WO2022080366A1

WO2022080366A1 - Separation membrane element production method and separation membrane element

Info

Publication number: WO2022080366A1
Application number: PCT/JP2021/037730
Authority: WO
Inventors: 正憲北野; 和輝池下
Original assignee: 住友化学株式会社
Priority date: 2020-10-15
Filing date: 2021-10-12
Publication date: 2022-04-21
Also published as: JP2022065306A

Abstract

In this separation membrane element, at least a portion of a laminate is wound around a hollow tube. The laminate is obtained by stacking a plurality of separation membrane units each comprising: a leaf having a first channel member interposed between two folds of a separation membrane; and at least a portion of layers of a second channel member that is to be stacked on the leaf. The respective separation membrane units are stacked on one another such that the positions of the folding portions of the respective separation membranes are not in alignment in the winding direction of the laminate. A production method for this separation membrane element comprises a step for stacking separation membrane units. The stacking step further comprises a first step for stacking a N-th tier separation membrane unit on a (N-1)-th tier separation membrane unit while a first region that includes at least a portion of the folding line of the separation membrane in the (N-1)-th tier separation membrane unit is being pressed.

Description

Separation membrane element manufacturing method and separation membrane element

The present invention relates to a method for manufacturing a separation membrane element and a separation membrane element.

It is known to use a separation membrane element to separate a specific fluid component from a raw material fluid such as a liquid or gas. The separation membrane element generally has a structure in which a laminate in which a separation membrane, a supply-side flow path member, a transmission-side flow path member, and the like are laminated is wound around a hollow tube. The laminated body is formed by forming a leaf in which a supply-side flow path member is sandwiched between the separation membranes folded in half, and laminating a plurality of separation membrane units in which the leaf and the transmission-side flow path member are overlapped. (For example, Japanese Patent No. 3570831 (Patent Document 1), Japanese Patent Application Laid-Open No. 2010-82575 (Patent Document 2), etc.). In such a laminated body, a plurality of laminated separation membrane units are laminated so as to be displaced at a predetermined pitch in the winding direction of the laminated body.

Japanese Patent No. 3570831 Japanese Unexamined Patent Publication No. 2010-82575

Since the leaf contained in the separation membrane unit is formed by folding the separation membrane in half, swelling is likely to occur at the fold portion of the separation membrane. When a plurality of separation membrane units are laminated in a state where the leaf is bulged, the thickness of the region where the fold portion of the leaf is arranged is increased in the portion where the separation membrane units are laminated, and the laminated separation membrane unit is warped. Will occur. If the separation membrane unit is further laminated in such a warped state, the stacking position of the leaf and the transmission side flow path member included in the separation membrane unit is displaced, and the separation membrane unit is accurately performed at the predetermined pitch. It becomes difficult to stack. If the separation membrane units are not laminated with high accuracy, the cross section of the portion where the laminated body is wound around the hollow tube does not become a perfect circle, and the shape becomes eccentric and the appearance tends to deteriorate.

It is an object of the present invention to provide a method for manufacturing a separation membrane element and a separation membrane element in which the separation membrane unit can be satisfactorily laminated and the shape of the portion where the laminate is wound around a hollow tube is good.

The present invention provides the following method for manufacturing a separation membrane element and a separation membrane element.
[1] A method for manufacturing a separation membrane element including a perforated hollow tube and a laminated body, in which at least a part of the laminated body is wound around the hollow tube.
The laminated body is
A plurality of separation membrane units including a leaf having a first flow path member interposed between the two-folded separation membranes and at least a part of layers constituting the second flow path member laminated on the leaf are laminated. ,and,
The separation membrane units are laminated so that the position of the fold portion of the separation membrane is displaced in the winding direction of the laminate.
The manufacturing method includes a step of laminating the separation membrane unit.
In the laminating step, when N is an integer of 2 or more, the first region including at least a part of the fold portion of the separation membrane contained in the separation membrane unit of the (N-1) layer was pressed. A method for manufacturing a separation membrane element, comprising a first step of laminating the separation membrane unit of the Nth layer on the separation membrane unit of the (N-1) layer in the state.
[2] The method for manufacturing a separation membrane element according to [1], wherein the pressing of the first region is performed so that the maximum distance between the surfaces of the separation membranes facing each other in the first region is less than 5 mm.
[3] The laminating step further includes a second step of laminating the (N + 1) th layer separation membrane unit on the Nth layer separation membrane unit laminated in the first step.
In the second step, the separation membrane unit of the (N + 1) layer is pressed in a state where the second region including at least a part of the fold portion of the separation membrane included in the separation membrane unit of the Nth layer is pressed. The method for manufacturing a separation membrane element according to [1] or [2], which is laminated.
[4] The method for manufacturing a separation membrane element according to [3], wherein the second step is performed while maintaining the state of pressing the first region in the first step.
[5] The laminating step further includes a third step of laminating the (N + 2) layer separation membrane unit on the (N + 1) th layer separation membrane unit laminated in the second step. ,
In the third step, the separation membrane of the (N + 2) layer is pressed while the third region including at least a part of the fold portion of the separation membrane included in the separation membrane unit of the (N + 1) layer is pressed. The method for manufacturing a separation membrane element according to [3] or [4], wherein the units are laminated.
[6] The method for manufacturing a separation membrane element according to [5], wherein the third step is performed while maintaining a state in which the second region is pressed in the second step.
[7] The pressing of the first region is performed by pressing the first pressing member.
The laminating step further includes a step of releasing the pressing of the first region by the first pressing member.
The method for manufacturing a separation membrane element according to [5] or [6], wherein the third step is performed in a state where the first pressing member after the release step presses the third region.
[8] The method for manufacturing a separation membrane element according to [7], wherein the pressing of the second region is performed by pressing the second pressing member.
[9] The separation membrane element according to any one of [1] to [8], wherein the separation membrane element is a spiral type separation membrane element in which the entire length of the laminated body is wound around the hollow tube. Production method.
[10] One of the first flow path member and the second flow path member is a supply-side flow path member for forming a flow path through which the raw material fluid flows, and the other is a permeation fluid that has passed through the separation membrane. The method for manufacturing a separation membrane element according to any one of [1] to [9], which is a permeation side flow path member for forming a flow path.
[11] The first flow path member is the supply side flow path member.
The method for manufacturing a separation membrane element according to [10], wherein the second flow path member is the permeation side flow path member.
[12] The method for producing a separation membrane element according to any one of [1] to [11], wherein the separation membrane has a porous layer and a gel layer provided on the porous layer.
[13] A separation membrane element including a perforated hollow tube and a laminated body, wherein at least a part of the laminated body is wound around the hollow tube.
The laminated body is
A plurality of separation membrane units including a leaf having a first flow path member interposed between the two-folded separation membranes and at least a part of layers constituting the second flow path member laminated on the leaf are laminated. ,and,
The separation membrane units are laminated so that the position of the fold portion of the separation membrane is displaced in the winding direction of the laminate.
The separation membrane is
It has a porous layer and a gel layer provided on the porous layer, and
After folding the separation membrane in half so that a load of 1 N / cm ² is applied to the entire crease, the maximum distance between the opposing surfaces of the separation membrane when the load is removed is 10 mm or more. can be,
The separation membrane element is
The winding direction distance between the positions of the fold portions of the separation membrane included in the two adjacent leaves via the second flow path member in the stacking direction of the laminated body is defined as WR.
When the value (C / n) obtained by dividing the outer peripheral length C of the hollow tube by the number n of the leaves contained in the laminated body is defined as the pitch P,
A separation membrane element having a standard deviation of 0.4 or less for the amount of deviation of the distance WR from the pitch P.
[14] The separation membrane element according to [13], wherein the separation membrane element is a spiral type separation membrane element in which the entire length of the laminated body is wound around the hollow tube.
[15] One of the first flow path member and the second flow path member is a supply side flow path member for forming a flow path through which the raw material fluid flows, and the other side allows the permeation fluid that has passed through the separation membrane to flow. The separation membrane element according to [13] or [14], which is a permeation side flow path member for forming a flow path.
[16] The first flow path member is the supply side flow path member.
The separation membrane element according to [15], wherein the second flow path member is the permeation side flow path member.

According to the method for manufacturing a separation membrane element of the present invention, the separation membrane unit can be satisfactorily laminated, and the separation membrane element having a good shape of a portion where the laminate is wound around a hollow tube can be manufactured. ..

It is a schematic perspective view which provided the partially developed part which shows the spiral type separation membrane element. It is a schematic perspective view which provided the partially developed part which shows the spiral type separation membrane element which provided the telescope prevention plate. It is a schematic sectional drawing which shows an example of the laminated body included in the spiral type separation membrane element. It is a schematic diagram for demonstrating an example of the manufacturing process of a spiral type separation membrane element. It is a schematic diagram for demonstrating the state in which the separation membrane unit with a bulge is laminated on the fold portion of the separation membrane. It is a schematic sectional drawing which shows an example of a separation membrane. It is the schematic sectional drawing which shows the other example of the separation membrane. It is a schematic cross-sectional view which shows an example of the leaf using the separation membrane shown in FIG. 7.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. All of the following drawings are provided to aid understanding of the present invention, and the size and shape of each component shown in the drawings may not necessarily match the size and shape of the actual component.

Hereinafter, the spiral type separation membrane element will be mainly described as an example, but the separation membrane element and the manufacturing method thereof of the present embodiment are not limited to the spiral type separation membrane element and the manufacturing method thereof. .. The separation membrane element of the present embodiment may be a separation membrane element having a structure in which at least a part of the laminated body is wound around a hollow tube. Specifically, it is a plate and frame type in which at least a part of the laminated body (for example, only one round) is wound around the outer circumference of the hollow tube, and the remaining laminated body is suspended from the hollow tube. It can also be applied to the separation membrane element.

<Manufacturing method of spiral type separation membrane element>
1 and 2 are schematic perspective views showing a spiral type separation membrane element with a partially developed portion. FIG. 3 is a schematic cross-sectional view showing an example of a laminated body included in a spiral type separation membrane element.

As shown in FIGS. 1 and 2, the spiral type

separation membrane elements

1a and 1b manufactured by the manufacturing method of the present embodiment (hereinafter, both may be collectively referred to as "separation membrane element 1") are referred to. It can be used to separate a specific fluid component from a raw material fluid containing at least a specific fluid component. The raw material fluid may be a gas or a liquid. The separation membrane element 1 is preferably a gas separation membrane element, and preferably allows a specific gas component to selectively permeate from the raw material gas. The specific gas component that the separation membrane contained in the gas separation membrane element selectively permeates is preferably an acid gas. Examples of the acid gas include carbon dioxide (CO ₂ ), hydrogen sulfide (H ₂ S), sulfur oxide (SO _x ), nitrogen oxide (NO _x ) and the like. The specific gas component is preferably carbon dioxide or hydrogen sulfide, more preferably carbon dioxide.

As shown in FIGS. 1 and 2, the separation membrane element 1 includes a perforated hollow tube 5 and a laminated body 7 (FIG. 3), and the entire length of the laminated body 7 is wound around the hollow tube 5. It is a thing. The separation membrane element 1 is preferably cylindrical.

As shown in FIG. 3, the laminated body 7 has a leaf 6 having a supply-side flow path member 3 (first flow path member) interposed between the separated membranes 10 folded in half, and a permeation layer 6 laminated on the leaf 6. A plurality of separation membrane units 9 including at least a part of the layers constituting the side flow path member 4 (second flow path member) are laminated. In the laminated body 7, the separation membrane unit 9 is laminated so that the position of the fold portion of the separation membrane 10 shifts in the winding direction of the laminate 7 (direction of the double arrow in FIG. 3), for example, at pitch P0. ing. In the laminated body 7, as shown in FIG. 3, since the outermost layer (lowermost side) is the transmission side flow path member 4 and the uppermost surface is the leaf 6, the outermost layer is the transmission side flow path member 4 and the outermost layer. The leaf 6 on the upper surface does not form the separation membrane unit 9 in the state of the laminated body 7 shown in FIG. In the laminated body 7 shown in FIG. 3, each of the separation membrane units 9 has a structure in which all the layers constituting the transmission side flow path member 4 are provided on the leaf 6. In the separation membrane element 1, the laminated body 7 is wound around the hollow tube 5.

As will be described later, when the permeation side flow path member 4 has a multilayer structure in which two or more layers are laminated, the laminate may be in the form of the laminate 7 shown in FIG. 3, and the laminate 7 shown in FIG. 3 may be used. On the uppermost leaf 6, at least a part of the layers constituting the permeation side flow path member 4 may be included. That is, if all the layers constituting the permeation side flow path member 4 are arranged on the lowest side, the laminated body will be in the form of the laminated body 7 shown in FIG. In this case, each of the separation membrane units 9 has a structure in which all the layers constituting the transmission side flow path member 4 are provided on the leaf 6. On the other hand, when only a part of the layers constituting the permeation side flow path member 4 is arranged on the lowermost side, the remaining layers among the plurality of layers constituting the permeation side flow path member 4 are arranged. Since the layer can be arranged on the leaf 6 of the uppermost layer, the laminated body has a different form of the laminated body 7 shown in FIG. In this case, the separation membrane unit 9 other than the uppermost layer has a structure in which all the layers constituting the transmission side flow path member 4 are provided on the leaf 6, and the separation membrane unit 9 of the uppermost layer is on the leaf 6. Has a structure including at least a part of the layers constituting the permeation side flow path member 4. In the state where the laminated body is wound around the hollow tube 5, the uppermost layer of the laminated body 7 described above is the leaf 6, or a plurality of layers constituting the transmission side flow path member 4. Regardless of whether it is a part of the layers, all or a part of the layers constituting the transmission side flow path member 4 arranged at the lowermost side of the laminated body 7 can form the outermost layer.

The pitch P0 in the laminated body 7 can be set to a preset value for laminating the leaves 6, and is based on the outer peripheral length C of the hollow tube 5 and the number n of the leaves 6 included in the laminated body 7. Can be set. The pitch P0 is, for example, C / n. The pitch P0 is a flow path member on the transmission side in the stacking direction of the laminated body 7 in a state before the laminated body 7 is wound around the hollow tube 5 (a state in which the separation membrane units 9 are stacked flat as shown in FIG. 3). It is the distance between the tip portions (the portions that become the vertices of the fold portions) of the fold portions of the separation membranes 10 of the two adjacent leaves 6 via 4. The distance between the tip portions of the fold portion is a direction orthogonal to the stacking direction (horizontal direction) of the laminated body 7, and is a distance in a direction orthogonal to the straight line formed by the tip portion of the fold portion.

It is preferable that the separation membrane element 1 further has a sealing portion for preventing mixing of the raw material fluid flowing through the supply side flow path member 3 and the permeation fluid flowing through the permeation side flow path member 4. The separation membrane element 1 is fixed with an outer peripheral tape, a telescope prevention plate 55 shown in FIG. 2, or the like in order to prevent the winding body 7 wound around the hollow tube 5 from being unwound or unwound. It may be provided with a member. The separation membrane element 1 may have an outer wrap (reinforcing layer) on the outermost circumference of the wound body in order to secure the strength against the load due to the internal pressure and the external pressure applied to the separation membrane element.

In the present embodiment, a case where the leaf 6 in which the supply side flow path member 3 is interposed between the separation membranes 10 folded in half and the transmission side flow path member 4 are provided on the leaf 6 as the separation film element 1 will be described. However, it is not limited to this. The separation membrane element may be a leaf having a transmission side flow path member 4 interposed between the separation membranes 10 folded in half, and a supply side flow path member 3 provided on the leaf.

FIG. 4 is a schematic diagram for explaining an example of a manufacturing process of a spiral type separation membrane element. FIG. 5 is a schematic diagram for explaining a state in which a separation membrane unit having a bulge is laminated on a fold portion of the separation membrane. Hereinafter, the case where the permeation side flow path member 4 has a single-layer structure will be described, but as described above, the permeation side flow path member 4 may have a multi-layer structure.

The method for manufacturing the separation membrane element 1 includes a step of laminating the separation membrane unit 9. The step of laminating the separation membrane unit 9 may be a step of laminating a structure in which the leaf 6 and the permeation side flow path member 4 are integrated in advance, and is a step of laminating the leaf 6 and the permeation side flow path member 4 in order. May be good.

As shown in FIGS. 4A and 4B, the first step of laminating includes at least a part of the fold portion of the separation membrane 10a included in the separation membrane unit 9a of the (N-1) layer. The first step of laminating the separation film unit 9b of the Nth layer on the separation film unit 9a of the (N-1) layer while pressing the region is included. As described above, for the separation membrane unit 9 of the specific layer, the leaf 6, the separation membrane 10, the supply side flow path member 3, and the transmission side flow path member 4 included in the separation membrane unit 9. , The same alphabet is attached to the sign of the corresponding number.

The laminating step may be a step of repeating the first step. In addition to the first step, the laminating step is a second step of laminating the (N + 1) th layer separation membrane unit 9c on the Nth layer separation membrane unit 9b as shown in FIG. 4 (c). As shown in (d) of FIG. 4, a third step of laminating the (N + 2) layer separation film unit 9d on the (N + 1) layer separation film unit 9c is included. May be good. The step of laminating may further include a step of laminating the leaf 6 (FIG. 3) constituting the uppermost surface of the laminated body 7 on the unit group in which a plurality of separation membrane units 9 are laminated.

Here, N is an integer of 2 or more, and is an integer of (n-1) or less when the number of leaves 6 included in the laminated body 7 shown in FIG. 3 is n. As described above, since the layer constituting the uppermost surface of the laminated body 7 is usually a leaf 6, the number n of the leaves 6 included in the laminated body 7 shown in FIG. 3 and the number of the separation membrane units 9 match. However, the number of separation membrane units 9 included in the laminated body 7 is (n-1). However, as described above, the permeation side flow path member 4 has a multi-layer structure, and at least a part of the layers constituting the permeation side flow path member 4 is laminated on the upper surface of the leaf 6 located at the uppermost layer. In that case, N is an integer less than or equal to n. n is an integer and may be selected according to the separation performance of the separation membrane element 1 and / or the size of the hollow tube 5 (outer peripheral length C) and the like. Although n is not particularly limited, it may be, for example, 5 or more, 8 or more, 10 or more, or 30 or less, and 20 or less.

According to the method for manufacturing the separation membrane element 1 of the present embodiment, the spiral type separation membrane element described later can be suitably manufactured. Hereinafter, each step of the laminating step will be described in detail.

(First step)
In the first step, the N layer is placed on the separation membrane unit 9a of the (N-1) layer so as to be displaced by the pitch P0 (FIG. 3) in the winding direction of the laminated body 7 (direction of the double arrow in FIG. 4). The eye separation membrane unit 9b is laminated. At this time, as shown in FIGS. 4A and 4B, the first region including at least a part of the fold portion of the separation membrane 10a included in the separation membrane unit 9a of the (N-1) layer is formed. By pressing, the N-th layer separation membrane unit 9b can be laminated in a state where the swelling of the fold portion of the separation membrane 10a is suppressed. For pressing the first region, it is preferable to press the separation membrane 10a via the transmission side flow path member 4a included in the separation membrane unit 9a.

Since the leaf 6 of the separation membrane unit 9 includes the separation membrane 10 folded in half, swelling is likely to occur at the fold portion of the separation membrane 10. Due to this bulge, in the separation membrane unit 9, the thickness of the separation membrane 10 on the fold portion side becomes large, and when the separation membrane unit 9 is placed on a horizontal plane, the vicinity of the region where the crease portion is located is warped. It is easy to become. In particular, when a unit group in which a plurality of separation membrane units 9 are laminated is formed, as shown in the left side portion in FIG. 5, the warp of the region where the crease portion is located tends to be large. When the next separation membrane unit 9 is laminated on the separation membrane unit 9 or the unit group in which the warp occurs, it becomes difficult to accurately stack the separation membrane unit 9 at a preset pitch P0.

Therefore, in the present embodiment, as shown in FIGS. 4A and 4B, the N-1th layer separation membrane unit 9b is included in the (N-1) th layer separation membrane unit 9a before laminating the Nth layer separation membrane unit 9b. The first region including at least a part of the fold portion of the separation membrane 10a is pressed. As a result, swelling and warpage generated in the separation membrane unit 9a of the (N-1) layer are suppressed, the separation membrane unit 9a or the unit group is brought closer to a flat state, and the fold portion is the shaft of the hollow tube 5. It is possible to approach a state parallel to the direction. Therefore, the separation membrane unit 9b of the Nth layer can be accurately laminated on the separation membrane unit 9a of the (N-1) layer at an appropriate pitch P0. Therefore, since the separation membrane 10 can be laminated without significantly deviating from the preset pitch P0, the cross-sectional shape of the wound body in which the laminated body 7 is wound around the hollow tube 5 can be made close to a perfect circle. , The separation membrane element 1 having a good appearance shape can be obtained. Further, it can be expected to suppress the deterioration of the separation performance of the separation membrane element 1.

In the manufacturing method of the present embodiment, for example, when the separation membrane 10 is folded in half, the separation membrane units 9 can be accurately laminated at an appropriate pitch P0 without making strong creases. In particular, when the separation membrane 10 has a porous layer and a gel layer provided on the porous layer as described later, if the separation membrane 10 is strongly creased, the gel in the gel layer may be biased or the like. Therefore, it is difficult to make strong creases. The production method of the present embodiment can also be suitably used when the separation membrane 10 that cannot strongly crease is used.

The first region is not particularly limited as long as it contains at least a part of the fold portion of the separation membrane 10a included in the separation membrane unit 9a of the (N-1) layer, and is 10% or more of the fold portion. It is preferable to include a range, 20% or more may be contained, and 30% or more may be contained. The first region may include the entire fold portion (100%). The first region may be provided at the central portion of the fold portion in the extending direction, or may be provided so as to include the end portion of the fold portion in the extending direction. The first region may be only one region such as the central portion in the extending direction of the fold portion, or two or more regions separated from each other such as both ends in the extending direction of the fold portion. It may be included.

The pressing of the first region is preferably performed by pressing the first pressing member 31 as shown in FIG. The first pressing member 31 is not particularly limited as long as it can press the first region. As shown in FIG. 4, for example, the first pressing member 31 may support a pressing portion having a flat pressing surface with a rod-shaped support portion, and may support the pressing portion having a curved pressing surface in a rod-like shape. It may be supported by a portion, or a roll may be used as the first pressing member and the surface of the roll may be used as the pressing portion. If the shape of the pressing surface is sharp like a needle, the separation membrane 10 (especially the gel layer if it has a gel layer) may be damaged. Therefore, the separation membrane 10 may be made into a shape that is not easily damaged. Preferably, the range of the first region described above is set so that the separation membrane 10 is not damaged by pressing.

The pressing of the first region is preferably performed so that the maximum distance between the surfaces of the separation films 10a facing each other in the first region is less than 5 mm, and may be 4 mm or less, or may be 3 mm or less. Further, it may be 0 mm or 0.5 mm or more. When the maximum distance is within the above range, the separation membrane units 9 can be laminated with high accuracy at an appropriate pitch P0. Further, even when the separation membrane 10 that cannot strongly crease is used, the separation membrane unit 9 can be laminated with high accuracy at an appropriate pitch P0. The surface of the separation membrane 10a means the inner surface of the separation membrane 10a folded in half. The maximum distance between the surfaces is the distance of the portion of the distance along the stacking direction of the laminated body 7 between the inner surfaces of the separation film 10a within the range of the first region, where the distance is the largest. To say.

(Second step)
In the second step, the separation film unit 9c of the (N + 1) layer is laminated on the separation film unit 9b of the Nth layer laminated in the first step so as to be displaced by the pitch P0 in the winding direction of the laminated body 7. In the second step, the state in which the first region is pressed in the first step is released, or the state in which the first region is pressed in the first step is maintained, and the Nth layer separation membrane unit 9b is further formed. The second region including at least a part of the fold portion of the separation membrane 10b contained in the above is pressed. For pressing the second region, it is preferable to press the separation membrane 10b via the transmission side flow path member 4b included in the separation membrane unit 9b. As a result, the separation membrane unit 9c of the (N + 1) layer can be laminated in a state where the swelling of the fold portion of the separation membranes 10a and 10b is suppressed.

In the unit group in which a plurality of separation membrane units 9 are laminated as described above, the warp of the region where the crease portion is located tends to be large (FIG. 5). Therefore, even when forming a unit group in which three or more layers of the separation membrane unit 9 are laminated as in the second step, the separation membrane unit of the Nth layer is formed before the separation membrane unit 9c of the (N + 1) th layer is laminated. The second region of the separation membrane 10b included in 9b is pressed. As a result, the swelling and warpage generated in the

separation membrane units

9a and 9b of the (N-1) layer and the Nth layer are suppressed, the unit group is brought closer to a flat state, and the fold portion is made of the hollow tube 5. It can be made closer to a state parallel to the axial direction. Therefore, the separation membrane unit 9c of the (N + 1) th layer can be accurately laminated on the separation membrane unit 9b of the Nth layer at an appropriate pitch P0. Therefore, since the separation membrane 10 can be laminated without significantly deviating from the preset pitch P0, the cross-sectional shape of the wound body in which the laminated body 7 is wound around the hollow tube 5 can be made close to a perfect circle. .. Further, it can be expected to suppress the deterioration of the separation performance of the separation membrane element 1.

In particular, in the second step, as shown in FIG. 4 (c), N before laminating the separation membrane unit 9c of the (N + 1) layer while maintaining the pressing of the first region in the first step. It is preferable to press the second region of the separation membrane 10b included in the separation membrane unit 9b of the layer. As a result, the swelling and warpage generated in the

separation membrane units

9a and 9b of the (N-1) layer and the Nth layer are further suppressed, the unit group is brought closer to a flat state, and the fold portion is inside. It is possible to bring the empty tube 5 closer to a state parallel to the axial direction.

The second region is not particularly limited as long as it includes at least a part of the fold portion of the separation membrane 10b included in the separation membrane unit 9b of the Nth layer. As the preferred form of the second region, the form described as the preferred form of the first region can be mentioned.

The pressing of the second region may be performed by the first pressing member 31 that pressed the first region, or may be performed by the second pressing member 32 that is different from the first pressing member 31. When the state in which the first region is pressed in the first step is released and the second region is pressed, the first pressing member 31 that has pressed the first region is moved to press the second region. You may. When pressing the second region while maintaining the pressing of the first region in the first step, it is preferable to press the second pressing member 32 as shown in FIG. The second pressing member 32 is not particularly limited as long as it can press the second region. As a preferable form of the second pressing member 32, the form described as a preferable form of the first pressing member 31 can be mentioned. When the second region is pressed by the second pressing member 32 while the first region is pressed by the first pressing member 31, the pressing surface of the first pressing member 31 and the pressing surface of the second pressing member 32 come into contact with each other. A recess that engages with a surface opposite to the pressing surface of the other pressing member may be provided on the pressing surface side of one pressing member so as not to interfere with each other.

Similar to the pressing of the first region, the pressing of the second region is preferably performed so that the maximum distance between the surfaces of the separation membranes 10b facing each other in the second region is less than 5 mm. The preferred range of the maximum distance is the same as the range described in Pressing the first region.

(Third step)
The step of laminating is a third step of laminating the separation film unit 9d of the (N + 2) layer on the separation film unit 9c of the (N + 1) layer so as to be displaced by the pitch P0 in the winding direction of the laminated body 7. May include. The step of laminating may further include a step of releasing the pressing of the first region by the first pressing member 31. The release step is preferably performed after the second step.

In the third step, the first pressing member after the step of releasing the pressed state of the second region in the second step or while maintaining the pressed state of the second region in the second step. 31 presses the third region including at least a part of the fold portion of the separation membrane 10c contained in the separation membrane unit 9c of the (N + 1) layer. In this state, the separation membrane unit 9d of the (N + 2) layer is laminated on the separation membrane unit 9c of the (N + 1) layer. As a result, the separation membrane unit 9d of the (N + 2) layer can be laminated in a state where the swelling of the fold portion of the separation membranes 10b and 10c is suppressed.

The first pressing member 31 may press the third region by moving from the pressing position of the first region to the pressing position of the third region after the release step. Therefore, the step of releasing may include a step of moving the first pressing member 31 from the position of pressing the first region to the position of pressing the third region. As shown in FIG. 4, it is preferable to press the separation membrane 10c via the transmission side flow path member 4c included in the separation membrane unit 9c.

In the unit group in which a plurality of separation membrane units 9 are laminated as described above, the warp of the region where the crease portion is located tends to be large (FIG. 5). Therefore, even when forming a unit group in which four or more separation membrane units 9 are laminated as in the third step, the (N + 1) th layer is separated before the (N + 2) th separation membrane unit 9d is laminated. The third region of the separation membrane 10c included in the membrane unit 9c is pressed. As a result, in particular, the swelling and warpage that occur in the

separation membrane units

9b and 9c of the Nth layer and the (N + 1) layer are suppressed, the unit group is brought closer to a flat state, and the fold portion is the shaft of the hollow tube 5. It is possible to approach a state parallel to the direction. Therefore, the separation membrane unit 9d of the (N + 2) layer can be accurately laminated on the separation membrane unit 9c of the (N + 1) layer at an appropriate pitch P0. Therefore, since the separation membrane 10 can be laminated without significantly deviating from the preset pitch P0, the cross-sectional shape of the wound body in which the laminated body 7 is wound around the hollow tube 5 can be made close to a perfect circle. .. Further, it can be expected to suppress the deterioration of the separation performance of the separation membrane element 1.

In particular, in the third step, as shown in FIG. 4D, before laminating the separation membrane unit 9d of the (N + 2) layer while maintaining the pressing of the second region in the second step, ( It is preferable to press the third region of the separation membrane 10c included in the separation membrane unit 9c of the N + 1) layer. The pressing of the third region may be performed by the first pressing member 31 moved from the pressing position of the first region. As a result, the swelling and warpage that occur in the

separation membrane units

9b and 9c of the Nth layer and the (N + 1) layer are further suppressed, the unit group is brought closer to a flat state, and the fold portion is hollow. It is possible to bring the tube 5 closer to a state parallel to the axial direction.

In the third step, the third region of the separation membrane unit 9c of the (N + 1) layer was pressed, and in the first step, the first region of the separation membrane unit 9a of the (N-1) layer was pressed. It may be done by the pressing member 31. According to this, since it can be performed by one first pressing member 31 for pressing the first region and the third region, it is not necessary to prepare a member for pressing each of the first region and the third region. , The number of parts of the device for manufacturing the laminated body 7 can be reduced. Alternatively, the pressing member (first pressing member 31 or second pressing member 32) that pressed the second region of the N-th layer separation membrane unit 9b in the second step is moved to press the third region. Alternatively, the third region may be pressed by a pressing member different from these.

The third region is not particularly limited as long as it includes at least a part of the fold portion of the separation membrane 10c included in the separation membrane unit 9c of the (N + 1) layer. The preferred form of the third region can be the same as the form described as the preferred form of the first region.

Similar to the pressing of the first region, the pressing of the third region is preferably performed so that the maximum distance between the surfaces of the separation membranes 10c facing each other in the third region is less than 5 mm. The preferred range of the maximum distance is the same as the range described in Pressing the first region.

The laminating step may be one in which the first set, which is a set of the first step to the third step, is performed once, or two or more times. In the laminating step, after performing the first set, one or more steps of the first step to the third step may be performed one or more times.

It is preferable that the step of laminating is repeated the third step after the first set. As a result, the separation membrane units 9 can be accurately laminated at an appropriate pitch P0 in a state where the unit group in which a plurality of separation membrane units 9 are laminated is brought close to a flat state. Further, by pressing the second region by the second pressing member 32, the first pressing member 31 and the second pressing member 32 are moved along with the stacking of the separation membrane units 9, and the fold portion of the separation membrane 10 is formed. A plurality of separation membrane units 9 can be laminated while pressing.

(Process of laminating the top leaf)
When the layer constituting the uppermost surface of the laminated body 7 shown in FIG. 3 is a leaf 6, the step of laminating constitutes the uppermost surface of the laminated body 7 after laminating all the separation membrane units 9 included in the laminated body 7. The step of laminating the leaves 6 to be formed may be included. The step of laminating the leaves 6 may be performed after the third step. By performing the step of laminating the leaves 6, the laminated body 7 can be formed. When the layer constituting the uppermost surface of the laminated body 7 is the separation membrane unit 9, this step is not normally performed.

The step of laminating the leaf 6 on the uppermost surface has been described in the third step except that the leaf 6 is laminated instead of laminating the separation membrane unit 9d of the (N + 2) layer described in the third step. It can be done by the procedure.

(Other processes)
The method for manufacturing the separation membrane element 1 includes a step of forming the laminate 7 through the above-mentioned step of laminating the separation membrane unit, and then winding the laminate 7 around the hollow tube 5 to form the wound body. Can be done. In the step of forming the wound body, for example, as shown in FIG. 3, one end of the transmission side flow path member 4 located in the outermost layer (lowermost side) of the laminated body 7 is fixed to the outer periphery of the hollow tube 5. , The hollow tube 5 may be rotated and the laminated body 7 may be wound around the hollow tube 5. As shown in FIG. 3, the hollow tube 5 is preferably provided at the end of the laminated body 7 on the side where the fold portion of the separation membrane 10 is located. As described above, the uppermost surface of the laminated body 7 is the leaf 6, but by winding the laminated body 7 around the hollow tube 5, the uppermost surface leaf 6 of the laminated body 7 becomes the outermost surface of the laminated body 7. It is in contact with the positioned transmission side flow path member 4.

The separation membrane element 1 can have a sealing portion for preventing mixing of the raw material fluid flowing through the supply side flow path member 3 and the permeation fluid flowing through the permeation side flow path member 4. Therefore, the method for manufacturing the separation membrane element 1 may include a step of forming a sealing portion. The step of forming the sealing portion includes, for example, a step of providing a sealing material on the surface of the leaf 6 when laminating the leaf 6 and the permeation side flow path member 4, and a step of curing the sealing material. be able to. The step of curing the encapsulating material is preferably performed after the step of forming the wound body.

In the step of providing the sealing material, for example, the sealing material is provided on the peripheral edge of the surface of the leaf 6 and / or the permeation side flow path member 4 so that the fold portion side of the separation membrane 10 opens (so-called envelope shape). Just do it. The sealing material may be provided so that the fold portion side of the separation membrane 10 opens at the peripheral edge of the surface of the separation membrane unit 9 on the leaf 6 side and / or the surface on the transmission side flow path member 4 side. The sealing material can be provided on the surface by coating, transfer or the like.

After forming the laminated body 7 by providing the sealing material as described above, the sealing material is infiltrated into the permeation side flow path member 4 interposed between the leaves 6 while winding the laminated body 7 around the hollow tube 5. Or spread the encapsulating material between the opposing leaves 6 via the permeation side flow path member 4. After that, a step of curing the sealing material is performed. In the step of curing the encapsulating material, the curing method may be selected according to the type of the encapsulating material. As a method for curing the encapsulating material, for example, when a thermosetting resin is used as the encapsulating material, the thermosetting resin may be cured by heating or the like, and the encapsulating material is heat-sealed. In the case of a sex adhesive, it may be cooled after being heated or the like. When an active energy ray-curable resin is used as the encapsulating material, it may be cured by irradiation with active energy rays, and when the encapsulating material is a material containing water or a solvent, water or the solvent is removed. You just have to dry it.

Although the method for manufacturing the spiral type separation membrane element has been described above, as described above, the method for manufacturing the separation membrane element of the present embodiment may be the method for manufacturing the plate & frame type separation membrane element. In the plate & frame type separation membrane element, a part of the laminated body is wound around a hollow tube, and the remaining part is suspended from the hollow tube. For example, in the plate & frame type separation membrane element, the laminated body is wound around the outer circumference of the hollow tube for one round, and the remaining portion is not wound. Therefore, even in the method for manufacturing the plate & frame type separation membrane element, when the separation membrane units are laminated, the pressing of the first region, the second region, or the third region is performed in the same manner as the method described above. It can be carried out. According to this, it is possible to manufacture a separation membrane element having a good shape at a portion where the laminated body is wound around a hollow tube.

<Spiral type separation membrane element>
As described above, the spiral type separation membrane element 1 of the present embodiment includes the perforated hollow tube 5 and the laminated body 7, and the laminated body 7 is wound around the hollow tube 5. The shape of the separation membrane element 1 and the fluid components separated by the separation membrane element 1 are as described above. Further, the description of the laminated body 7 is as described above. In the laminated body 7, a plurality of separation membrane units 9 are laminated, and the separation membrane units 9 are laminated so that the position of the fold portion of the separation membrane 10 shifts in the winding direction of the laminate 7.

In the separation membrane element 1, the separation membrane 10 has a porous layer and a gel layer provided on the porous layer, and the separation membrane 10 is applied with a load of 1 N / cm ² to the entire fold. The maximum distance between the opposing surfaces of the separation membrane 10 when this load is removed after folding in half is 10 mm or more.

The separation membrane element 1 is
The winding direction distance between the positions of the folds of the separation membrane 10 included in the two leaves 6 adjacent to each other via the transmission side flow path member 4 in the stacking direction of the laminated body 7 is defined as WR.
When the value (C / n) obtained by dividing the outer peripheral length C of the hollow tube 5 by the number n of the leaves 6 contained in the laminated body 7 is defined as the pitch P,
The standard deviation of the deviation amount of the distance WR from the pitch P is 0.4 or less.

As described above, the layer constituting the uppermost surface of the laminated body 7 is at least a part of the layer constituting the permeation side flow path member 4 on the leaf 6 or the leaf 6, and is the outermost surface (lowermost) of the laminated body 7. The side) is at least a part of the layers constituting the transmission side flow path member 4. It is preferable that the laminated body 7 has two or more separation membrane units 9 between the leaf 6 on the uppermost surface and at least a part of the layers constituting the transmission side flow path member 4 on the outermost surface.

The porous layer included in the separation membrane 10 functions as a support layer or a protective layer for the gel layer. The gel layer functions as a separation functional layer for selectively permeating a specific fluid component. As will be described later, the separation membrane 10 may have porous layers on both sides of the gel layer.

Folding the separation membrane 10 in half with a load of 1 N / cm ² means folding back the separation membrane 10 stacked on a horizontal plane and applying a load of 1 N / cm ² to the entire crease portion. The method of applying the load is as described in Examples described later, and the members whose surfaces to which the load is applied are flat surfaces made of metal are arranged so that the planes face each other to form a crease in the separation membrane 10. This is done by applying a load to the entire portion for 5 seconds.

The maximum distance between the opposing surfaces of the separation membrane 10 when the load is removed is 10 mm or more, may be 12 mm or more, may be 15 mm or more, and is usually 60 mm or less, 40 mm or less. It may be present, and may be 20 mm or less. The facing surface of the separation membrane 10 refers to the inner surface of the separation membrane 10 folded in half. The maximum distance between the opposing surfaces of the separation membrane 10 is the distance between the surfaces of the two-folded separation membrane 10 placed on the horizontal plane in the direction orthogonal to the horizontal plane. The distance of the part that grows.

The distance WR is the distance between the positions of the fold portions of the separation membrane 10 included in each of the two leaves 6 adjacent to each other via the transmission side flow path member 4 in the stacking direction of the laminated body 7. , The distance along the winding direction of the laminated body 7. The distance WR can be measured in a state where the laminated body wound around the hollow tube 5 in the separation membrane element 1 is unfolded, and is considered to be the above distance in the laminated body 7 wound around the hollow tube 5. Can be done. Distance WR refers to the maximum value of the distance between the creases measured for the entire crease. The distance WR is measured for each of the two leaves 6 included in the laminated body 7 and adjacent to each other via the transmission side flow path member 4 in the laminated body direction.

The pitch P is a value (C / n) obtained by dividing the outer peripheral length C of the hollow tube 5 by the number n of the leaves 6 contained in the laminated body 7. By setting the pitch P in this way, the laminated body 7 is made into a hollow tube so that a part of all the separation membranes 10 included in the laminated body 7 (near the fold portion) is in contact with the outer periphery of the hollow tube 5. It can be wound around 5.

The amount of deviation of the distance WR from the pitch P can be regarded as the difference between the preset pitch P and the actual pitch when the laminated body 7 is wound around the hollow tube 5. The amount of deviation is calculated for each of the distance WRs measured for each of the two adjacent leaves 6 described above.

The standard deviation of the deviation amount is the distance WR and the pitch P (where P = C / n (C represents the outer peripheral length of the hollow tube 5 and P represents the number of leaves 6 contained in the laminated body 7)). Then, it can be calculated by the formula (I) shown below.
Standard deviation of deviation amount = {Σ [(WR / P) -1] ² / n} ^0.5 (I)

The standard deviation of the deviation amount is 0.4 or less, preferably 0.3 or less, more preferably 0.25 or less, and may be 0.2 or less. It is considered that the smaller the standard deviation of the deviation amount, the smaller the difference between the preset pitch P and the actual pitch when the laminated body 7 is wound around the hollow tube 5.

According to the separation membrane element 1 having the above-mentioned separation membrane and having a standard deviation of the deviation amount within the above range, the distance WR is from the pitch P even in the wound body in which the laminate 7 is wound around the hollow tube 5. It is considered that the state is not significantly deviated. Therefore, the cross-sectional shape of the wound body can be made close to a perfect circle, and the separation membrane element 1 having a good external shape can be obtained. Further, it can be expected to suppress the deterioration of the separation performance of the separation membrane element 1.

In particular, in the separation membrane element 1, the separation membrane 10 contains a gel layer, and it is difficult to form strong creases when the separation membrane 10 is folded in half. Even in the separation membrane element 1 provided with such a separation membrane 10, a good winding shape can be obtained by keeping the standard deviation of the deviation amount within the above range.

The method for manufacturing the above-mentioned separation membrane element 1 is not particularly limited, and examples thereof include the above-mentioned method for manufacturing the separation membrane element 1.

The supply-side flow path member 3 provided in the separation membrane element 1 covers at least the end portion of the end portion of the separation membrane element 1 which is arranged so as to face the fold portion of the separation membrane 10 folded in half. 1 A cover portion may be provided. The first cover portion is preferably provided so as to wrap the end portion of the supply-side flow path member 3. The first cover portion may be a tape having an adhesive layer provided on the film, or may be formed by coating with a resin coating or the like. For example, when the material constituting the supply-side flow path member 3 has high rigidity, if the end portion of the supply-side flow path member 3 comes into contact with the separation membrane 10, damage such as piercing or damaging the separation membrane 10 occurs. Sometimes. Therefore, since the first cover portion is provided at the end portion of the supply side flow path member 3, the separation membrane 10 is damaged even when the separation membrane 10 and the end portion of the supply side flow path member 3 come into contact with each other. Can be suppressed. Examples of the first cover section include those described in International Publication No. 2018/186109.

The separation membrane element 1 may further have the above-mentioned sealing portion, and may be provided with an outer peripheral tape, a telescope prevention plate 55, and an outer wrap. Further, as described above, the separation membrane element is a leaf in which the transmission side flow path member 4 is interposed between the separation membranes 10 folded in half, and the supply side flow path member 3 is provided on the leaf. You may. When the permeation side flow path member 4 is interposed between the two-folded separation membrane 10, it is preferable to provide the permeation side flow path member 4 with the above-mentioned first cover portion.

Although the spiral type separation membrane element has been described above, the separation membrane element of the present embodiment may be a plate & frame type separation membrane element as described above. In the plate & frame type separation membrane element, a part of the laminated body is wound around a hollow tube, and the remaining part is suspended from the hollow tube. For example, in the plate & frame type separation membrane element, the laminated body is wound around the outer circumference of the hollow tube for one round, and the remaining portion is not wound. Therefore, even in the plate & frame type separation membrane element, the separation membrane has a porous layer and a gel layer provided on the porous layer, and the separation membrane is loaded with a load of 1 N / cm ² over the entire fold. After folding in half so as to be applied to, the maximum distance between the opposing surfaces of the separation membrane 10 when this load is removed is 10 mm or more, and the separation membrane element has a deviation of the distance WR from the pitch P. The standard deviation of the quantity can be 0.4 or less. According to this, the shape of the portion where the laminated body of the separation membrane element is wound around the hollow tube can be improved.

<Separation membrane module>
The separation membrane element can be used in the separation membrane module. The separation membrane module has one or more separation membrane elements. The separation membrane module is for discharging the raw material fluid supply port for supplying the raw material fluid to the separation membrane 10 (the portion communicating with the supply port 51 shown in FIGS. 1 and 2) and the permeation fluid that has passed through the separation membrane 10. A permeation fluid discharge port (a portion communicating with the first discharge port 52 shown in FIGS. 1 and 2) and a non-permeation fluid discharge port for discharging the raw material fluid that did not permeate the separation membrane 10 (FIGS. 1 and 2). A portion that communicates with the second discharge port 53 shown in the above). The raw material fluid supply port, the permeation fluid discharge port, and the non-permeation fluid discharge port may be provided in a container (hereinafter, may be referred to as “housing”) for accommodating the separation membrane element.

The housing can form a space for enclosing the raw material fluid flowing in the separation membrane module, and includes, for example, a tubular member such as stainless steel and a closing member for closing both ends of the tubular member in the axial direction. May have. The housing may have an arbitrary cylindrical shape such as a cylinder or a square cylinder, but the separation membrane element is usually cylindrical, and therefore, it is preferably cylindrical. Further, inside the housing, a partition may be provided to prevent mixing of the raw material fluid supplied to the supply port 51 and the impermeable fluid that has not penetrated the separation membrane 10 provided in the separation membrane element. can.

When two or more separation membrane elements are arranged in the housing, the raw material fluid supplied to each separation membrane element may be supplied in parallel or in series. Here, supplying the raw material fluid in parallel means that at least the raw material fluid is distributed and introduced into a plurality of separation membrane elements, and supplying the raw material fluid in series means that at least the raw material fluid is discharged from the separation membrane element in the previous stage. Introducing a permeable fluid and / or a non-permeable fluid into the separation membrane element in the subsequent stage.

<Separator>
The separation device can include at least one separation membrane module. The arrangement and number of separation membrane modules provided in the separation device can be selected according to the required processing amount, the recovery rate of a specific fluid component, the size of the place where the separation device is installed, and the like.

The separation device includes a supply-side space and a permeation-side space separated from each other by the separation film 10, a supply-side inlet for supplying a raw material fluid containing at least a specific fluid from the supply unit to the supply-side space, and a separation film 10. A permeation side outlet for discharging the permeated gas containing a specific gas that has permeated through the space from the permeation side space, and a non-permeation side outlet for discharging the raw material gas that did not permeate the separation film 10 from the supply side space. You may be prepared.

Hereinafter, each member and the like forming the separation membrane element 1 will be described.
(Separation membrane)
6 and 7 are schematic cross-sectional views showing an example of a separation membrane, and FIG. 8 is a schematic cross-sectional view showing an example of a leaf using the separation membrane shown in FIG. 7. The separation membrane described below is used in the separation membrane element and its manufacturing method described above, but it can also be used in a separation membrane element other than the above and its manufacturing method.

The separation membrane 10 is not particularly limited as long as it is a known one capable of selectively permeating a specific fluid component from the raw material fluid. The separation membrane is preferably a gas separation membrane. The separation membranes 10 and 10'(hereinafter, both are collectively referred to as "separation membrane 10") are the first porous layer 11 (porous layer) and the gel layer 15 provided on the first porous layer 11. It is preferable to have a second porous layer 12 (porous layer) on the side opposite to the first porous layer 11 of the gel layer. Further, as shown in FIGS. 6 and 7, the separation membrane 10 may have a third porous layer 13 on the side opposite to the gel layer 15 of the first porous layer 11, and the second porous layer 12 may have a third porous layer 13. The fourth porous layer 14 may be provided on the opposite side of the gel layer 15.

The separation membrane 10 including the first porous layer 11 and the gel layer 15 can be produced, for example, by applying a coating liquid containing a composition for forming the gel layer 15 onto the first porous layer 11. .. The coating liquid can contain a composition (hydrophilic resin, alkali metal compound, amino acid, etc., which will be described later) contained in the gel layer and a medium. Examples of the medium include a protonic polar solvent such as water, methanol, ethanol, 1-propanol, 2-propanol and other alcohols; a non-polar solvent such as toluene, xylene and hexane; and a ketone such as acetone, methyl ethyl ketone and methyl isobutyl ketone. , N-Methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and other aprotic polar solvents; and the like. One type of medium may be used alone, or two or more types may be used in combination as long as they are compatible with each other. Among these, a medium containing at least one selected from the group consisting of alcohols such as water, methanol, ethanol, 1-propanol and 2-propanol is preferable, and a medium containing water is more preferable.

As a method of applying the coating liquid on the first porous layer 11, slot die coating, spin coating method, bar coating, die coating method, blade coating, air knife coating, gravure coating method, roll coating coating, spray coating, dip coating, etc. Examples include a comma roll method, a kiss coat method, screen printing, and inkjet printing.

The gel layer 15 can be formed by removing the medium from the film of the coating liquid formed by applying the coating liquid on the first porous layer 11. Examples of the method for removing the medium include a method for evaporating and removing the medium from the film of the coating liquid by heating or the like. When the separation film 10 has the second porous layer 12, the second porous layer 12 may be laminated on the membrane of the coating liquid before removing the medium or after removing a part of the medium.

The separation membrane 10 may have a gel layer 15 at the position of the fold portion when folded in half to form the leaf 6, as in the separation membrane 10'shown in FIGS. 7 and 8. The gel layer 15 may not be present at the fold portion. Hereinafter, the separation membrane 10'in which the gel layer 15 does not exist at the fold portion will be described.

(Separation membrane with no gel layer at the crease and leaf with it)
The separation membrane 10'in which the gel layer 15 is not present at the fold portion has at least the third porous layer 13, the first porous layer 11 and the gel layer 15 in this order. As shown in FIG. 7, the separation membrane 10'may have the second porous layer 12 on the side opposite to the first porous layer 11 of the gel layer 15, and may be the same as the gel layer 15 of the second porous layer 12. May have a fourth porous layer 14 on the opposite side.

In the separation membrane 10', at least a non-separable functional region 18 in which the gel layer 15 and the first porous layer 11 do not exist is formed in the region including the crease portion when the separation membrane 10'is folded in half. When the separation membrane 10'has a second porous layer 12, it is preferable that the second porous layer 12 does not exist in the non-separable functional region 18. When the separation membrane 10'has a fourth porous layer 14, the fourth porous layer 14 may be present in the non-separable functional region 18.

The size of the non-separable functional region 18 is not particularly limited as long as it is a region including a crease portion when the separation membrane 10'is folded in half. The non-separable functional region 18 is located in two directions orthogonal to the extending direction of the fold portion from the fold position of the separation film 10', preferably in a range of 2 mm or more (the length of the non-separable functional region 18 in the extending direction). Is in the range of 4 mm), more preferably in the range of 4 mm or more (the length of the non-separable functional region 18 in the extending direction is in the range of 8 mm), and further preferably in the range of 5 mm or more (non-separable). The length of the functional region 18 in the extending direction is 10 mm or less), and usually 15 mm or less (the length of the non-separable functional region 18 in the extending direction is 30 mm).

When the separation membrane element is manufactured using the separation membrane 10', a filler 19 is provided in the non-separation functional region 18 in order to prevent the raw material fluid from flowing out from the non-separation functional region 18. Examples of the filler 19 include a resin material and the like. Examples of the resin material include those exemplified as the material used for the sealing material described later, and an adhesive is preferable. At least a part of the filler 19 provided in the non-separable functional region 18 has penetrated into the layers existing in the non-separable functional region 18 (first porous layer 11, third porous layer 13, fourth porous layer 14, etc.). May exist in.

The separation membrane 10'has a second cover portion 36 so as to cover at least the area where the non-separable functional region 18 is formed on the surface that becomes the outer side when folded in half (FIG. 8). The range covered by the second cover portion 36 may include the entire range in which the non-separable functional region 18 is formed, and includes at least the fold portion of the separation membrane 10'of the non-separable functional region 18. You may. By providing the second cover portion 36, the filler 19 provided in the non-separable functional region 18 seeps out from the layers (first porous layer 11, third porous layer 13, etc.) existing in the non-separable functional region 18. It can be suppressed. Examples of the form of the second cover portion 36 include the form described as the first cover portion which may be provided on the supply side flow path member 3, and more specifically, it is described in International Publication No. 2018/186109. Can be mentioned.

In the separation membrane containing the gel layer 15, if strong creases are formed when the separation membrane is folded in half to form a leaf, the gel layer is biased at the folds and a region where the gel layer does not exist is formed. There is a risk of In the region where the gel layer does not exist, the raw material fluid supplied to the separation membrane tends to flow out as it is, so that the separation function tends to deteriorate. In the separation membrane 10', a non-separable functional region 18 in which the gel layer 15 does not exist is provided in a region that becomes a fold portion when folded in half, and a filler 19 is provided in the non-separable functional region 18. As a result, the separation membrane 10'can form a crease in the region where the gel layer does not exist, and by providing the filler 19 in the non-separable functional region 18, the raw material fluid flows out from the non-separable functional region 18. Can be suppressed. As a result, it is possible to suppress a decrease in separation efficiency due to the separation membrane 10'.

As shown in FIG. 8, the leaf 6'can be formed by interposing the supply side flow path member 3 between the two-folded separation membranes 10'. The supply-side flow path member 3 used for the leaf 6'may have a first cover portion at an end portion arranged so as to face the fold portion of the separation membrane 10'. As a result, the end portion of the supply-side flow path member 3 is prevented from damaging the layers such as the filler 19 and the third porous layer existing in the non-separable functional region 18 of the separation membrane 10', and the non-separable function is suppressed. It is possible to suppress the outflow of the raw material fluid from the region 18.

In the leaf 6', a filler 19 is provided so as to fill the inside of the fold portion where the separation membrane 10'is folded in half. The filler 19 may be present between the gel layers 15 facing each other at the fold portion, or may be adhered between the gel layers 15 facing each other by the filler 19. The filler 19 may exist in a state of being infiltrated into the layer constituting the separation membrane 10'located around the non-separable functional region 18 and the supply-side flow path member 3.

The separation membrane 10'can be manufactured, for example, by using a raw material laminated sheet in which layers constituting the separation membrane 10'such as the third porous layer 13, the first porous layer 11, and the gel layer 15 are laminated. Specifically, a layer that does not exist in the non-separable functional region 18 such as the gel layer 15 is cut out from the raw material laminated sheet in the region that becomes the crease portion when the separation membrane 10'is folded in half, and the non-separable functional region. A material to be a filler 19 may be provided in 18. When the material to be the filler 19 is a curable resin or the like, the leaf 6'is provided with a separation membrane 10'with a supply-side flow path member 3 interposed therebetween before the material is cured. It can be manufactured by folding and curing the above material.

The separation membrane 10'shown in FIG. 7 has a third porous layer 13, a first porous layer 11, a gel layer 15, a second porous layer 12, and a fourth porous layer 14 in this order, and the non-separable functional region 18 is provided. , The third porous layer 13 and the fourth porous layer 14 are present, and the first porous layer 11, the gel layer 15, and the second porous layer 12 are not present. The non-separable functional region 18 fills at least a part of the portion where the first porous layer 11, the gel layer 15, and the second porous layer 12 do not exist, and penetrates at least a part of the third porous layer 13. The filler 19 is provided so as to do so. The filler 19 is preferably provided so as to fill the entire portion where the first porous layer 11, the gel layer 15, and the second porous layer 12 do not exist. The separation membrane 10'is a second cover portion arranged so as to cover at least a part of the range in which the non-separable functional region 18 is formed on the surface of the third porous layer 13 opposite to the first porous layer 11. Has 36.

In the leaf 6'shown in FIG. 8, the supply side flow path member 3 is interposed between the separated membranes 10'folded in half. In the leaf 6', the inner surfaces of the opposing separation membranes 10'are adhered to each other by the filler 19 provided at the fold portion, and the folded state of the separation membrane 10'can be fixed. In the leaf 6', the filler 19 exists in a state of being infiltrated into the layer constituting the separation membrane 10', the permeation side flow path member 4, and the supply side flow path member 3. A first cover portion may be provided at an end portion of the supply-side flow path member 3 facing the crease portion, and in this case, the filler 19 may permeate the first cover portion and supply. It does not have to penetrate the side flow path member 3.

(Gel layer)
The gel layer is used as a separation functional layer for selectively permeating a specific fluid component, and is particularly preferably a separation functional layer for selectively permeating a specific gas component. The gel layer contains a hydrophilic resin, and more preferably contains an alkali metal compound, an amino acid, an aminosulfonic acid, and / or an aminophosphonic acid. The gel layer may further contain a hydration reaction catalyst for improving the reaction rate of the specific gas component and the alkali metal compound, and adjusts the wettability with respect to the first porous layer and / or the second porous layer. It may contain a surfactant for this purpose.

The hydrophilic resin is a resin having a hydrophilic group such as a hydroxyl group or an ion exchange group, and contains a crosslinked hydrophilic resin that exhibits high water retention by having a network structure by cross-linking the molecular chains of the hydrophilic resin. Is more preferable. The hydrophilic group may be neutralized by an alkali metal compound or the like contained in the gel layer to form a salt.

The polymer forming the hydrophilic resin preferably has, for example, an acrylic acid alkyl ester, a methacrylic acid alkyl ester, a vinyl ester of a fatty acid, or a structural unit derived from a derivative thereof. Examples of the polymer exhibiting such hydrophilicity include a polymer obtained by polymerizing a monomer such as acrylic acid, itaconic acid, crotonic acid, methacrylic acid, and vinyl acetate, and specifically, an ion exchange group. Acrylic acid-vinyl alcohol, which is a copolymer of polyacrylic acid-based resin having a carboxyl group, polyitaconic acid-based resin, polycrotonic acid-based resin, polymethacrylic acid-based resin, etc., polyvinyl alcohol-based resin having a hydroxyl group, etc. Examples thereof include a polymerization system resin, an acrylic acid-methacrylic acid copolymer system resin, an acrylic acid-methyl methacrylate copolymer system resin, and a methacrylic acid-methyl methacrylate copolymer system resin. Among these, polyacrylic acid-based resin which is a polymer of acrylic acid, polymethacrylic acid-based resin which is a polymer of methacrylic acid, polyvinyl alcohol-based resin which is a saponified polymer of vinyl acetate, methyl acrylate and vinyl acetate. Acrylate-vinyl alcohol copolymer resin obtained by saponifying a copolymer, acrylic acid-methacrylic acid copolymer resin, which is a copolymer of acrylic acid and methacrylic acid, is more preferable, and polyacrylic acid and acrylate-. Vinyl alcohol copolymer-based resins are even more preferred.

The cross-linked hydrophilic resin may be prepared by reacting a polymer having a hydrophilic group with a cross-linking agent, or a monomer as a raw material of the polymer having a hydrophilic group and a cross-linking monomer may be prepared. It may be prepared by copolymerization. The cross-linking agent or cross-linking monomer is not particularly limited, and conventionally known cross-linking agents or cross-linking monomers can be used.

Examples of the cross-linking agent include epoxy cross-linking agents, polyhydric glycidyl ethers, polyhydric alcohols, poly-isocyanates, poly-aziridines, haloepoxy compounds, poly-aldehydes, poly-amines, organic metal-based cross-linking agents, metal-based cross-linking agents and the like. Examples thereof include conventionally known cross-linking agents. As the crosslinkable monomer, for example, divinylbenzene, tetraallyloxyethane, diallylamine, diallyl ether, N, N'-methylenebisacrylamide, trimethylolpropanetriallyl ether, pentaerythritol tetraallyl ether and the like are conventionally known. Examples include crosslinkable monomers. Examples of the cross-linking method include methods such as thermal cross-linking, ultraviolet cross-linking, electron beam cross-linking, radiation cross-linking, and photo-crosslinking, and methods described in JP-A-2003-26809 and JP-A-7-88171. Conventionally known methods can be used.

The alkali metal compound can reversibly react with a specific gas component dissolved in the gel layer. Thereby, the selective permeability of a specific gas component in the gel layer can be improved. The alkali metal compound contained in the gel layer may be one kind or two or more kinds. The alkali metal compound can also be in the form of a salt by neutralizing the hydrophilic group of the hydrophilic resin, the carboxy group of the amino acid, the sulfoxyl group of the aminosulfonic acid, or the phosphoxyl group of the aminophosphonic acid.

Examples of the alkali metal compound include alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides (for example, described in the pamphlet of International Publication No. 2016/0245223) and the like. In addition to the above, a compound forming a salt with an acidic compound such as citric acid may be used.

Amino acids, aminosulfonic acids, and aminophosphonic acids can improve the water retention of the gel layer. It is considered that amino acids, aminosulfonic acids, and aminophosphonic acids can be used in combination with an alkali metal compound to improve the affinity with a specific gas component that permeates the separation membrane in the gel layer. The carboxy group of amino acids, the sulfoxyl group of aminosulfonic acid, and the phosphoxil group of aminophosphonic acid are neutralized by alkali metal compounds, amines, ammonium compounds, etc. contained in the gel layer to form salts. May be. This makes it possible to improve the selective permeability of a specific gas component in the gel layer. The amino acid, aminosulfonic acid, and aminophosphonic acid contained in the gel layer may be one kind or two or more kinds. The amino acid may have an acidic dissociative group other than the carboxy group. The aminosulfonic acid group may have an acidic dissociative group other than the sulfoxyl group. The aminophosphonic acid group may have an acidic dissociative group other than the phosphoxyl group. These acidic dissociable groups may be neutralized with an alkali metal compound, an amine, an ammonium compound, or the like to form a salt. The acidic dissociable group referred to here is, for example, a phenolic hydroxyl group, a hydroxamic acid group (N-hydroxycarboxylic acid amide), or the like.

The amino acid, aminosulfonic acid, and aminophosphonic acid are not particularly limited. Examples of amino acids, aminosulfonic acids, and aminophosphonic acids include glycine, N, N-dimethylglycine, alanine, serine, proline, taurine, diaminopropionic acid, 2-aminopropionic acid, 2-aminoisobutyric acid, 3, 4-Dihydroxyphenylalanine, sarcosin, 3- (methylamino) propionic acid, N- (2-aminoethyl) glycine, N- (3-aminopropyl) glycine, N- (4-cyanophenyl) glycine, dimethylglycine, horse Uric acid, 4-amino horse uric acid, N- (4-hydroxyphenyl) glycine, hydantonic acid, iminodiacetic acid, iminodipropionic acid, N-isovalerylglycine, phenaceturic acid, N-tigroylglycine, acetulic acid, alani Luglycylglycine, benzoylglycylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 2-allylglycine, N-β-alanylglycine, N-acetyl-β-alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, It is preferably at least one selected from the group consisting of glutamic acid, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, tyrosine, valine, ornithine, citrulin, cystine, pipecolinic acid, and salts thereof. .. Amino acids, aminosulfonic acids, and aminophosphonic acids include glycine, N, N-dimethylglycine, alanine, serine, proline, taurine, diaminopropionic acid, 2-aminopropionic acid, 2-aminoisobutyric acid, 3,4-dihydroxy. It is preferably at least one selected from the group consisting of phenylalanine, sarcosine, iminodiacetic acid, and salts thereof.

An oxoacid compound can be mentioned as a hydration reaction catalyst when a specific gas component is an acid gas. The oxo acid compound is preferably an oxo acid compound of at least one element selected from the group consisting of a group 14 element, a group 15 element, and a group 16 element, and is preferably a tereric acid compound, a selenic acid compound, and a sub. It is more preferable that the compound is at least one selected from the group consisting of the hydric acid compound and the orthosilicic acid compound. The gel layer may contain one or more oxoacid compounds.

(1st porous layer and 2nd porous layer)
One of the first porous layer and the second porous layer can be a support layer for supporting the gel layer, and the other can be a protective layer for protecting the gel layer. The first porous layer and the second porous layer can be in direct contact with the gel layer. One of the first porous layer and the second porous layer is a layer to which a coating liquid containing a hydrophilic resin for forming a gel layer is applied, and the other is a layer in which the coating liquid is applied onto one of the porous layers. The coating layer formed by the above can be used as a layer for covering and protecting. The first porous layer and the second porous layer have highly porous gas permeability so as not to cause diffusion resistance of the raw material gas supplied to the gel layer in the separation membrane or a specific gas component contained in the raw material gas.

It is preferable that the first porous layer and the second porous layer are each formed of a resin material or an inorganic material. Examples of the resin material constituting the first porous layer and the second porous layer include polyolefin resins such as polyethylene (PE) and polypropylene (PP); polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), and polyfluor. Fluorine-containing resin such as vinylidene (PVDF); polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate; polystyrene (PS), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polyacrylonitrile (PAN), polyphenylene oxide (PPO), polyamide (PA), polyimide (PI), polyetherimide (PEI), polyetheretherketone (PEEK), high molecular weight polyester, heat resistant polyamide, aramid, polycarbonate, resins thereof Examples thereof include a mixture of two or more of the materials. Among these, from the viewpoint of water repellency and heat resistance, it is preferable to contain at least one of a polyolefin resin and a fluorine-containing resin, and one or more of polyethylene, polypropylene, and polytetrafluoroethylene may be contained. More preferred. The resin materials constituting the first porous layer and the second porous layer may be the same as each other or may be different from each other. Examples of the inorganic material constituting the first porous layer and the second porous layer include metal, glass, and ceramics.

The first porous layer and the second porous layer are not particularly limited as long as they are porous bodies. The first porous layer and the second porous layer may be independently, for example, a porous body in the form of a sheet such as a porous membrane, a non-woven fabric, a woven fabric, a foam, a mesh, or a net. The first porous layer and the second porous layer are preferably porous films from the viewpoint of being suitably used as a support layer or a protective layer for the gel layer while suppressing the diffusion resistance of a specific gas component. The porous film means a porous resin film. Examples of the porous membrane include a porous membrane obtained by a stretching method, a phase separation method, self-assembly, or crazing. The first porous layer and the second porous layer may be the same porous body or different porous bodies from each other.

(Third porous layer and fourth porous layer)
The third porous layer can be provided on the side opposite to the gel layer side of the first porous layer. The third porous layer can be used as a reinforcing layer for reinforcing the function of the first porous layer 11 as a support layer or a protective layer. The fourth porous layer can be provided on the side opposite to the gel layer side of the second porous layer. The fourth porous layer can be used as a reinforcing layer for reinforcing the function of the second porous layer as a protective layer or a support layer.

By providing the third porous layer and / or the fourth porous layer, it is possible to additionally impart strength that can withstand the pressure load applied to the separation membrane when a specific gas component in the raw material gas is selectively permeated. can.

It is preferable that the third porous layer and the fourth porous layer are independently formed of a resin material or an inorganic material. Examples of the resin material or the inorganic material constituting the third porous layer and the fourth porous layer include those described as the resin material or the inorganic material for forming the first porous layer and the second porous layer.

The third porous layer and the fourth porous layer may be independently in the form of a porous membrane, a non-woven fabric, a woven fabric, a foam, a net, or the like, and are preferably non-woven fabrics. Examples of the non-woven fabric include spunbond non-woven fabric, melt blow non-woven fabric, air-laid non-woven fabric, spunlace non-woven fabric, and card non-woven fabric.

(Hollow tube)
The hollow tube 5 is a conduit for collecting the permeated gas that has passed through the separation membrane 10 and discharging it from the spiral type separation membrane element 1. The hollow tube 5 preferably has heat resistance that can withstand the operating temperature conditions of the separation device provided with the separation membrane element 1. The hollow tube 5 is preferably a material having mechanical strength that can withstand the winding of the laminated body 7 wound around the hollow tube 5. As shown in FIGS. 1 and 2, the hollow tube 5 has a plurality of spaces in which the permeation gas flow path space formed by the permeation side flow path member 4 and the hollow space inside the hollow tube 5 are communicated with each other on the outer peripheral surface thereof. Has a hole 50 of.

(Supply side flow path member and transmission side flow path member)
The supply-side flow path member 3 and the permeation-side flow path member 4 promote turbulence (surface renewal of the film surface) of the permeation fluid that has permeated the raw material fluid and the separation film 10, and the permeation of the permeation fluid in the raw material fluid is permeated. It is preferable to have a function of increasing the speed and a function of minimizing the pressure loss of the supplied raw material fluid and the permeation fluid that has passed through the separation membrane 10. The supply side flow path member 3 and the permeation side flow path member 4 have a function as a spacer for forming a flow path of the raw material fluid and the permeation fluid, and a function of causing turbulence in the raw material fluid and the permeation fluid. Therefore, a mesh-like (net-like, mesh-like, etc.) one is preferably used. Since the flow path of the fluid changes depending on the shape of the mesh, the shape of the unit cell of the mesh is preferably selected from, for example, a square, a rectangle, a rhombus, a parallelogram, and the like, depending on the purpose. The material of the supply side flow path member 3 and the transmission side flow path member 4 is not particularly limited, but a material having heat resistance that can withstand the operating temperature conditions of the separation device provided with the separation membrane element 1 is preferable. The supply-side flow path member 3 and the transmission-side flow path member 4 may independently have a single-layer structure or a multi-layer structure. The supply-side flow path member 3 and the transmission-side flow path member 4 having a multi-layer structure preferably have a structure in which one or more types of mesh-like layers are laminated, and the laminated mesh-like layers have different mesh structures from each other. You may have.

(1st cover part and 2nd cover part)
When the first cover portion and the second cover portion are tapes, the film used as the base material of the tape is a polyolefin resin such as polyethylene (PE) or polypropylene (PP); polytetrafluoroethylene (PTFE), polyfluoride. Fluorine-containing resins such as vinyl (PVF) and polyvinylidene fluoride (PVDF); to polystyrene (PS), polyethersulfone (PES), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyimide (PI), polycyclo Examples thereof include xylenedimethylene terephthalate (PCT). The pressure-sensitive adhesive layer of the tape can be formed by using a known pressure-sensitive adhesive.

When the first cover portion and the second cover portion are resin-coated, the resin forming the resin coating includes, for example, an epoxy resin, a vinyl chloride copolymer resin, a vinyl chloride-vinyl acetate copolymer resin, and vinyl chloride. -Vinilidene chloride copolymer resin, vinyl chloride-acrylonitrile copolymer resin, butadiene-acrylonitrile copolymer resin, polyamide resin, polyvinyl butyral resin, polyester resin, cellulose derivative (nitrocellulose, etc.) resin, styrene- Examples thereof include butadiene copolymer resin, various synthetic rubber resins, phenol resin, urea resin, melamine resin, phenoxy resin, silicone resin, ureaformamide resin and the like. As the resin forming the resin coating, a known or commercially available adhesive may be used.

(Sealing part)
The sealing portion is provided to prevent mixing of the raw material fluid and the permeated fluid. The spiral type separation membrane element 1 can be formed by, for example, permeating the sealing material into the permeation side flow path member 4 and the separation membrane 10 or the supply side flow path member 3 and the separation membrane 10 and hardening. can. As the sealing material, a material generally used as an adhesive can be used. Examples of the adhesive include a thermosetting adhesive, a thermosetting adhesive, an active energy ray-curable adhesive and the like.

Examples of the resin contained in the sealing material used for the sealing portion include epoxy-based resin, urethane-based resin, silicone-based resin, vinyl chloride copolymer resin, vinyl chloride-vinyl acetate copolymer resin, and vinyl chloride-. Vinylidene chloride copolymer resin, vinyl chloride-acrylonitrile copolymer resin, butadiene-acrylonitrile copolymer resin, polyamide resin, polyvinyl butyral resin, polyester resin, cellulose derivative (nitrocellulose etc.) resin, styrene-butadiene Examples thereof include copolymerization type resin, various synthetic rubber type (epolymer type) resins, phenol type resin, urea type resin, melamine type resin, phenoxy type resin, ureaformamide type resin and the like. Among these, the sealing material is preferably an epoxy-based resin (resin for an epoxy-based adhesive).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

[Example 1]
(Preparation of separation membrane (1))
188 parts by mass of water as a medium, 4 parts by mass of crosslinked polyacrylic acid ("Acpec HV-501" manufactured by Sumitomo Seika Chemical Co., Ltd.) and non-crosslinked polyacrylic acid acid ("Acpana AP-40F" manufactured by Sumitomo Seika Chemical Co., Ltd.) as a hydrophilic resin. , 40% Na saponification) 0.8 parts by mass was charged with 10.5 parts by mass of cesium hydroxide monohydrate as a neutralizing agent, and the neutralization reaction was carried out with stirring. Then, 10 parts by mass of cesium carbonate as a carrier that reversibly reacts with CO ₂ , 1.5 parts by mass of potassium phosphite as a hydration reaction catalyst, and a surfactant as an additive (“Surflon S” manufactured by AGC Seimi Chemical Co., Ltd. -242 ") 1.2 parts by mass was added and mixed to obtain a coating liquid.

Hydrophobic PTFE porous membrane as the first porous layer (“Poaflon HP-010-50” manufactured by Sumitomo Electric Fine Polymer Co., Ltd., film thickness 50 μm, average pore size 0.1 μm) and PPS non-woven fabric (Hirose) as the third porous layer. A laminated sheet in which "PS0080") manufactured by Paper Manufacturing Co., Ltd. was laminated was prepared. After applying the coating liquid obtained above to the hydrophobic PTFE porous membrane side of this laminated sheet, the hydrophobic PTFE porous membrane (same as above) as the second porous layer is layered on it, and the hydrophobic PTFE after coating is applied. The porous membrane was dried at a temperature of about 120 ° C. for about 5 minutes to prepare a sheet raw material for a separation membrane having a layer structure of a third porous layer / first porous layer / gel layer / second porous layer.

While feeding out the sheet raw material produced above, it was cut into a size of 1050 mm in the width direction and 1575 mm in the length direction to obtain a cut piece. A sponge is impregnated with an aqueous surfactant solution in which a surfactant (“Surflon S-242” manufactured by AGC Seimi Chemical Co., Ltd.) and water are mixed at a ratio of 1:10, and applied to the periphery of the second porous layer of the cut piece. Then, it was naturally dried for 1 hour or more. After air-drying, a two-component mixed epoxy adhesive (viscosity 45,000 cP, manufactured by Alemco Products) was applied to the peripheral edge of the second porous layer at a supply amount of 0.045 g / mm. The cut piece and the fourth porous layer ((Hirose Paper Co., Ltd. “PS0080S” (PPS non-woven fabric)) having a size of 1050 mm in width × 1575 mm in length are bonded to each other via the applied adhesive to form a separation membrane. (1) was produced.

After spreading the separation membrane (1) on a horizontal plane, the separation membrane (1) was folded back in half. Prepare a member whose surface to which the load is applied is a metal flat surface, face each other on the flat surfaces of the member, and sandwich the entire portion of the separation membrane (1) to be a folded fold, and 1 N / cm ² . The load was applied for 5 seconds. After that, the distance between the opposite inner surfaces of the separation membrane (1) (distance in the direction orthogonal to the horizontal plane) was measured with a caliper, and the maximum distance among the above distances was determined and found to be 17 mm (Table). 1).

(Preparation of separation membrane unit)
A supply-side flow path member (SUS wire mesh, 50 × 50 mesh, width 1050 mm × length 813 mm) is placed on the fourth porous layer of the separation membrane (1), and the supply-side flow path member is sandwiched between them. The membrane (1) was folded in half to obtain a leaf (1). A two-component mixed epoxy adhesive (viscosity) as a sealing material on one surface of the leaf (1) at a supply amount of 0.045 g / mm to the three edge portions excluding the edge located at the crease portion. 45000 cP, manufactured by Alemco Products Co., Ltd.) was applied. Through the applied adhesive, the leaf (1) and the transmission side flow path member (SUS wire mesh, 50 × 50 mesh / 100 × 100 mesh / 50 × 50 mesh multi-layer structure) having a size of 1050 mm in width × 813 mm in length. Was bonded to obtain a separation membrane unit. The same operation was repeated to prepare 20 separation membrane units.

(Preparation of laminated body)
A plurality of lead spacers (SUS wire mesh, 50 × 50 mesh, width 1050 mm × length 1194 mm) as a transmission side flow path member forming the outermost layer of the laminated body at one end in the length direction and on the outer peripheral surface along the width direction. A hollow tube (made of SUS, diameter 25.4 mm, length 1260 mm) having a hole in the above was fixed with an adhesive tape. Of the lead spacers, the portion where the separation membrane unit was not arranged on the lead spacer was wound around a hollow tube, and the outer diameter was 50.8 mm. Subsequently, the lead spacer is placed on the horizontal plane so that the transmission side flow path member side of the first layer separation membrane unit is exposed (so that the lead spacer and the leaf of the separation membrane unit face each other). The separation membrane unit was placed on top. At this time, the first layer is separated so that the fold portion of the separation membrane is located on the hollow tube side on the lead spacer and the tip portion of the fold portion is parallel to the axial direction of the hollow tube. A membrane unit was placed.

Subsequently, the first region including the vicinity of the center of the fold portion of the separation membrane (1) included in the separation membrane unit of the first layer on the lead spacer was pressed by the first pressing member. The first pressing member pressed the fold portion of the separation membrane (1) via the transmission side flow path member included in the separation membrane unit of the first layer. The first pressing member has a pressing surface having a flat surface and a rectangular pressing surface having a rectangular shape supported by a rod-shaped support portion, and the pressing surface is parallel to the extending direction of the fold portion. The length in the direction is 300 mm, and the length in the direction orthogonal to the extending direction is 100 mm. The pressing by the first pressing member was performed so that the maximum distance between the surfaces of the separation membrane (1) was 2 mm in the first region pressed by the first pressing member (Table 1). This maximum distance was measured with a caliper.

The second layer separation membrane is placed on the first layer separation membrane unit so that the transmission side flow path member of the second layer separation membrane unit is exposed while the pressure of the first region is maintained by the first pressing member. The units were stacked. In the separation membrane unit of the second layer, the position of the tip portion of the fold portion of the separation membrane (1) is in the direction orthogonal to the fold portion, and the position of the separation membrane unit of the first layer is higher than that of the separation membrane (1). Was also laminated so as to be offset (shifted) in the direction away from the hollow tube. The distance between the tip portions of the fold portions of the separation membrane (1) in the first and second layer separation membrane units was set to 9.4 mm.

Next, while maintaining the pressing of the first region by the first pressing member, the second region including the vicinity of the center of the fold portion of the separation membrane (1) of the second layer separation membrane unit was pressed. The second region was set at a position where it did not interfere with the first pressing member. The second pressing member pressed the fold portion of the separation membrane (1) via the transmission side flow path member included in the second layer separation membrane unit. As the second pressing member, a member having the same structure as the first pressing member was used. The pressing by the second pressing member was performed so that the maximum distance between the surfaces of the separation membrane (1) in the separation membrane unit of the second layer was 2 mm in the second region.

The second layer is such that the transmission side flow path member of the third layer separation membrane unit is exposed while the pressing of the first region by the first pressing member and the pressing of the second region by the second pressing member are maintained. The third layer of the separation membrane unit was laminated on the separation membrane unit of the eye. The lamination of the third-layer separation membrane unit on the second-layer separation membrane unit was performed so as to have the same relationship as the lamination of the second-layer separation membrane unit on the first-layer separation membrane unit.

Subsequently, the pressing of the first region by the first pressing member was released while the pressing of the second region by the second pressing member was maintained. The first pressing member was moved to press the third region including the vicinity of the center of the fold portion of the separation membrane (1) of the third layer separation membrane unit. The third region was set at a position where it did not interfere with the second pressing member. The first pressing member pressed the fold portion of the separation membrane (1) via the transmission side flow path member included in the third layer separation membrane unit. The pressing by the first pressing member was performed in the same manner as the pressing performed in the first region.

While maintaining the pressing of the second region by the second pressing member and the pressing of the third region by the first pressing member, the three layers are exposed so that the transmission side flow path member of the fourth layer separation membrane unit is exposed. The fourth layer of the separation membrane unit was laminated on the separation membrane unit of the eye. The stacking of the fourth layer separation membrane unit on the third layer separation membrane unit was performed so as to have the same relationship as the stacking of the second layer separation membrane unit on the first layer separation membrane unit. The operation described in the operation of laminating the fourth layer separation membrane unit was repeated, and 20 separation membrane units were laminated. Then, the leaves were laminated so as to form the uppermost surface of the laminated body in the same manner except that the leaves were laminated instead of the separation membrane unit, and a laminated body with a hollow tube was obtained.

(Preparation of separation membrane element)
The hollow tube of the laminated body with the hollow tube was set on the winding chuck of the separation membrane element manufacturing apparatus, the hollow tube was rotated, and the laminated body was wound around the outer peripheral surface of the hollow tube. A polyimide tape was spirally wound around the outer peripheral surface of the wound body, and an adhesive or the like as a sealing material was cured to obtain a separation membrane element.

In the separation membrane element, the laminated body wound around the hollow tube is developed, and the two leaves 6 adjacent to each other via the permeation side flow path member 4 in the laminating direction of the laminated body 7 are separated contained in each leaf 6. The distance WR between the folds of the membrane (1) was measured. Distance WR was measured between two adjacent reefs 6, respectively. Using the measured WR, the standard deviation of the deviation amount of the distance WR from the pitch P (P = 9.4 mm) was determined based on the above formula (I), and it was 0.25 (Table 1). ..

[Comparative Example 1]
A separation membrane element was obtained in the same manner as in Example 1 except that the first pressing member and the second pressing member did not press the laminate. For the obtained separation membrane element, the standard deviation of the deviation amount of the distance WR from the pitch P was determined in the same manner as in Example 1 and found to be 1 (Table 1).

[Example 2]
(Preparation of Separation Membrane (2))
A sheet raw material was prepared in the same procedure as in the preparation of the separation membrane (1), and cut pieces were obtained. Next, the first porous layer is such that the third porous layer remains in a range of 5 mm (a range in which the total length is 10 mm) from the center of the cut piece in the length direction toward the length direction (two directions). , The gel layer, and the second porous layer were cut out and removed to form a non-separable functional region. An aqueous surfactant solution was applied to the peripheral edge of the second porous layer and the non-separable functional region and allowed to air dry for 1 hour or more. After air-drying, a polypropylene adhesive tape was attached so as to cover the non-separable functional region on the outer surface of the third porous layer, which becomes the outside when folded in half. Subsequently, a two-component mixed epoxy adhesive (viscosity 45,000 cP, manufactured by Alemco Products Co., Ltd.) was applied to the peripheral edge of the second porous layer and the non-separable functional region. The cut piece and the fourth porous layer ((Hirose Paper Co., Ltd. “PS0080S” (PPS non-woven fabric)) having a size of 1050 mm in width × 1575 mm in length are bonded to each other via the applied adhesive to form a separation membrane. (2) was produced.

After spreading the separation membrane (2) on a horizontal plane, the separation membrane (2) is folded back in half in the non-separation functional region, and the procedure described in Example 1 is performed to cover the entire folded portion. After applying a load of 1 N / cm ² , the distance between the opposing inner surfaces of the separation membrane (2) (distance in the direction orthogonal to the horizontal plane) was measured, and the maximum distance among the above distances was determined. , 17 mm (Table 1).

(Preparation of separation membrane unit)
A supply-side flow path member (SUS wire mesh, 50 × 50 mesh, width 1050 mm × length 813 mm) is placed on the fourth porous layer of the separation membrane (2) so as to sandwich the supply-side flow path member. The separation membrane (2) was folded in half so that the fold portion was located in the non-separable functional region to obtain a leaf (2). Using this leaf (2), 20 separation membrane units were prepared by the procedure described in Example 1.

(Manufacturing of laminated body and separation membrane element)
The laminated body and the separation membrane element were prepared by the same procedure as in Example 1 except that the separation membrane unit prepared by using the leaf (2) was used.

In the separation membrane element, the laminated body wound around the hollow tube is developed, and the two leaves 6 adjacent to each other via the permeation side flow path member 4 in the laminating direction of the laminated body 7 are separated contained in each leaf 6. The distance WR between the folds of the membrane (2) was measured. Distance WR was measured between two adjacent reefs 6, respectively. Using the measured WR, the standard deviation of the deviation amount of the distance WR from the pitch P (P = 9.4 mm) was determined based on the above formula (I), and it was 0.15 (Table 1). ..

1,1a, 1b Separation membrane element, 3,3a, 3b, 3c, 3d Supply side flow path member (first flow path member, second flow path member), 4, 4a, 4b, 4c, 4d Permeation side flow path Members (1st flow path member, 2nd flow path member), 5 hollow pipes, 6, 6'leaf, 7 laminates, 9, 9a, 9b, 9c, 9d separation membrane unit, 10, 10a, 10b, 10c , 10d, 10'separation membrane, 11 first porous layer (porous layer), 12 second porous layer (porous layer), 13 third porous layer, 14 fourth porous layer, 15 gel layer, 18 non-separable functional region, 19 Filler, 31 1st pressing member, 32 2nd pressing member, 36 2nd cover part, 50 holes, 51 supply port, 52 1st discharge port, 53 2nd discharge port, 55 telescope prevention plate.

Claims

A method for manufacturing a separation membrane element, which includes a perforated hollow tube and a laminated body, and in which at least a part of the laminated body is wound around the hollow tube.
The laminated body is
A plurality of separation membrane units including a leaf having a first flow path member interposed between the two-folded separation membranes and at least a part of layers constituting the second flow path member laminated on the leaf are laminated. ,and,
The separation membrane units are laminated so that the position of the fold portion of the separation membrane is displaced in the winding direction of the laminate.
The manufacturing method includes a step of laminating the separation membrane unit.
In the laminating step, when N is an integer of 2 or more, the first region including at least a part of the fold portion of the separation membrane contained in the separation membrane unit of the (N-1) layer was pressed. A method for manufacturing a separation membrane element, comprising a first step of laminating the separation membrane unit of the Nth layer on the separation membrane unit of the (N-1) layer in the state.
The method for manufacturing a separation membrane element according to claim 1, wherein the pressing of the first region is performed so that the maximum distance between the surfaces of the separation membranes facing each other in the first region is less than 5 mm.
The laminating step further includes a second step of laminating the (N + 1) th layer separation membrane unit on the Nth layer separation membrane unit laminated in the first step.
In the second step, the separation membrane unit of the (N + 1) layer is pressed in a state where the second region including at least a part of the fold portion of the separation membrane included in the separation membrane unit of the Nth layer is pressed. The method for manufacturing a separation membrane element according to claim 1 or 2, wherein the separation membrane element is laminated.
The method for manufacturing a separation membrane element according to claim 3, wherein the second step is performed while maintaining a state in which the first region is pressed in the first step.
The laminating step further includes a third step of laminating the (N + 2) th layer separation membrane unit on the (N + 1) th layer separation membrane unit laminated in the second step.
In the third step, the separation membrane of the (N + 2) layer is pressed while the third region including at least a part of the fold portion of the separation membrane included in the separation membrane unit of the (N + 1) layer is pressed. The method for manufacturing a separation membrane element according to claim 3 or 4, wherein the units are laminated.
The method for manufacturing a separation membrane element according to claim 5, wherein the third step is performed while maintaining a state in which the second region is pressed in the second step.
The pressing of the first region is performed by pressing the first pressing member.
The laminating step further includes a step of releasing the pressing of the first region by the first pressing member.
The method for manufacturing a separation membrane element according to claim 5 or 6, wherein the third step is performed in a state where the first pressing member after the release step presses the third region.
The method for manufacturing a separation membrane element according to claim 7, wherein the pressing of the second region is performed by pressing the second pressing member.
The method for manufacturing a separation membrane element according to any one of claims 1 to 8, wherein the separation membrane element is a spiral type separation membrane element in which the entire length of the laminate is wound around the hollow tube.
One of the first flow path member and the second flow path member is a supply-side flow path member for forming a flow path through which the raw material fluid flows, and the other is a flow path through which the permeated fluid that has passed through the separation membrane flows. The method for manufacturing a separation membrane element according to any one of claims 1 to 9, which is a permeation side flow path member for forming.
The first flow path member is the supply side flow path member, and is
The method for manufacturing a separation membrane element according to claim 10, wherein the second flow path member is the permeation side flow path member.
The method for manufacturing a separation membrane element according to any one of claims 1 to 11, wherein the separation membrane has a porous layer and a gel layer provided on the porous layer.
A separation membrane element comprising a perforated hollow tube and a laminate, wherein at least a part of the laminate is wound around the hollow tube.
The laminated body is
A plurality of separation membrane units including a leaf having a first flow path member interposed between the two-folded separation membranes and at least a part of layers constituting the second flow path member laminated on the leaf are laminated. ,and,
The separation membrane units are laminated so that the position of the fold portion of the separation membrane is displaced in the winding direction of the laminate.
The separation membrane is
It has a porous layer and a gel layer provided on the porous layer, and
After folding the separation membrane in half so that a load of 1 N / cm 2 is applied to the entire crease, the maximum distance between the opposing surfaces of the separation membrane when the load is removed is 10 mm or more. can be,
The separation membrane element is
The winding direction distance between the positions of the fold portions of the separation membrane included in the two adjacent leaves via the second flow path member in the stacking direction of the laminated body is defined as WR.
When the value (C / n) obtained by dividing the outer peripheral length C of the hollow tube by the number n of the leaves contained in the laminated body is defined as the pitch P,
A separation membrane element having a standard deviation of 0.4 or less for the amount of deviation of the distance WR from the pitch P.
The separation membrane element according to claim 13, wherein the separation membrane element is a spiral type separation membrane element in which the entire length of the laminated body is wound around the hollow tube.
One of the first flow path member and the second flow path member is a supply-side flow path member for forming a flow path through which the raw material fluid flows, and the other is a flow path through which the permeated fluid that has passed through the separation membrane flows. The separation membrane element according to claim 13 or 14, which is a permeation side flow path member for forming.
The first flow path member is the supply side flow path member, and is
The separation membrane element according to claim 15, wherein the second flow path member is the permeation side flow path member.