JP5825032B2 - Gas separation membrane module - Google Patents

Description

  The present invention relates to a gas separation membrane module that performs gas separation using a hollow fiber membrane, and in particular, even when a tube plate material that is relatively easy to cure and shrink is used, the sealing performance around the tube plate is sufficient. It is related with the gas separation membrane module etc. which are ensured by this and can be used favorably by high temperature by extension.

  Conventionally, as a separation membrane module for performing gas separation (for example, oxygen separation, nitrogen separation, hydrogen separation, water vapor separation, carbon dioxide separation, organic vapor separation, etc.) using a separation membrane having selective permeability, plates and frames are used. Types, tubular types, hollow fiber types, and the like. Among them, the hollow fiber type gas separation membrane module not only has the advantage that the membrane area per unit volume is the largest, but also is excellent in terms of pressure resistance and self-supporting properties, so it is industrially advantageous. It is widely used.

  A hollow fiber type gas separation membrane module generally includes a hollow fiber element having a hollow fiber bundle composed of a number of hollow fiber membranes having selective permeability, and a hollow casing for accommodating the hollow fiber element. One end or both ends of the hollow fiber bundle are fixed by a cured resin plate (tube plate).

  In general, the gas separation membrane has a higher gas permeation rate as the supplied gas is at higher temperature and pressure. Therefore, when a gas separation membrane module is used, it may be considered that the raw material gas is compressed by a compressor or the like before being supplied to the module. In some cases, the compressed gas may be about 149 ° C to 260 ° C.

  By the way, in the case of a module that separates a high-temperature mixed gas as described above, it is necessary to use a tube sheet material having heat resistance. Generally, such a tube sheet material is cured and contracted when cured. As a result, there is a problem that the sealing performance around the tube sheet may be insufficient. The present invention has been made in view of this point, and its purpose is to ensure a sufficient sealing performance around the tube sheet even when using a tube sheet material that is relatively easy to cure and shrink. An object of the present invention is to provide a separation membrane module that can be used satisfactorily even at high temperatures.

A gas separation membrane module according to one aspect of the present invention is:
A hollow fiber bundle in which a large number of hollow fiber membranes having gas separation performance are focused,
A casing in which the hollow fiber bundle is disposed;
A tube plate for fixing at least one end of the hollow fiber bundle,
A gas separation membrane module configured such that the outer peripheral surface of the tube sheet does not adhere to the inner peripheral surface of the casing,
Furthermore, a seal member is provided for sealing between the outer peripheral surface of the tube sheet and the inner peripheral surface of the casing.

Moreover, the manufacturing method of the gas separation membrane module of one form of the present invention includes:
A hollow fiber bundle in which a large number of hollow fiber membranes having gas separation performance are converged, a casing in which the hollow fiber bundle is disposed, and a tube plate that fixes at least one end of the hollow fiber bundle. A method for producing a gas separation membrane module comprising:
Applying a release agent to at least a portion of the inner peripheral surface of the casing that is in contact with the tube sheet;
Filling a portion of the casing with a thermosetting resin;
Forming the tube sheet by curing the thermosetting resin;
Providing a seal member between the outer peripheral surface of the tube sheet and the inner peripheral surface of the casing after the thermosetting resin is cured;
including.

In addition, the definition of the term in this specification is as follows.
“High temperature condition” or “high temperature” is intended to be within a range of 80 ° C. to 300 ° C., for example.
The “cylindrical container” is not limited to one opened at both ends, but includes one opened only at one end.

  According to the present invention, even when a tube sheet material that is relatively easy to cure and shrink is used, the sealing performance around the tube sheet is sufficiently secured, so that it can be used well even at high temperatures. A gas separation membrane module and the like are provided.

It is sectional drawing which shows typically the basic composition of the gas separation membrane module of one Embodiment of this invention. FIG. 2 is a partially enlarged view of FIG. 1. It is sectional drawing in AA of FIG.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In addition, in FIG. 2, the shape of the casing (detailed below) is shown more specifically as an example. Moreover, the structure demonstrated below shows an example of this invention to the last, and is not intending that the gas separation membrane module of this invention is limited to these structures.

  A gas separation membrane module (hereinafter also simply referred to as a module) 1001 shown in FIGS. 1 and 2 includes a hollow fiber bundle 1015 in which a number of hollow fiber membranes 1014 are converged, a casing 1010 that accommodates the hollow fiber bundle 1015, and a hollow fiber bundle 1015. Tube plates 1021 and 1022 provided at both ends of each. As an example, the module 1001 is of a so-called bore feed type, and a mixed gas (raw material gas) is supplied inside the hollow fiber membrane 1014.

  A conventionally known hollow fiber membrane 1014 can be used, and any material can be used as long as it has gas separation performance. As an example, polymer materials, particularly those made of glassy polymer materials at room temperature (23 ° C.) such as polyimide, polysulfone, polyetherimide, polyphenylene oxide, polycarbonate, etc. are preferable because of good gas separation performance. .

  The hollow fiber bundle 1015 is obtained by converging about 100 to 1,000,000 hollow fiber membranes 1014, for example. Although there is no restriction | limiting in particular in the shape of the bundled hollow fiber bundle 1015, A cylindrical shape is preferable as an example from a viewpoint of the ease of manufacture and the pressure resistance of a casing. Although FIG. 1 illustrates a form in which the hollow fiber membranes 1014 are arranged substantially in parallel, a form in which the hollow fiber membranes are cross-arranged may be used.

  The mixed gas separated by the hollow fiber membrane 1014 is not particularly limited. For example, a gas containing a gas having a high permeability and a gas having a low permeability having a permeation rate ratio of 2 or more with respect to the separation membrane. It may be a mixture. The gas separation membrane module 1001 of this embodiment can be used to separate a specific gas component from a mixed gas in various modes. For example, dehumidification of various gases, humidification of various gases, nitrogen enrichment, or oxygen enrichment may be performed.

  The tube sheets 1021 and 1022 are formed in a substantially disk shape (detailed below) corresponding to the shape of the casing 1010, and the ends of the hollow fiber bundles 1015 are fixed with the openings of the hollow fiber membranes 1014 held. To do. In this example, the tube sheet serves to seal between the hollow fiber membranes. The tube sheet may also be a thermoplastic resin such as polyethylene or polypropylene, or a thermosetting resin made of an epoxy resin or a urethane resin. Hereinafter, an example in which the tube sheet is a thermosetting resin will be described.

  As the epoxy resin for the tube plates 1021, 1022, for example, in the case of a nitrogen membrane module, the one described in JP-B-2-36287 can be used, and the organic vapor separation module can be used. In this case, those described in WO2009 / 0444711 can be used.

  As shown in FIG. 1, in this embodiment, the casing 1010 and the two tube plates 1021 and 1022 form one sealed space 1018 (having a permeated gas discharge port 1010 c as described later), and this sealed space 1018. A permeated gas that has permeated through the hollow fiber membrane 1014 is introduced therein. Further, the mixed gas space 1019a is formed by the casing 1010 and the tube plate 1021, and the non-permeated gas space 1019b is formed by the casing 1010 and the tube plate 1022.

  As shown in FIG. 1, the casing 1010 is provided in a substantially cylindrical shape as a whole. The casing 1010 has a mixed gas inlet 1010a for introducing the mixed gas into the casing 1010 on the upstream side (left side in the figure), and has an unpermeated gas outlet 1010b on the downstream side (right side in the figure). Has a permeate gas outlet 1010c. The number of permeate gas outlets 1010c may be one or plural. A plurality of permeate gas outlets 1010 c may be arranged at equal intervals along the side wall of the casing 1010.

  The mixed gas introduced from the mixed gas inlet 1010a enters each hollow fiber membrane 1014 from the end face of the tube plate 1021, and flows through the inside toward the downstream side. At this time, a part of the mixed gas becomes a permeated gas that has permeated out of the hollow fiber membrane 1014, and the permeated gas is fed into the sealed space 1018 and then discharged out of the casing through the permeated gas outlet 1010c. The On the other hand, the non-permeate gas that has not permeated through the hollow fiber membrane flows directly through the hollow fiber membrane 1014 toward the downstream side, and is sent out of the membrane from the downstream end face, and then through the non-permeate gas outlet 1010b. It is discharged out of the casing.

  The mixed gas inlet 1010a and / or the non-permeated gas outlet 1010b may be arranged such that the central axis thereof is aligned with the central axis of the casing 1010 (that is, the central axis of the hollow fiber bundle 1015). Moreover, the casing 1010 may have a cylindrical member 1011 and cap members 1012 (one is not shown) attached to both ends thereof, as in the example of FIG. The cylindrical member 1011 and the cap member 1012 may be made of metal as an example.

Specifically, the cylindrical member 1011 inside diameter is a hollow member of _{d 0,} the thick portion 1011a is at its end, 1011b are formed. The first thickness portion 1011a is provided in the vicinity of the end surface of the cylindrical member 1011, the inner diameter of this portion is formed smaller than the inner diameter d _0. The second thick portion 1011b is provided on the axially inner side than the first thickness portion 1011a, it is formed smaller than the inner diameter also the inside diameter d ₀ of this portion. The inner diameter of the portion between the thick portion 1011a and the thick portion 1011b is both thick portion 1011a, larger than the inner diameter of 1011b, may be a _{d 0} as an example.

  Corresponding to such a structure of the cylindrical member 1011, the tube sheet 1021 is formed in the following shape. That is, as shown in FIG. 2, the tube sheet 1021 is roughly divided into three parts having different diameters (a first part 1021a, a second part 1021b, and a third part 1021c in order from the outside). Of these, the diameter of the middle portion 1021b is set to be the largest. In this example, the boundary between the first portion 1021a and the second portion 1021b is a tapered surface. The boundary between the second portion 1021b and the third portion 1021c is a straight surface (a surface extending in a direction perpendicular to the central axis of the cylindrical member).

  When the separation membrane module 1001 is used, a force in a direction of pushing the tube plate into the cylindrical member 1011 is applied to the tube plate 1021 due to the pressure of the mixed gas. However, according to the configuration as shown in FIG. 2, the movement of the tube plate 1021 is restricted when a part of the tube plate 1021 comes into contact with the thick portion 1011b, so that the tube plate 1021 is pushed into the inside. There is no.

  Although not limited, a round shape may be provided in the connection portion 1021f between the second portion 1021b and the third portion 1021c of the tube sheet. Thereby, the stress concentration in this part is relieved and damage to the tube sheet can be prevented.

  The example of FIG. 2 shows a state in which the tube plate 1021 is a thermosetting resin, and the diameter of the tube plate 1021 is slightly reduced by curing shrinkage. In such a configuration, there is a possibility that a sufficient seal between the tube plate 1021 and the cylindrical member 1011 may not be ensured. Therefore, in the present embodiment, an annular seal member 1060 for sealing between the two members is provided. Is provided.

  As shown in FIG. 2, an annular step 1021s is formed on the outer periphery of the first portion 1021a of the tube sheet. The step portion 1021s and the inner peripheral surface of the cylindrical member 1011 cooperate to form an annular groove C1 as a whole, and an annular seal member 1060 is disposed in the groove C1.

  The seal member 1060 may be an annular part made of an elastic member and may be fitted into the recessed groove C1 (for example, an O-ring). Or the resin material for a seal | sticker is filled in the ditch | groove C1, and the resin material may harden | cure and may function as a sealing member. The cross-sectional shape of the O-ring may be circular or elliptical. As the “annular part made of an elastic member”, in addition to the O-ring, a V-packing having a substantially V-shaped cross section, a U-packing having a substantially U-shape, or the like may be used. Furthermore, for example, it may have a cross-sectional shape such as a rectangle, a polygon, or an X shape. In the example of FIG. 2, the seal member 1060 seals between the tube plate 1021 and the casing 1010, and also seals between the tube plate 1021 and the cap member 1012.

  Moreover, the structure shown by FIG. 2 is an example to the last, Comprising: This invention is not limited at all. For example, the diameters of the first portion 1021a and the third portion 1021c of the tube sheet may be the same. Or you may use the tube sheet comprised by the 1st part 1021a and the 3rd part 1021c. Further, the surface between the first portion 1021a and the second portion 1021b may be a straight surface instead of the tapered surface as shown in FIG. Similarly, the surface between the second portion 1021b and the third portion 1021c may be a tapered surface instead of the straight surface as shown in FIG. Further, the seal member 1060 seals between the tube plate 1021, the casing 1010, and the cap member 1012, but separately from the seal member between the tube plate 1021 and the casing 1010, the casing 1010 and the cap member 1012 A sealing member may be provided.

  3 is a cross-sectional view taken along line AA in FIG. As shown in this figure, recesses 1011d and 1011d may be formed at two locations on the inner peripheral surface of the cylindrical member 1011. In this case, the tube sheet member enters the recesses 1011d and 1011d and is hardened (detailed below). As a result, the tube sheet 1021 can be prevented from rotating. The number of recesses 1011d is not particularly limited, and may be only one, or may be three or more.

The method for manufacturing the gas separation membrane module 1001 having the above configuration may be as follows as an example. That is, the manufacturing method of this embodiment is
(A) A step of applying a release agent to at least a portion of the inner peripheral surface of the casing that is in contact with the tube sheet;
(B) filling a part of the casing with a thermosetting resin before curing;
(C) forming a tube sheet by curing the filled thermosetting resin;
(D) providing an annular sealing member between the outer peripheral surface of the tube sheet and the inner peripheral surface of the casing after the thermosetting resin is cured.

  By applying a release agent as in step (a) above, the tube sheet (epoxy resin as an example) is favorably released from the casing (metal as an example) in the curing step of step (c). . If a mold release agent is not used, the tube sheet does not leave the case when the resin is cured, and in some cases, cracks or the like may occur in the tube sheet.

  In the step (b), a mold (not shown) may be attached to the end of the cylindrical member 1011 and the tube sheet resin may be injected in that state. In this case, the mold has an annular convex portion corresponding to the step 1021s (see FIG. 2) of the tube plate, and the step 1021s is formed on the tube plate by this convex portion. Good.

  In the step (d), as described above, for example, an annular elastic member such as an O-ring may be fitted in the concave groove C1, or a resin is injected into the concave groove C1 and cured to seal the sealing member. 1060 may be formed.

  According to the gas separation membrane module 1001 of the present embodiment as described above, even when the seal between the outer peripheral surface of the tube plate and the inner peripheral surface of the casing is not ensured due to curing shrinkage of the tube plate 1021, Separately, since the seal member 1060 is provided, a sufficient seal between the two members can be secured.

  This is particularly advantageous for gas separation membrane modules used at high temperatures. That is, in general, a material that hardly cures and shrinks tends to have elasticity, a low glass transition temperature, and poor heat resistance. On the other hand, a tube sheet material excellent in heat resistance tends to be hardened and shrunk. If such a heat-resistant material is used and the tube sheet is bonded to the casing, stretching stress is applied due to hardening shrinkage of the tube sheet material, and there is a risk of cracks in the tube sheet. On the other hand, according to the present embodiment, adhesion of the tube sheet material is prevented by applying a release agent in the casing, and a seal between the tube sheet and the casing is secured by the annular seal member. . Therefore, it is possible to provide a gas separation membrane module in which cracks are prevented from occurring in the tube sheet and the sealing performance is sufficiently ensured.

  In the above description, one of the two tube plates 1021 and 1022 has been mainly described, but both tube plates 1021 and 1022 may have the same configuration. Or the structure as shown in FIG. 2 may be provided in only one tube sheet. Furthermore, the structure of the tube plate, the annular seal member, and the casing as in the present embodiment is applicable not only to the bore feed type module but also to the shell feed type module, and also to other types of modules. Is possible.

1001 Gas separation membrane module 1010 Casing 1010a Mixed gas inlet 1010b Non-permeated gas outlet 1010c Permeated gas outlet 1011 Cylindrical member 1011a, 1011b Thick part 1011d Recess 1012 Cap member 1014 Hollow fiber membrane 1015 Hollow fiber bundle 1018 Sealed space 1019a Mixed gas space 1019b Impermeable gas space 1021, 1022 Tube sheet 1021s Stepped portion 1060 Seal member C1 Annular groove

Claims (5)

A hollow fiber bundle in which a large number of hollow fiber membranes having gas separation performance are focused,
A cylindrical member surrounding the hollow fiber bundle, and a cap member provided at an end of the cylindrical member, and a casing in which the hollow fiber bundle is disposed;
First and second tube sheets for fixing the hollow fiber membranes at both ends of the hollow fiber bundle;
A seal member that seals between an outer peripheral surface of the first tube sheet and an inner peripheral surface of the casing;
The first tube sheet is configured such that an outer peripheral surface thereof does not adhere to an inner peripheral surface of the cylindrical member, and only one seal member is disposed between the first tube sheet and the casing. And being disposed in an annular groove formed of a step portion provided on the tube plate and a first portion having a constant inner diameter of the inner peripheral surface of the cylindrical member, Sealing between the first tube plate and the cap member in contact with the cap member;
Gas separation membrane module. The tubular member is formed with a thick portion having a partially reduced inner diameter, and the tubular portion of the first tube plate is brought into contact with the thick tube portion by contacting the first tube plate. The movement of the member inward in the axial direction is prevented,
The gas separation membrane module according to claim 1.   The gas separation membrane module according to claim 1 or 2, wherein the seal member is an annular elastic member fitted in the annular concave groove. A mixed gas space to which a mixed gas is supplied is formed between the cap member and the first tube sheet,
The gas separation membrane module according to any one of claims 1 to 3, wherein a gas separation is performed by introducing a mixed gas into the hollow fiber membrane from the first tube sheet side. A hollow fiber bundle in which a large number of hollow fiber membranes having gas separation performance are converged, a casing in which the hollow fiber bundle is disposed, and a first portion that fixes the hollow fiber membranes at both ends of the hollow fiber bundle. And a second tube sheet, a method for manufacturing a gas separation membrane module comprising:
Providing the casing having a cylindrical member surrounding the hollow fiber bundle and a cap member provided at an end of the cylindrical member;
Applying a release agent to at least a portion of the inner peripheral surface of the casing that is in contact with the first tube sheet;
Filling a portion of the casing with a thermosetting resin;
Forming the first tube sheet by curing the thermosetting resin;
Providing a seal member between the outer peripheral surface of the first tube sheet and the inner peripheral surface of the casing after the thermosetting resin is cured;
Including
In the step of providing the seal member, an annular groove formed of a step portion provided on the first tube sheet and a first portion having a constant inner diameter on the inner peripheral surface of the cylindrical member. The sealing member is disposed so that the sealing member also contacts the cap member and seals between the tube plate and the cap member.
A method for manufacturing a gas separation membrane module.

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