JP2020157196A - Gas Separation Membrane Complex and Method for Producing Gas Separation Membrane Complex - Google Patents

Abstract

To provide a gas separation membrane complex that prevents a flow rate and a concentration of separation gas from changing even in a high temperature-high humidity environment.SOLUTION: A gas separation membrane complex 1 has a support 2, and a gas separation membrane 5 provided on one side of the support 2. The gas separation membrane 5 has a polymer component 51 and an inorganic filler 52.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a gas separation membrane complex and a method for producing a gas separation membrane complex, and more particularly to a gas separation membrane complex having a gas separation membrane and a method for producing a gas separation membrane complex.

In recent years, in the fields of combustion equipment, air conditioning equipment, medical equipment, etc., gas separation membranes for separating and concentrating specific gases such as oxygen and nitrogen from a mixed gas in which two or more types of gases such as air are mixed. Research is being conducted. In the gas separation method using a gas separation membrane, a specific gas is separated and concentrated by utilizing the difference in the permeation rate when the gas permeates the gas separation membrane.

For example, Patent Document 1 describes a gas separation composite membrane including a gas separation layer containing poly (4-methylpentene-1) and a polyfumaric acid ester.

Japanese Unexamined Patent Publication No. 2017-164675

When the gas separation membrane is used for a long time under high temperature and high humidity of, for example, a fuel cell vehicle, the polymer component in the gas separation membrane shrinks, and the flow rate and concentration of the separated gas by the gas separation membrane increase. It may change and the gas separation performance may deteriorate.

An object of the present disclosure is to provide a gas separation membrane composite and a method for producing a gas separation membrane composite in which the flow rate and concentration of the separation gas are unlikely to decrease even under high temperature and high humidity.

The gas separation membrane composite according to the present disclosure includes a support and a gas separation membrane provided on one surface of the support, and the gas separation membrane contains a polymer component and an inorganic filler. To do.

The method for producing a gas separation membrane composite according to the present disclosure includes a first step of dispersing a polymer component and an inorganic filler in an organic solvent to prepare a liquid material, and supplying the liquid material to the water surface to supply the liquid material. The second step of producing a gas separation membrane on the water surface by evaporating the organic solvent from the above, and the third step of bringing the gas separation membrane into contact with one surface of the support to transfer the gas separation membrane to the support. It has a process.

According to the present disclosure, it is possible to obtain a gas separation membrane composite in which the flow rate and concentration of the separation gas do not easily decrease even at a high temperature.

FIG. 1 is a cross-sectional view of the gas separation membrane composite according to the embodiment of the present disclosure. FIG. 2 is a schematic view showing a method for producing a gas separation membrane composite according to an embodiment of the present disclosure. FIG. 3 is a graph showing the amount of change in the flow rate using the gas separation membrane composite of the examples of the present disclosure.

Hereinafter, embodiments of the present disclosure will be described with reference to FIGS. 1 and 2. FIG. 1 is a cross-sectional view of the gas separation membrane composite 1 according to the embodiment of the present disclosure. FIG. 2 is a schematic view showing a method for producing the gas separation membrane composite 1 according to the embodiment of the present disclosure.

As shown in FIG. 1, the gas separation membrane composite 1 according to the present embodiment includes a support 2 and a gas separation membrane 5 provided on one surface 4A of the support 2. The gas separation membrane 5 contains a polymer component 51 and an inorganic filler 52.

The gas separation membrane 5 can selectively separate and concentrate a specific gas from a mixed gas in which two or more types of gases are mixed. Since the speed of permeation through the gas separation membrane 5 differs depending on the type of gas, the gas can be separated and concentrated by this difference in speed. For example, when the rate at which oxygen permeates the gas separation membrane 5 is faster than the rate at which nitrogen permeates the gas separation membrane 5, oxygen-enriched air is obtained by separating and concentrating oxygen from air containing oxygen and nitrogen. be able to. A gas that penetrates the gas separation membrane 5 at a high speed and is separated and concentrated is called a separation gas. In the present embodiment, since the gas separation membrane 5 contains the inorganic filler 52, the flow rate and concentration of the separated gas in the gas separation membrane 5 are unlikely to change even under high temperature and high humidity, and good gas separation performance can be obtained. Can be kept. The reason is considered to be as follows. When the gas separation membrane 5 contains the inorganic filler 52, the inorganic fillers 52 adhered to the polymer chains come into contact with each other when the polymer component 51 in the gas separation membrane 5 tends to shrink due to heat, steam, or the like. Even so, since the polymer chains are fixed by the inorganic filler 52, voids between the chains can be secured. As a result, it is possible to prevent the polymer component 51 from shrinking too much. Therefore, it is considered that the flow rate and concentration of the separated gas are less likely to decrease even at a high temperature by ensuring a sufficient space in the gas separation membrane 5 for the separated gas to pass through.

The gas separation membrane 5 may be composed of one layer, or may be composed of a plurality of layers of two or more layers. When the gas separation membrane 5 is composed of a plurality of layers, the gas separation membrane 5 may include a separation layer for separating gas and a protective layer for protecting the separation layer. In the present embodiment, as shown in FIG. 1, the gas separation membrane 5 includes only the separation layer, and the separation layer itself functions as the gas separation membrane 5.

The gas separation membrane 5 contains a polymer component 51. The material of the polymer component 51 is not particularly limited, and can be appropriately selected so that the permeability coefficient of the separated gas is high.

The polymer component 51 preferably contains at least one compound selected from the group consisting of poly (4-methylpentene-1), siloxane compounds, monosubstituted polydiphenylacetylene, and disubstituted polydiphenylacetylene. In this case, since the gas separation membrane 5 has a high permeability coefficient to a gas such as oxygen, the gas separation performance of the gas separation membrane composite 1 is improved.

The gas separation membrane 5 contains an inorganic filler 52. The material of the inorganic filler 52 is not particularly limited, and a material that has a high permeability coefficient of the separated gas and does not easily deteriorate the gas separation performance at a high temperature can be appropriately selected.

The inorganic filler 52 preferably contains at least one compound selected from the group consisting of silica, alumina, titanium oxide, and glass frit. In this case, since the inorganic filler 52 is well dispersed in the gas separation membrane 5, the voids (free volume) between the polymer chains constituting the polymer between the inorganic fillers 52 are formed in the gas separation membrane 5. It is easy to be formed uniformly in the polymer component 51, and the shrinkage of the polymer component 51 is further suppressed. Therefore, it is easier to prevent a decrease in the flow rate and concentration of the separated gas even under high temperature and high humidity, and it is easy to maintain good gas separation performance of the gas separation membrane 5. Further, by using the above-mentioned inorganic material as the inorganic filler 52, the inorganic filler 52 swells due to absorption of moisture in a high humidity environment, and the shrinkage of the polymer component 51 in the gas separation membrane 5 is easily suppressed. .. As the inorganic filler 52, the above compounds may be used alone or in combination of two or more.

The inorganic filler 52 is preferably nanoparticles. Since the inorganic filler 52 is nanoparticles, the polymer component 51 easily enters the voids between the inorganic fillers 52 in the gas separation membrane 5, and the shrinkage of the polymer component 51 at high temperature can be further suppressed. it can. This makes it easier to prevent a decrease in the flow rate and concentration of the separated gas at high temperatures.

The average particle size of the inorganic filler 52 is preferably less than the thickness of the gas separation membrane 5. In this case, since the inorganic filler 52 is less likely to be exposed from the gas separation membrane 5, a uniform gas separation membrane 5 can be obtained. Further, the polymer component 51 easily enters the voids between the inorganic fillers 52 in the gas separation membrane 5, and the shrinkage of the polymer component 51 under high temperature and high humidity can be further suppressed. As for the average particle size of the inorganic filler 52, the Zetasizer Nano ZS manufactured by Malvern Panasonic is used, and the average particle size is the most frequently used particle size based on the number based on the measured value of the particle size distribution by the dynamic light scattering method. It can be calculated as the diameter.

The average particle size of the inorganic filler 52 is preferably 1000 nm or less. In this case, the polymer component 51 easily enters the voids between the inorganic fillers 52 in the gas separation membrane 5, and the voids between the inorganic fillers 52 become too large, so that the polymer chains of the polymer component 51 enter the voids. It becomes easier to suppress the contraction of the gap (free volume) between them. Therefore, it becomes easier to prevent the shrinkage of the polymer component 51 under high temperature and high humidity, and the flow rate and concentration of the separated gas under high temperature and high humidity are unlikely to change. The average particle size of the inorganic filler 52 is more preferably 10 nm or more and 50 nm or less. When the average particle size of the inorganic filler 52 is 10 nm or more, voids are easily secured by contact between the inorganic fillers 52 in the gas separation membrane 5, and the shrinkage of the polymer component 51 is further suppressed. Further, when the average particle size of the inorganic filler 52 is 50 nm or less, it becomes easier to prevent the gap between the inorganic fillers 52 from becoming too large and shrinking of the polymer component 51 in the gap. The average particle size of the inorganic filler 52 is particularly preferably 10 nm or more and 30 nm or less.

The amount of the inorganic filler 52 in the gas separation membrane 5 is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polymer component 51. When the amount of the inorganic filler 52 is 10 parts by mass or more, the gaps are easily secured by the contact between the inorganic fillers 52 in the gas separation membrane 5, and the shrinkage of the polymer component 51 is further suppressed. Further, when the amount of the inorganic filler 52 is 100 parts by mass or less, it becomes easy to prevent the inorganic filler 52 from aggregating, and the inorganic filler 52 is easily dispersed uniformly in the gas separation membrane 5. Therefore, the voids between the inorganic fillers 52 are likely to be uniformly formed in the gas separation membrane 5, and the shrinkage of the polymer component 51 is further suppressed even under high temperature and high humidity. The amount of the inorganic filler 52 in the gas separation membrane 5 is more preferably 20 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the polymer component 51.

The gas separation membrane 5 may further contain additives such as an antioxidant, a colorant, a plasticizer, and a dispersant, if necessary.

The thickness of the gas separation membrane 5 is preferably in the range of 0.05 μm or more and 0.2 μm or less. In this case, the permeation amount of the gas is increased, and the gas separation performance of the gas separation membrane composite 1 is enhanced. The thickness of the gas separation membrane 5 is more preferably in the range of 0.08 μm or more and 0.12 μm or less. When the gas separation membrane 5 is composed of a plurality of layers, the thickness of the gas separation membrane 5 means the total thickness of each layer constituting the gas separation membrane 5.

The gas separation membrane complex 1 has the gas separation membrane 5 described above and the support 2.

The material of the support 2 is not particularly limited, and a material having a strength capable of supporting the gas separation membrane 5 without affecting the gas separation performance of the gas separation membrane composite 1 may be used. The support 2 may be composed of one layer, or may be composed of a plurality of layers of two or more layers. In the present embodiment, as shown in FIG. 1, the support 2 has a two-layer structure including the fiber layer 3 and the porous membrane 4, but the support 2 has a one-layer structure having only the fiber layer 3. It may be present, or it may have a single-layer structure having only the porous membrane 4. Further, the support 2 may have a multilayer structure having a plurality of fiber layers 3 and one porous film 4, and may have a multilayer structure having one fiber layer 3 and a plurality of porous films 4. It may be a multilayer structure having a plurality of fiber layers 3 and a plurality of porous films 4. The support 2 may be formed of one or more layers capable of supporting the gas separation membrane 5 other than the fiber layer 3 and the porous membrane 4.

In the present embodiment, the porous membrane 4 is formed on one surface 3A of the fiber layer 3, and the gas separation membrane 5 is arranged on the surface 4A of the porous film 4 opposite to the fiber layer 3. Since the support 2 has the fiber layer 3, the support 2 can have high strength, so that the support 2 can satisfactorily support the gas separation membrane 5.

The material of the fiber layer 3 is not particularly limited as long as it is a layer containing fibers. Examples of fibers used in the fiber layer 3 include synthetic fibers such as polyester, polyphenylene sulfide, polyamide, polyimide, and polyamideimide, as well as natural fibers such as silk, cotton, wool, and linen. The fiber layer 3 may contain only one of these fibers, or may contain two or more of these fibers. The fiber layer 3 may be, for example, a non-woven fabric or a woven fabric.

The fiber layer 3 is a group consisting of polyester (melting point about 265 ° C.), polyphenylene sulfide (melting point about 295 ° C.), polyamide (melting point about 225 ° C.), polyimide (melting point about 260 ° C.), and polyamideimide (melting point about 300 ° C.). It preferably contains at least one fiber selected from. In this case, the support 2 including the fiber layer 3 can have good heat resistance. The fiber layer 3 more preferably contains polyester fibers, and further preferably contains polyethylene terephthalate fibers.

The fiber layer 3 preferably contains at least one fiber having a melting point of 200 ° C. or higher. In this case, since the support 2 including the fiber layer 3 can have more excellent heat resistance, the gas separation membrane composite 1 provided with the support 2 has excellent reliability even in a high temperature environment. Can be done. It is more preferable that the fiber layer 3 contains at least one fiber having a melting point of 225 ° C. or higher. The upper limit of the melting point of the fibers constituting the fiber layer 3 is not particularly limited, but the fiber layer 3 may be made of fibers having a melting point of, for example, 350 ° C. or lower. The fiber layer 3 may contain both a fiber having a melting point of 200 ° C. or higher and a fiber having a melting point of less than 200 ° C., or may contain only a fiber having a melting point of 200 ° C. or higher. When the fiber layer 3 contains only fibers having a melting point of 200 ° C. or higher, the support 2 including the fiber layer 3 can have particularly excellent heat resistance.

The thickness of the fiber layer 3 is preferably in the range of 10 μm or more and 500 μm or less. When the thickness of the fiber layer 3 is within this range, sufficient strength can be imparted to the support 2. The thickness of the fiber layer 3 is more preferably in the range of 50 μm or more and 300 μm or less.

The fiber layer 3 may contain components other than fibers. For example, the fiber layer 3 may contain a water repellent. As shown in FIG. 1, when the support 2 has both the fiber layer 3 and the porous film 4, the fiber layer 3 contains a water repellent agent, so that the porous film 4 is formed on one surface 3A of the fiber layer 3. When the porous film 4 is formed, it is possible to prevent the polyether sulfone-containing solution used for forming the porous film 4 from permeating too much into the fiber layer 3, and the porous film 4 can be stably formed. Therefore, the gas separation membrane 5 can be satisfactorily formed on the porous membrane 4 of the support 2.

As the water repellent, for example, a silicone-based water repellent, a fluorine-based water repellent, a mixed water-repellent agent of a silicone-based water repellent and a fluorine-based water repellent, and the like can be used. As the water repellent, it is preferable to use a fluorine-based water repellent, and it is particularly preferable to use a water repellent containing a fluoromethacrylate polymer.

When the fiber layer 3 contains a water repellent, the content of the water repellent is not particularly limited, and the surface 3A on which the porous film 4 of the fiber layer 3 is provided may be appropriately adjusted so as to exhibit sufficient water repellency. Good. If the water repellency of one surface 3A of the fiber layer 3 is too high, the adhesion between the fiber layer 3 and the porous film 4 is lowered. Further, if the water repellency of one surface 3A of the fiber layer 3 is too low, the porous film 4 is not stably formed. Therefore, the content of the water-repellent agent depends on the water-repellent performance of the water-repellent agent so that the porous film 4 is stably formed without impairing the adhesion between the fiber layer 3 and the porous film 4. It is preferable to adjust as appropriate.

The fiber layer 3 can contain a water repellent agent by applying a water repellent agent to the fiber layer 3. The water repellent may be applied to one surface 3A of the fiber layer 3, may be applied to the surface 3B opposite to the one surface 3A, or may be applied to both sides 3A and 3B of the fiber layer 3. However, if the water repellent is applied directly to the one surface 3A of the non-woven fabric, the water repellency becomes high and the adhesion between the fiber layer 3 and the porous film 4 tends to decrease. Therefore, the water repellent is applied to the one surface 3A of the fiber layer 3. It is preferable to apply only to the surface 4B on the opposite side.

In the present embodiment, the support 2 has a porous film 4 provided on one surface 3A of the fiber layer 3. The material of the porous membrane 4 is not particularly limited, and any material may be used as long as it has sufficient cavities formed in the porous membrane 4 and does not easily affect the gas separation performance of the gas separation membrane composite 1. The porous membrane 4 preferably contains, for example, a polyether sulfone. In this case, in the porous film 4, a dense layer having a relatively small average surface pore diameter and a hollow layer having an average surface pore diameter larger than that of the dense layer are stably formed, so that the support 2 has sufficient strength. It can be secured and the pressure loss of the porous membrane 4 can be reduced.

When the support 2 has both the fiber layer 3 and the porous film 4 as in the present embodiment, for example, a polyether sulfone-containing solution in which polyether sulfone is dissolved in a solvent is placed on one surface 3A of the fiber layer 3. It can be formed by immersing the fiber layer 3 coated with the polyether sulfone-containing solution in a water coagulating solution. As the solvent of the solution containing polyether sulfone, for example, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) and the like can be used. The concentration of the polyether sulfone in the solution containing the polyether sulfone is not particularly limited, and is appropriately adjusted so as to have a viscosity capable of satisfactorily coating the fiber layer 3.

When the support 2 has the porous film 4, the thickness of the porous film 4 is preferably in the range of 10 μm or more and 50 μm or less. In this case, the pressure loss of the porous membrane 4 can be reduced and sufficient strength can be secured. The thickness of the porous membrane 4 is more preferably in the range of 15 μm or more and 30 μm or less.

The thickness of the support 2 is preferably in the range of 20 μm or more and 550 μm or less. In this case, the support 2 has sufficient strength to support the gas separation membrane 5. The thickness of the support 2 is more preferably in the range of 60 μm or more and 350 μm or less.

The thickness of the gas separation membrane composite 1 is not particularly limited, but is preferably in the range of 20 μm or more and 550 μm or less, and more preferably in the range of 60 μm or more and 350 μm or less.

The method for producing the gas separation membrane composite 1 according to the present embodiment includes a first step of dispersing the polymer component 51 and the inorganic filler 52 in an organic solvent to prepare the liquid material 50, and supplying the liquid material 50 to the water surface. Then, in the second step of producing the gas separation membrane 5 on the water surface by evaporating the organic solvent from the liquid material 50, the gas separation membrane 5 is brought into contact with one surface 4A of the support 2 to form the gas separation membrane 5 as a support. It has a third step of transferring to 2.

First, the first step will be described. In the first step, as shown in FIG. 2, a liquid material 50 in which the polymer component 51 and the inorganic filler 52 are dispersed in an organic solvent is prepared in the container 60. The organic solvent used to prepare the liquid material 50 is not particularly limited, and one that evaporates well during the film formation of the gas separation film 5 described later can be used. Examples of organic solvents include tetrahydrofuran and 1-chlorobutane. One of these solvents may be used alone as the organic solvent, or two of these solvents may be used as a mixed solvent. The amount of the organic solvent is not particularly limited, and is appropriately adjusted so that the gas separation film 5 can be formed well.

In the first step, it is preferable to disperse the inorganic filler 52 in the organic solvent by ultrasonic vibration. In the present embodiment, as shown in FIG. 2, the ultrasonic homogenizer 63 is inserted into the container 62 connected to the container 60 by the pipe 61, and the inorganic filler 52 is dispersed in the organic solvent by ultrasonic vibration in the container 62. I'm letting you. By dispersing the inorganic filler 52 in the organic solvent by ultrasonic vibration, the inorganic filler 52 is more easily dispersed in the gas separation membrane 5, and the shrinkage of the polymer component 51 in the gas separation membrane 5 is more likely to occur. It is suppressed. Further, since the dispersibility of the inorganic filler 52 in the liquid material 50 is increased, the fluidity of the liquid material 50 can be improved, so that the gas separation film 5 can be easily formed into a good film. The liquid material 50 in which the inorganic filler 52 is well dispersed is supplied to the container 60 through the pipe 61. The liquid material 50 in the container 60 is supplied through the pipe 65 to the second step described later. When the amount of the liquid material 50 in the container 60 exceeds a certain amount, the liquid material 50 may be returned to the container 62 through the pipe 64, and the inorganic filler 52 may be dispersed again by ultrasonic vibration. Further, after preparing the liquid material 50, the liquid material 50 may be supplied to the second step after removing the agglomeration of the inorganic filler 52 by performing filtration using a filter.

Next, the second step will be described. In the second step, as shown in FIG. 2, the liquid material 50 is supplied to the water surface, and the organic solvent is evaporated from the liquid material 50 to prepare the gas separation membrane 5 on the water surface. Water 71 is contained in the manufacturing container 70 used in the water surface development method. The liquid material 50 is supplied from the container 60 through the pipe 65 into the water 71 in the manufacturing container 70. The liquid material 50 is supplied into the water 71 and diffuses and floats on the water surface, and the organic solvent evaporates. As a result, the gas separation membrane 5 is formed on the water surface of the water 71.

Next, the third step will be described. In the third step, as shown in FIG. 3, one surface 4A of the support 2 is brought into contact with the gas separation membrane 5, and the gas separation membrane 5 is transferred to the support 2. As shown in FIG. 2, three rollers 80, 81, 82 are arranged at positions in the manufacturing container 70 facing the water surface of the water 71. The support 2 is wound around the roller 81 in a roll shape. The roller 81 sends the support 2 to the water surface of the water 71. Next, the roller 80 brings the support 2 delivered from the roller 81 into contact with the gas separation membrane 5 floating on the water surface of the water 71 at the position of the roller 80. As a result, the gas separation membrane 5 floating on the water surface of the water 71 is transferred to the support 2. Then, the support 2 to which the gas separation membrane 5 is transferred, that is, the gas separation membrane composite 1, is wound by the roller 82, and the gas separation membrane 5 is continuously transferred to the support 2. As a result, it is possible to obtain a gas separation membrane composite 1 in which the gas separation membrane 5 is provided on one surface 4A of the support 2. By cutting the gas separation membrane composite 1 thus obtained into a predetermined shape and size, the gas separation membrane composite 1 having a desired shape and size can be obtained.

The method for producing the gas separation membrane composite 1 is not limited to the above method. For example, the gas separation membrane composite 1 may be formed by coating the surface 4A of the support 2 with a solution containing the material of the gas separation membrane 5. In this case, the liquid material 50 may be used as the material for the gas separation membrane 5. When the support 2 has a multi-layer structure having a plurality of layers, the support 2 may be manufactured and the gas separation membrane 5 may be formed continuously.

Hereinafter, the present disclosure will be specifically described with reference to Examples. The present disclosure is not limited to this embodiment.

1. 1. Preparation of Gas Separation Membrane Complex 1-1. Example 1
0.60 g of nanosilica particles (average particle size 15 nm) was added to 27.17 g of tetrahydrofuran, and the nanosilica particles were dispersed with an ultrasonic homogenizer at an output of 5 kW for 2 minutes while stirring with a stirrer to disperse the inorganic filler. Prepared. Next, 1.91 g of PDPA (monosubstituted polydiphenylacetylene) and 0.10 g of PDMS (polydimethylsiloxane) were added to 420.62 g of 1-chlorobutane, and while stirring with a stirrer, 2 at an output of 5 kW using a pressure homogenizer. PDPA and PDMS were dispersed for 1 minute to prepare a dispersion of polymer components. A dispersion of an inorganic filler is added to the dispersion of the polymer component, and 0.20 g of polyfumaric acid ester is further added, and then the component is used for 2 minutes at an output of 5 kW using a pressure homogenizer while stirring with a stirrer. Was dispersed to obtain a liquid material for a gas separation membrane containing 30 parts by mass of nanosilica particles with respect to 100 parts by mass of polymer components (PDPA and PDMS). The polyfumolic acid ester is not included in the polymer component because it is hydrolyzed and scattered. Similarly, a liquid material containing 5 parts by mass, 10 parts by mass, 20 parts by mass, and 50 parts by mass of nanosilica particles with respect to 100 parts by mass of the polymer component was obtained.

A gas separation membrane composite was produced using each of the liquid materials having different contents of the nanosilica particles obtained above. A liquid material is developed on the water surface to form a thin gas separation membrane, and the gas separation membrane is transferred to a 25 μm-thick polyether sulfone membrane formed using a polyether sulfone-containing solution (concentration: 30% by mass, solvent dimethylformamide). did. Then, the transfer of the gas separation membrane was repeated three times to obtain the gas separation membrane composite of Example 1 having four layers of gas separation membranes on the polyether sulfone membrane.

1-2. Example 2
A gas separation membrane composite of Example 2 was obtained in the same manner as in Example 1 except that nanosilica particles having an average particle size of 100 nm were used. In Example 2, a liquid material containing 10 parts by mass, 50 parts by mass, and 70 parts by mass of nanosilica particles was prepared with respect to 100 parts by mass of the polymer component, and the gas separation membrane composite was used using these liquid materials. I got a body.

1-3. Comparative Example 1
To 420.62 g of 1-chlorobutane, 1.91 g of PDPA (monosubstituted polydiphenylacetylene) and 0.10 g of PDMS (polydimethylsiloxane) were added, and PDPA was used for 2 minutes at an output of 5 kW using a pressure homogenizer while stirring with a stirrer. And PDMS were dispersed to prepare a dispersion of polymer components. After further adding 0.20 g of polyfumolic acid ester to the dispersion of the polymer component, the component is dispersed for 2 minutes at an output of 5 kW using a pressure homogenizer while stirring with a stirrer, and a liquid containing no nanosilica particles. Obtained the material.

A gas separation membrane composite was produced using the liquid material obtained above that does not contain nanosilica particles. A liquid material is developed on the water surface to form a thin gas separation membrane, and the gas separation membrane is transferred to a 25 μm-thick polyether sulfone membrane formed using a polyether sulfone-containing solution (concentration: 30% by mass, solvent dimethylformamide). did. Then, the transfer of the gas separation membrane was repeated three times to obtain a gas separation membrane composite of Comparative Example 1 having four layers of gas separation membranes on the polyether sulfone membrane.

2. 2. Measurement of Flow Rate Change Rate The flow rate change rate was measured as follows using the gas separation membrane composites of each Example and Comparative Example. A device (oxygen permeation device) in which oxygen flows in one direction from the valve to the gas separation membrane complex was prepared, and the gas separation membrane complex was arranged so that the gas separation membrane was on the valve side. Using this device, the pressure difference between the upstream of the valve and the downstream of the gas separation membrane composite was set to 98.0 kPa (735 mmHg). The time required for oxygen 5 cm ³ to permeate per unit area 10.2 cm ² of the gas separation membrane composite was measured. The initial oxygen flow rate was calculated from this measured value.

Next, the gas separation membrane composite was left in a pressure cooker at a temperature of 110 ° C. and a humidity of 85% Rh for 2000 hours. Then, using an oxygen permeation device, the oxygen flow rate after the heat treatment was calculated by the same method as described above.

From the calculated initial oxygen flow rate and the oxygen flow rate after the heat treatment, the flow rate change rate was calculated based on the following formula. The results are shown in Table 1 and FIG. 3 below.
Flow rate change rate (%) = 100 x (oxygen flow rate after heat treatment-initial oxygen flow rate) / initial oxygen flow rate

1 Gas Separation Membrane Complex 2 Support 5 Gas Separation Membrane 51 Polymer Component 52 Inorganic Filler

Claims (10)

With the support
A gas separation membrane provided on one surface of the support is provided, and the gas separation membrane contains a polymer component and an inorganic filler.
Gas separation membrane complex. The average particle size of the inorganic filler is less than the thickness of the gas separation membrane.
The gas separation membrane composite according to claim 1. The thickness of the gas separation membrane is 0.05 μm or more and 0.2 μm or less.
The gas separation membrane composite according to claim 2. The inorganic filler is nanoparticles.
The gas separation membrane composite according to any one of claims 1 to 3. The average particle size of the inorganic filler is 1000 nm or less.
The gas separation membrane composite according to any one of claims 1 to 4. The average particle size of the inorganic filler is 10 nm or more and 50 nm or less.
The gas separation membrane composite according to claim 5. The amount of the inorganic filler with respect to 100 parts by mass of the polymer component is 10 parts by mass or more and 100 parts by mass or less.
The gas separation membrane composite according to any one of claims 1 to 6. The inorganic filler comprises at least one compound selected from the group consisting of silica, alumina, titanium oxide, and glass frit.
The gas separation membrane composite according to any one of claims 1 to 7. The first step of preparing a liquid material by dispersing the polymer component and the inorganic filler in an organic solvent,
A second step of supplying the liquid material to the water surface and evaporating the organic solvent from the liquid material to form a gas separation membrane on the water surface.
A method for producing a gas separation membrane composite, comprising a third step of bringing one surface of a support into contact with the gas separation membrane and transferring the gas separation membrane to the support. In the first step, the inorganic filler is dispersed in the organic solvent by ultrasonic vibration.
The method for producing a gas separation membrane composite according to claim 9.

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