JPS609841B2 - fluid separation device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a membrane separation device using hollow fibers whose membrane walls have permselectivity for fluids.

In recent years, membrane separation methods using selectively permeable membranes have attracted attention as a method for separating some components from a fluid mixture consisting of multiple components, and have already been put into practical use in some cases.

Application fields of membrane separation methods include gas permeation, liquid permeation, dialysis, ultrafiltration, and reverse osmosis.Specific application examples include seawater desalination, brine desalination, various wastewater purification, Examples include protein purification, oil/water chicks, artificial kidneys, artificial lungs, and the separation of helium from natural gas. Various types of membrane separation devices have been proposed in the past, but the flat model,
Typical types are tubular membrane type and hollow fiber membrane type. Among these, the hollow fiber membrane type has a large number of hollow fibers whose membrane walls are selectively permeable to the fluid, which are placed in the device and brought into contact with the fluid, and the membrane area per unit volume of the device is extremely large. In addition, the hollow fiber body has pressure resistance, so a membrane support is not required, and the sealing mechanism that separates the untreated fluid from the permeated fluid is simple. However, none of the hollow fiber membrane type membrane separation devices proposed so far are satisfactory and have several drawbacks.

Mochiko Sho 39-28625 discloses an apparatus having a structure in which hollow fibers are accommodated in a tubular pressure-resistant container parallel to the axial direction, but in this structure, the hollow fibers are arranged parallel to each other. The drawback is that the hollow fibers come into contact with each other and the effective membrane area is small.

Furthermore, since the direction of fluid flow and the direction in which the hollow fibers are arranged are parallel, the flow of the fluid tends to become non-uniform, and locally there are areas where the flow velocity is abnormally low, causing concentration polarization and impeding the permeability of the device. There are downsides to it. Japanese Unexamined Patent Publication No. 47-8595 discloses that a cylindrical hollow fiber assembly manufactured by spirally winding hollow fibers fixed to a thin porous material around a processing fluid dispersion pipe is made into a tubular pressure-resistant container. It shows the structure in which it was housed.

Although this structure significantly improves the uniformity of the flow of the processing fluid, it has the disadvantage that the packing density of the hollow fibers is reduced because a large number of them are arranged between the hollow fiber layers of the porous material. Furthermore, the assembly process of the hollow fiber assembly is complicated, the assembly equipment becomes large-scale, and it is difficult to directly connect the hollow fiber grade/manufacturing process and the assembly process of the hollow fiber assembly. Japanese Patent Publication No. 50-5153 discloses a method in which a hollow fiber is spirally wound around a hollow cylindrical body, and then a pressure wall is formed at the end of the hollow fiber layer.

Although this method is preferable because it facilitates mechanization and automation of the assembly process of the hollow fiber assembly, in the process of winding the hollow fiber around a hollow cylinder, the hollow fiber with permselectivity has a higher Since the tension is inferior, strong tension cannot be applied, and therefore, the hollow fiber layer formed in the cylindrical portion easily collapses, making it difficult to form a layer with a stable shape. As a result of various studies aimed at improving the drawbacks of conventional methods, the present inventors found that in the step of arranging hollow fibers by winding them around the surface of a tubular body, thread-like or string-like A simple method of forming a cylindrical layer on the surface of the tubular body by repeatedly arranging the spacer and arranging the hollow fiber and the spacer so that they intersect is a simple method that improves membrane separation performance. The inventors have discovered that it is possible to manufacture an excellent hollow fiber assembly and have arrived at the present invention.

That is, in the present invention, hollow fibers having permselectivity for fluids are arranged to intersect with each other on the surface of a tubular body together with a filament-like or string-like spacer. A cylindrical layer consisting of a tubular body is formed, and a resin wall is provided at one end or both ends of the tubular body, and the hollow fiber passes through the resin wall in a fluidized state and closes to the outside. A fluid separation device characterized by comprising a hollow fiber assembly.The membrane separation device of the present invention has permselective hollow fibers arranged on the surface of a tubular body intersecting with thread-like or string-like substrates. Therefore, an appropriate gap is formed between adjacent hollow fibers, and each hollow fiber is firmly held without easily moving, so that the hollow fiber layer does not come loose, and therefore membrane separation is possible. In operation, the pus area works effectively and the flow of the processing fluid is uniform and there are no places where the flow rate is extremely low, so concentration polarization phenomenon hardly occurs and the permeation capacity is large.

Furthermore, in the present invention, the size and arrangement density of the filament-like or string-like spacer can be changed independently of the arrangement density of the hollow fibers, so the gap between adjacent hollow fibers can be freely adjusted, and the spacer in the form of a sheet can be changed. Unlike when a porous body is disposed, the hollow fiber packing density is not reduced unnecessarily. In addition, the hollow fiber assembly of the present invention can be manufactured by simply combining the traverse mechanism of the hollow fiber to be transferred and the rotation of the tubular body, and the assembly process can be easily mechanized and automated. The hollow fibers used in the present invention are not particularly limited as long as they have an outer diameter of 10 to 1000 microns, a hollow ratio of 3 to 80%, and have selective permeability to the fluid at the membrane end, but for example, cellulose acetate. , cellulose-based polymers such as hydroxyethyl cellulose, cyanoethyl cellulose, regenerated cellulose, polyvinyl alcohol, polyvinyl acetal, polyacrylonitrile, polyacrylate ester, polyethylene, polypropylene, polystyrene, polypynyl chloride, polytetrafluoroethylene, vinyl polymers such as polystyrene sulfonic acid-polyvinylbenzyltrimethylammonium polyelectrolyte complex, poly L-glutamate, nylon 4, nylon 6, nylon 60, polydimethylpiverazine fumaramide, polydimethylpiverazine isophthalamide, Polyamides such as polydimethylpiverazine terephthalamide, polyparaxylylene adipamide, polyparaxylylene isophthalamide, polyparaxylylene terephthalamide, polyparaphenylene terephthalamide, polyparaphenylene terephthalamide, etc. Lamido,
Examples include hollow fibers obtained from polyhydrazide, polyamide hydrazide, polybenzimidazole, polyimidazopyrrolone, polycarbonate, polyphenylene oxide, polysulfone, polyethylene terephthalate, polybutylene terephthalate, silicone resin, or collagen.

The tubular body used in the present invention is a columnar body whose axial length is 5 times or more the maximum length in the direction perpendicular to the central axis, and may be hollow or non-hollow, and may be cylindrical or prismatic. It may be.

Examples of suitable tubular bodies when the tubular body is used as a dispersion pipe for processing fluids or a concentrating pipe for concentrated fluids include porous porcelain pipes, porous metal pipes, porous plastic pipes, metal pipes with many holes, A plastic tube with slits in all directions,
There are porous fiber tubes manufactured by weaving glass fibers. If the tubular body does not need to be used as a dispersion tube or a concentrating tube, a general non-porous hollow fiber or a solid rod-like body may be used as the tubular body. In the present invention, a hollow fiber having permselectivity and a filament-like or string-like spacer can be arranged on the surface of a tubular body by winding them in a spiral around the outer periphery of the cylindrical part of the tubular body. well,
Alternatively, a method may be adopted in which the cylindrical portion is passed through both end faces of the tubular body without making one rotation around the outer periphery.

When using the latter method, the hollow fiber or spacer may be passed across the end face of the tubular body in a straight line, or a central axis may be provided at the end of the tubular body and the fiber may be passed across the outer periphery of the end face. A method may also be used in which the hollow fiber or spacer passes through this central axis, turns back at an angle of 180 degrees or less, and crosses the outer periphery again. Alternatively, it may be wound spirally around the cylindrical portion of the tubular body and passed through one or both end faces. It is essential to use different methods for arranging the hollow fibers and arranging the spacers. In other words, it is important that the hollow fibers and the baser are arranged so as to cross each other at different angles on the surface of the tubular body. That is, since the hollow fibers are arranged on the surface of the tubular body so as to intersect with the filament-like or string-like spacer at different angles, appropriate gaps are formed between adjacent hollow fibers. is firmly held without easily moving, and no lint is generated in the hollow fiber layer.Therefore, the membrane area works effectively in membrane separation operations, and the flow of the processing fluid is uniform, allowing it to be used in areas where the flow rate is extremely low. Since there is no concentration polarization phenomenon, the permeation ability is increased.The thread-like or string-like baser used in the present invention may be made of the same material as the hollow fiber having selective permeability, or may be made of a different material. Good.The form of the thread-like baser may be monofilament, multifilament, or spun yarn, and nylon thread, polyester thread, cotton thread, etc. can be used.Furthermore, as an example of the string-like baser, it is composed of fibers. Examples include strings, soft plastic tubes (hollow and solid), tape-like materials of not very wide width, the cross-sectional shape of which may be circular, triangular or cog-shaped. Good. In the present invention, the resin constituting the resin wall is preferably a fluid liquid before curing and solidifies into a hard resin, such as epoxy resin, silicone resin,
Polyurethane resin, phenol-formalin resin, unsaturated polyester resin, polyester acrylate resin, etc. are used.

In the present invention, the method of injecting resin to form a resin wall is to continuously apply a resin liquid onto the hollow fibers in a band shape in parallel with the arrangement of the hollow fibers in the process of arranging the hollow fibers in a tubular body. Alternatively, a method may be used in which the resin is infiltrated into the ends of the hollow fiber layer after the arrangement of the hollow fibers is completed. The resin wall may be formed at one end of the tubular body, or may be formed at both ends of the tubular body. In this case, it is preferable to form a resin wall that includes the ends of the hollow fiber layer inside, then cut the resin wall in a direction substantially perpendicular to the central axis and insert the hollow fibers on the outside of the resin wall. A resin wall is formed slightly inside the end of the hollow fiber layer, and the hollow fiber layer that slightly protrudes outside the resin wall is cut in a direction almost perpendicular to the central axis to open the hollow fibers outside the resin wall. □It is also possible to form an edge. The resin wall in the present invention does not necessarily have to be formed in a direction perpendicular to the central axis; for example, a hollow cylinder having a central axis near the central axis at one end or both ends of a cylindrical hollow fiber assembly. Alternatively, a long plate-like resin wall parallel to the central axis may be provided on the side surface of a cylindrical hollow fiber assembly.

The hollow fiber assembly manufactured in this manner is housed in a cylindrical pressure vessel by a conventional method, and a sealing mechanism is installed to prevent the fluid on the open end of the hollow fiber from mixing with the fluid on the hollow fiber layer side. used for fluid separation operations.

Specific application examples of the pus separation device of the present invention include helium recovery, hydrogen purification, gas permeation such as in an artificial lung, liquid permeation such as separating paraxylene from mixed xylene, dialysis such as in an artificial kidney, Purification of enzymes, oil/water separation, ultrafiltration such as recovery of paint from lightning coating wastewater, desalination of seawater and underground brine, purification of wastewater, recovery of useful substances from wastewater, reverse osmosis such as concentration of juice, etc. Laws, etc. can be mentioned.

The present invention will be explained in more detail below according to specific examples shown in the drawings, but the present invention is not limited thereto.

FIGS. 1, 2, and 3 vaguely show specific examples of how hollow fibers 4 having permselectivity and thread-like or string-like basers 6 are arranged on the surface of a tubular body in the present invention. It is illustrated in an easy-to-understand format. In FIG. 1, hollow fibers 4 (indicated by woven lines) having permselectivity are arranged in a spiral manner around the cylindrical portion of a tubular body 1, while a thread-like or string-like spacer 6 ( ) shows an example in which both end faces of the tubular body 1 are passed through in a straight line, and the cylindrical portion of the tubular body 1 is arranged in a manner such that it passes around the outer periphery without rotating once. In Fig. 2, a tubular body 1 having central axes at both ends is used, and a hollow fiber 4 having permselectivity is passed through both end faces in a folded manner via the central axis, and is approximately parallel to the central axis of the tubular body 1. An example is shown in which the thread-like or string-like spacer 6 is arranged in a spiral manner around the cylindrical part of the tubular body. In FIG. 3, a hollow fiber 4 having permselectivity is wound spirally around the cylindrical part of a tubular body and is arranged in such a way that one end surface is traversed in a straight line, while a thread-like or string-like spacer 6 is An example is shown in which it is arranged by winding it in a spiral around the cylindrical part of a tubular body. FIG. 4 shows a specific example of the method of arranging permselective hollow fibers and filament-like or string-like substrates on the surface of a tubular body in the present invention.

The rotation of the tubular body 1 is performed by surface-transmitting the rotation of a rotating cylindrical body having a drive shaft 3. The hollow fibers 4 are supplied through a thread guide of a traverser 5 that reciprocates parallel to the central axis of the tubular body 1, and are wound spirally around the cylindrical portion of the tubular body 1. On the other hand, the filament-like or string-like spacer 6 is supplied to the tubular body 1 from the direction opposite to the hollow fiber 4 through the yarn path guide of the traverser 7 that reciprocates in a direction parallel to the central axis of the tubular body 1. It is wound spirally around the cylindrical part. More specifically, in FIG. 4, the hollow fibers 4 are first fed through the thread guide of the traverser 5 and wound around the cylindrical portion of the tubular body 1 in a spiral manner. Next, the supply of the hollow fibers 4 is stopped, and a filament-like or string-like baser 6 is supplied to the tubular body 1 from the direction opposite to the hollow fibers 4 through the fiber path guide of the traverser 7 at a different angle from the hollow fibers, and onto the hollow fiber layer. Wrap it in a spiral. After that, the supply of the baser 6 is stopped and the supply V is again repeated at different angles to the baser of the hollow fiber 4, and the hollow fibers and the baser are alternately arranged at different angles, and the hollow fibers and the baser are alternately arranged on the surface of the tubular body 1. Forms a cylindrical layer consisting of hollow fibers and basers. It is also possible to arrange the hollow fiber or spacer so as to pass through the end face of the tubular body by the method shown in FIG.

The method of arranging hollow fibers and spacers in the present invention is not limited to the method shown in FIG. 4. For example, by appropriately selecting and combining the circular operation and reciprocating motion of the yarn guide that supplies the hollow fibers and the baser, the rotational motion around the central axis of the tubular body, and the reciprocating motion in the direction of the central axis, it is possible to Those skilled in the art will readily understand that the hollow fiber and spacer arrangements shown in the Figures and Figure 3 can be implemented. FIG. 5 shows a sectional view of a membrane separation device in which a hollow fiber assembly of the present invention is housed in a cylindrical container.

A hollow fiber assembly consisting of a tubular body 8 with a large number of holes, a processing fluid inlet pipe 11, a layer 9 of hollow fibers and a spacer, and a resin wall 10 is housed in a cylindrical casing 12. The hollow fiber assembly shown in Fig. 5 is based on the arrangement method of hollow fibers and spacers shown in Fig. 2. The hollow fibers are arranged so as to pass through both end faces of the tubular body, and the spacers are arranged so as to pass through both end faces of the tubular body. It is arranged by winding it around a cylindrical part in a spiral manner, and further has a resin wall formed at one end thereof substantially perpendicular to the central axis of the tubular body. In FIG. 5, a side plate 14 is provided in contact with the resin wall 10', sandwiching a disc 13 made of a porous material, and a side plate 15 is provided on the opposite side from the resin wall 10. Also, the side plates 14,1
C-rings 16, 17 are fitted into the casing 12 to support the casing 5, and elastic rings 18, 19, 20, 21 are arranged to provide a fluid seal. The processing fluid supplied to the inlet tube 11 flows through the inlet tube 11 into the layer 9 consisting of hollow fibers and spacers, which is fitted through the tube wall of the tube 8' having a plurality of holes therein. The permeated fluid that has permeated the wall of the hollow fiber passes through the inside of the hollow fiber, reaches the outer open end of the resin wall 10, passes through the disc 13 made of a porous material, and is collected at the permeated fluid outlet 23 and discharged. . On the other hand, the concentrated fluid that has not passed through the walls of the hollow fibers is taken out from the outlet pipe 22. In addition, in the opposite direction to the above operation, the processing fluid is passed through the outlet pipe 2.
It is also possible to supply the concentrated fluid to 2 and take out the concentrated fluid from the inlet pipe 11.

[Brief explanation of the drawing]

Figures 1, 2, and 3 schematically show specific examples of how hollow fibers having permselectivity and filament-like or string-like basers are arranged on the surface of a tubular body in the present invention. It is a diagram. FIG. 4 shows an example of a method of arranging permselective hollow fibers and thread-like or string-like basers on the surface of a tubular body in the present invention. FIG. 5 is a cross-sectional view of a membrane separation device equipped with the hollow fiber assembly of the present invention. 1... tubular body, 4...
・Hollow fiber, 6... Subaser, 10... Resin wall, 1
2...Cylindrical casing. Many 1 image, 2 images, 3 images, 4 images, 5 images

Claims (1)

[Claims] 1. Hollow fibers having selective permeability to fluids are arranged at a predetermined angle on the surface of the tubular body, and a thread-like or string-like spacer is arranged at a different arrangement angle from the hollow fibers, and this is repeated to form the tubular body. A cylindrical layer in which the hollow fibers and the spacers are arranged in an intersecting manner is formed on the surface of the body, and a resin wall is provided at one end or both ends of the tubular body, and the hollow fibers are connected to the resin wall. A fluid separation device comprising a hollow fiber assembly that penetrates a wall in a fluid-tight manner and is open to the outside.