JPS5816922B2 - Fluid separation device and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluid separation device using a permselective semipermeable membrane hollow filament (its purpose is to provide a fluid separation device with excellent fluid separation efficiency).

Taking advantage of the property of conventional permselective separation membranes that certain components of fluid mixtures or solutions pass through the membrane more easily than other components, only the pure solvent is leached out by applying pressure higher than the osmotic pressure to the solution. reverse osmosis, which concentrates specific components by applying pressure to a gas mixture; ultrafiltration, which separates specific components by applying pressure or vacuum to a liquid mixture; It is known to exchange and separate specific components from a fluid mixture or solution using principles such as forward osmosis, which separates specific components by utilizing differences in chemical potential, and dialysis, which removes specific components by concentration diffusion of solutes between solutions. There is.

A capillary or hollow filament is used as the separation membrane wall,
Material separation or exchange between fluid A inside the capillary and fluid B outside the capillary is possible.

Using a capillary tube is an effective technique that has three major advantages: the permeable membrane area that can be filled in a unit volume is large, and the capillary structure supports uniform external pressure or the weight of the membrane itself.

In devices using capillary tubes or hollow filaments, the permeable membrane area per thin capillary tube is extremely small, so a large number of capillary tubes are required to take advantage of the above advantages.

Regarding this capillary focusing method, a conventionally known device is one in which a large number of capillary bundles are focused in parallel, and both ends are embedded in a cast partition wall, and the ends of the epilation tube are opened.

For example, Japanese Patent Publication No. 39-28625 describes a fluid separation device in which a large number of permselective separation hollow filaments are housed in a cylindrical housing forming a processing chamber.

The fibers extend generally parallel to the longitudinal direction the length of the housing and pass through both ends of the cast bulkhead of the housing.

When a fluid mixture or solution as fluid B is pressurized and introduced into the processing chamber, the components to be separated pass through the membrane wall of the hollow filament as fluid A and go to chambers provided on the outside of both ends of the partition wall of the casing.

Further, the treated fluid B is taken out from the outlet of the housing.

As the permselective separation membrane, for example, a hollow filament made of an organic polymer, or a capillary made of a porous substrate on which a thin film of an organic polymer or an inorganic colloid is formed can be used.

As described above, a fluid separation device using capillaries is an effective technology, but as mentioned above, since a large number of capillaries are used, it is difficult to converge all the capillaries.

The quality of this fluid separation device is determined by whether each capillary acts equally on fluid separation.

That is, the fluid B flowing outside the capillary does not flow uniformly around each capillary, but forms a specific flow path.The separation of the fluid through the membrane wall of the capillary that does not participate in this flow is almost impossible. (There is no point in focusing a large number of capillaries.)

The aforementioned Japanese Patent Publication No. 39-28625 and Japanese Patent Publication No. 4
Both devices shown in 4-5526 have a configuration in which parallel capillary bundles extend across the housing and are embedded in the partition wall at both ends.

By converging the capillaries in parallel in this way, the number of capillaries that can be filled in a unit volume increases, but on the other hand, since each capillary is aligned in a row, capillaries that are separated from each other can interact with each other along their length. A defect that is easy to touch appears.

When such longitudinal contact occurs between the capillaries, there is virtually no fluid-material separation near the contact area and the separation efficiency is drastically reduced.

In particular, since the middle beam filaments made of organic polymers are mostly soft and flexible, the above-mentioned contact is likely to occur.

Furthermore, when the capillary bundle is focused in parallel, it is almost impossible to uniformly fill the cross section of the capillary bundle, and the packing density tends to vary.

In this case, the fluid B selectively flows through the portions of the capillary bundle where the packing density is coarse, and fluid separation hardly occurs in the portions where the capillary bundle is densely packed.

Therefore, the method of focusing the filaments in parallel has many drawbacks, and in order to solve these drawbacks, at least one or more selected partial capillary bundles 5 out of all the capillary bundles should intersect, It is clear that the structure must have uniform air gaps throughout the entire space.

On the other hand, US Pat. No. 3,422,008 discloses a fluid separation device in which a hollow filament is spirally wound around a porous core tube, but in such a device,
Since the hollow filament is spirally wound, the flow path of the fluid A within the filament is curved and becomes relatively long with respect to the storage container, which tends to increase the pressure loss of the fluid A.

Also, the fluid A may form precipitates or coagulate, which may cause blockage of the flow path.

In view of the above, the present inventors conducted research to provide a fluid separation device with excellent fluid separation efficiency and an easy-to-manufacture method, and arrived at the present invention as a result of research.

That is, the fluid separation device of the present invention has the following features: (1) ■ One or more hollow filaments made of permselective membranes are sequentially stacked, and the hollow filaments belonging to each layer are stacked one after the other, and the hollow filaments belonging to the adjacent layer are stacked one after another. In a fluid separation device composed of a hollow filament laminate that substantially crosses and overlaps the filaments, ◎ a porous core tube, an O partition, and a ○ container, (a) the hollow filaments are 10 to 15; Wrapping the hollow filament laminate having an intersection angle of 1° into a round rod shape around the porous core tube to form a bundle of hollow filament laminates with a porous core tube; (b) the bundle; (c) one or both ends of the bundle are open in the partition; (d) one end of the porous core tube is connected to the outside of the container; (e) A fluid separation device in which the partition wall is fixed to the container; The method for producing a fluid separation device of the present invention includes: (2) one or more hollow filaments made of a permselective membrane; is traversed through a pair of supports located substantially parallel to each other, and the intersecting angle of the hollow filaments is 10 to 5.
Winding at an angle of 45 degrees to obtain a hollow filament laminate in which the hollow filaments are sequentially laminated and the hollow filaments belonging to each layer are substantially cross-overlapping with the hollow filaments belonging to the adjacent layer, Next, the hollow filament laminate is wound around the porous core tube in the direction of the support to form a bundle of round rod-shaped hollow filament laminates, and the bundle is buried so that both ends of the bundle are supported by partition walls. Then, the partition wall is fixed to the container by a resin, and one end or both ends of the bundle are fixed to the partition wall.

A method for manufacturing a fluid separation device, which comprises assembling the porous core tube so as to open it at the container and communicate one end of the porous core tube with the outside of the container.

The present invention will be described below with reference to the drawings.

In FIG. 1, in the direction of the arrow, the hollow filaments 1 intersect with the hollow filaments belonging to adjacent layers at an intersection angle of about 10°.

Figure 1 shows an example of hollow filament stack 2 in which the number of filaments belonging to each layer is relatively small in order to clearly show the state of intersection of the hollow filament layers. When arranged in , two adjacent
The layer forms a fine shibori pattern over the entire surface of the layer.

This drawing pattern is formed continuously in the stacking direction, and for example, the hollow filaments belonging to any i-layer intersect with the hollow filaments belonging to the (i-1) and (i-layer 1) layers at the above-mentioned crossing angle. (where i is a positive integer).

FIG. 2 is a longitudinal sectional view of the fluid separation device according to the present invention.

That is, one or more hollow filaments 1 made of permselective membranes are sequentially laminated, and the filaments 1 belonging to each layer (e.g., layer i) belong to an adjacent layer (e.g., layer (i layer 1)). A round rod-shaped hollow filament bundle 3 is formed around the porous core tube 10 by the hollow filament laminate 2 which is substantially cross-overlapping with the filament 1'.
partition walls 13 and 14 that support both ends of the bundle.
It is stored in a container 4 having a

The hollow filament 1 is then opened on at least one end partition, 13 and 14 in this example.

On the outside of the partition wall 13, there is a distribution plate 6 having a supply lower part for the fluid A.
A focusing plate 8 having an outlet 9 for the fluid A is attached to the outside of the partition wall 14, and a sealing member 19, for example, is attached to the container 4.
and are fluid-tightly engaged by the engagement member 20.

On the other hand, the interior 12 of the porous core tube 10 communicates with the inflow passage 13 of the fluid B outside the container, and further passes through the processing chamber 15 outside the hollow filament through a plurality of holes 11 on the porous core tube. The fluid B reaches an outflow passage 5.

Fluid A and fluid B are assembled in a fluid-tight manner with respect to each other, except for the fluid separation that takes place via the permselective membrane wall of the hollow filament 1.

The apparatus of this example is suitable for separation operations such as dialysis, forward osmosis concentration, and ultrafiltration.

The fluid separation device shown in FIG. 3 is similar to the device shown in FIG. 2, except that the hollow filament 1 does not have an opening on the right partition 14.

In this figure, 6 and 7 are a focusing plate and an outlet for fluid A.

The device of this example is suitable for separation operations such as pressurized gas separation, reverse osmosis, and ultrafiltration.

The hollow filaments housed in the fluid separation device of FIGS. 2 and 3 are not parallel to each other along their lengths, but rather the layers of the constituent hollow filaments intersect and overlap.

For this reason, uniform voids are formed inside the laminated bundle of hollow filaments, so the fluid B flowing out from the porous core tube 10 can flow uniformly through these voids, preventing uneven flow or dead space from occurring. Therefore, excellent fluid separation efficiency can be obtained.

In addition, in the present invention, the hollow filaments are not essentially parallel, but are laminated bundles with a constriction pattern.
The arrangement of the hollow filaments opening at the partition wall 3 and the arrangement of the hollow filaments opening at the partition wall 14 at the right side exit are alternately located in the same laminated layer.

Therefore, even if the mixing state of the mixture of fluid A is non-uniform, there is an advantage that the fluid flowing out from the outlet 9 becomes more homogeneous.

FIG. 4 is a schematic diagram illustrating a method for manufacturing a fluid separation device according to the present invention.

That is, one or more hollow filaments 1 made of a permselective membrane are pulled out from the guide 22 after being tied together in a plurality of filaments as necessary to withstand the winding tension.

At this time, a tension adjustment mechanism (not shown) may be inserted if necessary.

On the other hand, supports 24 and 24' located substantially parallel and apart from each other and a pair of frame members 25 holding the supports (as shown in the figure, one of the frame members can also be used as the porous core tube 10).

) constitutes the frame 26. The frame 26 is rotated by a rotation mechanism (not shown) with its substantially symmetrical axis as the rotation axis 27, and the hollow filament 1 drawn out is rotated by a traverse mechanism 5 (
(partially shown).

The hollow filament laminate 2 is wound up onto the supports 24, 24' while traversing in the direction of rotation, forming a hollow filament laminate 2 as shown in FIG.

Next, if the supports 24 and 24' are flexible, they are removed as they are, or if they are rigid, they are removed while maintaining the lamination, and then the rotating shaft 27 and frame member 25 are removed and the supports are placed around the core tube 10. The hollow filament laminated bundle 3 in the shape of a round bar is formed by winding the filament in the direction shown in FIG.

The bundle 3 is housed in a container 4 as shown in FIG. 2 or 3, and partition walls 13 and 14 supporting both ends of the bundle 3 are attached with fixable partitions.

At this time, the partition walls 13 and 14 may be formed separately and then stored in the container 4.

At least one end bulkhead (13 and 14 in Figure 2)
, 13) in FIG. 4, the hollow filament is opened.

This is a second partition wall shaped with a fixable resin.
As shown in the figure, the hollow filament is opened by cutting at 13at13b, but in this case, the interior of the hollow filament is communicated with the outside world by cutting, and contamination during the manufacturing process inside the interior is less than reliability.

This requires the cleanliness of the hollow filament. Preferred in food or medical applications, especially in artificial kidneys.

The interior 12 of the porous core tube 10 communicates with the inflow passage 11 of the fluid B outside the container, and is assembled using, for example, a sealing member 19 so as to be fluid-tight to the outside.

The hollow filament laminate used in the apparatus shown in FIG. 2 and FIG.
102681, Japanese Patent Application No. 124556/1983), and can be assembled by being rolled around a porous core tube.

The intersection angle of the hollow filament laminate in the present invention can be selected from a wide range, and can be set to 10 to 45 degrees.

If the intersection angle is less than 10 degrees, the hollow filaments will become nearly parallel, and a squeeze pattern will not appear, making it difficult to expect the effects of the present invention.

In addition, if the crossing angle exceeds 45 degrees, manufacturing becomes difficult. For example, when winding a hollow filament around a bobbin as shown in Japanese Patent Application No. 102,681/1981, if the winding angle is extremely large (70 degrees or more), winding and mounting will be difficult. .

In the case of the method shown in FIG. 4, if the intersection angle is 45 degrees or more, the intersections will overlap significantly, which is not preferable.

Furthermore, the hollow filament laminate of the present invention is disclosed in Japanese Patent Publication No. 39-2
Unlike the parallel hollow filament assembly shown in No. 8625, it has a rigid shape retention property.

This is because the hollow filament laminate of the present invention is a laminate of intersecting hollow filaments, so the hollow filaments support each other at the intersections.

Therefore, the hollow filament laminate of the present invention does not come apart unlike parallel hollow filament aggregates, can be easily stored in a container, and there is no fear that the hollow filaments will break or be damaged when stored. do not have.

Furthermore, the hollow filament laminate according to the present invention can withstand a greater flow pressure of external liquid than a parallel hollow filament assembly.

As mentioned above, the hollow filaments support each other using their intersections as fulcrums, so even if, for example, a large amount of fluid B flows and a large flow pressure is applied, the flow pressure will concentrate on a certain filament and the hollow filament will locally This prevents problems such as unevenness, damage, and loss.

The porous core tube of the present invention includes a core tube having a plurality of holes and a porous structure having a large number of micropores, such as a core tube made of sintered metal.

The first effect of the porous core tube is that fluid B flows in a radial cross flow with respect to fluid A flowing inside the hollow filament.
can be distributed uniformly (examples in Figures 2 and 3);
Alternatively, fluid B can be uniformly flowed substantially in countercurrent to fluid A (Example 2, which will be described later).

In either case, in addition to the effect of the intersection of the hollow filament stacks, the performance of the fluid separation device is greatly improved.

The second effect is that it facilitates the production of bundles based on hollow filaments and further strengthens their shape retention.

Furthermore, if the method shown in FIG. 4 is adopted, the hollow filament laminate of the present invention can be easily manufactured, and since the hollow filaments form a constricted pattern throughout, the convergence is good and it is easy to handle. It's extremely simple.

Although the shape of the separation container can be any shape, it is preferable to use a container with a circular cross section because a bundle wound into a round rod shape is used.

A circular cross-section container is also preferred when pressure resistance is required.

The direction of flow of fluid A and fluid B may be reversed to that shown in FIG. 2).

In that case, the supply lower of fluid A, the distribution plate 6, the outlet 9, and the focusing plate are reversed (and/or the inflow passage 12 and outflow passage 5 of fluid B are reversed).

containers, distribution and focusing plates, and porous core tubes.

For example, anti-corrosion agents, corrosion-resistant light metals (e.g. corrosion-resistant aluminum)
It can be made of synthetic resin for mechanical materials or containers (for example, acrylic resin, polyamide resin, polyolefin resin, polyester resin).

These materials can also be used for the rotating shaft and frame member.

As the support, rigid materials such as containers can be used, and flexible materials such as single fibers or twisted yarns of natural fibers or synthetic fibers, synthetic resin tapes, fiber belts, split fiber bundles, etc. can be used.

Known materials can be used as the fixable resin for molding the partition wall.

Typical examples include natural rubber, synthetic rubber (eg silicone rubber), polyflex resin and epoxy resin.

The hollow filament used in the present invention may be any hollow filament that is flexible and exhibits permselectivity. For example, hollow filaments made of polyester, polyamide, polycarbonate, cellulose, or cellulose ester are effective; is 30μ ~ 3rd group,
A hollow filament laminate containing approximately 1,000 to 10,000,000 filaments is housed in a separate container.

Example 1 16 regenerated cellulose hollow filaments with an outer diameter of 300 μm and an inner diameter of 240 μm were spun together to form a yarn of 200 m as shown in Figure 4.
Parallel and spaced apart nylon fiber belt supports 24
, 24' are traversed through a frame 26 having a width of 18 CrrL assembled with a frame member 25 made of polycarbonate resin and a porous core tube 10 having approximately 80 holes evenly, while
It was wound at 0 degrees.

A stack 2 of 5,000 hollow filaments was obtained, wound around the core tube 10 in the direction of the support, and housed in an acrylic resin container 4 as shown in FIG.

Both ends of the hollow filament were filled with silicone rubber to form partition walls 13 and 14, and both ends were cut to open the hollow filament, as shown in FIG.

It was assembled as a separation device and used for dialysis operation.

As fluid A, use 2 parts by weight of saline solution at 4 or 17 vtin.
from the supply lower through the hollow filament 1 to the outlet 9 at a rate of
2, through the core tube 10, the treated material 15 flows radially across the hollow filament 1 as a cross flow, and is discharged from the outflow passage 5.

The salt concentration of fluid A obtained from outlet 9 is 0.29%.
showed excellent performance.

Example 2 A fluid separation device 1 similar to Example 1 except that eight holes 11 in the porous core tube 10 were provided only in the vicinity of the partition wall 14 was assembled and subjected to dialysis operation.

Deionized water, which is fluid B in the processing chamber 15, was flowed substantially countercurrently to the saline solution, which is fluid A in the filament.

The salt concentration of fluid A obtained from outlet 9 had decreased to 0.27%.

・Example 3 160 polyethylene terephthalate hollow filaments with an outer diameter of 55 μm and an inner diameter of 30 μm were spun together, and as shown in FIG. Composite support 24, 24'
A frame member 25 made of stainless steel and a non-cast steel sintered porous core tube 1
While traversing the frame 26 having a width of 100mm assembled in the above step, the winding was wound at a winding angle of about 25 degrees.

A laminate 2 of about 2,000,000 hollow filaments was obtained, and after removing the stainless steel support, they were wound around the core tube 10 in the direction of the support, and a pressure-resistant material made of stainless steel as shown in Fig. 3 was obtained. It was stored in container 4.

Fill both ends of the hollow filament with epoxy resin and partition wall 1
3.14 was made, and a hollow filament was opened that cut only the partition wall 13.

It was assembled as a separation device and used for pressurized gas separation operation.

A mixed gas of 63% helium/37% oxygen was supplied as fluid B by a compression pump at a rate of 18.5 N77 LVhr from the inlet passage 12 and discharged from the outlet passage 3.

The pressure applied in the separation vessel 4 was maintained at 50.9/cyyt.

When such an operation is performed, helium 94 is released from the fluid A extraction lower
%/6% oxygen was obtained at a rate of 10.8 NmVhr.

As described above, high purity .\lium gas was obtained in high yield from low purity helium mixed gas using the apparatus of the present invention.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a stack of hollow filaments filled into a container of a fluid separation device according to the present invention. 2 and 3 are longitudinal sectional views of the fluid separation device of the present invention. FIG. 4 is a schematic diagram showing a method of manufacturing a fluid separation device of the present invention. FIG. 5 is an enlarged longitudinal sectional view showing the cutting position of the partition wall. In the drawings, 1... hollow filament, 2...
...Hollow filament laminate, 3...Hollow filament laminate bundle, 4...Container, 5.
...Fluid B outflow passage, 6...Distribution plate (
or focusing plate), 7... Fluid A supply port (or outlet), 8... Focusing plate, 9... Fluid A outlet, 10... ...Porous core tube, 11...
... Core tube hole, 12 ... Fluid B inflow passage, 13.14 ... Partition wall, 15 ... Processing chamber, 19 ... Seal member, 20... Engaging member, 21... Hollow filament package, 23... Traverse mechanism, 24...
Support body, 25... Frame member, 26... Frame, 27... Rotating shaft.

Claims (1)

[Claims] 1 Hollow filament laminate in which one or more hollow filaments made of permselective membranes are sequentially laminated, and the hollow filaments belonging to each layer are substantially cross-overlapping with the hollow filaments belonging to the adjacent layer. In a fluid separation device consisting of a body, a porous core tube, a partition wall, and a container, the hollow filaments form an intersection angle of 10 to 45 degrees = the hollow filament laminate is connected to the porous core tube. A bundle of hollow filament laminates with porous core tubes formed in a round rod shape around the periphery of the bundle is attached to the partition wall so that both ends of the bundle are supported, and at least one end of the bundle is supported. A fluid separation device 02 in which the porous core tube is opened at a partition wall, one end of the porous core tube communicates with the outside of the container, and the partition wall is fixed to the container. One or more hollow filaments are traversed through a pair of supports located substantially parallel to each other and wound up so that the intersection angle of the hollow filaments is 10 to 45 degrees, and the hollow filaments are sequentially laminated and each layer is A hollow filament laminate is obtained in which the hollow filaments belonging to each other are substantially cross-overlapping with the hollow filaments belonging to the adjacent layer, and then the hollow filament laminate is wrapped around the porous core tube. Rolling in the direction of the support body to form a bundle of round bar-shaped hollow filament laminates, supporting and engaging both ends of the bundle with partition walls, and further housing the partitions in a container with a fixable resin, A method for manufacturing a fluid separation device, in which at least one end of the bundle is opened at a partition wall and one end of the porous core tube is communicated with the outside of the container.