JPS6271513A - Method of fixing end part of gas separation module - Google Patents

Abstract

PURPOSE:To easily fix the end part of a gas separation module using porous material pipes by embedding the end part of the pipe in inorg. granular particles having <=35 deg. angle of repose and higher sp.gr. than a sealing material and then packing the sealing material. CONSTITUTION:Inorg. granular particles 5 having <=35 deg. angle of repose, a low thermal expansion coefficient and heat resistance are uniformly packed in many clearances at the end parts of many porous glass tubes 4. About 32-60-mesh granular particles 5 are used. The sp.gr of the granular particle 5 must be sufficiently higher than that of a sealing liq. After the granular particles 5 are densely packed, a liq. caking or curable sealing material is filled in the clearances in the granular particle-packed layer in a wet state. The sealing material need not be liq. at ordinary temp. and the materials which is liquefied by heating or whose viscosity is remarkably decreased on heating can be used.

Description

[Detailed Description of the Invention] (Field of Industrial Application) In recent years, gas separation technology using membranes has attracted attention as an inexpensive and energy-saving gas separation technology, and research is being actively conducted for its industrial practical application. For industrial practical application, it is important to develop separation membrane materials with high separation performance as well as inexpensive, compact, and reliable modules. The present invention relates to a method for manufacturing a gas separation module using porous material tubes, and more specifically, to a method for fixing the ends of a gas separation module.

(Prior Art) The present inventors have already disclosed a method for fixing the ends of the module with a sealing material when manufacturing a gas separation module that has a large number of porous material tubes built into the outer tube at low cost and easily. Showa No. 60-19020, No. 60-1220
No. 08 and '60-122027. Gas separation modules manufactured by these methods are manufactured at low temperature and low pressure, for example, 50°C.

There are no particular problems when operating at 5 atmospheres. However, when it is desired to operate at high temperature and high pressure, such as 200° C. and 20 atm, there is a problem in heat and pressure resistance, and it cannot be used under such operating conditions.

(Objective of the Invention) The present invention aims to overcome such problems and provide a method for fixing the ends of a module that can inexpensively and easily manufacture a gas separation module incorporating a large number of porous inorganic material tubes. purpose.

(Structure and operation of the invention) The present invention solves the above-mentioned conventional problems by fixing the ends of the module using inorganic powder and granular material and a liquid solidifying or hardening sealant. The summary is as follows.

(1) A cylinder that is open at both ends is made into a substantially upright shape, the lower end of which is closed to the extent that liquid assimilable or curable sealing material does not leak, and there is a void inside the cylinder at least at the ends. In a method in which a plurality of porous inorganic material tubes are inserted and arranged and their ends are fixed with a liquid solidifying or hardening sealant, the plurality of porous inorganic material tubes are inserted and arranged to rest in a tube. An inorganic powder having an angle of 35 degrees or less and a specific gravity higher than that of the sealing material is charged so that the end of the porous inorganic material tube is buried, and then a liquid solidifying or hardening material is charged. 1. A method for fixing an end of a gas separation module, which comprises injecting a sealing material to fill voids inside an inorganic powder layer with a mixed phase, and then solidifying or hardening the sealing material.

(2) The method according to item 1 above, wherein vibration is applied while or after charging the inorganic powder to fill the powder.

(3) The method according to item 1 above, wherein either or both of the inorganic powder and the sealant are heated.

(4) The method according to item 1 above, in which a low-viscosity, solvent-free polyimide varnish is used as the sealing material.

The present invention will be explained in detail below.

In order to improve the heat and pressure resistance of the gas separation module, it is necessary to fix the ends of multiple porous inorganic material tubes with a sealing material that has sufficient adhesive strength and pressure resistance at the temperature and pressure used.
Must be sealed airtight. In this case, the sealing material must be evenly filled into the gaps at the ends of a bundle of multiple porous inorganic tubes, so the sealing material must be in liquid form, and the liquid sealing material must be melted by heating and then injected. Possible methods include cooling and solidifying the material, or injecting a liquid thermosetting sealant and then heating and hardening it.

However, since the difference in coefficient of thermal expansion between the solidified or hardened sealing material and the porous material tube is generally too large, cracks occur when the sealing material is cooled.

For example, low viscosity solvent-free polyimide varnish (trade name: IMID-ALLO), which is particularly excellent as a curable sealant,
Y: When manufacturing a module by fixing the end of a porous glass tube using Toshiba Chemical Co., Ltd., the coefficient of thermal expansion of the polyimide resin after heat curing is 100 times larger than that of the porous glass tube. Therefore, when the resin is cooled from the curing temperature to room temperature, residual stress may cause cracks in the glass tube or cracks in the polyimide resin. To avoid this, it is necessary to use a sealing material that hardens at room temperature, or the sealing material must be relatively soft and easily deformed after solidifying or hardening. I can't stand it. Further, the problem of differences in thermal expansion coefficients also occurs when a manufactured module is used for processing high-temperature gases.

The present inventors first filled the gap to be airtightly sealed with inorganic powder, and then wet-filled the gap inside the inorganic powder layer with a liquid solidifying or hardening sealing material.
It has been found that by subsequently solidifying or hardening, it is possible to solve the problem of cracking due to residual stress caused by differences in thermal expansion coefficients.

Although the powder or granular material is not particularly limited, an inorganic material having a small coefficient of thermal expansion, heat resistance, and low cost is preferable, such as alumina powder, silica powder, chamotte powder, glass powder, and slag powder. In order to uniformly fill the large number of narrow gaps at the ends of a large number of porous inorganic material tubes, it is desirable that the angle of repose of the powder and granular material be as small as possible, and the angle of repose of the granular material is preferably 35° or less, preferably 25° or less. good. If the angle of repose is greater than 35°, the ends of the multiple porous material tubes will be narrowed.

The angle of repose of a powder or granule differs depending on the uniformity of the particle size and shape of the powder or granule, and a spherical powder or granule with a relatively large and uniform particle size exhibits an extremely small angle of repose.

However, if the particle size is too large compared to the gap to be filled, it becomes difficult to fill uniformly, so there is a limit naturally. The minimum gap to be filled is 1.5 m.
In the case of a particle size of about 32 to 60 mesh, the particle size is preferably about 32 to 60 mesh. The angle of repose of spherical blast furnace slag grains of 32 to 48 mesh is 2.
4°, which is one of the preferred powders.

In addition, if the particle size range is too wide and the particle sizes are uneven, not only will the angle of repose become large, but also the liquid solidifying or hardening sealing material will fill the voids inside the filled powder layer. In this case, all the air in the voids inside the powder layer cannot be completely replaced by the sealing liquid, so when solidified or hardened, a large number of zeids or blisters occur, making it impossible to achieve an airtight seal.

When filling a powder layer into a gap to be airtightly sealed, it is necessary to fill the gap tightly and uniformly.

For this purpose, it is desirable to fill the powder layer as tightly and uniformly as possible while completely filling the powder or by applying vibration after filling. If the sealing liquid is not filled tightly, the required amount of wet sealing liquid will increase, and if it is solidified or hardened and cooled, the residual stress caused by the difference in the coefficient of thermal expansion will increase, causing damage to the porous material pipe. becomes.

Furthermore, the filling of the powder must be uniform. f In the case of uniform sealing liquid, when the sealing liquid filled wet is assimilated or hardened and cooled, porous formation occurs due to the residual stress caused by the difference in coefficient of thermal expansion between the densely filled part and the loosely filled part. Cracks occur in the quality material pipe.

In addition, the specific gravity of the granular material needs to be sufficiently larger than the specific gravity of the sealing liquid that is wet-filled. If the specific gravity of the granular material is not large enough, part of the granular material layer will float up υ when the sealing liquid is wet-filled, and a dense and uniform filling state cannot be maintained. As a result, cracks occur in the porous material tube as described above.

The sealing material that is wet-filled does not necessarily have to be liquid at room temperature. Something that becomes liquid when heated,
Alternatively, if the viscosity is significantly reduced, one or both of the powder and the solidified or curable sealing material may be heated before use.

In the present invention, an inorganic material tube, such as a porous glass tube, is used as the porous material tube from the viewpoint of heat resistance and pressure resistance, but ceramic materials, sintered metal materials, etc. can also be used as the tube material.

1 to 3 are diagrams illustrating an embodiment of the present invention. Silicon putty 2 was rolled to a thickness of about 1 m on a steel bottom plate 1, and an aluminum cylinder 3 with an outer diameter of 79 fl, a thickness of 2 ws, and a length of 20 J, the surface of which was chromate-treated, was set as shown in FIG. On the other hand, a porous glass tube 4 with a reduced outer diameter at the end as shown in FIG.
．． A porous glass tube bundle was made by bundling 1,320 8 m long tubes in a close-packed state, and the porous glass tubes 4 were set perpendicularly to the bottom plate 1 so that the tips of the porous glass tubes 4 were buried in the silicon putty layer 2, as shown in FIG. Next, in the gap between the aluminum cylinder 3 and the end of the porous glass tube bundle, and in the gap between the end of the porous glass tube and the end of the porous glass tube, a particle size of 32 to 48 mesh, an angle of repose of 24°, A packed bed of spherical blast furnace slag 5 having a hardening apparent ratio of i 1.75 was made as uniformly and densely as possible while vibrating the bottom plate 1 to form a packed bed as shown in FIG.

The powder and granular material filled in this state was maintained at 80°C.

-Shi-Q11T'V4! (1) Polyimide varnish was injected little by little between the porous glass tube bundle and the aluminum cylinder 30. The varnish was completely injected until the injected varnish wetted the powder layer 5 and the voids between the powder particles were completely filled with the varnish. Thereafter, the varnish was held at 130°C for 30 minutes and then at 160°C for 24 hours to completely cure the varnish. The same operation was performed on the other end, and after cooling, the bottom plate was removed, the silicone was removed, and both ends were fixed and sealed to produce a raw porous glass tube bundle.

The porous glass tube bundle 7 with both ends fixed and sealed is housed in the module shell 6 as in the fourth factor, and the inner wall of the module shell 6 and the outer periphery of the aluminum cylinder 3 fixing the end of the glass tube bundle 7 are The gas separation module shell was airtightly sealed with a gap of 0 g/g. This module was used to separate and concentrate specific components of gaseous gold from a mixed gas. The mixed gas is supplied from the supply gas port 9, and the porous glass tube bundle 7
The gas flowed through each glass tube toward the non-permeable gas outlet (J, omitted in the drawing) at the right end. During this time, the gas that permeated through the pores in the wall of each glass tube flowed out through the permeated gas outlet 10.The central part of the module shell 6 An expansion joint 11 is connected to and supported by a support rod 12.

(Effects of the Invention) According to the present invention, it has become possible to inexpensively and easily manufacture a gas separation module that includes several hundred to several thousand porous material tubes and has excellent pressure resistance and heat resistance.

[Brief explanation of drawings]

Figures 1 to 3 are diagrams illustrating one implementation of the method according to the present invention. Fig. 2 is a side sectional view illustrating the state of the tube installed to fill it with powder and granular material and sealing material; Fig. 3 is a side sectional view illustrating the state of the tube installed to fill it with powder and granular material and sealing material; FIG. 4 is a side cross-sectional view of a gas separation module incorporating a bundle of porous glass tubes with fixed ends in accordance with the present invention. 1...Bottom board, 2...Silicon top layer, 3...7
A/ Miniram cylinder, 4...Porous glass tube, 5.
...Spherical blast furnace slag powder, 6.Module shell, 7.Porous glass tube bundle, 8.0 ring, 9
... Supply gas inlet, 10... Permeate gas outlet, 11.
...Expansion joint, 12...Support rod. Agent Patent attorney Masaaki Akizawa Mitsunobu 2 pieces 2 illustrations=Yu===22 figures

Claims (4)

[Claims] (1) A cylinder with both ends open is made almost upright, and its lower end is closed to the extent that liquid solidifying or hardening sealing material does not leak, and the cylinder has a void inside at least at the ends. In a method in which a plurality of porous inorganic material tubes are inserted and arranged and their ends are fixed with a liquid solidifying or hardening sealant, the plurality of porous inorganic material tubes are inserted and arranged to rest in a tube. An inorganic powder having an angle of 35 degrees or less and a specific gravity higher than that of the sealing material is charged so that the end of the porous inorganic material tube is buried, and then a liquid solidifying or hardening material is charged. A method for fixing an end of a gas separation module, characterized in that a sealing material is injected to wet-fill voids inside an inorganic powder layer, and then the sealing material is solidified or hardened. (2) The method according to claim 1, wherein vibration is applied while or after charging the inorganic powder to fill the powder. (3) The method according to claim 1, wherein either or both of the inorganic powder and the sealing material are heated. (4) The method according to claim 1, wherein a low viscosity solvent-free polyimide varnish is used as the sealing material.