JP2005169233A - Porous cylindrical body module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous cylindrical body module capable of keeping an installation space of an airtight container small while being capable of supplying a sweep gas. <P>SOLUTION: A gas supply line 19 for sending the sweep gas from a first end portion 20 of the porous cylinder 12 is provided, which can increase a hydrogen gas permeability of the peripheral wall 24 by flowing the sweep gas and furthermore can increase the yield even if a supply pressure of materials gas is not increased. At this time, since the gas supply line 19 is provided on the first end portion 20 side of the porous cylinder 12, the supply of the sweep gas and the recovery of the separated hydrogen gas are carried out at the same end portion side in the longitudinal direction of the porous cylinder 12. Therefore, since the installation space of a reaction vessel 60 is not enlarged unlike the case where the supply and the recovery are carried out mutually at the opposite sides, the installation space of the reaction vessel 60 can be kept small despite the ability to supply the sweep gas. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a porous cylinder module in which a plurality of porous cylinders are bundled and a sweep gas can be supplied into the porous cylinder.

  For example, there is known a gas separation device including a porous cylinder having a porous peripheral wall capable of selectively permeating a specific gas in an airtight container. This porous cylinder is made of, for example, a ceramic porous material such as alumina formed in a cylindrical shape. For example, a raw material gas containing the specific gas is supplied into an airtight container and the outside of the porous cylinder The specific gas is separated by collecting the specific gas permeated from the inside through the open end. In such a gas separation device, in order to obtain a large gas flow rate with as small a volume as possible, the porous cylinder is generally used in the form of a module in which a plurality of bundles are bundled apart from each other in the radial direction. It has been.

By the way, the yield of gas in the above-described porous cylindrical module can be increased by increasing the supply pressure of the raw material gas supplied into the hermetic container, for example, but the above porous material has low strength. Therefore, the upper limit of supply pressure is relatively low. Therefore, a yield is increased by flowing a sweep gas from the other open end of the porous cylinder toward the one open end (see, for example, Patent Documents 1 to 4).
JP 2003-210951 A JP 2002-346332 A JP 2002-355523 A Japanese Patent Laid-Open No. 2003-144861

  However, the conventional porous cylinder module capable of supplying the sweep gas as described above, sends the sweep gas from one end side of the porous cylinder of the hermetic container, and supplies the gas and the sweep gas separated from the other end side. It is configured to collect. For this reason, since the sweep gas introduction port and the gas recovery port are provided at positions opposite to each other in the airtight container, the porous cylinder module capable of supplying the sweep gas has a disadvantage that the installation space of the airtight container becomes large. was there.

  The present invention has been made in the background of the above circumstances, and an object of the present invention is to provide a porous cylindrical module that can keep the installation space of an airtight container small while being able to supply a sweep gas. .

  In order to achieve such an object, the gist of the present invention is that (a) a cylindrical peripheral wall having a porous peripheral wall through which a predetermined gas can be permeated and opened at both ends and at a predetermined interval from each other. A plurality of porous cylinders bundled with each other, and (b) the plurality of porous cylinders having a dense peripheral wall through which the predetermined gas cannot permeate and having both ends open. A dense cylinder integrally bundled with the body at a predetermined interval; and (c) the gas discharged from one end thereof located on the same side in the longitudinal direction of the plurality of porous cylinders. A connecting path for guiding the dense cylinder from one end located on the same side as one end; and (d) the other end of each of the plurality of porous cylinders for feeding a sweep gas from the other end. And a sweep gas supply unit provided on the side.

  In this way, since the porous cylinder module in which the dense cylinder and the plurality of porous cylinders are bundled, their one ends are connected to each other by the connection path, The module has a gas passage that reciprocates in the porous cylinder so that it flows from the other end to one end and in the dense cylinder from one end to the other, so that it can pass through the peripheral wall of the porous cylinder. Then, the gas that has entered the inside flows through the inside and is discharged from one end to the connecting path, flows through the connecting path to the dense cylindrical body from one end, and further flows through the inside and is recovered from the other end. The In addition, since the sweep gas supply unit for feeding the sweep gas from the other end of the porous cylinder is provided, even if the supply pressure of the raw material gas is not increased, the sweep gas is allowed to flow through the peripheral wall. The yield can be increased by increasing the transmittance of the predetermined gas. At this time, since the sweep gas supply unit is provided on the other end side of the porous cylinder, the supply of the sweep gas and the recovery of the separated gas are performed on the same end side in the longitudinal direction of the porous cylinder. Done. Therefore, since the installation space for the airtight container is not increased by providing the sweep gas supply unit as in the case where these are performed on opposite sides, the installation space for the airtight container can be reduced while the sweep gas can be supplied. A porous cylinder module that can be maintained is obtained.

  Preferably, the porous cylinder module includes a gas chamber surrounded by a dense wall through which the predetermined gas cannot pass, and the plurality of porous cylinders and the dense cylinder. Including a hollow sealing body hermetically fixed to the plurality of porous cylinders and the dense cylinder so that one end of the gas cylinder is opened into the gas chamber, and the connection path is configured by the gas chamber It is. In this way, a plurality of porous cylinders and dense cylinders are integrally bundled at one end thereof with a hollow sealing body, and one end thereof is opened in the gas chamber provided therein. This allows the gas chamber to function as the connection path. For this reason, since a plurality of porous cylinders and dense cylinders are bundled and a connection path is formed at the same time, the structure is simplified and the manufacture is facilitated as compared with the case where these are shared by different members. There are advantages.

  Preferably, the porous cylinder module is made of a dense material that cannot transmit the predetermined gas, and the other ends of the plurality of porous cylinders and the dense cylinder are separated from one surface thereof. The sweep gas supply unit is provided on the other surface of the support including a support that penetrates the surface and is airtightly fixed. In this way, since the plurality of porous cylinders and the dense cylinder are fixed to the support and are integrally bundled at the other end thereof, there is an advantage that the handling becomes easy. When the porous cylinder module is used in an airtight container or the like, the sweep gas supply unit provided on the other surface of the support is connected to the sweep gas supply path of the airtight container, and the dense cylinder What is necessary is just to connect the other end of a body to the gas recovery path of an airtight container. In addition, it is preferable that the dense cylindrical body protrudes to the other end side from the porous cylindrical body, for example, but is not limited to such a positional relationship, and the other end can be connected to the gas recovery path independently. It is enough if

  Further, in the aspect in which the support is fixed to the other end, preferably, the predetermined gas is made of a dense material that is not permeable and a gas chamber is formed between the other surface of the support. A cover member that is airtightly fixed to the support and has a through-hole that functions as the sweep gas supply unit by communicating the gas chamber to the outside. The other end is opened in the gas chamber, and the other end of the dense cylindrical body is opened outside the gas chamber through the lid member. In this way, a hollow sealing body having a gas chamber surrounded by a dense wall by the support and the lid member is configured, and the lid member functions as a sweep gas supply unit. A through hole is provided, and the other ends of the plurality of porous cylinders are opened into the gas chamber and connected to the through hole, that is, the sweep gas supply unit via the gas chamber. The end passes through the lid member and is opened to the outside of the gas chamber independently of the porous cylinder. That is, a plurality of porous cylinders and dense cylinders are integrally bundled at the other end thereof, and a sweep gas supply unit is provided, and the other end of the dense cylinder is opened outside the gas chamber. The Therefore, it is possible to form a structure in which a plurality of porous cylinders and dense cylinders are bundled, and at the same time, a sweep gas is supplied only to the plurality of porous cylinders and gas is recovered from the dense cylinders. Therefore, the structure is simplified and the manufacturing is facilitated as compared with the case where these are shared by separate members, and the sweep gas supply section is connected to the sweep gas supply path in an airtight manner and the dense cylindrical body is connected. There is an advantage that no other airtight sealing structure is provided by simply connecting the end to the gas recovery path in an airtight manner.

  Note that only one through hole may be provided, but a plurality of through holes may be provided. The through hole may be provided in a tubular member protruding from the lid member so as to extend toward the side opposite to the other end of the porous cylinder. If it does in this way, the other end of a porous cylinder can be easily connected to the sweep gas supply path by connecting a sweep gas supply path to this tubular member.

  Further, in the aspect in which the support is fixed to the other end, preferably, the support is made of a porous material that is permeable to the sweep gas, and the plurality of porous cylinders are formed on the other surface of the support. It includes a lid member which is fixed by closing the other end opening and through which the other end of the dense cylindrical body is passed. In this way, the other end of the porous cylindrical body is blocked by the porous lid member, so that it passes through the peripheral wall of the porous cylindrical body as compared with the case where it is completely exposed. The gas that has entered the inside is prevented from flowing backward toward the other end. In such a configuration, innumerable through holes that allow the sweep gas to permeate are substantially provided in the lid member, so that the lid member is hermetically covered with an appropriate member such as a constituent member of an airtight container. Thus, the sweep gas supply unit can be connected to the sweep gas supply path. Note that “closing the other end opening” is not limited to a state in which the other end surface of the porous cylindrical body is closed by providing the lid member in close contact with the other surface of the support body, but from the other surface of the support body. It may be in a state where it is separated from the other end face and closed, that is, a gap is formed between them.

  For example, while the support is configured with a sufficiently large difference dimension with respect to the distribution region of the plurality of porous cylinders and the dense cylinders, a sweep gas supply path and a gas recovery path are formed in the hermetic container, The peripheral edge is hermetically attached to the end face of the lid member constituting the hermetic container, and the other end of the dense cylinder is hermetically connected to the gas recovery path, and one end of the porous cylinder is hermetically accommodated in the hermetic container do it.

  Preferably, one end of each of the plurality of porous cylinders and the dense cylinder is positioned on one plane. If it does in this way, when fixing the end with a hollow sealing body and making it open | release in a gas chamber, while adhering work becomes easy, there exists an advantage which can reduce the magnitude | size of the gas chamber.

  Preferably, the dense cylindrical body has the other end protruding beyond the other ends of the plurality of porous cylindrical bodies. In this way, since the other end of the dense cylindrical body connected to the gas recovery path independently of the porous cylindrical body protrudes, there is an advantage that the connection becomes easy. More preferably, the other ends of the plurality of porous cylinders are positioned on one plane, and the dense cylinder has the other ends protruding beyond the one plane. If it does in this way, there exists an advantage which can accommodate easily the other end of a plurality of porous cylinders in a gas chamber.

  Preferably, in the porous cylindrical module, the hollow sealing body is fixed to one end of the plurality of porous cylindrical bodies and the dense cylindrical body, and the support is fixed to the other end thereof. It is a thing. In this way, a plurality of porous cylinders and dense cylinders are integrally bundled by fixing the hollow sealing body and the support body to both ends thereof, and one end thereof serves as a connection path. Opened into a functioning gas chamber. Therefore, at the same time as being bundled, a gas passage is formed from the other end of the porous cylinder to the other end via one end of the porous cylinder, the connection path, and one end of the dense cylinder, and the plurality of porous cylinders One end is closed by a hollow sealing body. Therefore, simply install the porous cylinder module in the airtight container, and connect the sweep gas supply path and gas recovery path provided in the airtight container to the sweep gas supply section and the other end of the dense cylinder, respectively. Thus, a filter structure can be obtained in which the specific gas can flow through the gas passage only through a path through which the specific gas permeates the peripheral wall of the porous cylindrical body without providing any other sealing structure. As a result, since the airtight sealing structure of the entire airtight container and the airtight structure of the porous cylinder module can be configured separately, it is necessary to change the sealing structure of the airtight container according to the size of the porous cylinder module In addition, there is an advantage that the assembling work in the airtight container is simplified.

  In the above configuration, when one surface of the support is covered with a dense lid member having the through-hole to form a gas chamber between them, a plurality of porous cylinders are simultaneously bundled The other end of the body is opened into the gas chamber. Therefore, the other ends of the plurality of porous cylinders are closed by the support and the lid member, and communicated with the common through-hole, so that the sweep gas supply unit is installed in the airtight container. It becomes easier to connect to.

  Furthermore, when the sealing structure of the porous cylindrical module is constituted by a hollow sealing body, a support and a lid member as described above, the porous cylindrical body is sealed with a glass sealing material when installed in an airtight container. In the case where there is no need to hermetically seal using a hollow sealing body, a porous sealing body having a predetermined pore diameter that substantially functions as a filter is provided on the outer peripheral surface of the porous cylindrical body. Further, since the porous film can be formed after the support and the lid member are bonded, there is an advantage that the bonding strength can be easily secured.

  Incidentally, in the structure in which the porous cylinder is hermetically sealed to the flange member or the like when the porous cylinder is installed in the hermetic container, the sealing step is performed after the porous film is formed. Therefore, it is necessary to lower the firing temperature for sealing so that the formed porous film does not deteriorate, so that it is difficult to ensure the bonding strength due to the low firing temperature. there were.

  Preferably, the dense cylinder is uniform around the center of gravity of the plurality of porous cylinders and the entire dense cylinder in a distribution area in a plane perpendicular to the longitudinal direction. It is arranged with a random distribution. In this way, the relatively high-strength dense cylindrical body is arranged in the distribution region without being biased with respect to its center of gravity, so that the mechanical strength of the entire module is suitably ensured. For example, in the case of one, it is preferably arranged in the center, and in the case of two or more, it is preferably arranged at equal intervals on a circle whose center coincides with the center of gravity of the distribution region.

  Preferably, a plurality of the dense cylinders are arranged on the outer peripheral side of the plurality of porous cylinders. In this way, since the relatively low-strength porous cylinder is located on the inner peripheral side of the plurality of relatively high-strength dense cylindrical bodies, the porous cylinder is located on the outer peripheral side. Compared with the case where it does, the failure | damage of the porous cylinder is suppressed.

  The dense cylinder functions as a passage for the specific gas separated, and does not contribute to the gas separation itself. Therefore, it is sufficient to provide a flow cross-sectional area that does not cause the flow resistance of the gas that has passed through the porous cylinder, and if it is excessively provided, the space utilization efficiency is lowered. For this reason, in terms of space utilization efficiency, a small number is preferable as long as a necessary flow cross-sectional area can be secured, and the space utilization efficiency is highest when one is used. In the case where the number is small, it is preferable to dispose on the inner peripheral side of the porous cylindrical body in consideration of the distribution of mechanical strength.

  The dense cylindrical body may be configured with the same opening area as the porous cylindrical body, but may be configured with an opening area smaller or larger than that. However, if it is excessively large, the volume occupied by the porous cylinder contributing to gas separation in the total volume of the porous cylinder module will be small, so the yield will be reduced, and if it is excessively small, the flow resistance will be increased. Reducing the yield. Therefore, it is preferable that the opening area of the dense cylindrical body is set to an appropriate size according to the gas flow rate in the plurality of porous cylindrical bodies.

  In addition, for example, a cylindrical shape is preferably used as the porous cylinder and the dense cylinder, but other shapes such as a square cylinder may be used.

  In addition, the number of porous cylinders is determined to be an appropriate plural number of two or more according to the size and application of the airtight container used, and the number of dense cylinders is the flow resistance and the space as described above. One or more appropriate numbers are determined in consideration of utilization efficiency and the like.

  Preferably, the hollow sealed body forms the gas chamber between the plurality of porous cylinders and a support part through which one end of the dense cylinder passes, and the support part. In this way, it is constituted by a lid portion hermetically fixed to one surface of the support portion. In this way, the porous cylinder and the dense cylinder are bundled by the support part, and the gas chamber is formed by fixing the lid part to the support part. The gas chamber is formed, for example, by a recess provided on at least one of the support portion and the lid portion so as to face the other.

  Preferably, the porous cylinder module includes a functional layer having a predetermined function fixed to an inner wall surface of the dense cylinder. If it does in this way, the gas which permeate | transmitted the porous cylinder and flowed into the dense cylinder will be made to contact the functional layer provided in the inner wall surface in the process of flowing toward the other end. Therefore, the porous cylindrical module can be used for various purposes such as gas modification according to the function of the functional layer. That is, the peripheral wall of the dense cylindrical body does not allow the predetermined gas to permeate, so even if any layer (or film) is formed on the inner wall surface, it does not affect the permeation performance of the entire module, and the dense wall Since the gas is brought into contact with the inner wall surface for a long time in the process of flowing through the cylinder, it can be reacted with the gas suitably by providing a functional layer on the inner wall surface. For example, when the catalyst layer is provided as a functional layer, removal, reduction, or detoxification of harmful components in the separated gas can be performed according to the configuration of the catalyst. When the adsorption layer is provided as a functional layer, it is possible to adsorb and remove or reduce impurities such as moisture in the separated gas depending on the configuration of the adsorption material.

  That is, the porous cylindrical module of the present invention is suitably used for gas separation without forming a functional layer, and for adsorbing and removing a minute amount of impurities in a gas by providing a functional layer. For example, in gas separation applications, it is used for separation of hydrogen gas from a mixed gas of hydrogen and nitrogen, separation of hydrogen from a mixed gas of hydrogen and methane, separation of hydrogen from a mixed gas of hydrogen and oxygen, etc. obtain. The gas to be separated is not limited to hydrogen, and can be used as an appropriate mixed gas as long as it is a gas molecule having a different molecular diameter (a larger difference is more preferable).

  The porous cylinder module includes one or a plurality of porous cylinders closed at the other end in addition to the plurality of porous cylinders open at both ends. May be. Since the sweep gas is not sent into the porous cylinder whose other end is closed, it is disadvantageous compared to the case where the sweep gas is sent from the other end of all the porous cylinders. Even if the cylinder is provided, there is no particular functional problem.

  Preferably, the porous cylindrical module has a constituent member made of a ceramic material. Ceramic materials are excellent in environmental resistance and can be suitably used for gas separation. As the ceramic material, for example, alumina / ceramics or a mixed material of alumina and silica (for example, mullite) is preferable, but is not limited thereto.

  The porous cylindrical body is preferably made of ceramics, synthetic resin, metal, or the like, but is particularly preferably made of alumina, mullite, or the like.

  The hollow sealing body, the support body, and the lid member are preferably made of ceramics, synthetic resin, or metal, and are particularly preferably made of alumina, mullite, or the like.

  Further, the constituent material of the dense cylinder is preferably made of the same material or the same material as the porous cylinder, the hollow sealing body, and the support, but is not limited thereto. For example, a synthetic resin material or a metal material may be used. However, when the porous cylindrical module is used in an environment where the temperature changes drastically, it is desirable that the porous cylindrical module is made of a material having as small a difference in thermal expansion coefficient as possible from other constituent materials, such as Kovar. Metal is preferably used.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the following embodiments, the drawings are appropriately simplified or modified, and the dimensional ratios, shapes, and the like of the respective parts are not necessarily drawn accurately.

  FIG. 1 is a perspective view showing the entirety of a porous cylindrical module (hereinafter referred to as a module) 10 according to an embodiment of the present invention, and FIG. 2 shows a cross section along the longitudinal direction with an intermediate portion omitted. FIG. In these drawings, the module 10 has a longitudinal shape extending in one direction and is radially separated from a plurality of, for example, six porous cylinders 12 separated from each other in the radial direction. One dense cylinder 14 provided in parallel, end caps 16 and 18 fitted to both ends of the porous cylinder 12 and the dense cylinder 14, respectively, and the end cap 16 of the end cap 16 is opposite to the end cap 18 A gas supply pipe 19 projecting from the other side 42 is provided. In this embodiment, the porous cylinder 12 corresponds to a porous cylinder, the dense cylinder 14 corresponds to a dense cylinder, and the end cap 18 corresponds to a hollow sealing body.

  The porous cylinder 12 has, for example, an outer diameter of about 6 (mm), an inner diameter of about 4 (mm), a length dimension of about 400 (mm), and a cross section having an annular shape, In the figure, the first end 20 located on the left side and the second end 22 located on the right side are opened. The porous cylinder 12 is made of porous alumina ceramics having a porosity of about 30 to 40 (%), for example, and has a large number of fine pores having an average pore diameter of about 4 (nm), for example. Are formed so as to communicate from the surface 26 to the inner surface 28 of the peripheral wall 24, and the peripheral wall 24 is configured to allow a predetermined gas such as nitrogen or hydrogen to pass therethrough.

  The dense cylinder 14 has, for example, an outer diameter of about 6 (mm), an inner diameter of about 4 (mm), and a length dimension of about 500 (mm), and a circular cross section. In the figure, the first end 30 located on the left side and the second end 32 located on the right side are opened. The dense cylinder 14 is made of, for example, a dense alumina ceramic having a porosity of about 0 to 5 (%), that is, sufficiently denser than the porous cylinder 12, and the peripheral wall 34 is made of gas. It is comprised so that it cannot permeate | transmit. Further, the gas supply pipe 19 is also a dense cylinder similarly configured from alumina / ceramics or the like in the same size and shape except that the length of the gas supply pipe 19 is different from that of the dense cylinder 14.

  Each of the end caps 16 and 18 is made of a dense alumina ceramic similar to the dense cylinder 14 and has a substantially disk shape. The end cap 16 has an annular stepped portion 46 formed on one surface 42 opposite to the end cap 18, and a recess 48 formed on the inner periphery thereof. The recess 48 is provided with seven through holes 36 and 40 that penetrate from the one surface 38 toward the recess 48 in the thickness direction. Of these seven through-holes 36 and 40, one (through-hole 36) is located at the center of the end cap 16, and the remaining six (through-holes 40) are arranged on the circumference of the circumference at regular intervals. That is, for example, they are arranged at intervals of about 60 degrees.

  The end cap 18 is configured in the same shape as the end cap 16 and is disposed symmetrically, and has an annular stepped portion 46 on one surface 44 opposite to the end cap 16. And a recess 48 is further formed on the inner periphery thereof. The recess 48 includes, for example, seven through holes 52 and 53 that penetrate from the one surface 44 side to the other surface 50. Of these seven through holes 52 and 53, one (through hole 53) is located at the center of the end cap 18, and the remaining six (through holes 52) are arranged at regular intervals on the circumference of the circumference. Has been. The diameter of the circumference where the through hole 52 is arranged is the same as the diameter of the circumference where the through hole 40 is arranged.

  Further, disk-shaped end covers 54 and 55 for closing the recesses 48 and 48 are airtightly fixed to the one surfaces 42 and 44 of the end caps 16 and 18 with a sealing material 56 such as seal glass. Gas chambers 58a and 58b are formed between them. The end covers 54 and 55 are also made of dense alumina / ceramics and the like, similarly to the end caps 16 and 18, and do not allow gas to pass therethrough. However, the end cover 55 fixed to the end cap 16 is provided with a through hole 57 positioned coaxially with the through hole 36 in the center portion in the thickness direction, and at a position on the outer peripheral side than that. A through hole 59 penetrating in the direction is provided.

  The porous cylinder 12 and the dense cylinder 14 are pierced through the through holes 36, 40, 52, and 53 of the end caps 16 and 18 and the through hole 57 of the end cover 55 thus configured. Is also hermetically fixed with a sealing material 56 such as seal glass. Further, the gas supply pipe 19 is pierced through the through hole 59 provided in the end cover 55, and one end thereof is opened in the gas chamber 58a and the other end is positioned outside the gas chamber 58a. It has been.

  As a result, as apparent from FIG. 2 above, the porous cylinder 12 is opened in the gas chamber 58a formed between the end cap 16 and the end cover 55 whose first end 20 is dense, The second end portion 22 is opened in a gas chamber 58b formed between the dense end cap 18 and the end cover 54, while the dense cylinder 14 has a first end portion 30 at the end cap 16. The second end portion 32 is opened into the gas chamber 58b on the end cap 18 side while being protruded and opened to the other surface 42 side. Therefore, when the gas passes through the peripheral wall 24 of the porous cylinder 12 and enters the inside thereof, the gas flows from the opened second end portion 22 into the gas chamber 58b and enters the dense cylinder 14 with the second gas. What flows from the end portion 32 flows through the inside toward the first end portion 30 and flows out from the opened first end portion 30. In this embodiment, the end cap 16 corresponds to the support body, the end cover 55 corresponds to the lid member, and the end cap 18 and the end cover 54 constitute a hollow sealing body. The gas chamber 58b corresponds to a connection path.

  The gas fed from the gas supply pipe 19 enters the gas chamber 58 a on the end cap 16 side, spreads in the gas chamber 58 a, and enters the porous cylinder 12 from the first end 20. This gas also flows in the porous cylinder 12 from the left side to the right side in the figure, enters the dense cylinder 14 via the gas chamber 58b, and is discharged from the first end 30 thereof. In this embodiment, the gas supply pipe 19 corresponds to a sweep gas supply unit.

  The module 10 configured as described above includes end caps 16 and 18, end covers 54 and 55, porous cylinders 12, dense cylinders having the above-described characteristics using well-known ceramic manufacturing techniques. The cylinder 14 and the gas supply pipe 19 are manufactured, and these are combined and fixed. The end caps 16 and 18 and the end covers 54 and 55 are formed by, for example, powder press molding and cutting, and the porous cylinder 12, the dense cylinder 14 and the gas supply pipe 19 are formed by, for example, extrusion molding or cold isostatic pressure. It is molded by pressure molding and cutting. In addition, materials having different sintering characteristics or materials containing additives depending on the desired porosity are appropriately used. In addition, in order to obtain necessary dimensional and shape accuracy, grinding is appropriately performed after sintering.

  And after manufacturing each component, for example, while letting dense cylinder 14 penetrate end cap 16, porous cylinder 12 is inserted and fixed with sealing material 56, respectively, and end cap 18 is attached to the other end side of them. They are fitted together and fixed with a sealing material 56, and end covers 55 and 54 are fitted into the one surface 42 of the end cap 16 and the one surface 44 of the end cap 18, and fixed with the sealing material 56. The module 10 is manufactured by fitting the gas supply pipe 19 and fixing it with the sealing material 56. Note that the fixing order is not limited to the above, and is determined as appropriate so that the manufacture is easy.

  FIG. 3 is a schematic diagram for explaining the usage state of the module 10. In the figure, the module 10 is fixed in the reaction vessel 60 using a fixing device (not shown), and the open end (first end 30) of the dense cylinder 14 protruding from the end cap 16 is connected to the left end by the joint 62. The gas recovery path (gas outlet port) 64 provided in the section is hermetically connected. The gas supply pipe 19 is airtightly connected to the sweep gas supply path 65 by a joint 63. The reaction vessel 60 is configured to be airtight, and includes a gas introduction port 66 provided on a side surface located on the lower side in the figure, and a gas discharge port 67 provided with a valve 61 on the side surface located on the upper side. It is provided. The gas recovery path 64 is provided in a lid 68 of the reaction vessel 60, and the lid 68 is airtightly attached to the vessel body by a fastening device such as a bolt (not shown). A gas supply source 72 is connected to the gas inlet 66 via a valve 70, while a measuring device 76 for measuring a gas flow rate and the like is connected to the gas recovery path 64 via a valve 74. ing. A sweep gas supply source 80 is connected to the sweep gas supply path 65 via a valve 78. That is, the module 10 is arranged in an airtight reaction vessel 60, and the dense cylinder 14 is airtightly connected to the gas recovery path 64 and the gas supply pipe 19 is airtightly connected to the sweep gas supply path 65. There is no airtight partition in the reaction vessel 60.

  In such an apparatus configuration, the valves 61, 70, 74, and 78 are opened to supply a predetermined source gas such as a mixed gas of nitrogen and hydrogen from the gas supply source 72 into the reaction vessel 60 and the sweep gas supply source 80. When a predetermined sweep gas, such as argon, is supplied to the gas supply pipe 19, the reaction vessel 60 is configured to be airtight, so that hydrogen gas having a small molecular diameter in the supplied raw material gas is the only flow path. It passes through the peripheral wall of a certain porous cylinder 12 and flows into the inside thereof. Further, the sweep gas flows into the porous cylinder 12 via the gas chamber 58 a in the end cap 16. In the figure, the arrows indicate the direction of gas flow. The source gas and the sweep gas that have flowed into the porous cylinder 12 flow toward the gas chamber 58b, and further flow into the dense cylinder 14 via the gas chamber 58b. Then, gas is guided from the dense cylinder 14 to the measuring device 76 through the gas recovery path 64. That is, since the gas flow path is configured in this way, the gas recovery path 64 side of the dense cylinder 14 has a relatively negative pressure, so that when gas is supplied from the gas supply source 72 at an appropriate pressure. The gas that permeates through the peripheral wall 24 of the porous cylinder 12 flows through the dense cylinder 14.

  Moreover, since the sweep gas fed from the first end 20 of the porous cylinder 12 cannot permeate the peripheral wall 24 of the porous cylinder 12 due to the large molecular diameter of argon, it goes directly to the second end 22. This flow facilitates the inflow of hydrogen gas that permeates the peripheral wall 24. Therefore, the yield is remarkably increased as compared with the case where no sweep gas is introduced. In addition, since the dense cylinder 14 is airtightly connected to the gas recovery path 64, the raw material gas introduced into the reaction vessel 60 is gas only through a path passing through the porous cylinder 12 and the dense cylinder 14. It is sent to the collection path 64. Therefore, the gas flow rate measured by the measuring device 76 is the permeation flow rate of the module 10. Since nitrogen gas has a large molecular diameter and cannot pass through the peripheral wall 24 of the porous cylinder 12, it is discharged from the gas discharge port 67.

Table 1 below shows a case in which a mixed gas of hydrogen and nitrogen is flowed with various changes in the constituent material of the porous cylinder 12 of the module 10, the supply pressure of the raw material gas, the presence or absence of a sweep gas, etc. in such an apparatus configuration It shows the result of measuring the permeation flow rate. The mixing ratio of the source gases was 50:50 in molar ratio, and argon was supplied as the sweep gas at a pressure of 0.1 (MPa). In each of the following examples, the configuration was the same as that described above, except that the pore diameter of the porous cylinder 12 was changed by changing the constituent material. As shown below, it became clear that the permeated gas concentration of hydrogen gas, that is, the yield was remarkably increased by flowing the sweep gas at any pore diameter and supply gas pressure. The permeated gas concentration is evaluated by using H ₂ + N ₂ as 100 (mol%) for the gas recovered from the gas recovery path 64.

[Table 1]
Example 1 Example 2 Example 3 Example 4
Porous cylindrical material Alumina Alumina Alumina Alumina
+ Silica + Silica porous cylindrical pore diameter (nm) 4 4 0.5 0.5
Gas supply pressure (MPa) 0.2 0.3 0.3 0.5
Permeability coefficient ratio _{(H 2 / N 2) 3.5} 3.5 20.5 20.5
H ₂ permeate gas concentration (mol%)
No sweep gas 65.1 69.7 89.3 92.4
With sweep gas 77.2 76.9 94.5 94.1

  In short, according to the present embodiment, the module 10 in which the dense cylinder 14 and the plurality of porous cylinders 12 are bundled is connected to the module 10 because one end thereof is connected to each other by the gas chamber 58b. Reciprocates in the porous cylinder 12 so as to flow from the first end 20 to the second end 22 and in the dense cylinder 14 to flow from the second end 32 to the first end 30. Since the gas passage is formed, the gas that has permeated through the peripheral wall 24 of the porous cylinder 12 and entered the inside thereof flows through the inside and is discharged from the second end portion 22 to the gas chamber 58b. Then, it flows into the dense cylinder 14 from the second end portion 32, further flows through the inside thereof, and is collected from the first end portion 30. In addition, since the gas supply pipe 19 for feeding the sweep gas from the first end 20 of the porous cylinder 12 is provided, the peripheral wall can be obtained by flowing the sweep gas without increasing the supply pressure of the raw material gas. The hydrogen gas permeation rate permeating through 24 can be increased and the yield can be increased. At this time, since the gas supply pipe 19 is provided on the first end 20 side of the porous cylinder 12, the supply of the sweep gas and the recovery of the separated hydrogen gas are performed in the longitudinal direction of the porous cylinder 12. Performed on the same end side. For this reason, the installation space for the reaction vessel 60 is not increased as in the case where these are performed on the opposite sides, so that the installation space for the reaction vessel 60 can be kept small while the sweep gas can be supplied.

  In the present embodiment, the plurality of porous cylinders 12 and the dense cylinders 14 are integrally bundled at the second end portions 22 and 32 thereof by the end cap 18 and the end cover 54, and are provided therein. When the end portions 22 and 32 are opened in the gas chamber 58b, the gas chamber 58b functions as a connection path. Therefore, since a plurality of porous cylinders 12 and dense cylinders 14 are bundled and a connection path is formed at the same time, the structure is simplified and the manufacture is facilitated as compared with the case where these are shared by different members. There are advantages.

  In this embodiment, the plurality of porous cylinders 12 and the dense cylinders 14 are fixed to the end cap 16 so that they are integrally bundled at the first end portions 20 and 30. There is an advantage that becomes easier.

  Next, another embodiment of the present invention will be described. In the following embodiments, portions common to the above-described embodiments are denoted by the same reference numerals, and description thereof is omitted.

  The module 82 shown in FIG. 4 has an end cap 84 that is configured in the same manner except that the outer diameter is larger than that of the end cap 16, and an end cover that closes the recess. The configuration is substantially the same as that of the module 10 except that the end cover 86 is provided instead of the end cover 86. The end cover 86 is provided with an average pore diameter of, for example, about 10 (μm) that is sufficiently larger than the porous cylinder 12, and is made of a porous material that is permeable to the sweep gas such as argon. It consists of. The end cover 86 is provided with only one through hole through which the dense cylinder 14 passes, and the gas supply pipe 19 is not attached.

  As shown in the figure, such a module 82 is accommodated in a reaction vessel 92 having flanges 88 and 90, and an end cover 86 is hermetically sandwiched between the flanges 88 and 90 and used. The reaction vessel 92 is provided with a sweep gas supply path 65 in a cover 94 that forms an airtight space with the end cover 86, and the sweep gas supply path 65 is open to the airtight space. Other installation configurations are the same as those of the module 10.

  In the module 82 configured as described above, when the sweep gas is supplied from the sweep gas supply path 65, it passes through the porous end cap 84 and flows into the porous cylinder 12. In addition, permeation of hydrogen gas is promoted by the sweep gas, and the yield is increased. That is, the module 82 does not have the gas chamber 58a completed by itself like the module 10, but a gas chamber is substantially formed between the module 82 and the cover 94. There is no. In this embodiment, the end cover 86 constitutes a sweep gas supply unit.

  In this embodiment, the end cover 86 is provided for the purpose of suppressing the hydrogen gas that has permeated into the porous cylinder 12 from flowing backward from the end on the end cap 84 side and being discharged. It can be made unnecessary by appropriately adjusting the supply conditions of the source gas and the sweep gas.

  The module 96 shown in FIG. 5 has a catalyst layer 98 fixed to the inner wall surface of the dense cylinder 14, but the other configuration is exactly the same as the module 10. The catalyst layer 98 is made of alumina containing platinum at a ratio of about 0.1 (wt%), for example, and is provided over the entire length of the dense cylinder 14 with a thickness dimension of about 100 (μm), for example. ing. In such a module 96, when gas flows into the dense cylinder 14 via the porous cylinder 12 and the gas chamber 58, the gas flows toward the open end 30 while being in contact with the catalyst layer 98 provided on the inner wall surface. You can make it. Therefore, since gas reacts with the catalyst in the flow process, for example, harmful gas can be removed.

For example, when the gas sent from the gas supply source 72 is a mixed gas of H ₂ , H ₂ O, and O ₂ , when the gas is flowed at a flow rate of about 100 (ml / min), the CO concentration in the mixed gas is While it was 1000 (ppm) on the supply side, it was reduced to about 8 (ppm) on the outlet side. Further, when the flow rate was set to about 1000 (ml / min) at the same supply side concentration, the CO concentration on the outlet side could be reduced to about 50 (ppm). In addition, when the mixed gas to be introduced is a mixture of air and hydrogen, the VOC concentration on the supply side is about 10000 (ppm) at a flow rate of about 1000 (ml / min). On the outlet side, it could be reduced to about 500 (ppm).

Further, in place of the catalyst layer 98 as described above, another catalyst layer may be provided to remove a minute amount of impurities in the gas. Further, an adsorption layer 100 may be provided instead of the catalyst layer 98. For example, when the adsorption layer 100 containing magnesium and a lithium compound is provided, CO ₂ in the gas can be removed. Moreover, when the adsorption layer 100 is comprised with a silica gel, a molecular sieve, etc., it is possible to remove the trace amount water contained in gas.

  As mentioned above, although this invention was demonstrated in detail with reference to drawings, this invention can be implemented also in another aspect, A various change can be added in the range which does not deviate from the main point.

1 is a perspective view illustrating an overall configuration of a module 10 according to an embodiment of the present invention. It is a figure which shows the longitudinal cross-section of the module 10 of FIG. It is a figure which shows typically the use condition which installed the module 10 of FIG. 1 in the reaction container 60. FIG. It is sectional drawing corresponding to FIG. 3 for demonstrating the structure of the module 10 of the other Example of this invention. It is sectional drawing corresponding to FIG. 2 for demonstrating the structure of the module 10 of the further another Example of this invention.

Explanation of symbols

10: porous cylinder module, 12: porous cylinder, 14: dense cylinder, 16: end cap (support), {18: end cap, 54: end cover} (hollow sealing body), 19: gas Supply pipe (sweep gas supply unit), 20: first end (other end), 24: peripheral wall, 60: reaction vessel

Claims (5)

A plurality of porous cylindrical bodies having a porous peripheral wall through which a predetermined gas can permeate and having both ends open and bundled at a predetermined interval;
A dense cylinder having a dense peripheral wall through which the predetermined gas cannot permeate and having both ends open and bundled integrally with the plurality of porous cylinders at predetermined intervals. Body,
A connection path for introducing the gas discharged from one end located on the same side in the longitudinal direction of the plurality of porous cylinders into the dense cylinder from one end located on the same side as the one end; ,
And a sweep gas supply section provided on the other end side of the plurality of porous cylinder bodies for feeding a sweep gas from the other end of each of the plurality of porous cylinder bodies. The gas chamber is provided with a dense wall through which the predetermined gas cannot permeate, and the plurality of porous cylinders and the plurality of the dense cylinders are opened in the gas chamber. 2. The porous cylinder module according to claim 1, wherein the porous cylinder body and a hollow sealing body that is airtightly fixed to the dense cylinder body are included, and the connection path is constituted by the gas chamber. A support body made of a dense material through which the predetermined gas cannot pass, and a plurality of porous cylinders and a support body in which the other end of the dense cylinder penetrates from one surface to the other and is airtightly fixed. The porous cylindrical module according to claim 1, wherein the sweep gas supply unit is provided on the other surface of the support. The predetermined gas is made of a dense material that is impermeable to the gas, and is gastightly fixed to the support so as to form a gas chamber with the other surface of the support, and the gas chamber communicates with the outside. A lid member having a through-hole that functions as the sweep gas supply unit, and the other ends of the plurality of porous cylinders are opened into the gas chamber and the other ends of the dense cylinders The porous cylindrical module according to claim 3, wherein the porous cylindrical module is opened outside the gas chamber through the lid member. It is made of a porous material that allows the sweep gas to pass therethrough, and is fixed to the other surface of the support by closing the other end openings of the plurality of porous cylinders, and the other end of the dense cylinder penetrates. The porous cylindrical module according to claim 3, which includes a lid member that is made to move.

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