WO2022138127A1

WO2022138127A1 - Fluid separation membrane module, fluid separation membrane plant, and purified fluid

Info

Publication number: WO2022138127A1
Application number: PCT/JP2021/044860
Authority: WO
Inventors: 柿山創; 田中慧; 三原崇晃
Original assignee: 東レ株式会社
Priority date: 2020-12-21
Filing date: 2021-12-07
Publication date: 2022-06-30
Also published as: JPWO2022138127A1

Abstract

The purpose of the present invention is to provide a fluid separation membrane module with which, when using a fluid separation membrane having a high tensile modulus, it is possible to suppress breaks or damage to the fluid separation membrane when a stack of fluid separation membranes are stored in a module. According to one embodiment of the present invention, in this fluid separation membrane module containing fluid separation membranes and spacers, the tensile modulus of the fluid separation membranes is 1 GPa or more, and at least some of the spacers are fibres or rods have a bulk compression percentage of 10% to 95% as measured by the JIS L 1013 (2010) B method.

Description

Fluid Separation Membrane Modules, Fluid Separation Membrane Plants, and Purified Fluids

The present invention relates to a fluid separation membrane module, a fluid separation membrane plant, and a purified fluid.

The membrane separation method is known as a method for selectively separating and purifying a specific gas component from a mixture containing a plurality of gas components. Since the membrane separation method utilizes the pressure difference, it has the advantage of consuming less energy than other separation / purification methods.

The gas separation membrane used in the membrane separation method is characterized in that the gas permeability of a specific gas component (permeated gas) is higher than that of other gas components (non-permeated gas). Polymer membranes and inorganic membranes are known as gas separation membranes, but inorganic membranes are preferably used in applications where heat resistance and chemical resistance are required.

The gas separation membrane is used as a gas separation membrane module filled in a partitioned space in order to increase the membrane area per unit volume. When the gas separation membrane is a hollow fiber membrane, as a hollow fiber membrane module containing a plurality of hollow fiber membranes, when the gas separation membrane is a flat membrane, a spiral in which a flat membrane-like gas separation membrane is wound around a central pipe. Used as a mold module. As a method for modularizing an inorganic film, a method for bundling and modularizing a plurality of hollow filamentous carbon films is known (for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2017-13004

Patent Document 1 describes, as a method for manufacturing a separation membrane module using a hollow filamentous carbon film having two or more partial regions having different carbon contents in the length direction, both ends of the hollow filamentous carbon film are bound with a curable resin. Further, a method of manufacturing a resin wall by fixing one end or both ends thereof to a housing is disclosed. However, since the hollow filamentous carbon film is hard and brittle, and the bundle of the hollow filamentous carbon film has poor contractility in the circumferential direction, in the method of Patent Document 1, when both ends of the hollow filamentous carbon film are bound with a curable resin. In addition, the end of the hollow filamentous carbon film may be caught in the curable resin mold, or the bundle of hollow filamentous carbon films stored in the curable resin mold may be stressed in the shrinkage direction, resulting in damage to the carbon film. there were. On the other hand, if the number of carbon films stored in the module is reduced in order to prevent damage to the carbon film, in addition to impairing the film area per unit volume, a sparse part of the carbon film is generated in the module to be separated. There was a risk of a short path of fluid.

In order to solve the above problems, the present invention has the following configurations. That is, the present invention is as follows.

A fluid separation membrane module including a fluid separation membrane and a spacer, wherein the fluid separation membrane has a tensile elastic modulus of 1 GPa or more, and at least a part of the spacer is a bulk measured by the JIS L 1013 (2010) B method. A fluid separation membrane module which is a fiber or rod having a high compressibility of 10% or more and 95% or less.

A fluid separation membrane module including a fluid separation membrane and a spacer, the tensile elasticity of the fluid separation membrane is 1 GPa or more, and at least a part of the spacer has a compressibility measured by JIS L 1096 (2010). A fluid separation membrane module which is a film, non-woven fabric, woven fabric, or knitted fabric of 10% or more and 95% or less.

A fluid separation membrane module including a fluid separation membrane and a spacer, wherein the fluid separation membrane has a tensile elastic modulus of 1 GPa or more, and at least a part of the spacer has a deformation strength measured by JIS Z 8844 (2019). Hereinafter, it may be described as "σ _10% "), which is a fluid separation membrane module in which particles are 0.1 kPa or more and 100 kPa or less.

In the fluid separation membrane module of the present invention, since the bundle L is imparted with contractility in the circumferential direction by the spacer, even if the tensile elastic modulus of the fluid separation membrane is 1 GPa or more, when the bundle L is housed in the module. Damage to the fluid separation membrane can be suppressed.

It is a schematic diagram which shows the cross section including the outflow port of the fluid to be separated of one aspect of the fluid separation membrane module of this invention. It is a schematic diagram which shows one aspect of the method of measuring the circumference when the measuring thread is wound around the bundle L of this invention. It is a schematic diagram which shows one aspect of the arrangement of the fluid separation membrane and a spacer of this invention. It is a schematic diagram which shows another aspect of the arrangement of the fluid separation membrane and a spacer of this invention. It is a schematic diagram which shows another aspect of the fluid separation membrane module of this invention.

The fluid separation membrane module of the present invention (hereinafter, may be simply referred to as "module") is a fluid separation membrane module including a fluid separation membrane and a spacer, and the tensile elastic modulus of the fluid separation membrane is 1 GPa or more. The spacer is characterized in that at least a part of the spacer is a fiber or a rod having a bulk high compressibility of 10% or more and 95% or less as measured by the JIS L 1013 (2010) B method.

The module of the present invention is a fluid separation membrane module including a fluid separation membrane and a spacer, and the tensile elastic modulus of the fluid separation membrane is 1 GPa or more, and at least a part of the spacer is JIS L 1096 (2010). It is characterized in that it is a film, a non-woven fabric, a woven fabric, or a knitted fabric having a compressibility of 10% or more and 95% or less as measured in 1.

The module of the present invention is a fluid separation membrane module including a fluid separation membrane and a spacer, and the tensile elastic modulus of the fluid separation membrane is 1 GPa or more, and at least a part of the spacer is JIS Z 8844 (2019). It is characterized in that the particles have a deformation strength measured in 1 (hereinafter, may be referred to as “σ _10% ”) of 0.1 kPa or more and 100 kPa or less.

In the module of the present invention, assuming that the bundle L is a bundle of all the fluid separation membranes and spacers in the fluid separation membrane module, the total fineness is in the direction orthogonal to the long axis of the fluid separation membrane on the outer circumference of the bundle L. It is preferable that the peripheral length when the false twisted polyethylene terephthalate yarn (hereinafter referred to as a measuring yarn) of 3000 dtex and 480 filament is wound once satisfies the following formula 1.

0.50 ≤ L ₂ / L ₁ ≤ 0.95 ・・・ Equation 1
[In the formula, L ₁ represents the circumference of the bundle L when the measurement thread is pulled with a force of 5 N / m with respect to the circumference of the bundle L, and L ₂ represents the circumference of the bundle L with the measurement thread. On the other hand, it represents the circumference of the bundle L when pulled with a force of 50 N / m. ]
Hereinafter, the present invention will be described with reference to the drawings with reference to the present invention. However, the present invention is not limited to this example.

FIG. 1 shows a schematic cross-sectional view of one aspect of the fluid separation membrane module of the present invention. FIG. 1 is a schematic cross-sectional view of a module containing a hollow thread-shaped fluid separation membrane, including an inflow port of the fluid to be separated.

The module of the present invention includes a fluid separation membrane and a spacer. That is, in the module of the present invention, the fluid separation membrane 1 and the spacer 3 are housed in the vessel 10 having the outflow port 8 of the fluid to be separated. The fluid separation membrane 1 of FIG. 1 has a hollow portion 2.

Further, in the module of the present invention, the fluid separation membrane is fixed at the potting site. Regarding this, the fluid separation membranes 1 bundled in parallel in FIG. 1 have both ends fixed to each other (potting) at the potting portion 7 and fixed to the vessel 10.

The fluid separation membrane 1 penetrates the potting portion 7 and is connected to an external flow path (a flow path for recovering the fluid that has passed through the fluid separation membrane), which is not shown, from the outlet 9 of the permeated fluid of the vessel 10. Will be done.

The module of the present invention is characterized in that the bundle L can be contracted in the circumferential direction even though the tensile elastic modulus of the fluid separation membrane is 1 GPa or more. As described above, in the conventional technique, a bundle of fluid separation membranes having a tensile elasticity of 1 GPa or more has poor contractility in the circumferential direction. There is a problem that the fluid separation membrane is damaged because the fluid separation membrane is caught on the edge of the element casing or stress is applied to the bundle of the fluid separation membrane in the contraction direction. The module of the present invention imparts contractility in the circumferential direction to the bundle L by accommodating a spacer having contractility together with the fluid separation film, and improves workability when storing the bundle L in the element casing. Damage to the fluid separation membrane due to stress concentration in the circumferential direction can be suppressed.

The state in which the bundle L has contractility in the circumferential direction means a state in which the outer diameter of the bundle L becomes smaller when an external force such as purging the bundle L is applied in the circumferential direction of the bundle L. The external force referred to here represents an external force within a range in which the fluid separation membrane is not damaged. Further, in one aspect of the present invention, it is preferable that a force that causes the outer diameter of the bundle L to return to its original value acts when the external force is removed. By doing so, the gap between the bundle L and the element casing or the like can be reduced, and the short path of the fluid to be separated can be suppressed.

In one embodiment of the present invention, at least a part of the spacer has a bulk high compression ratio (hereinafter, may be referred to as “B _c ”) measured by the JIS L 1013 (2010) B method of 10% or more and 95%. The following fibers or rods. When B _c is 10% or more, the bundle L can be contracted by applying an external force. B _c is preferably 20% or more, and more preferably 50% or more. On the other hand, when B _c is 95% or less, deformation of the fluid separation membrane in the vicinity of the spacer when the bundle L is contracted can be suppressed, so that damage to the membrane can be suppressed. B _c is preferably 90% or less, more preferably 80% or less.

The fiber or rod as a spacer preferably has a bulk high compressive elastic modulus (hereinafter, may be referred to as “ _Be ”) measured by the JIS L 1013 (2010) B method of 30% or more and 100% or less. .. When _Be is 30% or more, a force for restoring the outer diameter of the bundle L works when the external force for contracting the bundle L is removed. _Be is preferably 40% or more, and more preferably 50% or more. On the other hand, the upper _limit of Be is not particularly limited, but is preferably 100% or less.

In another aspect of the present invention, at least a part of the spacer is a film having a compressibility measured by JIS L 1096 (2010) (hereinafter, may be referred to as “ _Cr ”) of 10% or more and 95% or less. Non-woven fabrics, woven fabrics, and knitted fabrics. When _Cr is 10% or more, the bundle L can be contracted by applying an external force. The _Cr is preferably 20% or more, more preferably 50% or more. On the other hand, when _Cr is 95% or less, deformation of the fluid separation membrane in the vicinity of the spacer when the bundle L is contracted can be suppressed, so that damage to the membrane can be suppressed. _Cr is preferably 90% or less, more preferably 80% or less.

The film, non-woven fabric, woven fabric, and knitted fabric as spacers preferably have a compressive elastic modulus (hereinafter, may be referred to as “Ce”) measured by JIS L ₁₀₉₆ (2010) of 30% or more and 100% or less. .. When _Ce is 30% or more, a force for restoring the outer diameter of the bundle L works when the external force for contracting the bundle L is removed. _Ce is preferably 40% or more, more preferably 50% or more. On the other hand, the upper limit of _Ce is not particularly limited, but is preferably 100% or less.

As yet another aspect of the present invention, at least a part of the spacer has a deformation strength (hereinafter, may be referred to as “σ _10% ”) measured by JIS Z 8844 (2019) of 0.1 kPa or more and 100 kPa or less. It is a particle. When σ _10% is 0.1 kPa or more, the movement of the fluid separation membrane in the vicinity of the spacer when the bundle L is contracted can be suppressed, so that the damage to the membrane can be suppressed. σ _10% is preferably 1 kPa or more, and more preferably 5 kPa or more. On the other hand, when σ _10% is 100 kPa or less, the bundle L can be contracted by applying an external force. σ _10% is preferably 50 kPa or less, and more preferably 10 kPa or less.

The particles as spacers preferably have a fracture strength (hereinafter, may be referred to as “σ _F ”) measured by JIS Z 8844 (2019) of 2 times or more and 10000 times or less of σ _10% . When σ _F is more than twice σ _10% , a force for restoring the outer diameter of the bundle L works when the external force for contracting the bundle L is removed. σ _F is preferably 10 times or more of σ _10% , and more preferably 100 times or more. On the other hand, the upper limit of σ _F is not particularly limited, but is preferably 10000 times or less of σ _10% .

In the module of the present invention, assuming that the bundle L is a bundle of all the fluid separation membranes and spacers in the module, it is preferable that the circumference of the bundle L satisfies the above formula 1. Regarding this, the bundle L is a bundle of all the fluid separation membranes 1 and the spacer 3 in FIG. 1.

FIG. 2 shows a schematic diagram of one aspect of a method of measuring the circumference of the outer circumference of the bundle L when the measuring thread is wound once in a direction orthogonal to the long axis of the fluid separation membrane. As described above, the measurement yarn means a false-twisted polyethylene terephthalate yarn having a total fineness of 3000 dtex and 480 filaments.

The circumference of the bundle L of the present invention is measured using a measuring thread. That is, in the bundle L; 13 in FIG. 2, the measuring thread 14 is wound around the outer circumference of the bundle L in a direction orthogonal to the long axis of the fluid separation membrane. One end of the measuring thread 14 is fixed, and the weight 15 is fixed to the other end.

The circumference of the bundle L is the length of the portion around which the measuring thread is wound. That is, in the circumference 16 of the bundle L; 13 in FIG. 2, after the start point and the end point at which the measurement thread 14 goes around the bundle L; 13 are set to points A and B, the bundle L is removed and the measurement thread is straightened. It can be expressed by the distance between points A and B.

In the fluid separation membrane module of the present invention, the circumference of the bundle L when the measurement thread is pulled with a force of 5 N / m with respect to the circumference of the bundle L is L ₁ , and the measurement thread is with respect to the circumference of the bundle L. When the circumference of the bundle L when pulled with a force of 50 N / m is expressed as L ₂ , it is preferable that L ₂ / L ₁ is 0.50 or more and 0.95 or less. When L ₂ / L ₁ is 0.50 or more, the ratio of the fluid separation membrane contained in the bundle L increases, so that the membrane area per module unit volume can be increased. L ₂ / L ₁ is more preferably 0.60 or more, and further preferably 0.75 or more. On the other hand, when L ₂ / L ₁ is 0.95 or less, the bundle L is imparted with contractility in the circumferential direction, so that damage to the fluid separation membrane when the bundle L is housed in the module is suppressed. be able to. L ₂ / L ₁ is more preferably 0.90 or less, and even more preferably 0.85 or less.

As the above-mentioned measuring yarn, the length when a load of 5 N is applied in the fiber axis direction is L ₃ , and the length when a load of 50 N is applied in the fiber axis direction is L ₄ , and L ₄ / L. Use a measuring thread in which ₃ is 1.05 or less.

The mixed gas and mixed liquid to be separated by the module of the present invention are not particularly limited, but for example, a carbon dioxide separation / storage system from exhaust gas of a power plant, a blast furnace, etc., and a gas in a coal gasification combined power generation. Examples include removal of sulfur components from the converted fuel gas, purification of biogas and natural gas, and purification of hydrogen from organic hydride. That is, in the module of the present invention, the fluid separation membrane is preferably a gas separation membrane.

In the module of the present invention, the cross-sectional shape of the vessel is preferably elliptical or circular, and more preferably circular, from the viewpoint of improving the pressure resistance of the vessel. Here, the cross section of the vessel means the cross section of the vessel perpendicular to the length direction of the fluid separation membrane. Examples of the material of the vessel include metal, resin, fiber reinforced plastic (FRP), and the like, which can be appropriately selected depending on the environment of the installation location and the situation in which the vessel is used. In applications where pressure resistance and heat resistance are required, a metal having both strength and formability is preferable, and stainless steel or the like is more preferable.

The outflow port of the fluid to be separated, which is arranged in the vessel, has a function of guiding the fluid to be separated to the fluid separation membrane. When the fluid separation membrane is used in the total volume filtration method, it is sufficient to have one inflow port of the fluid to be separated, and when it is used in the cross flow filtration method, the outflow port of the fluid to be separated is combined. It is preferable to have two or more places. There may be a plurality of outflow ports of the fluid to be separated as long as the mechanical strength of the vessel is maintained. In this case, it is preferable to dispose a cloth such as mesh or felt between the outflow port and the fluid separation membrane within a range that does not obstruct the passage of the fluid, and it is effective in diffusing the fluid and protecting the fluid separation membrane.

In the module of the present invention, as a method of fixing the fluid separation membrane to the vessel, a method of directly fixing the fluid separation membrane to the inner surface of the vessel with a potting material, or a separation membrane element in which a plurality of fluid separation membranes are fixed by the potting material is used. Examples thereof include a method of fixing in the vessel via an adapter or the like (for example, an O-ring or the like) capable of ensuring liquidtightness or airtightness. Since only the separation membrane element can be replaced when the performance of the separation membrane element deteriorates over time, it is preferable to fix the separation membrane element in the vessel via an adapter or the like.

The potting portion of the module or the separation membrane element may be one place or a plurality of places, but is omitted from the viewpoint of sufficiently fixing the position of the fluid separation membrane and maintaining the effective surface area of the fluid separation membrane. It is preferable to fix the two ends of the plurality of fluid separation membranes bundled in a straight line with a potting material. Further, both ends of the fluid separation membrane may be fixed with a potting material at one place in a state where a plurality of bundled fluid separation membranes are bent into a U shape, or only one end of the fluid separation membrane is fixed with the potting material. The other end may be sealed by means other than the potting material.

Further, the separation membrane element of the present invention may have a casing (hereinafter referred to as "element casing") different from the vessel. The element casing preferably has an outflow port for the fluid to be separated. The shape of the element casing is not particularly limited as long as it does not interfere with the storage in the vessel. Examples of the material of the element casing include metal, resin, fiber reinforced plastic (FRP) and the like, which can be appropriately selected depending on the situation in which the element casing is used. Resin is preferable because it has high followability to the curing shrinkage of the potting material, and polyphenylene sulfide, polytetrafluoroethylene, polyethylene, polypropylene, polyether ether ketone, polyphenylene ether, and polyether because it has both moldability and chemical resistance. Idyl, polyamide-imide and polysulfone are more preferred.

The inner diameter of the element casing is preferably L ₂ / π or more and 1.5 L ₁ / π or less. When the inner diameter of the element casing is L ₂ / π or more, the fluid separation membrane in the bundle L is not subjected to an excessive force and the fluid separation membrane is less likely to be damaged. The inner diameter of the element casing is more preferably (L ₁ + L ₂₎ / 2π or more, and further preferably L ₁ / π or more. On the other hand, when the inner diameter of the element casing is 1.5 L ₁ / π or less, the film area per element unit volume can be increased. The inner diameter of the element casing is more preferably 1.2 L ₁ / π or less, and further preferably 1.1 L ₁ / π or less.

In the embodiment in which the bundle L is not housed in the element casing and the bundle L is directly fixed to the inner surface of the vessel with a potting material, the preferable inner diameter of the element casing is the preferred inner diameter of the vessel.

Further, the module of the present invention may have a central pipe or the like in the element casing. In this case, it can be regarded as a bundle L including the central pipe and the like.

Examples of the potting material include a thermoplastic resin and a thermosetting resin. Further, other additives may be contained.

Examples of the thermoplastic resin used as the potting material include polyethylene, polyether sulfone, polystyrene, polyphenylene sulfide, polyarylate, polyester, liquid crystal polyester, polyamide, polymethylmethacrylate and the like. Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, urethane resin, urea resin, phenol resin, melamine resin, silicone resin and the like. Two or more of these may be used. Among these, epoxy resin and urethane resin are preferable from the viewpoint of balance of moldability, curing time, adhesiveness, hardness and the like.

Examples of additives preferably used in potting materials include fillers, surfactants, silane coupling agents, rubber components and the like. Examples of the filler include silica, talc, zeolite, calcium hydroxide, calcium carbonate and the like, which have effects such as suppression of curing heat generation, strength improvement and thickening. Further, the surfactant and the silane coupling agent have the effects of improving the handleability when the potting material is mixed and improving the infiltration property between the carbon films for fluid separation when the potting material is injected. In addition, the rubber component has the effect of improving the toughness of the cured and molded potting material. The rubber component may be contained in the form of rubber particles.

The fluid separation membrane is a membrane in which the permeability of a specific component (permeable component) contained in the fluid to be separated is higher than that of other components (non-permeable component). The shape of the fluid separation membrane is not particularly limited and may be a flat membrane or a hollow fiber membrane. However, when the separation membrane module is used, the membrane area per module unit volume tends to be large, so that the fluid is fluid. The separation membrane is preferably a hollow fiber membrane. When the fluid separation membrane is a hollow fiber membrane, the inner diameter of the hollow fiber membrane is preferably 10 μm or more and 2,000 μm or less. By setting the inner diameter of the hollow fiber membrane to 10 μm or more, the permeability of the fluid can be improved. The inner diameter of the hollow fiber membrane is more preferably 20 μm or more, further preferably 50 μm or more. On the other hand, by setting the inner diameter of the hollow fiber membrane to 2,000 μm or less, the outer diameter of the hollow fiber membrane can be reduced, so that the membrane area of the fluid separation membrane per unit volume in the case of a fluid separation membrane module can be increased. Can be done. The inner diameter of the fluid separation membrane is more preferably 1,000 μm or less, further preferably 500 μm or less.

Examples of the fluid separation membrane include a zeolite membrane, a metal-organic framework (MOF) membrane, an inorganic membrane such as a carbon membrane, and a polymer membrane. When the fluid separation membrane module is used in a harsh environment such as high temperature or acid basicity, the fluid separation membrane is preferably an inorganic membrane having excellent heat resistance and chemical resistance, and may be a zeolite membrane or a carbon membrane. preferable. Above all, a carbon film is more preferable.

Zeolite membranes suitable as fluid separation membranes include aluminosilicates, for example, membranes made of NaX type (FAU), ZSM-5, MOR, silicalite, A type and the like. Two or more of these may be used. Zeolites are preferably those having a Si / Al ratio similar to that of the zeolite that is secondarily grown by a hydrothermal synthesis reaction.

Suitable MOF membranes as fluid separation membranes include, for example, Cu-BTC, MOF-5, IRMOF-3, MIL-47, MIL-53, MIL-96, MMOF, SIM-1, ZIF-7, ZIF-8. , ZIF-22, ZIF-69, ZIF-90 and the like. Two or more of these may be used.

Suitable carbon films for the fluid separation film include, for example, polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, total aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, and diallyl phthalate resin. , A film obtained by carbonizing a lignin resin, a urethane resin, or the like. Two or more of these may be used.

Suitable polymer films for the fluid separation film include, for example, aromatic polyimide, cellulose acetate, polysulfone, aromatic polyamide, polyetherimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyether ether ketone, polytetrafluoroethylene. , Polyfluoride vinylidene, poly (1-trimethylsilylpropin), polydimethylsiloxane, polyvinyltrimethylsilane, poly (4-methylpentene), ethylcellulose, natural rubber, poly (2,6-dimethyloxide phenylene), low density polyethylene, Examples thereof include a film made of high-density polyethylene, styrene, polyethylmethacrylate, polycarbonate, polyester, aliphatic polyamide, polymethylmethacrylate, polyvinyl alcohol, silicone and the like. Two or more of these may be used.

Nanoparticles and the like can be added to the fluid separation membrane in order to improve the permeability of the permeable component. Examples of nanoparticles include silica, titania, zeolite, metal oxide, MOF, carbon nanotube (CNT) and the like.

The fluid separation membrane of the present invention may include a support. When the fluid separation membrane of the present invention includes a support, it is more preferable that the support is arranged only on one surface of the fluid separation membrane.

Examples of the support include porous inorganic materials such as alumina, silica, cordierite, zirconia, titania, bicole glass, zeolite, magnesia, and sintered metal, polysulfone, polyethersulfone, polyamide, polyester, and cellulose-based polymers. A porous organic material containing at least one polymer selected from the group consisting of homopolymers such as vinyl polymers, polyphenylene sulfides, polyphenylene sulfide sulfones, polyphenylene sulfones, and polyphenylene oxides and copolymers, and porous organics made of carbonizable resins. Examples thereof include a porous carbon material obtained by carbonizing the material. Examples of the carbonizable resin include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, total aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, and urethane. Examples include resin. Two or more of these may be used.

Further, it is preferable that the fluid separation membrane of the present invention has a coating layer (hereinafter referred to as coating layer 1) on at least a part of the surface thereof. When the fluid separation membrane of the present invention has the coating layer 1, it is more preferable that the coating layer 1 is arranged only on one surface of the fluid separation membrane.

The coating layer 1 is a layer that covers at least a part of the surface of the fluid separation membrane. Can be coated to improve separation selectivity.

Examples of the coating layer 1 include a layer containing at least one compound selected from the group consisting of polyolefin, fluororesin, polystyrene, silicone, microporous polymer (PIM), phenol resin, and urethane resin. Since it is easy to coat the surface of the fluid separation membrane, it is more preferable to contain at least one compound selected from the group consisting of silicone and PIM.

The abundance ratio of the above compound contained in the coating layer 1 is preferably 20 wt% or more and 100 wt% or less with respect to the total weight of the coating layer 1 of 100 wt%. When the abundance ratio of the compound contained in the coating layer 1 is 20 wt% or more, the physical characteristics of the compound are easily reflected in the physical properties of the coating layer 1. The abundance ratio of the compound contained in the coating layer 1 is more preferably 50 wt% or more, further preferably 80 wt% or more.

Examples of the polyolefin suitable as the compound in the coating layer 1 include polyethylene, polypropylene, polymethylpentene and the like.

Examples of the fluororesin suitable as the compound in the coating layer 1 include tetrafluoroethylene and the like.

Examples of the silicone suitable as the compound in the coating layer 1 include polydimethylsiloxane.

The phenol resin suitable as the compound in the coating layer 1 is a resin obtained by reacting phenols with aldehydes, and for example, a water-soluble phenol resin solution in which phenols and aldehydes are polycondensed and a water-soluble phenol resin solution. It is a phenolic resin formed by an opposite diffusion reaction with a hardening gas.

The above-mentioned water-soluble phenol resin solution contains, for example, a phenol resin obtained by reacting phenols including phenol, cresol, resorcinol, bisphenol A, and other substituted phenols with an aldehyde compound or the like under an alkaline catalyst. Etc. are included.

Examples of the curing gas for the water-soluble phenolic resin solution include acidic gases such as carbon dioxide, hydrogen sulfide, sulfur oxides, nitrogen oxides, inorganic acids (hydrogen chloride and the like), organic acids (carboxylic acids and the like), and the like. Examples thereof include a gas that produces an acid by reacting with a water-soluble phenol resin solution such as an ester (organic ester, inorganic ester, etc.). A plurality of curing gases may be mixed and used, or a mixed gas with an inert gas may be used.

Since it is highly safe, it is preferable to use carbon dioxide or methyl formate as the curing gas of the water-soluble phenol resin solution, and it is more preferable to use carbon dioxide.

The urethane resin suitable as the compound in the coating layer 1 is a resin obtained by a double addition reaction of a polyol compound and a polyisocyanate compound. For example, a double addition reaction with a mixed solution of a phenol resin which is a polyol compound and a polyisocyanate compound. It is a urethane resin formed by an opposite diffusion reaction with an amine gas that acts as a catalyst for the above.

Examples of the above-mentioned phenol resin include phenol resins obtained by reacting phenols including phenol, cresol, resorcinol, bisphenol A, and other substituted phenols with aldehyde compounds and the like under an alkaline catalyst. Will be.

The polyisocyanate compound is an organic compound having two or more isocyanates in one molecule, and includes aliphatic and aromatic polyisocyanate compounds, and modified products thereof. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexanediisocyanate and the like, and examples of the aromatic polyisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate and the like. Examples of these modified products include carbodiimide modified products and prepolymer modified products.

Examples of the amine gas used for forming the urethane resin include triethylamine, dimethylethylamine, dimethylisopropylamine and the like.

The thickness of the coating layer 1 is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less. When the thickness of the coating layer 1 is 0.1 μm or more, the portion of the surface of the fluid separation film to be coated can be reliably coated. The thickness of the coating layer 1 is more preferably 1 μm or more, further preferably 2 μm or more. On the other hand, when the thickness of the coating layer 1 is 100 μm or less, the filling rate of the fluid separation membrane in the fluid separation membrane module and the permeability of the fluid to be separated can be maintained. The thickness of the coating layer 1 is more preferably 50 μm or less, further preferably 20 μm or less.

The thickness of the coating layer 1 can be measured, for example, by observing the cross section of the fluid separation membrane having the coating layer 1 with a transmission electron microscope (SEM) or the like. The cross section of the fluid separation membrane having the coating layer 1 is formed by embedding the fluid separation membrane having the coating layer 1 in a resin or the like that can be distinguished from the coating layer 1 at the time of observation, and cutting in a direction perpendicular to the depth direction of the coating layer 1. Obtained by doing.

When the fluid separation membrane is a hollow fiber, the tensile elastic modulus of the fluid separation membrane is preferably 1.5 GPa or more. By setting the tensile elastic modulus of the fluid separation membrane to 1.5 GPa or more, deformation of the fluid separation membrane is further suppressed, so that hollow crushing of the fluid separation membrane during module fabrication or operation can be suppressed. The tensile elastic modulus of the fluid separation membrane is more preferably 2.0 GPa or more, further preferably 3.0 GPa or more. On the other hand, the upper limit of the tensile elastic modulus of the fluid separation membrane is not particularly limited, but is preferably 500 GPa or less, and when it is 500 GPa or less, damage during transportation or module operation can be suppressed. The tensile elastic modulus is more preferably 300 GPa or less, and further preferably 100 GPa or less.

The tensile elastic modulus of the fluid separation membrane can be measured by a tensile test.

In the module of the present invention, when the fluid separation membrane has a support or a coating layer 1, the tensile elastic modulus of the fluid separation membrane having the support or the coating layer 1 is regarded as the tensile elastic modulus of the fluid separation membrane.

In the module of the present invention, the fluid separation membrane preferably has a bending radius of 100 cm or less. When the bending radius of the fluid separation membrane is 100 cm or less, it is possible to suppress the breakage of the fluid separation membrane during the production or operation of the module. The bending radius is more preferably 10 cm or less, further preferably 5 cm or less. On the other hand, the lower limit of the bending radius of the fluid separation membrane is not particularly limited, but 0.1 cm or more is preferable, and 0.1 cm or more improves the morphological stability when the fluid separation membrane is handled as a bundle. Module manufacturing efficiency is improved. The bending radius is more preferably 0.2 cm or more, and further preferably 0.5 cm or more.

The bending radius of the fluid separation film is obtained from the radius of the cylinder in which the fluid separation film is sampled from the module by 10 cm or more and the sampled fluid separation film is wound 360 ° or more along the normal direction of the cylinder so that the fluid separation film does not break. be able to. When the bending radius of the fluid separation film is 1.5 cm or more, the angle at which the sampled fluid separation film is wound along the normal direction of the cylinder is appropriately reduced for evaluation, and the radius of the cylinder at which the fluid separation film does not break is determined. , Can be regarded as the bending radius of the fluid separation film.

In the module of the present invention, when the fluid separation membrane has a support or a coating layer 1, the bending radius of the fluid separation membrane having the support or the coating layer 1 is regarded as the bending radius of the fluid separation membrane.

The water permeability of the fluid separation membrane of the present invention is preferably 0 μL / hr / m ² / Pa or more and 100 μL / hr / m ² / Pa or less. A fluid separation membrane having a water permeability of 100 μL / hr / m ² / Pa or less can be suitably used as a gas separation membrane because the pore diameter of the separation functional layer is small. The water permeability of the fluid separation membrane is more preferably 10 μL / hr / m ² / Pa or less, further preferably 1 μL / hr / m ² / Pa or less.

The permeability of the fluid separation membrane can be calculated by the following formula 3 from the amount of permeated water recovered from the outflow port of the permeation fluid of the module when pure water is supplied from the outflow port of the fluid to be separated of the module. can.

Water permeability (μL / hr / m ² / Pa) = Q _w / (P × T × A) ・・・ Equation 3
[In Equation 3, Qw represents the amount of permeated water (μL), P represents the pressure of the feed water (Pa), T represents the water permeation time (hr), and A represents the fluid separation membrane having the coating layer 1. Represents the film area (m ² ). ]
In the module of the present invention, when the fluid separation membrane has a support or a coating layer 1, the water permeability of the fluid separation membrane having the support or the coating layer 1 is regarded as the water permeability of the fluid separation membrane.

The spacer is arranged in the module together with the fluid separation membrane, and has the effect of imparting contractility in the circumferential direction to the bundle L, which is a bundle of all the fluid separation membranes and the spacer in the module. The arrangement of the fluid separation membrane and the spacer in the bundle L is not particularly limited, and the fluid separation membrane may be arranged around the spacer, or the spacer may be arranged around the bundle of the fluid separation membrane, and the fluid may be arranged. Spacers may be arranged between the separation membranes. The arrangement may be a combination of these. It is more preferable that at least a part of the spacer is arranged between the fluid separation membranes because the passage of the fluid to be separated becomes uniform.

The spacer is not particularly limited, but is preferably selected from the group consisting of films, non-woven fabrics, woven fabrics, knitted fabrics, fibers, rods, and particles. Two or more of these may be combined. Since it is easy to place between the fluid separation membranes, the spacer when the fluid separation membrane is a flat membrane is preferably a film, a non-woven fabric, a woven fabric, or a knitted fabric, and when the fluid separation membrane is a hollow fiber membrane, the spacer is It is preferably a fiber and a rod.

Examples of the spacer include polyester, nylon, polyolefin, fluororesin, polyacetal, thermoplastic elastomer, metal oxide and the like. Two or more of these may be used.

When the spacer is a fiber, the spacer may be a monofilament or a multifilament, but a multifilament is preferable because it is flexible and has excellent handleability. Further, it is more preferable to use false twisted yarn as the spacer because it is bulky and it is easy to secure the distance between the fluid separation membranes. As the false twisted yarn suitable as a spacer, polyester yarn and nylon yarn are preferable because false twisting is easy.

Further, since the spacer can be uniformly arranged around the fluid separation membrane when the fluid separation membrane is a hollow fiber, the present invention also has an embodiment in which the spacer spirally covers the circumference of one or more fluid separation membranes. Is one of the preferred embodiments of.

3 and 4 show a schematic diagram of one aspect in which a spacer spirally covers the periphery of one or more fluid separation membranes. FIG. 3 is a schematic view of one embodiment in which one spacer 3 is spirally covered with one fluid separation membrane 1 at intervals of pitch 12, and FIG. 4 is a schematic view of two fluid separation membranes. It is a schematic diagram of one aspect in which two spacers 3 are spirally covered with an interval of pitch 12 with respect to 1.

The coating around the fluid separation membrane by the spacer may be a single covering in which the spacer is wound once or a double covering in which the spacer is doublely wound around the fluid separation membrane.

Further, multi-stage covering in which the second spacer is further spirally wound with respect to a plurality of fluid separation membranes in which the first spacer is spirally wound is also one of the preferred embodiments of the present invention. Hereinafter, the first spacer and one or more fluid separation membranes wound by the first spacer are collectively referred to as a bundle S, and the second spacer and one or more bundles S wound by the second spacer are collectively referred to as a bundle M. A plurality of fluid separation membranes, a bundle S, and a bundle M may be collectively formed as a bundle L.

As one preferred embodiment of the present invention, it is preferable that the occupied volume of the second spacer in the bundle M is smaller than the occupied volume of the first spacer in the bundle M. Since the occupied volume of the second spacer in the bundle M is smaller than the occupied volume of the first spacer in the bundle M, it is easy to secure the distance between the fluid separation membranes. Therefore, when the viscosity of the fluid to be separated is high. It can be suitably used even when the fluid to be separated has a large amount of agglomerating components. The ratio of the occupied volume of the first spacer to the bundle M to the occupied volume of the second spacer in the bundle M (that is, "the occupied volume of the first spacer in the bundle M" / "the second occupied volume in the bundle M". The occupied volume of the spacer is more preferably 1.2 or more, and further preferably 1.5 or more. On the other hand, the upper limit of the ratio of the occupied volume of the first spacer to the occupied volume of the bundle M to the occupied volume of the second spacer in the bundle M is not particularly limited, but is preferably 100 or less, and the module volume is preferably 100 or less. The membrane area of the fluid separation membrane can be secured. The ratio of the occupied volume of the first spacer to the occupied volume of the bundle M to the occupied volume of the second spacer in the bundle M is more preferably 50 or less, and further preferably 10 or less.

As another preferred embodiment of the present invention, it is preferable that the occupied volume of the second spacer in the bundle M is larger than the occupied volume of the first spacer in the bundle M. Since the occupied volume of the second spacer in the bundle M is larger than the occupied volume of the first spacer in the bundle M, the fluid separation membranes in the bundle M are close to each other, so that the tensile load of the bundle M is improved. And the handleability is improved. The ratio of the occupied volume of the second spacer to the bundle M to the occupied volume of the first spacer in the bundle M (that is, "the occupied volume of the second spacer in the bundle M" / "the first occupied in the bundle M". The occupied volume of the spacer is more preferably 1.2 or more, and further preferably 1.5 or more. On the other hand, the upper limit of the ratio of the occupied volume of the second spacer to the occupied volume of the bundle M to the occupied volume of the first spacer in the bundle M is not particularly limited, but is preferably 100 or less, and the module volume is preferably 100 or less. The membrane area of the fluid separation membrane can be secured. The ratio of the occupied volume of the second spacer to the occupied volume of the bundle M to the occupied volume of the first spacer in the bundle M is more preferably 50 or less, and further preferably 10 or less.

The occupied volume of the spacer is adjusted so that the first spacer or the second spacer collected from the bundle M of a certain length is stored in a cylindrical container and the weight is 0.15 g / cm ² with respect to the cross-sectional area of the cylinder. The height L ₀ of the spacer after placing the circular plate on the spacer and leaving it for 1 minute can be measured and calculated from the following formula 4.

Occupied volume of spacer = cross section of cylinder x L ₀ ... Equation 4
By evaluating the area of the boronoy region of the fluid separation film in the cross section perpendicular to the longitudinal direction of the module, the dispersibility of the fluid separation film in the module can be evaluated. Here, the area of the Voronoi region is the area of the region partitioned by the Voronoi division. Voronoi division is a method of dividing a plane surrounded by generatrix, which has a plurality of generatrix, by a perpendicular bisector between adjacent generatrix and an intermediate line between the generatrix and the generatrix adjacent to each other. That is, the higher the dispersibility of the fluid separation membrane in the module, the more uniform the area of the Voronoi region of the fluid separation membrane.

As one aspect of the present invention, it is preferable that the area of the Voronoi region of the fluid separation film in the cross section perpendicular to the longitudinal direction of the module satisfies the following formula 2. When S _{0 ≦ r <50} / S _{50 <r ≦ 100} is larger than 0.5, the number of fluid separation membranes housed in the outer edge of the module having a large volume increases, so that the membrane area per module unit volume is increased. be able to. S _{0 ≦ r <50} / S _{50 <r ≦ 100} is more preferably 1 or more, and further preferably 1.5 or more. On the other hand, when S _{0 ≦ r <50} / S _{50 <r ≦ 100} is smaller than 10, the gap between the bundle L and the element casing and the like can be reduced, and the short path of the fluid to be separated can be suppressed. S _{0 ≦ r <50} / S _{50 <r ≦ 100} is more preferably 5 or less, and further preferably 2 or less.

0.5 <S _{0 ≤ r <50} / S _{50 <r ≤ 100} <10 ... Equation 2
[In the equation, S _{0≤r <50} is the area of the boronoy region of the fluid separation membrane in the region where the distance from the center of the fluid separation membrane storage region is 0% or more and less than 50% of the radius of the fluid separation membrane storage region. Representing an average value, S _{50 <r ≦ 100} is the area of the boronoy region of the fluid separation membrane in the region where the distance from the center of the fluid separation membrane storage region is more than 50% and 100% or less of the radius of the fluid separation membrane storage region. Represents the average value. ]
The cross section perpendicular to the longitudinal direction of the module is perpendicular to the longitudinal direction of the fluid separation membrane of the module after injecting thermosetting resin from the outflow port of the fluid to be separated of the module to fix the position of the fluid separation membrane in the module. Obtained by cutting on a surface. The area of the Voronoi region of the fluid separation membrane can be obtained by image analysis of the above cross section. More specifically, by performing Voronoi division with the center of gravity of each fluid separation membrane in the above cross-sectional image as the generatrix and the boundary line of the fluid separation membrane storage region as the generatrix, the area of the Voronoi region can be determined for each fluid separation membrane. Can be calculated. Examples of the boundary line of the fluid separation membrane storage region include the inner surface of the element casing or vessel, and the outer surface of the central pipe or the like. S _{0 ≦ r <50} is the boronoy region in the fluid separation membrane in which the boronoy region is included in the region where the distance from the center of the fluid separation membrane storage region is 0% or more and less than 50% of the radius of the fluid separation membrane storage region. Representing the average value of the area, S _{50 <r ≦ 100} is a fluid in which the boronoy region is included in a region where the distance from the center of the fluid separation membrane storage region is more than 50% and 100% or less of the radius of the fluid separation membrane storage region. Represents the average value of the area of the boronoy region in the separation fluid. For the fluid separation membrane in which the boronoy region overlaps on the circumference where the distance from the center of the fluid separation membrane storage region is 50% of the radius of the fluid separation membrane storage region, S _{0 ≦ r <50} and S _{50 <r.} Not included in any of _{≦ 100} .

As one aspect of the present invention, a coating layer (hereinafter referred to as coating layer 2) may be provided on the surface of the spacer. The presence of the coating layer 2 on at least a part of the surface of the spacer can control the friction between the fluid separation membrane and the coating layer 2, reduce the friction and prevent damage to the fluid separation membrane due to stress concentration. Friction can be increased to fix the position of the spacer. In particular, in an embodiment in which at least a part of the spacer is arranged between the membranes of the fluid separation membrane, it is possible to uniformly pass the fluid to be separated by suppressing the displacement of the spacer during the production or operation of the separation membrane module. can. In addition, damage to the surface of the fluid separation membrane due to friction between the fluid separation membrane and the spacer can be further suppressed. The above-mentioned coating layer 1 may be provided on at least a part of the surface of the fluid separation membrane.

The coating layer 2 may have the same composition as the coating layer 1 or may have a different composition. Further, the coating layer 1 and the coating layer 2 may have a clear boundary or may be integrated.

As one aspect of the present invention, the fluid separation membrane is fixed at the potting portion, and a coating layer (hereinafter referred to as coating layer 3) may be provided on the surface of the potting portion on the inner side of the fluid separation membrane module.

As one aspect of the present invention, the coating layer 3 is preferably an elastomer. Since the coating layer 3 is an elastomer, the vibration of the fluid separation membrane in the vicinity of the potting portion during the production or operation of the module is reduced, and damage to the fluid separation membrane can be suppressed.

Examples of the elastomer suitable for the coating layer 3 include a thermosetting elastomer and a thermoplastic elastomer, which are appropriately selected according to the operating conditions of the module. Examples of the thermosetting elastomer include vulcanized rubber, urethane rubber, silicone rubber, and fluororubber. Examples of the thermoplastic elastomer include polystyrene-based elastomers, olefin-based elastomers, polyvinyl chloride-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and acrylic-based elastomers.

The coating layer 3 may have the same composition as the coating layer 1 and the coating layer 2, or may have a different composition. Further, the coating layer 3, the coating layer 1 and the coating layer 2 may have a clear boundary or may be integrated. From the viewpoint of workability at the time of manufacturing the fluid separation membrane module, it is preferable that the coating layer 1, the coating layer 2, and the coating layer 3 have the same composition.

The thickness of the coating layer 3 is preferably 10 μm or more and 50,000 μm or less. When the thickness of the coating layer 3 is 10 μm or more, it is possible to reduce the vibration of the fluid separation membrane in the vicinity of the potting portion during operation of the fluid separation membrane module. The thickness of the coating layer 3 is more preferably 100 μm or more, further preferably 1000 μm or more. On the other hand, when the thickness of the coating layer 3 is 50,000 μm or less, the surface area of the fluid separation membrane can be sufficiently secured. The thickness of the coating layer 3 is more preferably 20000 μm or less, further preferably 10,000 μm or less.

The thickness of the coating layer 3 can be measured, for example, by observing the cross section of the potting portion having the coating layer 3 with a transmission electron microscope (SEM) or the like. The cross section of the potting portion having the coating layer 3 is formed by embedding the potting portion having the coating layer 3 with a resin or the like that can be distinguished from the coating layer 3 at the time of observation, and cutting in a direction perpendicular to the depth direction of the coating layer 3. Obtained at.

In the fluid separation membrane module of the present invention, the composition of the coating layer can be analyzed by elemental analysis of the coating layer or the like.

FIG. 5 shows a schematic cross-sectional view of another aspect of the fluid separation membrane module of the present invention. FIG. 5 is a schematic cross-sectional view of a module containing a hollow thread-shaped fluid separation membrane and having coating layers 1 to 3 including an inflow port of the fluid to be separated.

The module of the present invention preferably has a coating layer 1 on at least a part of the surface of the fluid separation membrane. That is, the fluid separation membrane 1 of FIG. 5 has a hollow portion 2 and a coating layer 1; 4 on the surface.

The module of the present invention preferably has a coating layer 2 on the surface of the spacer. That is, the spacer 3 in FIG. 5 has a coating layer 2; 5 on its surface.

In the module of the present invention, the fluid separation membrane is fixed at the potting portion, and it is preferable that the coating layer 3 is provided on the surface of the potting portion on the inner side of the fluid separation membrane module. Regarding this, the fluid separation membranes 1 bundled in parallel in FIG. 5 have both ends fixed to each other (potting) at the potting portion 7 and fixed to the vessel 10. The potting site 7 has a coating layer 3; 6 on the inner surface of the fluid separation membrane module.

The fluid separation membrane plant of the present invention (hereinafter, may be simply referred to as "plant") is a plant including the fluid separation membrane module of the present invention. The plant preferably includes pretreatment equipment, purified fluid recovery equipment, by-product fluid recovery equipment, etc. in addition to the module. The pretreatment equipment is equipment for removing impurities from the separation target fluid before separation and adjusting the composition of the separation target fluid before separation. The purified fluid recovery facility is a facility for recovering a purified fluid from which unnecessary components have been removed from the fluid to be separated before separation, and further purifying or supplying the purified fluid to a pipeline or the like as necessary. The by-product fluid recovery facility is a facility that recovers the by-product fluid removed from the separation target fluid before separation and discharges it after detoxification as an example. In the plant of the present invention, the module and the pretreatment equipment, the purified fluid recovery equipment, the by-product fluid recovery equipment are connected by pipes, etc., and the fluid to be separated before separation is continuously separated into the purified fluid and the by-product fluid. Is preferable.

The plant preferably includes a plurality of modules according to the processing amount of the fluid to be separated. The plurality of modules may be connected in series to the fluid to be separated, or may be connected in parallel. From the viewpoint of module manufacturing efficiency, the modules are preferably connected in series, and from the viewpoint of being able to partially replace the modules, the modules are preferably connected in parallel. A preferred embodiment of the plant of the present invention is an embodiment in which modules are connected in series and modules connected in series are further connected in parallel. By doing so, it is possible to achieve both the merits of connecting modules in series and the merits of connecting modules in parallel.

The mixed gas and mixed liquid to be separated by the plant of the present invention are not particularly limited, but for example, a carbon dioxide separation / storage system from exhaust gas of a power plant, a blast furnace, etc., and a gas in a coal gasification combined power generation. Examples include removal of sulfur components from the converted fuel gas, purification of biogas and natural gas, and purification of hydrogen from organic hydride. That is, in the plant of the present invention, the fluid separation membrane is preferably a gas separation membrane.

The purified fluid of the present invention is a fluid purified by the fluid separation membrane module of the present invention. The purified fluid may be purified by including another purification step or an additional step before and after the purification step in the module of the present invention, or may be mixed with a purification fluid purified by a different purification step. Other purification steps and different purification steps include, for example, distillation, adsorption, absorption and the like. Further, as an additional step, for example, component adjustment to be mixed with another fluid can be mentioned.

Since the purification fluid of the present invention consumes a small amount of energy required for purification in the module, it can be suitably used in various industrial applications as a purification fluid having a low environmental load.

Next, regarding the method for manufacturing a module of the present invention, a spacer is spirally wound around a fluid separation membrane to form a bundle S, and a bundle L composed of a plurality of bundles S is inserted into an element casing or a vessel, and a potting material is used. The case of fixing will be described as an example.

One fluid separation membrane is used as the core thread, and the spacer is spirally wound to form a bundle S. Examples of the device for spirally winding the spacer include a covering twisting machine and a double covering twisting machine.

A plurality of the obtained bundles S are bundled into a bundle L, inserted into the element casing or vessel, and then one end or both ends of the covering carbon film are potted with a potting material. As a method of storing the bundle L in the element casing or vessel, a contraction force in the circumferential direction is applied to the end of the bundle L to reduce the outer diameter of the end of the bundle L, and then the bundle L is stored in the element casing or vessel. preferable. Further, as a potting method, for example, a centrifugal potting method in which centrifugal force is used to permeate between fluid separation membranes, and a static potting material in which a fluidized potting material is sent by a metering pump or a head and permeated into a carbon film for fluid separation is allowed to stand. Examples include the potting method.

It is preferable to cut the potted fluid separation membrane at the potting site to open the fluid separation membrane. It is preferable to attach a cap as a pipe joint member to the cut surface of the fluid separation membrane module so that it can be connected to an external flow path (a flow path for collecting the fluid that has passed through the fluid separation membrane, etc.).

The mixed fluid to be separated by the module of the present invention is not particularly limited, but for example, a carbon dioxide separation / storage system from exhaust gas of a power plant, a blast furnace, etc., and a gasified fuel in a coal gasification combined power generation. Examples include removal of sulfur components from gas, purification of biogas and natural gas, and purification of hydrogen from organic hydride.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation in each Example and Comparative Example was performed by the following method.

(Tension elastic modulus of fluid separation membrane)
A 100 mm fluid separation membrane was sampled from the module, and the cross-sectional area was calculated by observing the cross-section SEM.

Subsequently, both ends of the sampled fluid separation membrane were reinforced with an adhesive by 1 cm, and the reinforced portion was fixed to the chuck of a tensile tester (TENSILON (registered trademark) / RTM-100, manufactured by Toyo Baldwin Co., Ltd.), and the sample length was obtained. The tensile elastic modulus (GPa) was measured under the conditions of 80 mm and a tensile speed of 10 mm / min. The measurement was performed 10 times each, and the average value indicated by two significant figures was taken as the tensile elastic modulus of the fluid separation membrane.

(Spacer bulk high compressibility and bulk high compressibility elastic modulus)
Spacers were sampled from the fluid separation membrane modules of Examples 1 to 6 and Comparative Example 2, and the bulk high compressibility and the bulk high compressibility were measured according to the JIS L 1013 (2010) B method.

(Compressibility of spacer and compressibility)
Spacers were sampled from the fluid separation membrane modules of Example 7 and Comparative Example 3, and the compressibility and compressibility were measured according to JIS L 1096 (2010).

(Deformation strength and fracture strength of spacer)
Spacers were sampled from the fluid separation membrane modules of Example 8 and Comparative Example 4, and the deformation strength and fracture strength were measured according to JIS Z 8844 (2019).

(Shrinkability of bundle L in the circumferential direction (L ₂ / L ₁ ))
The measurement thread was wound around the outer circumference of the bundle L in a direction orthogonal to the major axis of the fluid separation membrane, and the circumference of the bundle L when the pulling force of the measurement thread was changed was measured. The circumferential contractility (L ₂ / L ₁ ) of the bundle L is the measurement thread with respect to the circumference L ₁ of the bundle L when the measurement thread is pulled with a force of 5 N / m with respect to the circumference length of the bundle L. Was calculated by the circumference L ₂ of the bundle L when pulled with a force of 50 N / m with respect to the circumference of the bundle L.

(Storability of bundle L in element casing)
An attempt was made to store the bundle L in the element casing in a state where stress in the circumferential direction was applied to the end portion. The trial was performed 5 times each, and when the fluid separation membrane was not caught on the edge of the element casing even once, it was evaluated as "good", and when it was caught even once, it was evaluated as "bad".

(Damage to the fluid separation membrane during module fabrication)
The produced module was visually observed, and if the fluid separation membrane was found to be broken through the acrylic pipe, which is the vessel, it was judged to be damaged. If no breakage is observed visually, the outflow port of the fluid to be separated of the module is sealed except at one place, and the entire module is supplied with compressed air of 0.2 MPaG from the outflow port of the unsealed fluid to be separated. Was immersed in water. When air bubbles were generated from the opening of the fluid separation membrane, it was judged as “presence”, and when no air bubbles were generated, it was judged as “no damage”.

(Dispersibility of the fluid separation membrane in the cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ))
For the manufactured module, thermosetting resin is injected from the outflow port of the fluid to be separated of the acrylic pipe to fix the position of the fluid separation film in the module, and then the vicinity of the center of the longitudinal direction of the module is in the longitudinal direction of the fluid separation film. A cross-sectional image was obtained by cutting on a vertical plane. Voronoi division was performed with the center of gravity of each fluid separation film in the obtained cross-sectional image as a generatrix and the inner surface of the acrylic pipe as a generatrix, and the area of the Voronoi region was calculated for each fluid separation film.

The average value of the area of the boronoy region and the distance from the center of the acrylic pipe in the fluid separation membrane in which the boronoy region is included in the region where the distance from the center of the acrylic pipe is 0% or more and less than 50% of the radius of the acrylic pipe Obtain the average value of the area of the boronoy region in the fluid separation membrane in which the boronoy region is included in the region of more than 50% and 100% or less of the radius of the acrylic pipe, and calculate S _{0 ≦ r <50} / S _{50 <r ≦ 100} . did.

(Ratio of the occupied volume of the first spacer to the bundle M to the occupied volume of the second spacer to the bundle M) ("Occupied volume of the first spacer to the bundle M" / "The second spacer to occupy the bundle M" Occupied volume ")
The bundle M was sampled from the fluid separation membrane modules of Examples 4 and 5, and the first spacer and the second spacer were sampled from the bundle M, respectively. The sampled first spacer or second spacer was placed in a cylindrical container, and a circular plate whose weight was adjusted to 0.15 g / cm ² with respect to the cross-sectional area of the cylinder was placed on the spacer and left for 1 minute. The height L ₀ of the latter spacer was measured, the occupied volumes of the first spacer and the second spacer were calculated from the following formula 4, and the ratio between the two was calculated.

Occupied volume of spacer = cross section of cylinder x L ₀ ... Equation 4
(Water permeability of fluid separation membrane)
Pure water of 0.1 MPaG was supplied from the outflow port of the fluid to be separated of the prepared fluid separation membrane module, and the pure water that had passed through the fluid separation membrane was recovered from the outlet of the permeated fluid for 10 minutes. From the amount of pure water recovered, the water permeability of the fluid separation membrane was calculated by the following formula 3.

Water permeability (μL / hr / m ² / Pa) = Q _w / (P × T × A) ・・・ Equation 3
[In Equation 3, Q _w represents the amount of permeated water (μL), P represents the pressure of the feed water (Pa), T represents the water permeation time (hr), and A represents the membrane area (m) of the fluid separation membrane. ² ) is represented. ]
In addition, the permeability of the fluid separation membrane was not evaluated for the module in which the breakage of the fluid separation membrane during module fabrication was "Yes".

(Bending radius of fluid separation membrane)
A fluid separation membrane of 10 cm or more was cut out from the produced fluid separation membrane module, and the radius of the cylinder in which the fluid separation membrane did not break when the cut out fluid separation membrane was wound at 360 ° or more along the normal direction of the cylinder was obtained. Five or more fluid separation films were cut out, and the average value of the radii of the obtained cylinders represented by one significant digit was taken as the bending radius of the fluid separation film having the coating layer 1.

In Example 4, the bending radius of the fluid separation membrane having the coating layer 1 was obtained by the same measurement. In addition, the bending radius of the fluid separation membrane was not evaluated for the module in which the damage of the fluid separation membrane during module fabrication was "presence".

(Thickness of coating layer 3)
Epoxy resin was injected from the outflow port of the fluid to be separated of the fluid separation membrane module of Example 6 and cured. Subsequently, the fluid separation membrane module was cut in a direction perpendicular to the depth direction of the coating layer 3, and the vicinity of the potting site was observed with a microscope SEM (VHX-7000 manufactured by KEYENCE CORPORATION) (magnification: 1000 times). The thickness of the coating layer 3 was measured at five or more points, and the average value indicated by one significant digit was taken as the thickness of the coating layer 3 of the fluid separation membrane module.

(Manufacturing Example 1)
10 parts by weight of polyacrylonitrile (PAN) (MW 150,000) manufactured by Polyscience, 10 parts by weight of polyvinylpyrrolidone (PVP) (MW 40,000) manufactured by Sigma Aldrich, and 80 parts by weight of dimethyl sulfoxide (DMSO) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Was mixed and stirred at 100 ° C. to prepare a spinning stock solution.

After cooling the obtained undiluted spinning solution to 25 ° C., using a concentric triple mouthpiece, DMSO 80% by weight aqueous solution from the inner tube, the spinning undiluted solution from the middle tube, and DMSO 90% by weight aqueous solution from the outer tube, respectively. After discharging at the same time, the yarn was led to a coagulation bath made of pure water at 25 ° C. and wound on a roller to obtain a raw yarn. The obtained raw yarn was washed with water and then dried at 25 ° C. for 24 hours using a circulation dryer to prepare a precursor of a hollow yarn-like porous carbon film.

The precursor of the obtained porous carbon film was passed through an electric furnace at 250 ° C. and heated in an air atmosphere for 1 hour to perform infusibilization treatment to obtain infusible yarn. Subsequently, the infusible yarn was carbonized at a carbonization temperature of 650 ° C. to obtain a fluid separation membrane of Production Example 1, which is a carbon film for fluid separation having an outer diameter of 300 μm and an inner diameter of 100 μm.

(Example 1)
A 170 dtex polyester false twisted yarn, which is a spacer, was spirally wound around a core yarn of one fluid separation membrane of Production Example 1 at a pitch of 1 cm.

100 fluid separation films of Production Example 1 around which polyester false twisted yarn is wound are bundled, stored in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and both ends of the acrylic pipe are used with epoxy resin. Was statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 1 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation membrane was 3.2 GPa, the bulk high compressibility of the spacer was 47.1%, the bulk high compressibility was 77.9%, and the bundle L was in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.86, storage of bundle L in element casing is "good", no damage to fluid separation membrane during module fabrication, dispersibility of fluid separation membrane in cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) was 1.0, the water permeability of the fluid separation membrane was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 2)
A 170 dtex polyester false twisted yarn, which is a spacer, is spirally wound around one fluid separation membrane of Production Example 1 at a pitch of 1 cm, and a 170 dtex polyester false twisted yarn, which is a spacer, is spirally wound at a pitch of 1 cm. Wrapped in a spiral.

100 fluid separation films of Production Example 1 in which polyester false twisted yarn is double-wound are bundled, stored in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and acrylic using an epoxy resin. Both ends of the pipe were statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 2 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation membrane was 3.2 GPa, the bulk high compressibility of the spacer was 47.1%, the bulk high compressibility was 77.9%, and the bundle L was in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.68, storage of bundle L in element casing is "good", no damage to fluid separation membrane during module fabrication, dispersibility of fluid separation membrane in cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) was 0.98, the water permeability of the fluid separation membrane was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 3)
A 170 dtex polyester false twisted yarn, which is a spacer, is spirally wound around one fluid separation membrane of Production Example 1 at a pitch of 1 cm, and a 170 dtex polyester false twisted yarn, which is a spacer, is spirally wound at a pitch of 1 cm. Wrapped in a spiral.

Acrylic pipe with 25 fluid separation films of Production Example 1 in which Polyestes false twisted yarn is double-wound, 75 fluid separation films of Production Example 1 bundled around it, and an outflow port of the fluid to be separated. It was housed in (inner diameter 5 mm), and both ends of the acrylic pipe were statically potted using epoxy resin. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 3 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation membrane was 3.2 GPa, the bulk high compressibility of the spacer was 47.1%, the bulk high compressibility was 77.9%, and the bundle L was in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.85, storage of bundle L in element casing is "good", no damage to fluid separation membrane during module fabrication, dispersibility of fluid separation membrane in cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) was 2.0, the water permeability of the fluid separation membrane was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 4)
One fluid separation membrane of Production Example 1 is used as a core yarn, and four fluid separation membranes in which 170 dtex polyester false twisted yarn, which is the first spacer, is spirally wound at a pitch of 1 cm are bundled, and further, a second fluid separation membrane is bundled. A 170 dtex polyester false twisted yarn, which is a spacer, was spirally wound at a pitch of 1 cm.

Twenty-five fluid separation films (corresponding to 100 fluid separation films) of Production Example 1 in which polyestes false twisted yarn is wound in multiple stages are bundled and stored in an acrylic pipe (inner diameter 5 mm) having an outflow port for the fluid to be separated. Then, using an epoxy resin, both ends of the acrylic pipe were statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 4 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation film was 3.2 GPa, the bulk high compressibility of the spacer was 47.1%, the bulk high compressibility was 77.9%, and the bundle L was in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.77, storage of bundle L in element casing is "good", no damage to fluid separation film during module fabrication, dispersibility of fluid separation film in cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) is 1.0, and the ratio of the occupied volume of the first spacer to the occupied volume of the bundle M to the occupied volume of the second spacer in the bundle M is 1.6. The water permeability of the fluid separation film was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 5)
One fluid separation membrane of Production Example 1 is used as a core yarn, and four fluid separation membranes in which 170 dtex polyester false twisted yarn, which is the first spacer, is spirally wound at a pitch of 5 cm are bundled, and further, a second fluid separation membrane is bundled. A 170 dtex polyester false twisted yarn, which is a spacer, was spirally wound at a pitch of 0.5 cm.

Twenty-five fluid separation films (corresponding to 100 fluid separation films) of Production Example 1 in which polyestes false twisted yarn is wound in multiple stages are bundled and stored in an acrylic pipe (inner diameter 5 mm) having an outflow port for the fluid to be separated. Then, using an epoxy resin, both ends of the acrylic pipe were statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 5 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation film was 3.2 GPa, the bulk high compressibility of the spacer was 47.1%, the bulk high compressibility was 77.9%, and the bundle L was in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.77, storage of bundle L in element casing is "good", no damage to fluid separation film during module fabrication, dispersibility of fluid separation film in cross section (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) is 1.0, and the ratio of the occupied volume of the first spacer to the occupied volume of the bundle M to the occupied volume of the second spacer in the bundle M is 0.2. The water permeability of the fluid separation film was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 6)
A 170 dtex polyester false twisted yarn, which is a spacer, was spirally wound around a core yarn of one fluid separation membrane of Production Example 1 at a pitch of 1 cm.

100 fluid separation films of Production Example 1 around which polyester false twisted yarn is wound are bundled, stored in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and both ends of the acrylic pipe are used with epoxy resin. Was statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane.

Subsequently, a 10 wt% hexane solution (hereinafter referred to as PDMS solution) of polydimethylsiloxane (Silgard manufactured by Toray DuPont) was injected from the outflow port of the fluid to be separated. After the surface of the fluid separation membrane is sufficiently immersed in the PDMS solution, the Silkard solution is discharged from the outflow port of the fluid to be separated, and after drying, it is heated in an oven at 70 ° C. for 30 minutes to form coating layers 1 to 3. The fluid separation membrane module of Example 6 was obtained.

The fluid separation membrane module of Example 6 has a coating layer 1, a coating layer 2 and a coating layer 3 made of PDMS which is silicone.

As a result of evaluation by the above method, the tensile elasticity of the fluid separation membrane is 3.6 GPa, the bulk high compressibility of the spacer is 47.1%, the bulk high compressive elasticity is 77.9%, and the bundle L is in the circumferential direction. Shrinkage (L ₂ / L ₁ ) is 0.91, the storage of bundle L in the element casing is "good", the fluid separation membrane is not damaged during module fabrication, and the dispersibility of the fluid separation membrane in the cross section is "no". (S _{0 ≦ r <50} / S _{50 <r ≦ 100} ) is 0.95, the water permeability of the fluid separation membrane is 1 μL / hr / m ² / Pa or less, the bending radius of the fluid separation membrane is 10 cm or less, and the coating layer 3 The thickness of was 100 μm.

(Example 7)
A 56 dtex polyester false twisted yarn was flat knitted with a weft knitting machine to produce a flat knitted fabric as a spacer having 70 wales per 2.54 cm and 70 courses per 2.54 cm.

Subsequently, 100 fluid separation membranes of Production Example 1 were arranged on the flat knitted fabric, and a sheet was prepared in which each fluid separation membrane and the flat knitted fabric were bonded at both ends of the fluid separation membrane. The sheet is wound in a weeping shape to prepare a bundle L composed of a flat knitted fabric as a spacer and the fluid separation film of Production Example 1, stored in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and an epoxy resin. Both ends of the acrylic pipe were statically potted one by one using. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 7 was obtained.

As a result of evaluation by the above-mentioned method, the tensile elasticity of the fluid separation membrane was 3.2 GPa, the compressibility of the spacer was 52.3%, the compressibility was 81.2%, and the contractility of the bundle L in the circumferential direction (L). ₂ / L ₁ ) is 0.57, the storage capacity of the bundle L in the element casing is "good", the damage of the fluid separation membrane during module fabrication is "no", and the dispersibility of the fluid separation membrane in the cross section (S _{0 ≦} ) _{r <50} / S _{50 <r ≦ 100} ) was 0.88, the water permeability of the fluid separation membrane was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Example 8)
Micropearl SP (manufactured by Sekisui Chemical Co., Ltd.), which is a particle, was immersed in a polyethylene glycol solution, drained, and then sprinkled on the surface of the fluid separation membrane of Production Example 1. Subsequently, 100 fluid separation films of Production Example 1 sprinkled with the spacer Micropearl SP were bundled, stored in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and using an epoxy resin. Both ends of the acrylic pipe were statically potted one by one. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the fluid separation membrane module of Example 8 was obtained.

As a result of evaluation by the above method, the tensile elasticity of the fluid separation film is 3.2 GPa, the deformation strength of the spacer is 80 kPa, the breaking strength is 100 MPa, and the contractility of the bundle L in the circumferential direction (L ₂ / L ₁ ) is 0. .91, the storage capacity of the bundle L in the element casing is "good", the damage of the fluid separation film during module fabrication is "no", and the dispersibility of the fluid separation film in the cross section (S _{0 ≦ r <50} / S _{50 < r ≦ 100} ) was 0.79, the water permeability of the fluid separation film was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

(Comparative Example 1)
100 fluid separation films of Production Example 1 were bundled and housed in an acrylic pipe (inner diameter 5 mm) having an outflow port of the fluid to be separated, and both ends of the acrylic pipe were statically potted using epoxy resin. After the epoxy resin was cured, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane.

As a result of evaluation by the above-mentioned method, the tensile elasticity of the fluid separation film was 3.2 GPa, the circumferential contractility of the bundle L (L ₂ / L ₁ ) was 0.99, and the storage capacity of the bundle L in the element casing was achieved. Is "defective", the damage of the fluid separation film during module fabrication is "yes", the dispersibility of the fluid separation film in the cross section (S _{0 ≤ r <50} / S _{50 <r ≤ 100} ) is 0.31, and the bending radius is 0.31. It was 10 cm or less.

(Comparative Example 2)
A fluid separation membrane module of Comparative Example 2 was obtained in the same manner as in Example 1 except that a stainless wire having a wire diameter of 0.3 mm was used as a spacer instead of the 170 dtex polyester false twisted yarn.

As a result of evaluation by the above-mentioned method, the tensile elasticity of the fluid separation film is 3.2 GPa, the bulk high compressibility of the spacer is 0%, the bulk high compressibility is 0%, and the contractility of the bundle L in the circumferential direction (L). ₂ / L ₁ ) is 0.98, the storage capacity of the bundle L in the element casing is "poor", the damage of the fluid separation membrane during module fabrication is "yes", and the dispersibility of the fluid separation membrane in the cross section (S _{0 ≦} ) _{r <50} / S _{50 <r ≦ 100} ) was 0.42, and the bending radius was 10 cm or less.

(Comparative Example 3)
A fluid separation membrane module of Comparative Example 3 was obtained in the same manner as in Example 5 except that a stainless mesh having an opening of 100 μm was used instead of a flat knit using 56 dtex polyester false twisted yarn.

As a result of evaluation by the above-mentioned method, the tensile elastic modulus of the fluid separation film was 3.2 GPa, the compressibility of the spacer was 5%, the compressible elastic modulus was 50%, and the contractility of the bundle L in the circumferential direction (L ₂ / L ₁ ). ) Is 0.98, the storage of the bundle L in the element casing is "poor", the damage of the fluid separation film at the time of module fabrication is "yes", and the dispersibility of the fluid separation film in the cross section (S _{0≤r <50} /). S _{50 <r ≦ 100} ) was 0.88, and the bending radius was 10 cm or less.

(Comparative Example 4)
The fluid separation membrane modules of Example 6 and Comparative Example 4 were obtained except that stainless particles were used instead of Micropearl SP.

As a result of evaluation by the above method, the tensile elasticity of the fluid separation film is 3.2 GPa, the deformation strength of the spacer is 1 GPa or more, the breaking strength is 1 GPa or more, and the contractility of the bundle L in the circumferential direction (L ₂ / L ₁ ). Is 0.97, the storage capacity of the bundle L in the element casing is "poor", the damage of the fluid separation membrane during module fabrication is "presence", and the dispersibility of the fluid separation membrane in the cross section (S _{0 ≦ r <50} / S). _{50 <r ≦ 100} ) was 0.95, the water permeability of the fluid separation film was 1 μL / hr / m ² / Pa or less, and the bending radius was 10 cm or less.

1: Fluid separation membrane 2: Hollow part 3: Spacer 4: Coating layer 1
5: Coating layer 2
6: Coating layer 3
7: Potting site 8: Outlet of the fluid to be separated 9: Outlet of the permeated fluid 10: Vessel 11: Thickness of the coating layer 3 12: Pitch 13: Bundle L
14: Measuring thread 15: Weight 16: Perimeter of bundle L A: Start point or end point where measurement thread goes around bundle L: End point or start point where measurement thread goes around bundle L

Claims

A fluid separation membrane module that includes a fluid separation membrane and spacers.
The tensile elastic modulus of the fluid separation membrane is 1 GPa or more, and the tensile elastic modulus is 1 GPa or more.
A fluid separation membrane module in which at least a part of the spacer is a fiber or rod having a bulk high compressibility of 10% or more and 95% or less as measured by the JIS L 1013 (2010) B method.
The fluid separation membrane module according to claim 1, wherein the fiber or rod has a bulk high compressive elastic modulus of 30% or more and 100% or less as measured by the JIS L 1013 (2010) B method.
A fluid separation membrane module that includes a fluid separation membrane and spacers.
The tensile elastic modulus of the fluid separation membrane is 1 GPa or more, and the tensile elastic modulus is 1 GPa or more.
At least a part of the spacer is a fluid separation membrane module which is a film, a non-woven fabric, a woven fabric, or a knitted fabric having a compressibility of 10% or more and 95% or less as measured by JIS L 1096 (2010).
The fluid separation membrane module according to claim 3, wherein the film, the non-woven fabric, the woven fabric, and the knitted fabric have a compressive elastic modulus of 30% or more and 100% or less as measured by JIS L 1096 (2010).
A fluid separation membrane module that includes a fluid separation membrane and spacers.
The tensile elastic modulus of the fluid separation membrane is 1 GPa or more, and the tensile elastic modulus is 1 GPa or more.
At least a part of the spacer is a fluid separation membrane module having a deformation strength (hereinafter, may be referred to as “σ 10% ”) measured by JIS Z 8844 (2019) of 0.1 kPa or more and 100 kPa or less. ..
The particle according to claim 5, wherein the fracture strength (hereinafter, may be referred to as "σ F ") measured by JIS Z 8844 (2019) is 2 times or more and 10000 times or less of the σ 10% . Fluid separation membrane module.
Assuming that the bundle L is a bundle of all the fluid separation membranes and spacers in the fluid separation membrane module, a temporary fineness of 3000 dtex and 480 filaments is provided in the direction orthogonal to the long axis of the fluid separation membrane on the outer circumference of the bundle L. The fluid separation membrane module according to any one of claims 1 to 6, wherein the circumference of the twisted polyethylene terephthalate yarn (hereinafter referred to as measurement yarn) when wound around the twisted polyethylene terephthalate yarn satisfies the following formula 1.
0.50 ≤ L 2 / L 1 ≤ 0.95 ・・・ Equation 1
[In the formula, L 1 represents the circumference of the bundle L when the measurement thread is pulled with a force of 5 N / m with respect to the circumference of the bundle L, and L 2 represents the circumference of the bundle L with the measurement thread. On the other hand, it represents the circumference of the bundle L when pulled with a force of 50 N / m. ]
The fluid separation membrane module according to any one of claims 1 to 7, wherein the fluid separation membrane is a carbon membrane.
The fluid separation membrane module according to any one of claims 1 to 2 or 7 to 8, wherein the spacer is a false twisted yarn.
The fluid separation membrane module according to any one of claims 1 to 2 or 7 to 8, wherein the spacer spirally covers the periphery of one or more of the fluid separation membranes.
At least a part of the spacer is arranged between the membranes of the fluid separation membrane.
The fluid separation membrane module according to any one of claims 1 to 10, wherein the coating layer 1 is provided on at least a part of the surface of the fluid separation membrane.
11. The fluid separation according to claim 11, wherein the coating layer 1 contains at least one compound selected from the group consisting of polyolefins, fluororesins, polystyrenes, silicones, microporous polymers (PIMs), phenolic resins, and urethane resins. Membrane module.
The fluid separation membrane module according to any one of claims 1 to 12, which has a coating layer 2 on the surface of the spacer.
The fluid separation membrane is fixed at the potting site,
The fluid separation membrane module according to any one of claims 1 to 13, which has a coating layer 3 on the surface of the potting portion on the inner side of the fluid separation membrane module.
The fluid separation membrane module according to claim 14, wherein the coating layer 3 has a thickness of 10 μm or more and 50,000 μm or less.
When the first spacer and one or more fluid separation membranes wound by the first spacer are combined to form a bundle S, the first spacer spirally covers the circumference of the one or more fluid separation membranes.
When the second spacer and one or more bundles S wound by the second spacer are combined to form a bundle M, the second spacer spirally covers the circumference of one or more bundles S.
The fluid separation membrane module according to any one of claims 1 to 15, wherein the occupied volume of the second spacer in the bundle M is larger than the occupied volume of the first spacer in the bundle M.
When the first spacer and one or more fluid separation membranes wound by the first spacer are combined to form a bundle S, the first spacer spirally covers the circumference of the one or more fluid separation membranes.
When the second spacer and one or more bundles S wound by the second spacer are combined to form a bundle M, the second spacer spirally covers the circumference of one or more bundles S.
The fluid separation membrane module according to any one of claims 1 to 15, wherein the volume occupied by the second spacer in the bundle M is smaller than the volume occupied by the first spacer in the bundle M.
The fluid separation membrane module according to any one of claims 1 to 17, wherein the area of the boronoy region of the fluid separation membrane in the cross section perpendicular to the longitudinal direction of the fluid separation membrane module satisfies the following formula 2.
0.5 <S 0 ≤ r <50 / S 50 <r ≤ 100 <10 ... Equation 2
[In the equation, S 0≤r <50 is the area of the boronoy region of the fluid separation membrane in the region where the distance from the center of the fluid separation membrane storage region is 0% or more and less than 50% of the radius of the fluid separation membrane storage region. Representing an average value, S 50 <r ≦ 100 is the area of the boronoy region of the fluid separation membrane in the region where the distance from the center of the fluid separation membrane storage region is more than 50% and 100% or less of the radius of the fluid separation membrane storage region. Represents the average value of. ]
The fluid separation membrane module according to any one of claims 1 to 18, wherein the water permeability of the fluid separation membrane is 0 μL / hr / m 2 / Pa or more and 100 μL / hr / m 2 / Pa or less.
The fluid separation membrane module according to any one of claims 1 to 19, wherein the bending radius of the fluid separation membrane is 0.1 cm or more and 100 cm or less.
A fluid separation membrane plant comprising the fluid separation membrane module according to any one of claims 1 to 20.
Purified fluid purified by the fluid separation membrane module according to any one of claims 1 to 20.