JP6671032B2 - Gas separation composite membrane and gas separation module - Google Patents

Description

  The present invention relates to a gas separation composite membrane and a gas separation module.

  In recent years, in the fields of combustion equipment, air conditioning equipment, medical equipment, and the like, research and development of a gas separation composite membrane for separating and concentrating oxygen and nitrogen from air containing oxygen has been advanced (for example, see Patent Document 1). .

JP-A-6-126140

  In order to obtain a high concentration and high flow rate of oxygen or nitrogen by the gas separation composite membrane, it is preferable that both the separation characteristics and the permeation characteristics for separating oxygen and nitrogen in the gas separation composite membrane are excellent. However, there is a problem that it is difficult to form a gas separation composite membrane having both excellent separation characteristics and permeation characteristics because the separation characteristics and the permeation characteristics are contradictory.

  Therefore, an object of the present invention is to provide a gas separation composite membrane having both excellent separation characteristics and permeation characteristics of oxygen and nitrogen in air.

  A gas separation composite membrane according to one embodiment of the present invention includes a first gas separation layer containing poly (4-methylpentene-1) and polyfumarate.

  Further, a gas separation module according to one embodiment of the present invention includes a gas separation composite membrane having the above-described characteristics.

  The present invention can provide a gas separation composite membrane having both excellent separation characteristics and permeation characteristics of oxygen and nitrogen in air.

It is a schematic diagram showing an example of composition of a gas separation composite membrane concerning an embodiment. It is a figure showing an example of the manufacturing method of the gas separation composite membrane concerning an embodiment. It is the schematic which shows the other example of a structure of the gas separation composite membrane which concerns on embodiment. It is the schematic which shows the other example of a structure of the gas separation composite membrane which concerns on embodiment. It is the schematic which shows the other example of a structure of the gas separation composite membrane which concerns on embodiment. It is an external appearance perspective view showing the composition of the gas separation module concerning an embodiment. FIG. 2 is an exploded perspective view illustrating a configuration of a gas separation module according to the embodiment. It is a schematic diagram which shows the principle of the gas separation of the gas separation module which concerns on embodiment. It is a figure showing the constituent material of the gas separation composite membrane concerning an example and a comparative example. It is a figure which shows the structure and membrane characteristic of the gas separation composite membrane | membrane which concerns on an Example and a comparative example.

  In the following embodiments, a description will be given of a gas separation composite membrane having excellent separation characteristics and permeation characteristics of oxygen and nitrogen in air.

  Here, in the gas separation composite membrane, the separation characteristics of oxygen and nitrogen refer to characteristics capable of separating oxygen and nitrogen from air, and are characteristics indicated by a separation coefficient described in detail later. Further, in the gas separation composite membrane, the oxygen and nitrogen permeation characteristics refer to characteristics capable of permeating oxygen and nitrogen, and are characteristics indicated by oxygen and nitrogen permeation coefficients described later in detail.

  A gas separation composite membrane according to one embodiment of the present invention includes a first gas separation layer containing poly (4-methylpentene-1) and polyfumarate.

  According to this, since poly (4-methylpentene-1) allows oxygen to permeate more easily than nitrogen, it is possible to efficiently separate oxygen and nitrogen. Further, since the polyfumarate has a property that the separation layer is easily spread on the water surface, by utilizing this property, the separation layer can be easily formed by the water surface development method. In addition, since a separation layer having a uniform film quality can be produced when produced by the water surface spreading method, it is possible to provide a gas separation composite membrane excellent in both oxygen and nitrogen separation characteristics and permeation characteristics.

  Further, the first gas separation layer may further contain a siloxane compound.

  According to this, the material constituting the separation layer by the siloxane-based compound spreads on the water surface and is easily bonded, so that the separation layer can be easily transferred to the support layer. As the siloxane compound, a copolymer of polydimethylsiloxane and styrene or the like can be used.

  Further, the first gas separation layer may further include monosubstituted polydiphenylacetylene or disubstituted polydiphenylacetylene.

  According to this, mono-substituted polydiphenylacetylene or disubstituted polydiphenylacetylene can easily transmit oxygen as compared with nitrogen, so that the separation characteristics and the transmission characteristics of oxygen and nitrogen can be improved. The monosubstituted polydiphenylacetylene or disubstituted polydiphenylacetylene includes poly (1- (pt-butylphenyl) -2-phenylacetylene) and poly (1- (p-trimethylsilylphenyl) -2-phenylacetylene. ) Can be used.

  Further, the first gas separation layer is provided on a support layer made of a porous material, and a mono-substituted polyfumarate and a siloxane compound are provided between the support layer and the first gas separation layer. A second gas separation layer containing polydiphenylacetylene or disubstituted polydiphenylacetylene may be provided.

  According to this, since the separation layer easily adheres to the support layer, the separation layer can be suppressed from peeling off from the support layer.

  Further, a protective layer containing a polyfumarate and a siloxane-based compound may be provided on the first gas separation composite membrane.

  According to this, even if the siloxane compound moves from the separation layer to the support layer side when the gas permeates the separation layer, the siloxane compound is replenished from the protective layer to the separation layer. Thereby, deterioration of the separation layer can be suppressed. Further, since the protective layer is easily spread on the water surface by containing the polyfumarate, the protective layer can be easily formed by the water surface spreading method.

  Further, a gas separation module according to one embodiment of the present invention includes a gas separation composite membrane having the above-described characteristics.

  According to this, it is possible to provide a gas separation module including a separation layer having the above-described characteristics.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Each of the embodiments described below shows one specific example of the present invention. Numerical values, shapes, materials, constituent elements, arrangement positions of constituent elements, connection forms, and the like shown in the following embodiments are merely examples, and do not limit the present invention. In addition, among the components in the following embodiments, components not described in the independent claims indicating the highest concept are described as arbitrary components.

(Embodiment)
[1. Configuration of gas separation composite membrane]
First, the configuration of the gas separation composite membrane according to the present embodiment will be described. FIG. 1 is a schematic diagram illustrating an example of the configuration of the gas separation composite membrane.

  As shown in FIG. 1, the gas separation composite membrane 1 according to the present embodiment includes a support layer 10 and a separation layer 12.

  The support layer 10 is, for example, a substrate in which a nonwoven fabric is coated with a porous material. Note that the configuration of the support layer 10 is not limited to this configuration, and any other configuration may be used as long as gas can pass from one surface to the other surface.

  The separation layer 12 is made of, for example, a material containing at least poly (4-methylpentene-1) and polyfumarate. The separation layer 12 is formed on the support layer 10.

  In the gas separation composite membrane 1 of the present embodiment, air is supplied from the separation layer 12 side. A part of the supply air permeating to the support layer 10 side becomes a gas having a high oxygen concentration (oxygen-enriched gas), and the remaining air not permeating the gas separation composite membrane 1 is a gas having a high nitrogen concentration (nitrogen-enriched gas). Gas).

Here, the time during which a unit volume of oxygen permeates a unit area separation layer at a unit pressure difference is defined as an oxygen permeability coefficient PO ₂ [cc / sec · cmHg · cm ² ], and a unit volume of nitrogen is defined as a unit at a unit pressure difference. The time required to pass through the separation layer having the area is referred to as a nitrogen permeability coefficient PN ₂ [cc / sec · cmHg · cm ² ]. PO ₂ / PN _{2 is referred} to as a separation coefficient α. As the value of the oxygen permeability coefficient PO ₂ is large, the flow rate of oxygen passing through the separation layer 12 is made for many, it can be said that good a separation layer 12 of the transmission characteristic of the oxygen. In addition, it can be said that the larger the value of the separation coefficient α, the better the separation layer 12 that separates and concentrates oxygen and nitrogen and has excellent separation characteristics.

  Note that the separation layer 12 corresponds to the first gas separation layer in the present invention.

  Hereinafter, a method for producing the gas separation composite membrane 1 will be described.

  FIG. 2 is a diagram illustrating a method for manufacturing the gas separation composite membrane 1. The gas separation composite membrane 1 is formed on the support layer 10 by a water surface spreading method. The water surface spreading method is a method in which another film is brought into contact with a film-like substance that has been spread and floated on the water surface, and the film-like substance is transferred onto another film.

  As shown in FIG. 2, water 32 is put in a production container 30 used for the water surface spreading method, and rollers 34a, 34b and 34c are arranged at positions facing the water surface. The support layer 10 is wound in a roll shape around the roller 34a. The roller 34b is a roller for bringing the support layer 10 into contact with the separation layer 12 when transferring the separation layer 12 to the support layer 10. The roller 34c is a roller for winding the support layer 10 onto which the separation layer 12 has been transferred, that is, the gas separation composite membrane 1.

  In the water surface development method, first, a liquid material 12a in which a material constituting the separation layer 12 and an organic solvent are blended is prepared in a container 36. The liquid material 12a is supplied from the container 36 to the water 32 of the manufacturing container 30 through the pipe 38. The liquid material 12a supplied into the water 32 diffuses and floats on the surface of the water, and the organic solvent evaporates, forming the separation layer 12 in the form of a film. Here, the support layer 10 sent out from the roller 34a is brought into contact with the separation layer 12 floating on the surface of the water 32 at the position of the roller 34b. As a result, the separation layer 12 floating on the surface of the water 32 is transferred to the support layer 10, and the gas separation composite membrane 1 in which the separation layer 12 is stacked on the support layer 10 is completed. Then, the separation layer 12 is continuously transferred to the support layer 10 while the support layer 10 to which the separation layer 12 is transferred, that is, the gas separation composite membrane 1 is wound up by the roller 34c. Thereby, a large-area gas separation composite membrane 1 can be obtained.

  Then, the gas separation composite membrane 1 having a desired shape and size is obtained by cutting the large-area gas separation composite membrane 1 into a predetermined shape and size.

  The material forming the separation layer 12 is not limited to the above-mentioned poly (4-methylpentene-1) and polyfumarate, but may be, for example, poly (4-methylpentene-1) and polyfumarate. It may contain a siloxane compound.

  Further, the material forming the separation layer 12 is not limited to the above-mentioned poly (4-methylpentene-1) and polyfumarate, but may be, for example, poly (4-methylpentene-1) and polyfumarate. It may contain substituted polydiphenylacetylene or disubstituted polydiphenylacetylene. Further, the material forming the separation layer 12 may further include mono-substituted polydiphenylacetylene or di-substituted polydiphenylacetylene in addition to poly (4-methylpentene-1), fumaric acid ester, and siloxane compound. .

  The configuration of the gas separation composite membrane 1 is not limited to the configuration described above, and may be another configuration. For example, a configuration like the following gas separation composite membranes 2 to 4 may be used. 3 to 5 are schematic diagrams showing another example of the configuration of the gas separation composite membrane.

  The gas separation composite membrane 2 shown in FIG. 3 has the same configuration as the gas separation composite membrane 1 except that an undercoat layer 14 is provided between the support layer 10 and the separation layer 12. That is, the gas separation composite membrane 2 has a configuration in which the support layer 10, the undercoat layer 14, and the separation layer 12 are laminated in this order.

  The undercoat layer 14 is made of, for example, a material containing a polyfumaric acid ester, a siloxane-based compound, and monosubstituted polydiphenylacetylene or disubstituted polydiphenylacetylene. By providing the undercoat layer 14 between the support layer 10 and the separation layer 12, the separation layer 12 is easily adhered to the support layer 10, so that the separation layer 12 can be prevented from peeling off from the support layer 10. .

  Note that the undercoat layer 14 corresponds to the second gas separation layer in the present invention.

  Further, the gas separation composite membrane 3 shown in FIG. 4 has the same configuration as the gas separation composite membrane 1 except that a protective layer 16 is provided on the separation layer 12. The protective layer 16 is made of, for example, a material containing a polyfumarate and a siloxane-based compound. By providing the protective layer 16 on the separation layer 12 in the gas separation composite membrane 3, even if the siloxane compound moves from the separation layer 12 to the support layer 10, the siloxane compound is transferred from the protection layer 16 to the separation layer 12. Can be replenished, so that deterioration of the separation layer 12 can be suppressed.

  Further, the gas separation composite membrane 4 shown in FIG. 5 includes an undercoat layer 14 on the support layer 10 and a protective layer 16 on the separation layer 12. That is, the configuration is a combination of the configurations of the gas separation composite membranes 2 and 3 described above.

[2. Gas separation module]
Next, an example of a gas separation module using the above-described gas separation composite membrane 1 will be described.

  FIG. 6 is an external perspective view illustrating the configuration of the gas separation module according to the embodiment. FIG. 7 is an exploded perspective view showing the configuration of the gas separation module according to the embodiment.

  As shown in FIG. 6, the gas separation module 40 has a configuration in which a plurality of frames 42 each having the gas separation composite membrane 1 provided on both sides are stacked. Note that a support body 43 is disposed above and below the stacked frame bodies 42. A gap 44 is provided between the frame bodies 42, air flows in from one end of the gap 44, and nitrogen-enriched gas having a reduced oxygen concentration and an increased nitrogen concentration flows out from the other end. .

  Each frame 42 has a plurality of openings 45, as shown in FIG. The gas separation composite membrane 1 is provided on both surfaces of the frame 42 so as to cover the plurality of openings 45. Here, the gas separation membrane 1 is attached to the frame 42 with the support layer 10 side facing inward (the frame 42 side) and the separation layer 12 side facing out. The oxygen-enriched gas having an increased oxygen concentration permeated through the gas separation composite membrane 1 at the position of the opening 45 flows out of an outlet 46 provided in the frame 42. The size and position of the plurality of openings 45 may be any. Further, a plurality of openings 45 may be provided.

  FIG. 8 is a schematic diagram illustrating the principle of gas separation of the gas separation module 40. FIG. 8 schematically shows a cross section of the frame body 42 and the gas separation composite membrane along the line VIII-VIII shown in FIG.

  As shown in FIG. 8, when air flows in from one end of the gap 44 of the gas separation module 40, a part of the flowed air passes through the gas separation composite membrane 1, passes through the frame 42, and flows out of the frame 42. Outflow from 46. The air that has not passed through the gas separation composite membrane 1 flows out from the other end of the gap 44 of the gas separation module 40. At this time, the air that has passed through the gas separation composite membrane 1 has a high oxygen concentration, and the air that has not passed through the gas separation composite membrane 1 has a low oxygen concentration and therefore has a high nitrogen concentration. As described above, the air flowing into the gas separation module 40 is separated into an oxygen-enriched gas having a high oxygen concentration and a nitrogen-enriched gas having a high nitrogen concentration.

  The gas separation composite membrane used for the gas separation module 40 is not limited to the configuration of the gas separation composite membrane 1, but may be a configuration such as the gas separation composite membranes 2 to 4.

  Hereinafter, examples of the gas separation composite membrane will be described. In the examples described below, a gas separation composite membrane having the same configuration as the above-described gas separation composite membranes 2 and 4 was manufactured. FIG. 9 shows the materials constituting each layer used in each of the examples and the comparative examples, and the organic solvents used when preparing the liquid material containing them. The liquid material was adjusted with an organic solvent so that the components constituting each layer had the ratios shown in the figure. Each organic solvent used was mixed at the weight ratio shown in the figure.

  Next, a layered undercoat layer, a separation layer and a protective layer were prepared by diffusing and floating on the water surface and evaporating the organic solvent using the above-mentioned water surface spreading method. Then, according to the configuration of each gas separation composite membrane, by sequentially transferring onto a support layer made of a porous polyether sulfone material having a thickness of 180 μm, each layer is laminated on the support layer. Was prepared.

  Further, as a comparative example, a gas separation composite membrane was produced using a membrane not containing poly (4-methylpentene-1) as described in Patent Document 1. That is, in the gas separation composite membrane of this comparative example, after the four undercoat layers shown in FIG. 9 were laminated on the same support layer used in each example, the protective layer A shown in FIG. It has a layered configuration. In this configuration, the undercoat layer also serves as the separation layer.

FIG. 10 is a diagram illustrating membrane characteristics of the gas separation composite membrane according to each of the examples and the comparative example. As the membrane characteristics, the oxygen permeation coefficient PO ₂ , nitrogen permeation coefficient PN ₂ , separation coefficient α (= PO ₂ / PN ₂ ), oxygen concentration, and oxygen flow rate of each gas separation composite membrane were measured. The oxygen permeability coefficient PO ₂ and the nitrogen permeability coefficient PN ₂ are such that 5 cc of oxygen or nitrogen permeates a gas separation composite membrane having an area of 10.2 cm ² when the pressure difference between both sides of the gas separation composite membrane is 73.5 cmHg. It was calculated from the time [sec] required to perform the measurement. The oxygen concentration and the oxygen flow rate are as follows: when the pressure difference between both sides of the gas separation composite membrane is 61.2 kPa, the oxygen concentration [%] in the gas (oxygen-enriched gas) that has passed through the gas separation composite membrane having an area of 334 cm ² . And the flow rate [L / min] of the oxygen-enriched gas.

As shown in FIG. 10, in each of Examples 1 to 6, a higher separation coefficient α was obtained than in the comparative example. Therefore, it can be seen that the gas separation composite membranes according to Examples 1 to 6 have improved oxygen separation characteristics as compared with the gas separation composite membrane according to the comparative example. In any of Examples 1 to 6, a small oxygen permeability coefficient PO ₂ were obtained than in Comparative Example. Therefore, the gas separation composite membranes according to Examples 1 to 6 have a higher oxygen permeation amount and improved oxygen permeation characteristics than the gas separation composite membrane according to the comparative example. From the above, it can be said that the gas separation composite membranes according to Examples 1 to 6 have both excellent oxygen separation characteristics and oxygen permeation characteristics.

  As described above, the gas separation composite membrane according to the embodiment and the modification of the present invention has been described, but the present invention is not limited to this embodiment.

  For example, the gas separation composite membrane may have any configuration of the above-described gas separation composite membranes 1 to 4, and the gas separation composite membranes 1 to 4 may include a plurality of separation layers 12, undercoat layers 14, and protective layers 16. It is good also as composition provided with a layer.

  Also, the above-described method for manufacturing the gas separation composite membrane 1 is an example, and the method for manufacturing the gas separation composite membrane is not limited to the above-described water surface development method, and may be manufactured by another manufacturing method.

  Further, the configuration and combination of the above-described materials are merely examples, and the materials constituting the separation layer, the undercoat layer, and the protective layer of the gas separation composite membrane are not limited to the above-described materials, and may be other materials and combinations. .

  In addition, the numbers used above are all examples for specifically describing the present invention, and the present invention is not limited to the illustrated numbers.

  As described above, the gas separation composite membrane according to one or more aspects has been described based on the embodiments and the examples. However, the present invention is not limited to the embodiments and the examples. Unless departing from the spirit of the present invention, various modifications conceivable to those skilled in the art may be applied to the present embodiment and examples, and a form constructed by combining components in different embodiments and examples may be one. Or you may be included in the range of several aspects.

  INDUSTRIAL APPLICABILITY The present invention can be applied to a gas separation composite membrane used for an automobile, an air conditioner, a medical device, or the like having a combustion device.

1, 2, 3, 4 Gas separation composite membrane 10 Support layer 12 Separation layer (first gas separation layer)
12a Liquid material 14 Undercoat layer (second gas separation layer)
Reference Signs List 16 protection layer 30 manufacturing container 32 water 34a, 34b, 34c roller 36 container 38 tube 40 gas separation module 42 frame 43 support 44 gap 45 opening 46 outflow

Claims (5)

A first gas separation layer containing poly (4-methylpentene-1) and polyfumarate ,
The first gas separation layer is provided on a support layer made of a porous material,
A gas separation composite membrane comprising a second gas separation layer between the support layer and the first gas separation layer, the second gas separation layer containing a polyfumarate, a siloxane-based compound, and mono- or poly-substituted polydiphenylacetylene. . The composite gas separation membrane according to claim 1, wherein the first gas separation layer further contains a siloxane compound. The gas separation composite membrane according to claim 1, wherein the first gas separation layer further includes monosubstituted polydiphenylacetylene or disubstituted polydiphenylacetylene. The gas separation composite membrane according to any one of claims 1 to 3 , further comprising a protective layer including a polyfumarate ester and a siloxane-based compound on the first gas separation composite membrane. A gas separation module comprising the gas separation composite membrane according to any one of claims 1 to 4 .

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