JPS63224714A - Gas separator - Google Patents

Abstract

PURPOSE:To maintain partition performance for a long period, by partitioning both the passing chamber of a gaseous raw material and a permeated gas chamber in a fluid-tight state by means of a sealing member made of metal provided between the inner wall of a pressure resistant vessel and a resin wall, this resin wall and an elastic member made of a metal. CONSTITUTION:Hollow yarn 4 having gas permeability penetrates a resin wall 6 and an aperture end 9 is positioned in the inside of a permeated gas chamber 10. Both the passing chamber 8 of a gaseous raw material and a permeated gas chamber 10 are partitioned in a fluid-tight state by means of a structure constituting of a sealing member 11 made of metal provided between the inner wall of a pressure resistant vessel 3 and a resin wall 6, this resin wall 6 and an elastic member 12 made of metal which is provided between the face of the side opposite to the contact face of the resin wall 6 and the sealing member 11 made of metal and the stepped part 3' of the inner wall of the pressure resistant vessel 3 and presses the resin wall 6. Ceramic powder is mixed into the surface part 6' of the contact face of the resin wall 6 and the sealing member 11 made of metal.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a gas separation device, and more specifically, it has the ability to selectively permeate a gas of a specific component from a mixed gas consisting of various components. It has a built-in yarn bundle assembly consisting of a large number of hollow fibers, and has a special structure to isolate the raw material mixed gas passage chamber and the permeated gas chamber in a fluid-tight state, especially for separating high temperature and high pressure raw material gas. The present invention relates to a gas separation device that is useful.

(Prior art and its problems) As a device for separating a gas of a specific component from a mixed gas consisting of various components, it has the ability to selectively permeate a gas of a specific component from the mixed gas, that is, it has gas selective permeability. 2. Description of the Related Art A gas separation device is known that includes a built-in fiber bundle assembly consisting of a large number of hollow fibers. In such a gas separation device, generally, the raw material gas, which is a mixed gas, comes into contact with the outer surface side of the body of the hollow fiber, and the gas having a specific component permeates through the wall of the hollow fiber and enters the inside of the hollow fiber. The specific component gas is separated from the source gas by taking out the permeated gas of the specific component from the open end of the hollow fiber. Therefore, in such a gas separation device, it is necessary to separate the source gas passage chamber through which the source gas passes and the permeate gas chamber through which the permeate gas of a specific component passes in a fluid-tight state.

In conventional gas separation devices, at least one end of a fiber bundle consisting of a large number of hollow fibers is fixed in an open state through each hollow fiber as a means for isolating the raw material gas passage chamber and the permeated gas chamber. A structure is adopted that combines a resin wall made of thermosetting resin and a sealing member such as a synthetic resin O-ring provided between the inner wall of the dispensing device container and the resin wall. There is. However, since the above synthetic resin O-rings are generally manufactured from fluororesin or silicone resin, they operate at relatively low temperatures and pressures (approximately 10
Although it can withstand long-term use at temperatures below 0° C. and about 100 Kg/cm2G or below, it has the disadvantage that it cannot be used at high temperatures and high pressures, or even if it can be used, its service life is short and impractical.

If a metal O-ring is used to enable the gas separation device to be used at high temperatures and high pressures, the resin wall may be deformed, such as by creating impressions on the surface of the resin wall that comes into contact with the metal O-ring, resulting in poor sealing. , the function of isolating the source gas passage chamber and the permeated gas chamber is reduced.

(Object of the Invention) The present invention is directed to high temperature up to about 200°C and about 200 kg7
A gas separation device that has a gas-selective permeability hollow fiber bundle and is equipped with an isolation structure between a source gas chamber and a permeated gas chamber that can maintain isolation performance for a long period of time even when operated under high pressure conditions of up to cm2G. The purpose is to provide

(Structure of the Invention) The present invention provides a fiber bundle consisting of a large number of hollow fibers having gas selective permeability, and a yarn bundle consisting of a large number of hollow fibers having gas selective permeability, and the fibers are housed in a cylindrical pressure-resistant container having a raw material gas inlet, a permeated gas outlet, and an unpermeated gas outlet. At least one end of the bundle is provided with a fiber bundle assembly consisting of a thermosetting resin wall through which each of the hollow fibers is fixed in an open state, and the body of the hollow fibers is present to allow the raw material gas to pass therethrough. In a gas separation device in which a chamber and a permeate gas chamber in which an open end of the hollow fiber exists are separated in a flow-tight state, a structure for isolating the source gas passage chamber and the permeate gas chamber in a flow-tight state. but,
(A) A metal sealing member provided between the inner wall of the pressure vessel and the resin wall; (B) The resin wall in which ceramic powder is mixed in at least the surface layer of the surface that contacts the metal sealing member. and (C) a metal elastic member provided between the surface of the resin wall opposite to the surface that contacts the metal sealing member and the inner wall of the pressure-resistant container. It is a separation device.

(Preferred embodiment of the invention) The invention is illustrated in the accompanying drawings.

FIG. 1 is a cross-sectional view showing a structural part of an embodiment of the gas separation apparatus of the present invention for separating a source gas passage chamber and a permeated gas chamber in a fluid-tight state.

In Figure 1, raw material gas inlet 1, permeated gas outlet 2
In a cylindrical pressure-resistant container 3 having an unpermeated gas outlet (not shown), a fiber bundle 5 formed by bundling a large number of hollow fibers 4 having gas selective permeability, and one end of the fiber bundle 5 are fixed. A yarn bundle assembly is provided, which includes a resin wall 6 having a cylindrical shape. The hollow fibers 4 penetrate the resin wall 6 and are fixed to the resin wall 6 so that their ends are open. Hollow fiber 4
The body portion 7 of the hollow fiber 4 is present in the source gas passage chamber 8, and the open end 9 of the hollow fiber 4 is present in the permeation gas chamber 10. The raw material gas passage chamber 8 and the permeation gas chamber 10 are defined by a "metal sealing member" 11 provided between the inner wall of the cylindrical pressure vessel 3 and the resin wall 6.
, the “resin wall” 6 , and the metal sealing member 11 of the resin wall 6
A metal seal member 11 is provided between the surface opposite to the surface in contact with the resin wall 6 and the stepped portion 3' of the inner wall of the pressure vessel 3.
The "metal elastic member" 12 is pressed against the inner wall of the pressure vessel 3 via the "metal elastic member" 12, and is isolated in a fluid-tight state. Metal seal member 11 for resin wall 6
Ceramic powder is mixed in the surface layer 6' of the surface that comes into contact with.

The raw material gas, which is a mixed gas consisting of various components, enters the pressure vessel 3 from the raw gas inlet 1 and passes through the raw material gas passage chamber 8.
, a specific gas passes through the pipe wall of the hollow fiber 4 and enters the hollow part of the hollow fiber 4 , collects in the permeate gas chamber 10 from the open end 9 of the hollow fiber 4 , and exits from the permeate gas outlet 2 . It is discharged.

The pressure in the raw material gas passage chamber is generally 10 to 300 kg/
cm2G, the pressure difference between the raw material gas passing chamber and the permeated gas chamber is generally 10 to 200 Kg/cm2, and the temperature of the raw material gas is generally operated at atmospheric temperature to 200°C.

The hollow fibers 4 may be of any type as long as they have gas selective permeability, that is, the ability to selectively permeate a specific gas component from a mixed gas consisting of various components, such as cellulose, Hollow fibers made from polymeric organic materials such as cellulose acetate, polypropylene, polyacrylonitrile, polysulfone, aromatic polyamide, aromatic polyimide, and inorganic materials such as glass and ceramics can be used. In particular, from the viewpoint of heat resistance, hollow fibers made of aromatic polyimide are preferred among hollow fibers made of inorganic materials and hollow fibers made of polymeric organic materials. Generally, the hollow fiber 4 has an outer diameter of about 50 to 3000 μm, and a tube wall thickness of
Approximately 10 to ioo.

It is μm.

The fiber bundle 5 formed by bundling a large number of hollow fibers 4 may be either a fiber bundle having a core tube inside or a coreless fiber bundle. The fiber bundle may be either a "fiber bundle in which the hollow fibers are arranged substantially in parallel" or a "fiber bundle in which the hollow fibers are arranged in an intersecting manner."

Furthermore, the yarn bundle 5 may be bound at one or several points around its periphery with a suitable binding material, preferably an elastic binding material.

The yarn bundle 5 generally has an outer diameter of about 1 to 50 cm.
Preferably, the length is about 5 to 40 cm, and the length is about 20 to 500 cm, preferably 25 to 400 cm.

The density of the hollow fibers 4 constituting the fiber bundle 5 is expressed as a percentage, which is the ratio of the area occupied by all the hollow fibers to the total cross-sectional area of the fiber bundle 5.
The packing density of the hollow fibers is preferably about 20 to 80%, particularly 25 to 70%.

As the thermosetting resin for forming the resin wall 6, urethane resin, epoxy resin, acrylate resin,
Examples include silicone resins, phenols, f-resins, etc. Epoxy resins, particularly phenol novolac type epoxy resins, are preferred especially for high temperature and high pressure gas separation devices. In manufacturing the yarn bundle assembly, the rotational viscosity is about 0.01 to 5000 poise, especially 0.05 to 50 poise.
It is preferable to use a zero-voice liquid thermosetting resin as a raw material and to cure it using an appropriate curing agent and curing accelerator to form the resin wall 6.

The curing agent for epoxy resins may be any known thermosetting agent made of alicyclic carboxylic acid, aromatic carboxylic acid, aromatic polyamine, etc., such as hexahydrophthalic anhydride, phthalic anhydride, maleic anhydride. , pyromellitic dianhydride, methylnadic anhydride, benzophenone tetracarboxylic dianhydride, diaminophenyl sulfone,
Examples include diaminodiphenylmethane and metaphenylenediamine.

In addition, examples of the curing accelerator include 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methyl-imidazole, tri-2.4.6-dimethylaminomethylphenol, penzyldimethylamine, and tri-2.4.6-dimethylaminomethylphenol. Boron fluoride
Examples include monoethylamine.

Examples of the ceramic powder mixed in the surface layer 6' of the resin wall 6 include powders of alumina, silica, titanium, silicon carbide, silicon nitride, etc. In order to increase the surface hardness of the surface layer 6', Particularly preferred are silicon carbide and silicon nitride. The purpose of mixing ceramic powder into the resin wall 6 is to increase the surface hardness of the surface of the resin wall 6 that comes into contact with the metal sealing member 11, so the thickness of the surface layer 6' may be approximately 5 to 10 mm. , even if it is made larger than that, there is no point in increasing the amount of ceramic powder consumed. The amount of ceramic powder mixed into the surface layer 6' varies depending on the type of resin, the type of ceramic powder, the particle size, etc., but it should be selected appropriately so that the surface hardness of the surface layer 6' is 94 or more on the Shore D hardness. .

As a method for forming the surface layer 6' on the resin wall 6, the yarn bundle 5 is formed by centrifugal molding from the yarn bundle 5 and a liquid thermosetting resin.
When manufacturing a yarn bundle assembly in which a resin wall is formed on at least one end of the yarn bundle assembly, a ceramic powder is mixed into a thermosetting resin, and the difference in density between the ceramic powder and the resin is utilized to manufacture the yarn bundle assembly. It is preferable to form the surface layer 6' at the same time.

An example of a method for forming the surface layer portion 6' will be described with reference to FIGS. 2 and 3.

FIG. 2 is a schematic view of an example of a centrifugal forming apparatus for a yarn bundle assembly, and FIG. 3 is a schematic cross-sectional view showing one end of the yarn bundle assembly immediately after forming.

In FIG. 2, molds 23 and 24 are provided at both ends of a support 22 that is rotatable about a rotating shaft 21, and a fiber bundle consisting of a large number of hollow fibers is provided at the center of the bottom surface of the mold 23. A recess 23' having a diameter corresponding to the outer diameter of 25 is formed.

When manufacturing the yarn bundle assembly, one end of the yarn bundle 25 is coated with adhesive or the like in advance to prevent the resin injected into the mold during centrifugal molding from entering the inside of the hollow fibers. In the sealed state, it is put into the recess 23' of the mold 23, the other end is put into the mold 24, and fixed to the support 22. Support body 22
While rotating, a liquid thermosetting resin containing ceramic powder, a hardening agent, and optionally a hardening accelerator is injected into the molds 23 and 24. The rotation speed of the support 22 is selected so that a centrifugal force of 10 to 500 G is applied to the resin, and the density of the ceramic powder is about 1.1 times or more, preferably 1.2 times or more, the density of the resin. By selecting a combination of ceramic powder and resin such that A ceramic powder mixed layer is formed.

In FIG. 3, a resin wall 26 is formed at the end of the yarn bundle assembly taken out from the centrifugal molding device after the resin has been cured by the above molding, and a resin wall 26 is formed on the end surface of the resin wall 26 in the yarn bundle axial direction. Surface layer portion 26 in which ceramic powder is mixed
' is formed, and each hollow fiber of the fiber bundle 25 has a resin wall 26.
A mixed layer 27 in which ceramic powder is mixed in resin is formed at the end of the thread bundle 25, passing through the thread bundle 25.

By cutting the end of the yarn bundle of the yarn bundle assembly along line A-A in FIG. 3, an open end of each hollow fiber is formed,
A yarn bundle assembly according to the present invention is manufactured.

By using the mold 23 having the recess 23' as described above, it is possible to manufacture a yarn bundle assembly material in which almost no ceramic powder is mixed in the section cut along the line A-A in FIG. In order to cut the ends of the fiber bundle 25, it is possible to easily form open ends of the hollow fibers without using a special knife.

The metal sealing member 11 may be made of metal such as stainless steel or nickel alloy, and may be of any material as long as it can isolate the source gas passage chamber and the permeated gas chamber. In order to minimize deformation of the surface layer 6' of the resin wall 6 in contact with the metal sealing member 11, an O-ring, particularly a hollow metal O-ring, is preferable since the linear pressure required for sealing is relatively small.

The metal elastic member 12 is preferably a disc spring, a spiral spring, or the like made of a metal such as carbon steel, silicon-manganese steel, or manganese-chromium steel.

The metal elastic member 12 needs to have a repulsive force that can apply the linear pressure necessary for sealing to the metal seal member 11 via the resin wall 6. Also, if necessary, a disc spring,
It is also possible to provide a spring seat between the spiral spring or the like and the resin wall 6 to apply a uniform linear pressure using the metal seal member 11. □ (Effects of the invention) Even when the gas separation device of the present invention is used under harsh conditions of high temperature and high pressure, it is possible to isolate the raw material gas passage chamber and the permeated gas in a fluid-tight state, and even in that state. This is a device that can maintain stability for a long period of time.

This is because the structure for isolating the raw material gas passing chamber and the permeated gas chamber in a fluid-tight state in the gas separation device of the present invention is configured as described above, so that the metal sealing member is not likely to be deformed. This is because the surface layer of the resin wall that comes into contact with the metal seal member is difficult to deform, and the metal elastic member always provides the necessary sealing strength to the metal seal member. When used at high temperatures, dimensional changes due to the difference in thermal expansion between the pressure container and the resin wall are quite large, but such dimensional changes can be absorbed by the metal elastic member, and the resin wall Creep deformation that occurs when subjected to compressive force under high temperature and high pressure for a long period of time can also be absorbed by the metal elastic member. Therefore, the necessary sealing pressure can be applied to the metal seal member for a long period of time.

Example Using the apparatus shown in Fig. 2, 4000 aromatic polyimide hollow fibers (outer diameter 400 μm, inner diameter 200 μm) were prepared as a yarn bundle.
A thread bundle made of books bundled into a cylindrical shape (outer diameter 40 mm, length 100 mm)
100O, and as a liquid thermosetting resin composition for forming the resin wall, a phenol novolak type epoxy resin (manufactured by Shell Co., Ltd., trade name Epicote 154), a curing agent (methylnadic anhydride), and a curing accelerator. (2-ethyl-4-methyl-imidazole) resin liquid (density 1.2 g/ctn3) and silicon carbide powder (particle size 1 to 10 μm, true density 3.2 g/am3). A yarn bundle assembly was manufactured by centrifugally molding a mixture containing 15% by weight of powder at a temperature of 78°C and a centrifugal force of 200G. A silicon carbide powder mixed layer having a thickness of about 7 mm was formed on the end face of the resin wall.

A metal O-ring (manufactured by Nippon Palcar Co., Ltd., silver-plated metal hollow O-ring) is used as the metal sealing member, and a tool steel 5K-5 disk spring is used as the metal elastic member to create the isolation structure shown in Figure 1. We have manufactured a gas separation device with At room temperature and pressure, the metal O-ring has 10 Kg/mmO
The repulsive force of the disc spring was adjusted to apply linear pressure.

Introducing 2008g/7cm2G of nitrogen gas from the raw material gas inlet, closing the unpermeated gas outlet, and opening the permeated gas outlet to the atmosphere so that a differential pressure of 200Kg/cm2 is applied to the tube wall of the hollow fiber. The entire gas separation apparatus was maintained at a temperature of 150°C.

A sealing test was conducted by maintaining this state for 6 months, and it was found that the sealing properties between the source gas passage chamber and the permeated gas chamber were maintained well. After the sealing test was completed, the depth of the indentation on the surface of the silicon carbide powder-containing surface layer of the resin wall that came into contact with the metal O-ring was 10 μm.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing a structural part for separating a raw material gas passage chamber and a permeated gas chamber in a fluid-tight state in one embodiment of the gas separation device of the present invention, and FIG. FIG. 3 is a schematic view of an example of a centrifugal forming apparatus for a bundle assembly; FIG. 3 is a schematic cross-sectional view showing one end of the yarn bundle assembly immediately after forming; 1 is a raw material gas inlet, 2 is a permeated gas outlet, 3 is a pressure vessel, 4 is a hollow fiber, 5 is a fiber bundle, 6 is a resin wall, 6' is a resin wall surface layer mixed with ceramic powder, 8 10 is a raw material gas passage chamber, 10 is a permeated gas chamber, 11 is a metal seal member,
12 is a metal elastic member, 22 is a support body, 23 is a mold, 2
5 is a yarn bundle. Patent applicant Ube Industries Co., Ltd. Figure 1 6'3' 1 Figure 2 Figure 3

Claims (3)

[Claims] (1) A fiber bundle consisting of a large number of hollow fibers having gas selective permeability, and at least one end portion of the fiber bundle are placed in a cylindrical pressure-resistant container having a raw material gas inlet, a permeated gas outlet, and an unpermeated gas outlet. , a fiber bundle assembly consisting of a thermosetting resin wall through which each of the hollow fibers passes and which is fixed in an open state is provided, and a raw material gas passage chamber in which the body of the hollow fiber exists and In a gas separation device, a structure for isolating the raw material gas passage chamber and the permeation gas chamber in a fluid-tight manner is (
A) a metal seal member provided between the inner wall of the pressure-resistant container and the resin wall; (B) the resin wall in which ceramic powder is mixed in at least the surface layer of the surface that contacts the metal seal member; and (C) a gas separation comprising a metal elastic member provided between the surface of the resin wall opposite to the surface that contacts the metal sealing member and the inner wall of the pressure vessel. Device. (2) Gas separation according to claim 1, characterized in that the resin wall (B) has a filled layer of ceramic particles preferentially distributed in the surface layer of the surface that contacts the metal sealing member. Device. (3) The gas separation device according to claim 2, wherein the packed layer of ceramic particles is formed by centrifugal molding of a resin mixed with ceramic powder.