like. However, it takes about several weeks to reach such an equilibrium state. Therefore, when the pore distribution measurement method used in the present embodiment is performed, the porous body 10 having the first liquid 20 attached in the pores 11 is converted to a known concentration D by a distribution method as described below. who is attained equilibrium when immersed in a reference solution E _{1 to Z 30} in _{1 to Z} are preferred. When such a distribution method is used, the equilibrium state can be achieved easily and in a short time. Below, an example of the distribution system which achieves the equilibrium state will be described.

  A flow system that achieves an equilibrium state when the porous body with the first liquid adhering in the pores is immersed in a reference solution having a known concentration is a method in which the column is filled with the porous body and the column has a known concentration. Each of the reference solutions is continuously supplied so that the concentration of each reference solution and the concentration of the first liquid in the solution discharged from the column corresponding to the reference solution are the same. is there. Hereinafter, an example of an equilibrium state forming apparatus using this distribution method will be specifically described. The concentration of the reference solution and the concentration of the first liquid in the solution discharged from the column corresponding to the reference solution need not be completely the same. It includes what can be seen.

FIG. 8 is a schematic diagram of an example of an equilibrium state forming apparatus used in the present embodiment. Equilibrium forming apparatus 100 used in this embodiment, as shown in FIG. 8, and the porous member 10A of the first liquid is attached to the pores, the saturation concentration of the first liquid is a second a C _S Each of the liquids forms an equilibrium state with a plurality of reference solutions in which the first liquid is dissolved at different known concentrations. Specifically, the equilibrium state forming apparatus 100 used in the present embodiment is connected to the column 110 filled with the porous body 10A and the reference solutions 121A, 121B, 121C, 121D having different known concentrations connected to the column 110, respectively. A plurality of reference solution tanks 120A, 120B, 120C, and 120D to be stored, and provided between the column 110 and the reference solution tanks 120A, 120B, 120C, and 120D, and selectively from each of the reference solution tanks 120A, 120B, 120C, and 120D Supply means 130 for supplying the reference solutions 121A, 121B, 121C, 121D of the respective concentrations to the column 110, a concentration measuring means 140 for measuring the concentration of the first liquid in the solution discharged from the column 110, and the column 110 The known concentration of the reference solution supplied to the column and discharged from the column 110 By comparing the density of the liquid is provided and determining equilibrium state determining means 150 whether or not the equilibrium state. In the present embodiment, a storage tank 160 for storing the solution discharged from the column 110 is provided on the downstream side of the concentration measuring means 140. Below, each component is demonstrated more concretely.

  The column 110 is not particularly limited as long as it can be filled with the porous body 10A and can pass the reference solutions 121A, 121B, 121C, 121D.

  The reference solution tanks 120A, 120B, 120C, and 120D are not particularly limited as long as they are connected to the column 110 and can store the reference solutions 121A, 121B, 121C, and 121D having respective concentrations.

  The supply unit 130 is not particularly limited as long as it can selectively supply the reference solutions 121A, 121B, 121C, and 121D having respective concentrations from the reference solution tanks 120A, 120B, 120C, and 120D to the column 110. In the present embodiment, the supply means 130 selectively supplies the reference solutions 121A, 121B, 121C, 121D of the respective concentrations to the column 110, and valves 131A, 131B, 131C, 131D, and the reference solutions 121A, 121B, 121C. , 121D to the column 110, and a supply pipe 133 for connecting the reference solution tanks 120A, 120B, 120C, 120D and the column 110 to each other.

  One end of the supply pipe 133 is connected to the column 110, and the other end is branched into four supply pipes 133a, 133b, 133c, and 133d. The other ends of the supply pipes 133a, 133b, 133c, and 133d are The reference solution tanks 120A, 120B, 120C, and 120D are connected respectively.

  The valves 131A, 131B, 131C, and 131D are respectively provided in the supply pipes 133a, 133b, 133c, and 133d from which the supply pipe 133 is branched. By selectively opening one of them, the reference solutions 121A and 121B are selectively provided. , 121C, 121D can be supplied to the column 110. In this embodiment, four valves 131A, 131B, 131C, and 131D are used. However, a valve that can supply only one of the reference solutions from the four reference solutions 121A, 121B, 121C, and 121D is used as a branching portion. It may be provided.

  The pump 132 is provided in a non-branched portion of the supply pipe 133, and the reference solutions 121A, 121B, 121C, and 121D stored in the reference solution tanks 120A, 120B, 120C, and 120D by one pump 132, respectively. Can be supplied to the column 110. The supply pipe 133, the pump 132, and the valves 131A, 131B, 131C, and 131D are not particularly limited.

The concentration measuring means 140 is not particularly limited as long as it can measure the concentration of the first liquid in the solution discharged from the column 110. In the present embodiment, the concentration measuring means 140 is connected to the column 110 via the discharge pipe 141. Here, when the first liquid is water and the second liquid is dimethyl ether (DME: CH ₃ OCH ₃ ), since each boiling point is significantly different, it can be easily separated. Can be used to easily measure the concentration of water in the solution discharged from the column 110.

  The equilibrium state determination unit 150 is particularly capable of determining whether or not the equilibrium state is obtained by comparing the known concentration of the reference solution supplied to the column 110 with the concentration of the solution discharged from the column 110. It is not limited. For example, as shown in FIG. 8, a personal computer connected to the concentration measuring means 140 can be used. In this personal computer, known concentrations of the reference solutions 121A, 121B, 121C, and 121D are stored in advance, and the concentration and concentration measuring means 140 of each of the reference solutions 121A, 121B, 121C, and 121D stored in the personal computer are stored. It is possible to determine whether or not an equilibrium state has been reached by comparing the concentration of the solution measured by the above. That is, the concentration of each of the reference solutions 121A, 121B, 121C, and 121D is compared with the concentration of the solution measured by the concentration measuring unit 140, and when these concentrations are the same or nearly the same, an equilibrium state is reached. In other cases, it can be determined that the equilibrium state has not been reached.

  The storage tank 160 is not particularly limited as long as it can store the solution discharged from the column 110.

  Next, the operation of the equilibrium state forming apparatus 100 used in the present embodiment will be described. First, as shown in FIG. 9, in order to selectively supply the reference solutions 121A, 121B, 121C, and 121D having respective concentrations to the column 110, any one of the valves 131A, 131B, 131C, and 131D is opened (SA1). ). Then, a reference solution with a known concentration is supplied to the column 110 from any of the reference solution tanks 120A, 120B, 120C, and 120D by the pump 132 (SA2).

  Then, the reference solution supplied to the column 110 comes into contact with the porous body 10A packed in the column 110. Then, the reference solution is a solution in which the concentration of the first liquid in the reference solution varies depending on the concentration of the first liquid in the reference solution, and the concentration of the first liquid contained is different. It is discharged from the column 110 (SA3). That is, when a reference solution having a known concentration is supplied to the column 110, the amount of the first liquid adhering in the pores of the porous body 10A is reduced to the pores of the porous body 10A in an equilibrium state at the known concentrations. When the amount is larger than the amount of the first liquid adhering to the inside, the first liquid adhering in the pores of the porous body 10A is dissolved in the reference solution, and the first liquid in the reference solution is dissolved. The concentration of liquid increases. On the other hand, the amount of the first liquid attached in the pores of the porous body 10A is larger than the amount of the first liquid attached in the pores of the porous body 10A in an equilibrium state at a known concentration of the reference solution. When the amount is small, the first liquid dissolved in the reference solution adheres to the pores of the porous body 10A, and the concentration of the first liquid in the reference solution decreases. In this way, the concentration of the first liquid in the reference solution changes, and the reference solution supplied to the column 110 is discharged from the column 110 as a solution having a different concentration of the first liquid contained.

  The solution discharged from the column 110 flows into the concentration measuring means 140 through the discharge pipe 141, and the concentration measuring means 140 measures the concentration (SA4).

  Next, the concentration of the solution measured by the concentration measuring means 140 is compared with the known concentration of the reference solution supplied to the column 110 (SA5), and the concentration of the measured solution is supplied to the column 110. The reference solution is continuously fed to the column 110 until the concentration is the same or nearly the same. Thus, when the reference solution is continuously supplied to the column 110, the first liquid adhering in the pores of the porous body 10A is dissolved in the reference solution, or the first liquid in the reference solution is porous. The amount of the first liquid adhering in the pores of the porous body 10A is gradually increased in the equilibrium state at a known concentration of the reference solution. It approaches the amount of the first liquid adhering to the pores.

  When the concentration of the solution discharged from the column 110 is the same as or almost the same as the concentration of the reference solution continuously supplied from the reference solution tank, the first liquid has adhered to the pores. It can be regarded as an equilibrium state when the porous body is immersed in the reference solution. Here, the equilibrium state when the porous body 10A having the first liquid adhered in the pores is immersed in the reference solution, and the solution discharged from the column 110 in the equilibrium state forming apparatus used in the above-described embodiment. This is strictly different from a state in which the concentration of is the same or nearly the same as the concentration of the reference solution continuously supplied from the reference solution tank. However, the amount of the first liquid adhering in the pores of the porous body 10A is very small relative to the amount of the reference solution. Therefore, even if the first liquid adhering in the pores of the porous body 10A is dissolved in the reference solution, or the first liquid in the reference solution further adheres in the pores of the porous body 10A, the reference solution The change in the concentration of the first liquid inside is extremely small. From this, it is discharged from the column 110 in the equilibrium state when the porous body 10A having the first liquid adhered in the pores is immersed in the reference solution and in the equilibrium state forming apparatus 100 used in the above-described embodiment. The state in which the concentration of the obtained solution is the same or substantially the same as the concentration of the reference solution continuously supplied from the reference solution tank can be regarded as the same. By performing such an operation for each reference solution, an equilibrium state corresponding to each reference solution can be achieved.

  As described above, since the equilibrium state forming apparatus 100 used in the present embodiment considers that the equilibrium state has been reached as described above, the time required for achieving the equilibrium state can be shortened.

  As described above, according to the equilibrium state forming apparatus 100 used in the present embodiment, the porous body 10A having the first liquid attached in the pores can be easily and in a short time when immersed in the reference solution. An equilibrium state can be achieved.

  In the equilibrium state forming apparatus 100 used in the present embodiment, the equilibrium state is achieved as described above. However, the solution discharged from the column is supplied to the column again as a reference solution, and the first solution in the reference solution is supplied. A state in which the concentration of the first liquid and the concentration of the first liquid in the solution discharged from the column corresponding to the reference solution are the same or substantially the same may be regarded as an equilibrium state. Even if it does in this way, the effect similar to the equilibrium state formation apparatus 100 mentioned above will be acquired.

  Specifically, unlike the equilibrium state forming apparatus 100 described above, for example, as shown in FIG. 10, the solution discharged from the column 110 is again passed through the reference solution tanks 120A, 120B, 120C, and 120D. The equilibrium state forming apparatus 200 provided with the circulation means 270 for supplying to the column 110 is mentioned. Hereinafter, the components of the equilibrium state forming apparatus 200 shown in FIG. 10 will be specifically described.

  The circulation means 270 includes a circulation pipe 271 for supplying the solution discharged from the column 110 to the reference solution tank, and control valves 272A and 272B for controlling which reference solution tank the solution discharged from the column 110 is supplied to. 272C, 272D.

  One end of the circulation pipe 271 is connected to the discharge pipe 141 on the downstream side of the concentration measuring means 140 and the other end is branched into four to become circulation pipes 271a, 271b, 271c, 271d, each of which is a reference solution tank 120A, It is connected to 120B, 120C, 120D. The circulation valves 272A, 272B, 272C, and 272D for controlling whether or not the solution discharged from the column 110 is supplied to each of the reference solution tanks 120A, 120B, 120C, and 120D are circulation pipes 271a, 271b, 271c, and 271d. Are intervened in each. The equilibrium state forming apparatus 200 is provided with a storage tank valve 261 so that the solution does not flow into the storage tank 260 when the solution discharged from the column 110 is circulated. In addition, since the other component is the same as that of the equilibrium state formation apparatus 100 mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  Then, when the reference solution is supplied from the reference solution tank to the column 110 as in the above-described equilibrium state forming apparatus 100, the reference valve circulation valve corresponding to the supplied reference solution is opened and the storage tank valve 261 is closed. Thus, the solution discharged from the column 110 can be circulated.

  By performing such an operation for each reference solution, an equilibrium state corresponding to each reference solution can be achieved in the same manner as the equilibrium state forming apparatus 100 described above. When the solution discharged from the column 110 reaches an equilibrium state, the opened valve and the circulation valve are closed and the storage tank valve 261 is opened to discharge the solution reaching the equilibrium state to the storage tank 260. can do.

Further, by equilibrium forming apparatus 300 shown in FIG. 11, and the porous member 10A of the first liquid is attached to the pores, the first saturation concentration of the first liquid to the second liquid is a C _S 1 Can be achieved with each of a plurality of reference solutions prepared by dissolving different liquids at different known concentrations.

  Specifically, an equilibrium state forming apparatus 300 shown in FIG. 11 includes a column 110 filled with a porous body 10A, and storage tanks 320A and 320B connected to the column 110 for storing a first liquid and a second liquid, respectively. And a supply means 330 that is provided between the storage tanks 320A and 320B and mixes the first liquid and the second liquid stored in the storage tanks 320A and 320B at a desired ratio and supplies the mixed liquid to the column 110. Concentration measuring means 140 for measuring the concentration of the first liquid in the solution discharged from the column 110 through the discharge pipe 141 connected to the column 110, and the first in the mixed solution supplied to the column 110 An equilibrium state determination unit 150 that determines whether or not an equilibrium state is obtained by comparing the concentration of the liquid in the liquid and the concentration of the first liquid in the solution discharged from the column 110; Are provided with a circulation means 370 for supplying the solution to the side column 110 is discharged and the discharge pipe 141 from the column 110 connected to the. The equilibrium state forming apparatus 300 is provided with a storage tank 360 for storing the solution discharged from the column 110 on the downstream side of the concentration measuring means 140, similarly to the equilibrium state forming apparatus 100 described above. Further, a storage tank valve 361 is provided on the downstream side of the discharge pipe 141 for preventing the solution from flowing into the storage tank 360 when the solution discharged from the column 110 is circulated. Below, each component is demonstrated more concretely.

  The storage tanks 320A and 320B are not particularly limited as long as they can store the first liquid or the second liquid. However, it goes without saying that when storing the first liquid on one side, the second liquid must be stored on the other side.

  The supply unit 330 is provided between the storage tanks 320A and 320B, mixes the first liquid and the second liquid stored in the storage tanks 320A and 320B at a desired ratio, and supplies the mixed liquid to the column 110. There is no particular limitation as long as it can be used. In the present embodiment, the supply means 330 includes valves 331A and 331B for mixing the first liquid and the second liquid stored in the storage tanks 320A and 320B at a desired ratio to obtain a mixed liquid, A pump 132 for supplying the mixed liquid to the column 110 and a supply pipe 133 connecting the storage tanks 320 </ b> A and 320 </ b> B and the column 110 are included.

  One end of the supply pipe 133 is connected to the column 110, and the other end is branched into two supply pipes 333a and 333b. The other ends of the supply pipes 333a and 333b are connected to the storage tanks 320A and 320B, respectively. Has been.

  The valves 331A and 331B are respectively provided in supply pipes 333a and 333b branched from the supply pipe 133, and the first liquid stored in the storage tanks 320A and 320B is adjusted by adjusting the valves 331A and 331B. A mixed liquid in which 321A and the second liquid 321B are mixed at a desired ratio can be supplied to the column 110. In the equilibrium state forming apparatus 300 used in the present embodiment, the two valves 331A and 331B are used, but the desired ratio of the first liquid 321A and the second liquid 321B stored in the storage tanks 320A and 320B is used. It is also possible to provide a valve that can be supplied at

  The pump 132 is provided in a non-branched portion of the supply pipe 133 so that the liquid mixture mixed at a desired ratio by one pump 132 can be supplied to the column 110. The supply pipe 133, the pump 132, and the valves 331A and 331B are not particularly limited.

  The circulation unit 370 is not particularly limited as long as it can supply the solution discharged from the column 110 to the column 110 again by connecting the supply unit 330 and the discharge pipe 141. In the equilibrium state forming apparatus 300 used in the present embodiment, the circulation means 370 connects the supply pipe 133 upstream of the pump 132 with the column 110 as a base point and the discharge pipe 141 downstream of the concentration measurement means 140. 371 and a circulation valve 372 that is provided in the circulation pipe 371 and controls the liquid flowing through the circulation pipe 371. In addition, since the other component is the same as that of the equilibrium state formation apparatus 100 mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  Next, the operation of the equilibrium state forming apparatus 300 used in this embodiment will be described. First, as shown in FIG. 12, in order to supply a mixed liquid obtained by mixing the first liquid and the second liquid in a desired ratio to the column 110, the valves 331A and 331B correspond to the predetermined ratio. It can be opened (SC1). For example, when only the pure second liquid not containing the first liquid is supplied to the column 110, the valve 331A is not opened and only the valve 331B is opened. In addition, when a mixed liquid having a ratio of the first liquid and the second liquid of 1: 100 is supplied to the column 110, the valve 331A and the valve 331B are opened so as to be a mixed liquid of that ratio. Then, the mixed liquid mixed at a desired ratio is supplied to the column 110 (SC2).

  Then, the mixed liquid supplied to the column 110 comes into contact with the porous body 10A filled in the column 110. Then, the liquid mixture becomes a solution in which the concentration of the first liquid in the liquid mixture changes depending on the concentration of the first liquid in the liquid mixture, and the concentration of the first liquid contained is different. It is discharged from the column 110 (SC3). That is, when the mixed liquid is supplied to the column 110, the amount of the first liquid adhering in the pores of the porous body 10A is equal to the porous body 10A in an equilibrium state at the concentration of the first liquid in the mixed liquid. When the amount of the first liquid adhering in the pores is larger than the first liquid, the first liquid adhering in the pores of the porous body 10A is dissolved in the mixed liquid, and the mixed liquid The concentration of the first liquid inside increases. On the other hand, the amount of the first liquid adhering in the pores of the porous body 10A corresponds to the first liquid adhering in the pores of the porous body 10A in the equilibrium state in the concentration of the first liquid in the mixed liquid. When the amount is less than the amount of the first liquid, the first liquid dissolved in the mixed liquid adheres to the pores of the porous body 10A, and the concentration of the first liquid in the mixed liquid is low. Become. In this way, the concentration of the first liquid in the mixed liquid changes, and the mixed liquid supplied to the column 110 is discharged from the column 110 as a solution having a different concentration of the first liquid contained.

  The solution discharged from the column 110 flows into the concentration measuring means 140 through the discharge pipe 141, and the concentration measuring means 140 measures the concentration of the first liquid in the solution (SC4).

  Next, the concentration of the first liquid in the solution measured by the concentration measuring means 140 is compared with the concentration of the first liquid in the solution measured in the same manner (SC5). Then, it passed through the concentration measuring means 140 until the concentration of the first liquid in the solution measured by the concentration measuring means 140 is the same as or substantially the same as the concentration of the first liquid in the previously measured solution. The solution is supplied to the column 110 again through the circulation pipe 371. Thus, when the same solution is continuously supplied to the column 110, the first liquid adhering in the pores of the porous body 10A is dissolved in the solution, or the first liquid in the solution is dissolved. Since it further adheres in the pores of the porous body 10A, the amount of the first liquid adhering in the pores of the porous body 10A gradually increases in the equilibrium state at the concentration of the first liquid in the solution. It approaches the amount of the first liquid adhering in the pores of the porous body 10A, and eventually reaches an equilibrium state. And by performing such operation for every liquid mixture which mixed the 1st liquid and the 2nd liquid with the desired ratio, the equilibrium state according to each liquid mixture can be achieved. When the solution discharged from the column 110 reaches an equilibrium state, the opened valve and circulation valve are closed and the storage tank valve 361 is opened to discharge the solution that has reached the equilibrium state to the storage tank 360. can do.

  As described above, even when the equilibrium state forming apparatus 300 is used, the same effect as that of the above-described equilibrium state forming apparatus 100 can be obtained.

(Embodiment 2)
In the first embodiment, in the residual amount calculating step (S4), as the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10, the first liquid remaining in the pores 11 of the porous body 10 is used. The weight of 20 was calculated, and finally the distribution of the pore diameter w of the pores 11 of the porous body 10 was calculated using the value. In this embodiment, as described below, the residual amount calculating step ( In S4), the volume of the first liquid 20 remaining in the pores 11 of the porous body 10 is calculated as the residual amount of the first liquid 20 remaining in the pores 11 of the porous body 10, and the value is calculated as Finally, the distribution of the pore diameter w of the pores 11 of the porous body 10 is calculated.

Specifically, in the remaining amount calculation step (S4), for example a known concentration D _n reference solutions E _n 30 in the porous body 10 is immersed equilibrium with the first in the reference solution E _n 30 during the by multiplying the amount of the reference solution E _n 30 to the difference between the equilibrium concentration a _n and the known concentration D _n of the liquid 20, moles or porous of the first liquid 20 obtained by dissolving from within the pores 11 of the porous body 10 Since the number of moles of the first liquid 20 newly adhered in the pores 11 of the body 10 can be calculated, the porous body 10 is _{converted into} a reference solution E having a known concentration D 1 to _y as described below. The volume of the first liquid 20 remaining in the pores 11 of the porous body 10 when immersed in 1 to _y30 and brought into an equilibrium state can be calculated. In the following description, it is _{assumed that} the concentration of the first liquid 20 in the reference solutions E _{1 to y} 30 _{increases in} the order of the reference solutions E ₁ , E ₂ .

First, the first in the pores 11 liquid 20 is not attached porous body 10 to a known concentration of D ₁ reference solutions E ₁ is not in equilibrium with the time the first reference solution E in the _first immersion in Request equilibrium concentration _{a 1} liquid. Then, as described above, the number of moles of the first liquid 20 newly adhered in the pores 11 of the porous body 10 when immersed in the reference solution E ₁ having a known concentration D ₁ and brought into an equilibrium state is as follows. It is obtained by multiplying the difference between the equilibrium concentration A ₁ of the first liquid 20 in the reference solution E ₁ and the known concentration D ₁ by the amount of the reference solution E ₁ . Then, it is possible to calculate the volume of the first liquid 20 remaining in the pores 11 of the porous body 10 at the time of the equilibrium state by immersing the porous body 10 from the number of moles based solution E _1.

Next, determine the equilibrium concentration A ₂ of the porous body 10 as it first liquid 20 of the reference solution E ₂ at the time of the equilibrium state by immersing the reference solution E ₂ of known concentration D _2. Then, the equilibrium concentration A ₁ and the number of moles of the first liquid 20 remaining in the pores 11 of the porous body 10, the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium concentration A ₂ the difference between the number of moles, as described above, is obtained by multiplying the amount of the reference solution E ₂ to the difference between the equilibrium concentration a ₂ and a known concentration D ₂ of the reference solution E ₂ a first liquid 20 in the . Therefore, the number of moles of the first liquid 20 remaining in the pores 11 of the porous body 10 at the equilibrium concentration A ₂ is the first number remaining in the pores 11 of the porous body 10 at the equilibrium concentration A ₁ obtained previously. the number of moles of liquid, obtained by adding the number of moles obtained by multiplying the amount of the reference solution E ₂ to the difference between the equilibrium concentration a ₂ and known concentration D ₂ of the reference solution E ₂ a first liquid 20 in the It will be a thing. Then, calculates a first volume of liquid 20 remaining in the pores 11 of the porous body 10 at the time of from the molar number was calculated by adding the equilibrium the porous body 10 is immersed in the reference solution E ₂ be able to.

And by performing such operation about each reference _| standard solution E1- _y , it remains in the pore 11 of the porous body 10 in the equilibrium state with respect to each of the reference _| standard solutions E1- _z30 of known density _| concentration D1- _z. The volume of the first liquid 20 can be calculated.

  Next, assuming that the obtained volume is obtained from the volume calculating step (S5-1), the distribution of the pore diameter w of the pores 11 of the porous body 10 is calculated by performing the same operation as in the first embodiment. To do.

According to the present embodiment, the distribution of the pore diameter w of the pores 11 of the porous body 10 can be calculated more easily than in the first embodiment. Incidentally, instead of calculating the first volume of liquid 20 remaining in the pores 11 of the porous body 10 at the time of the equilibrium state of the porous body 10 is immersed in the reference solution E _2, the equilibrium concentration A ₁ the difference between the number of moles of the first liquid 20 remaining in the pores 11 of the porous body 10, the number of moles of the first liquid 20 remaining in the pores 11 of the porous body 10 in the equilibrium concentration a _2, i.e. the difference between the equilibrium concentration a ₂ and known concentration D ₂ of the reference solution first liquid 20 in the E ₂ from those obtained by multiplying the amount of the reference solution E _2, the remaining in the pores 11 of the porous body 10 By calculating the volume difference (V ₂ −V ₁ ) of _one liquid 20 and substituting it into the above equation 8, the distribution of the pore diameter w of the pores 11 of the porous body 10 is finally calculated. May be.

<Example>
Coal is used as the porous body, water is used as the first liquid, and liquefied dimethyl ether (liquefied DME) is used as the second liquid. was determined the relationship between the concentration ratio _C 1~y / _{C S} and coal pore size _{W 1~y.}

<Comparative Example 1>
Similar to the example, using coal as the porous body, water as the first liquid, and liquefied dimethyl ether (liquefied DME) as the second liquid, and the water in the liquefied DME outside the coal pores by molecular dynamics simulation. was determined the relationship between the concentration ratio _C 1~y / _{C S} and coal pore size _{W 1~y.}

  The cell used for this simulation is shown in FIG. As shown in FIG. 13, coal pore walls 510 a and 510 </ b> A (in which particles resembling carbon atoms are spread) are arranged in the central portion of the cell 500. Then, water 520 (in which particles struck by water molecules are spread) is arranged in a region sandwiched between the coal pore walls 510a and 510A, and above and below the coal pore walls 510a and 510A and the water 520. Are arranged with DME 530a and 530b (particles resembling DME molecules). In this simulation, the Lennard-Jones (12-6) type potential shown in the following formula 10 is used as the potential, and the values shown in the following Table 1 are used as parameters of this formula.

  Then, the simulation is performed until the set temperature is set to 85 K and the molecular motion speed is adjusted so as to satisfy the Maxwell-Boltzmann distribution at the set temperature until the equilibrium state is reached (until 10 ns elapses) from the state shown in FIG. Went. After the simulation, the concentration of water dissolved in DME outside the coal pores was measured. The number of water molecules and DME molecules outside the pores used in this comparative example was determined by a trial method so that a capillary phase separation phenomenon occurred.

In this comparative example, simulation was performed with the pore diameter W being 1.60 nm, 2.28 nm, and 2.96 nm, and the pore length at that time being 7 times the pore diameter W, and in the liquefied DME outside the coal pores. It was determined for water content ratio relationship between the _C 1 to y / _{C S} and coal pore diameter _{W 1 to y.}

<Comparative example 2>
Coal is used as the porous body, water is used as the first liquid, and liquefied dimethyl ether (liquefied DME) is used as the second liquid, “M. Miyahara, K. Suzuki and M. Okazaki, J. Chem. Eng. Jpn, 30. , 683 (1997) ”, which shows the relationship between the pore diameter and the water concentration in the organic solvent in which capillary phase separation occurs, is expressed in the following formula 11 by ν _W and γ obtained in the step of implementing the example. , _{W 1 to y,} to determine the relationship between water concentration ratio _C 1 to y / _{C S} and coal pore diameter _{W 1 to y} of substituting x in a liquefied DME outside coal pores.

(Calculation result)
The relationship between water concentration ratio C _{1 to y /} C _S and coal pore diameter W in the liquid DME outside coal pores in Example and Comparative Examples 1 and 2 shown in FIG. 14. Here, the solid line in FIG. 14 indicates the calculation result obtained by the example, the white circle indicates the calculation result obtained by the comparative example 1, and the broken line indicates the calculation result obtained by the comparative example 2.

  From FIG. 14, it was found that the calculation results of the example and the comparative example 1 almost completely matched. That is, when the pore size distribution measuring method according to the first embodiment is used, the water content in the liquefied DME when dehydration occurs in the coal due to the water concentration in the liquefied DME when dehydration occurs in the coal and the hygroscopicity of the coal. Since the concentration can be measured, it was found that it can be used to measure the pore size distribution of coal.

  On the other hand, the calculation result of Comparative Example 2 is different from the calculation result of Example and Comparative Example 1, and when the method of Comparative Example 2 is used, the water concentration in liquefied DME when dehydration occurs in coal is evaluated relatively high. Therefore, when the pore size distribution of coal was measured using it, it was found that a pore size distribution in which the pore size of coal was evaluated relatively small was obtained.

1 is a schematic view of a porous body according to Embodiment 1. FIG. FIG. 3 is a schematic diagram illustrating a state in which a first liquid is attached in the pores of the porous body according to the first embodiment. In Embodiment 1, it is the schematic which shows the state which immersed the porous body with which the 1st liquid adhered in the pore in the tank satisfy | filled with the 2nd liquid. 3 is a diagram showing a sequence of a pore diameter distribution measuring method according to Embodiment 1. FIG. It is a figure which shows the model of the contact state of the 1st liquid in the porous body pore which concerns on Embodiment 1, and a 2nd liquid. It is a figure which shows the sequence of the adsorption potential creation process using the adsorption isotherm concerning Embodiment 1. FIG. It is a figure which shows the sequence of the pore evaluation process using the variation | change_quantity of the residual amount of the 1st liquid which remains in the pore of the porous body which concerns on Embodiment 1. FIG. It is the schematic of an example of the equilibrium state formation apparatus used in Embodiment 1. FIG. It is a figure which shows the operation | movement sequence of an example of the equilibrium state formation apparatus used in Embodiment 1. FIG. It is the schematic which shows the other example of the equilibrium state formation apparatus used in Embodiment 1. FIG. It is the schematic which shows the other example of the equilibrium state formation apparatus used in Embodiment 1. FIG. It is a figure which shows the operation | movement sequence of the other example of the equilibrium state formation apparatus used in Embodiment 1. FIG. 6 is a schematic view of a cell used in Comparative Example 1. FIG. It is a graph showing the relationship between water concentration C / C _S and coal pore diameter W in the liquid DME outside coal pores.

Explanation of symbols

10, 10A Porous body 11 Pore 15a, 15b Pore wall 20, 321A First liquid 30, 121A-121D Reference solution 50 tank 100, 200, 300 Equilibrium state forming apparatus 110 Column 120A-120D Reference solution tank 130 Supply means 131A-131D, 331A, 331B Valve 132 Pump 133, 133a-133d, 333a, 333b Supply pipe 140 Concentration measuring means 141 Discharge pipe 150 Equilibrium state determining means 160, 260, 360 Reservoir 270, 370 Circulating means 271, 271a-271d , 371 Circulation pipe 272A-272D Control valve 320A, 320B Storage tank 321B Second liquid 372 Circulation valve

Claims (7)

A first porous body liquid adheres to the pores, the first saturation concentration of the liquid was dissolved the first liquid to the second liquid is a C _S at a known concentration D _{1 to Z} The first liquid remaining in the pores of the porous body without being dissolved in the reference solutions E1 to _z due to a capillary phase separation phenomenon when immersed in the reference solutions E1 to _z to be in an equilibrium state. A pore diameter distribution measuring method for measuring the pore diameter w and the distribution of the pores of the porous body based on the residual amount,
The consists porous body having the same composition or similar composition, the adsorption potential [Delta] [Psi] ₁ of the first liquid to the sample porous O _{1 to y} having only pores of the respective dimensions of known pore size W _{1 to y ˜y} (W 1- _y , x) (where x represents the position in the pore diameter direction with the center of the pore of the specimen porous body as the origin) is determined for each specimen porous body O 1- _y . Adsorption potential creation process;
_{Substituting the} adsorption potentials ΔΨ 1 _-y (W 1 _-y , x) into the following formulas 1 and 2 and solving the equations 1 and 2 so as to eliminate x ₀ , the sample porous body O ₁ each pore diameter _{W 1 to y} and the specimen equilibrium concentration ratio _(C 1~y _/ C S) _(wherein in _~y, the specimen _{C 1 to y} is having only respective dimensions of the pore diameter _{W 1 to y} A sample equilibrium concentration ratio relationship creation step for _obtaining a relationship with the first and second liquids in the second liquid in the porous bodies O 1 to _y ).
Said known concentration D _{1 to Z} of the reference solution E _{1 to Z} in the foregoing the reference solution E _{1 to Z} at the time of the porous body by dipping equilibrium equilibrium concentration of the first liquid A _{1 to Z} the equilibrium concentration ratio of each reference solution _{E 1 to Z} of the measured and the known concentration _{D 1 to Z} for each reference solution _{E 1 to Z} of the known concentration _{D 1~z (a 1~z / C S} ) An equilibrium concentration ratio calculating step for calculating
Based on the weight of the porous material at equilibrium for each reference solution E _{1 to Z} of the porous body dry weight and the known density D _{1 to Z,} or concentration _{D. 1 to} the reference solution E _{1 to Z The} porous body in an equilibrium state with respect to each of the reference solutions E 1 to _{z having} the known concentrations D _{1 to z based on z} , the amount of each of the reference solutions E _{1 to z,} and the equilibrium concentration A 1 to _z A residual amount calculating step of calculating a residual amount of the first liquid remaining in the pores of
Reference solution of known concentration D _{1 to Z} of the reference solution E _{1 to Z} residual amounts of the first liquid remaining in the pores of the porous material at equilibrium with respect to each said known concentration D _{1 to Z} A pore evaluation step of evaluating the pore diameter w of the porous body and the distribution of the pore diameter w based on the equilibrium concentration ratio (A 1 _-z / C _S ) for each of E 1 _-z. A pore diameter distribution measuring method characterized by the above.

In claim 1, the adsorption potential creation step comprises:
The thickness t of the first adsorption film of the liquid corresponding to the specimen porous O _{1 to y} the same or the first sorption isotherm and the adsorption isotherm of the vapor of the liquid to the non-porous body made of similar composition An adsorption isotherm measurement process for measuring
The vapor pressures P 1 to _z of the first liquid on the adsorption isotherm and the thicknesses t 1 to _{z of} the first liquid adsorption film corresponding to the vapor pressures P 1 to _z are _expressed by the following Equation 3. A Δφ calculating step of substituting and calculating the relationship between the thickness t of the first liquid adsorption film on the surface of the non-porous body and Δφ (t);
And a ΔΨ calculation step of calculating the adsorption potential ΔΨ (W, x) from the following equation 4 using the relationship between the thickness t of the first liquid adsorption film and Δφ (t). To measure the pore size distribution.

3. The pore evaluation step according to claim 1, wherein the pore evaluation step _{calculates the} equilibrium from the residual amount of the first liquid remaining in the pores of the porous body for each equilibrium concentration ratio (A 1− _z / C _S ). A volume calculation step of calculating the volume of the first liquid remaining in the pores of the porous body for each concentration ratio (A 1 _-z / C _S );
_{Corresponding to} the equilibrium concentration ratio (A 1 _-z / C _S ) based on the relationship between the pore diameters W _{1 -y} of the sample porous bodies O _{1 -y} and the sample equilibrium concentration ratio (C 1 _-y / C _S ) A pore diameter calculating step of calculating pore diameters _B1 to _z of the pores of the porous body respectively determined by
The difference in volume of the first liquid remaining in the pores of the porous body in the two adjacent equilibrium concentration ratios (A 1 _-z / C _S ) and the two adjacent equilibrium concentration ratios (A _1- and a pore size distribution calculating step of calculating a distribution of pore diameter w of the pores of the porous body from the pore diameter B _{1 to z} of the pores of the porous body is determined in correspondence to the _{z /} C _S) A method for measuring a pore size distribution. 4. The pore diameter distribution measuring method according to claim 1, wherein the pore diameter of the porous body is in the range of 1 to 50 nm. In any one of claims 1 to 4, wherein the porous body, the first liquid to a second liquid the first saturation concentration of the liquid is C _S of the first liquid in the pores is adhered Is equilibrated in a reference solution E 1- _z dissolved in a known concentration D 1- _z ,
Fill the column with the porous body,
The continuously supplied each reference solution _{E 1 to Z} of the known concentration _{D 1 to Z} in the column, corresponding to the reference solution _{E 1 to Z} concentration _{D 1 to Z} of each reference solution _{E 1 to Z Then} , the pore size distribution measuring method is characterized in that the concentration of the first liquid in the solutions F 1 to _z discharged from the column is the same. 6. The pore size distribution measuring method according to claim 5, wherein the solutions F 1 to _z discharged from the column are supplied to the column again as the reference solutions E 1 to _{z having} the concentrations D 1 to _z . In any one of Claims 1-6, a said 2nd liquid has a higher saturated vapor pressure than a said 1st liquid,
In the residual amount calculating step, after reaching the equilibrium state, only the second liquid of the first liquid and the second liquid attached in the pores of the porous body is evaporated. The weight of the porous body is measured, and the residual amount of the first liquid remaining in the pores of the porous body is calculated by subtracting the dry weight of the porous body from the weight of the porous body. Method for measuring pore size distribution.

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