Technical field
[0001]
The present invention relates to a quality evaluation method and evaluation apparatus of the gas separation membrane, a method for measuring the actual separation factor of the mixed gas and an apparatus for the measurement.
BACKGROUND
[0002]
Microporous membrane, such as a zeolite film is frequently used as a means for separating a multicomponent gas, as a quality evaluation method of the film is evaluated by using the ideal separation factor Patent Document 1. Moreover, the cited document 2, have been made the measurement of the actual separation factor indicating the actual separation factor using a mixed gas in addition to the ideal separation factor.
[0003]
　In the cited document 1, a gas is supplied at a constant pressure, the gas flow coming transmitted measured by the flow meter, when this determines the gas separation performance by a gas permeation rate Q obtained by the following formula, the ratio of Q obtaining the α ideal separation factor of the gas from (a Q of easy gas component passes through the separation membrane, the ratio obtained by dividing the Q of difficult gas component passes through the separation membrane) is disclosed.
Q = {gas permeation rate (cm 3 · STP)} ÷ {membrane area (cm 2 ) × Time (sec) × Pressure difference (cmHg)}
　in the cited document 2, alpha = (Q 1 / Q 2 ) / ( P 1 / P 2 to determine the ideal separation factor in the formula) Here, Q 1 and Q 2 are each, the amount of transmission of high permeability gas and low permeability gas [mol · (m 2 · s) -1 indicates], P 1 and P 2 , respectively, It shows the pressure [Pa] of the highly permeable gas and low permeability gas is the feed gas.
[0004]
　Further, in the cited document 2, alpha '= (Q' 1 / Q ' 2 ) / (P' 1 / P ' 2 to determine the actual separation factor in the formula) is disclosed. Here, Q ' 1 and Q' 2 , respectively, the amount of transmission of high permeability gas and low permeability gas [mol · (m 2 · s) -1 indicates], P ' 1 and P' 2 respectively show the partial pressure [Pa] of the highly permeable gas and low permeability gas in the feed gas.
CITATION
Patent Document
[0005]
Patent Document 1: JP 2009-34614 JP
Patent Document 2: JP 2012-66242 JP
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　How to evaluate the separation performance of the separation membrane by the ideal separation factor of the Patent Documents 1 and 2, each of the two-component gas through a separation membrane as a single component gas, since it can be calculated from the flow rate and pressure measurement has the advantage that it is simple, has a disadvantage that actual separation factor alpha 'and there is off, which is a direct assessment of the actual separation membrane.
[0007]
　In fact according to Patent Document 2, for example, in the separation of carbon dioxide and methane, the ideal separation factor is 89, it is described that the actual separation factor is 73 (herein paragraph [0118] and paragraph [0120] ).
[0008]
　On the other hand, the actual separation factor of Patent Document 2 alpha 'has the advantage that as the evaluation of the actual separation membrane shows an actual performance, the component quantitative analysis of the separation membrane permeate gas, gas chromatography must be done with, it has the disadvantage that it takes time to evaluate.
[0009]
　Calculating actual separation factor using the actual gas chromatography is required to follow a complicated procedure as follows.
[0010]
　Step 1: Before permeation test, a calibration curve is prepared for each gas species of the mixed gas using a gas chromatography.
[0011]
　Step 2: collected mixed gas supply side, the composition of the mixed gas based on a calibration curve was analyzed by gas chromatography, with controlled to a predetermined mixture ratio, maintaining the pressure of the supply-side constant.
[0012]
　Step 3: perform permeation test, the permeate side of the gas were taken and analyzed for their composition by gas chromatography.
[0013]
　Step 4: measuring the gas permeability of a flowmeter.
[0014]
　Step 5: Analysis results of gas chromatography repeat steps 3 and 4 of the process to stabilize.
[0015]
　Step 6: concentration of each component in the permeate side, calculates the actual separation factor of the transmission amount of the supply side of the gas partial pressure and the gas.
[0016]
　The advantage of the prior art, in view of the shortcomings, the present invention is ideally advantages of simplicity of the evaluation means separation factor maintains, methods and evaluation determining an actual separation factor, which shows the performance of a real separation membrane to provide a device.
Means for Solving the Problems
[0017]
　The present inventors have led to the completion the prior art advantages, in view of the shortcomings, the method and the evaluation device calculates the actual separation factor by a simple evaluation means.
[0018]
　The present invention 1 provides a quality evaluation method for a gas separation membrane for separating a gas mixture comprising mixed gas permeation hard second component gas of the gas separation membrane than the first component gas and the first component gas, the a step of calculating a first transmission of the component gas when transmitting one component gas in the gas separation membrane as a single component gas (1), the time for transmitting the gas separation membrane and the second component gas as a single component gas a step of calculating a step of calculating the permeability of the two-component gas (2), the ideal separation factor of the gas separation membrane for gas mixture from the ratio of the permeability of the first component gas to the permeability of the second component gas is calculated and (3), for each of a plurality of gas separation membrane, by utilizing the correlation between the actual separation factor representing the separation performance for the actual gas mixture the ideal separation factor obtained in advance, step (3) the ideal separation factor calculated by Characterized in that it comprises a step (4) for converting the separation factor.
[0019]
　The present invention 1, the ideal separation factor obtained in step (3), for each of a plurality of gas separation membrane, and the actual separation factor representing the separation performance for the actual gas mixture the ideal separation factor obtained in advance and characterized by converting the actual separation factor by utilizing the correlation, between the ideal separation factor and the actual separation factor the finding that there is a correlation between the present invention has been completed 1 It has become an opportunity.
[0020]
　Here, the transmittance is the amount represented by the gas permeability rate ÷ {membrane area × time × pressure difference}, the unit is, mol / (m 2 is a sPa). Further, the ideal separation factor, the transparency of the transparent easy gas separation membrane Q 1 and, the permeability of the permeable hard gas separation membrane Q 2 When, Q 1 / Q 2 is a coefficient calculated by .
[0021]
　Moreover, the actual separation factor, (Q ' 1 / Q' 2 ) / (P ' 1 / P' 2 is a coefficient represented by), Q ' 1 and Q' 2 , respectively, having high permeability gas and permeability of low permeability gas (mol / (m 2 indicates sPa)), P ' 1 and P' 2 are respectively the partial pressure of the highly permeable gas and low permeability gas in the feed gas it is. Q ' 1 and Q' 2 is a permeability which is measured by the flow rate measurement unit of the gas concentration measurement unit and integrating flowmeter such as a gas chromatography and the like, the unit is mol / (m 2 is a sPa). P ' 1 and P' 2 is a gas partial pressure of each gas in the feed gas.
[0022]
　Correlation between the ideal separation factor and the actual separation factor may be a linear correlation may be a linear correlation. If there is some correlation between the ideal separation factor and the actual separation factor, it is possible to convert from the ideal separation factor of the actual separation factor according to the relationship.
[0023]
　The present invention 2, the porous support gas separation membrane is pore size 0.6nm or less of the zeolite membrane on the porous support is a film - a composite of a zeolite film, a mixed gas of hydrogen ( H 2 ), oxygen (O 2 ), nitrogen (N 2 ), carbon dioxide (CO 2 ), methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), sulfur hexafluoride ( SF 6 ), propane (C 3 H 8 ), propylene (C 3 H 6 ), and water (H 2 O) being formed from two gases selected from the group consisting of and wherein according to the present invention 1 a quality evaluation method of the gas separation membrane.
[0024]
　The present invention 3 is a quality evaluation method of the gas separation membrane according to the present invention 2, wherein the zeolite membrane has the following pore 10-membered ring pore.
[0025]
　The present invention 4 is a quality evaluation method of the gas separation membrane according to the present invention 2 or the present invention 3, wherein a zeolite membrane containing a zeolite structure of the MFI type.
[0026]
　The present invention 5, the gas separation membrane is a porous support a porous pore size 0.4nm or less of the zeolite film is a film on a support - a composite of a zeolite film, a mixed gas of hydrogen ( H 2 ), oxygen (O 2 ), nitrogen (N 2 ), carbon dioxide (CO 2 ), methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), sulfur hexafluoride ( SF 6 ), propane (C 3 H 8 ), propylene (C 3 H 6 ), and water (H 2 O) being formed from two gases selected from the group consisting of and wherein according to the present invention 1 a quality evaluation method of the gas separation membrane.
[0027]
　The present invention 6 is a quality evaluation method of the gas separation membrane according to the present invention 5, characterized in that it has a pore zeolite membrane 8 membered ring pores below.
[0028]
　The present invention 7, the zeolite membrane is quality evaluation method for a gas separation membrane according to the present invention 5 invention or 6, characterized in that it comprises a zeolite structure of the CHA type.
[0029]
　The present invention 8 is a quality evaluation unit of the gas separation membrane for separating a gas mixture, the first gas supply unit for supplying the respective gas separation membrane of single component gas which is the component gases in the gas mixture and the second gas supply unit When the single component gas definitive when allowed to permeate the gas separation membrane, a second measuring a first pressure measuring unit for measuring the pressure of the non-permeate side gas of the gas separation membrane, the pressure on the permeate side gas of the gas separation membrane a pressure measuring section, and a flow rate measurement section for measuring the flow rate of the permeate side gas of the gas separation membrane, a gas separation membrane having a gas concentration measuring unit for measuring the concentration of each component gas contained in the permeate side gas of the gas separation membrane a quality evaluation device, the first pressure measuring unit, and the ideal separation factor calculating section for calculating the ideal separation factor of the single component gas from the measurement result of the second pressure measuring unit and the flow measuring unit, a plurality of gas separation membranes respect, the ideal separation factor calculating section Meta ideal separation factor and the flow rate measurement portion and the computing means including a correlation map obtained previously obtained correlation between the actual separation factor representing the separation performance of the actual gas mixture obtained using the gas concentration measurement unit characterized in that it comprises a.
[0030]
　The present invention 8 is a quality evaluation unit of the gas separation membrane which utilizes a measurement method of the present invention 1. Ideal separation factor is calculated in the ideal separation factor calculation unit that calculates an ideal separation factor obtained from permeability of the single component gas.
[0031]
　For a plurality of gas separation membrane, between the actual separation factor representing the separation performance of the actual gas mixture obtained using the ideal separation factor and the flow rate measurement unit and the gas concentration measurement unit as determined by the ideal separation factor calculating section correlation map obtained the correlation in advance, housed within the computing means, is used when converting the ideal separation factor to the real separation factor.
[0032]
　The present invention 9 is the quality evaluation apparatus of the gas separation membrane of the present invention 8, further calculating means, by using a gas selection instruction unit for selecting a gas to be supplied to the gas separation membrane, the flow rate measurement portion and the gas concentration measurement unit characterized in that it has a correlation map creation unit that creates a correlation map between the calculated ideal separation factor by the real separation factor and the ideal separation factor calculation unit that represents the separation performance of the actual gas mixture obtained. As the supply means of the gas mixture, even to supply a mixture of single-component gas of the first gas supply unit and the second gas supply unit may, or the first gas and the second gas and a predetermined ratio in 2008 it may be filled with mixed gas cylinder be one that supplied separately prepared.
[0033]
　The present invention 9, further quality evaluation apparatus of the gas separation membrane of the present invention 8, since it has a correlation map creation unit, it is possible to perform automatically all the calculating actual separation factor.
Effect of the invention
[0034]
　According to the present invention, in ease of evaluation means ideal separation factor, it is possible to determine the actual separation factor, which shows the performance of a real separation membrane.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035]
A quality evaluation unit of the gas separation membrane according to [1] first embodiment.
2 is a diagram showing the correlation of permeability ratio in the single component test (ideal separation factor) and permeability ratio upon mixing the test (actual separation factor).
DESCRIPTION OF THE INVENTION
[0036]
　Hereinafter, with reference to the drawings will be exemplified in detail preferred embodiments of the present invention. However, the dimensions of the components described in this embodiment, the material, shape, unless their relative positions and so forth is not intended to limit the scope of the invention thereto, merely illustrative example only.
[0037]
　Figure 1 shows an example of the quality evaluation apparatus of the gas separation membrane according to the present invention (1). The flow of solid arrow actual gas in FIG. 1, dashed line arrow indicates the flow of data.
[0038]
　Two gases are respectively housed the first gas cylinder in the first gas supply unit (3) and a second gas supply unit (4) and (32) to the second gas cylinder (42), the flow rate of feed gas, the first regulator (31), a second regulator (41) is controlled by the first flow controller (33) and a second flow controller (43).
[0039]
　When measuring the ideal separation factor is one of the gas from the gas or the second gas cylinder from the first gas cylinder (32) as a single component gas (42) is supplied to the separation membrane module (5), the selected performing a first regulator (31), a second regulator (41), a first flow controller (33) and a second flow controller (43) adjusted by the.
[0040]
　The pressure of the gas which does not pass through the gas separation membrane (51) is measured by the first pressure measuring unit (61), the pressure of the gas passing through the gas separation membrane (51) is measured by the second pressure measuring unit (62) It is. The feed-side pressure gas is adjusted by the first back-pressure valve (63), the pressure on the permeate side gas is adjusted by the second back-pressure valve (64).
[0041]
　Ideal separation factor is calculated by the ideal separation factor calculation unit in the arithmetic unit (7) (71). Information for calculation of the ideal separation factor, the gas separation membrane (dashed line) non-permeate side pressure measured by the first pressure measuring unit (61), a gas separation membrane measured by the second pressure measuring unit (62) permeate side pressure (dashed line) can be calculated from the amount of transmission of information from the supplied gas to be measured by the flow measuring unit which will be described later (81).
[0042]
　Next, the actual separation factor, but the mixed gas is to measure by supplying to the separation membrane module (5), will be described below in order.
[0043]
　Mixing ratio and gas flow rates of the two mixed gas is first regulator (31), a second regulator (41), a first flow controller (33), although controlled using the second flow controller (43), mixed when the ratio becomes constant, confirming perform concentration measurement of each component gas using a gas chromatography (FIG. 1, the gas concentration measurement unit (82)). Then, keeping the pressure of the feed gas side, constant using first back-pressure valve (63).
[0044]
　Gas that has passed through the gas separation membrane (51) passes through the second back-pressure valve (64), through the three-way valve (66) is sent to the gas concentration measurement unit to (82) flow measuring unit (81) Te, and the flow rate of the permeate side gas, the concentration of each component of the two-kind mixed gas being measured.
[0045]
　Each data measured is created correlation map is sent to the correlation map creation unit (73) (72), it is sent to the arithmetic unit for converting the ideal separation factor to the real separation factor (not shown), the actual separation coefficient is output.
[0046]
　Non-permeate side gas of the gas separation membrane (51) passes through the exhaust port (65), the permeate side gas outlet of the gas separation membrane (51) (83), through (84), and is discharged as an exhaust gas to the outside .
[0047]
　Instructions or flow gas how to the gas selection instruction section in the computing means (7) by (74), made the first gas supply unit (3) and a second gas supply unit (4).
[0048]
　Actually described below result of measuring the ideal separation factor and the actual separation factor using a quality evaluation unit (1) of the gas separation membrane shown in FIG.
[0049]
　Gas separation membranes (51) used a synthesized CHA-type zeolite membrane on a porous support. The present invention, on principle, not limited to the zeolite membrane may be a separation membrane such as a hollow fiber membrane.
[0050]
　Single component testing, CO 2 gas and CH 4 was performed using the two gases in gas. CO 2 flow rate of the gas was set to 10L / min, CH 4 gas flow rate were also the same 10L / min. Temperature was 40 ° C., the pressure is back pressure valve (63), adjusted with (64), the total pressure was 0.4 MPa.
[0051]
　CHA-type zeolite membrane was subjected to prepared test those having five separation factor.
[0052]
　Mixed gas test was performed using the CHA-type zeolite membrane used for single component testing, CO 2 gas and CH 4 gas mixture of the gas, a molar ratio CO 2 / CH 4 was 50/50, the gas flow rate CO 2 gas and 5L / min, CH 4 and the gas is also well 5L / min. Temperature and total pressure were the same as the single-component gas.
[0053]
　Correlation map created from the measurement result is Fig. The horizontal axis in transmittance ratio in the single component test (ideal separation factor), the vertical axis represents transmittance ratio upon mixing test (actual separation factor). Turning to FIG 2, a very high linearity is observed, the linear correlation coefficient is 0.9979, and most on a straight line riding five data.
[0054]
　By using this correlation map, CO 2 gas and CH 4 calculating actual separation factor reliable simply measuring the ideal separation factor is a permeability ratio in the single component testing using two gases of gas It can be performed.
Industrial Applicability
[0055]
　By using a correlation map which measurement has been previously obtained easily ideal separation factor, a high utility value since the calculation of the actual separation factor becomes possible to represent the actual separation performance of the gas separation membrane.
DESCRIPTION OF SYMBOLS
[0056]
1: Gas separation membranes of the quality evaluation device
3: the first gas supply unit
4: second gas supply unit
5: the separation membrane module
7: calculation means
31: first regulator
32: first gas cylinder
33: first flow controller
41: the second regulator
42: second gas cylinder
43: second flow controller
51: gas separation membranes
61: a first pressure measuring unit
62: second pressure measuring section
63: first back-pressure valve
64: second back-pressure valve
65: exhaust port
66 : three-way valve
71: the ideal separation factor calculation unit
72: correlation map
73: correlation map creation unit
74: gas selection instruction unit
81: flow measuring unit
82: gas concentration measuring unit
83, 84: exhaust port

The scope of the claims
[Requested item 1]
　The mixed gas to a quality evaluation method for a gas separation membrane for separating,
　the mixed gas than the first component gas and the first component gas comprises a second component gas hardly passes through the gas separation membrane,
　the first component gas the first step to calculate the permeability of the component gas (1), when transmitting to the gas separation membrane as a single component gas
　second when transmitting to the gas separation membrane and the second component gas as a single component gas and step (2) to calculate the permeability of the component gas,
　the ideal separation factor of the gas separation membrane for the gas mixture from the ratio of the permeability of the first component gas to the permeability of the calculated second component gas a calculation step (3),
　for each of a plurality of gas separation membrane, by utilizing the correlation between the actual separation factor representing the separation performance for the actual gas mixture with previously obtained the ideal separation factor, in the step (3) And step (4) to convert to the calculated ideal separation factor actual separation factor, Te
quality evaluation method of the gas separation membrane which comprises a.
[Requested item 2]
　Porous support wherein the gas separation membrane is pore size 0.6nm or less of the zeolite membrane on the porous support is a film - a composite of a zeolite film,
　the mixed gas, hydrogen (H 2 ) , oxygen (O 2 ), nitrogen (N 2 ), carbon dioxide (CO 2 ), methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), sulfur hexafluoride (SF 6 ) , propane (C 3 H 8 ), propylene (C 3 H 6 ), and water (H 2 gas separation according to claim 1, characterized in that it is formed from two gases selected from O) consisting of the group quality evaluation method of the film.
[Requested item 3]
　Quality evaluation method of the gas separation membrane of claim 2, wherein the zeolite membrane is characterized by having the following pore 10-membered ring pore.
[Requested item 4]
　Quality evaluation method for a gas separation membrane according to claim 2 or claim 3 wherein the zeolite membrane is characterized in that it comprises a zeolite structure of the MFI type.
[Requested item 5]
　The gas separation membrane porous support on the pore size 0.4nm following zeolite membrane film porous support - a composite of a zeolite film,
　the mixed gas, hydrogen (H 2 ), oxygen (O 2 ), nitrogen (N 2 ), carbon dioxide (CO 2 ), methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), sulfur hexafluoride (SF 6 ), propane (C 3 H 8 ), propylene (C 3 H 6 ), and water (H 2 gas separation membrane according to claim 1, characterized in that it is formed from two gases selected from O) consisting of the group quality evaluation method.
[Requested item 6]
　Quality evaluation method for a gas separation membrane according to claim 5, wherein the zeolite membrane has the following pore 8 membered ring pores.
[Requested item 7]
　Quality evaluation method for a gas separation membrane according to claim 5 or claim 6 wherein the zeolite membrane is characterized in that it comprises a zeolite structure of the CHA type.
[Requested item 8]
　The mixed gas is quality evaluation unit of the gas separation membrane for separating,
　with each of the first gas supply unit for supplying a gas separation membrane and the second gas supply unit to a single component gas which is the component gases of the mixed gas,
　the definitive single component gas when allowed to permeate the gas separation membrane,
　a first pressure measuring unit for measuring the pressure of the non-permeate side gas of the gas separation membrane,
　the measure of the pressure on the permeate side gas of the gas separation membrane and second pressure measuring section,
　and a flow rate measurement section for measuring the flow rate of the permeate side gas of the gas separation membrane,
　and a gas concentration measurement unit for measuring the concentration of each component gas contained in the permeate side gas of the gas separation membrane
of a quality evaluation unit of the gas separation membrane having,
　first pressure measuring unit, and the ideal separation factor calculating section for calculating the ideal separation factor of the single component gas from the measurement result of the second pressure measuring unit and the flow measuring unit,
　a plurality respect of the gas separation membrane, wherein Previously obtained correlation obtained a correlation between the actual separation factor representing the virtual separation factor separation performance of the ideal separation factor and the flow rate measuring unit and the actual gas mixture obtained using the gas concentration measurement unit determined by the computing unit and map,
quality evaluation unit of the gas separation membrane, characterized in that it comprises a calculating means including a.
[Requested item 9]
　In the quality evaluation apparatus of the gas separation membrane of claim 8,
　further to the arithmetic unit
　and the gas selection instruction unit for selecting a gas to be supplied to the gas separation membrane,
　calculated by using the flow rate measuring unit and the gas concentration measurement unit , a correlation map creation unit that creates a correlation map between the actual real separation factor representing the separation performance of a gas mixture of ideal separation factor calculated by the ideal separation factor calculating unit has
quality evaluation unit of the gas separation membrane having a.