WO2021060557A1

WO2021060557A1 - Separation membrane module and separation method

Info

Publication number: WO2021060557A1
Application number: PCT/JP2020/036610
Authority: WO
Inventors: 沙綾中野; 日高　秀人; 和也前川
Original assignee: 三菱ケミカル株式会社
Priority date: 2019-09-27
Filing date: 2020-09-28
Publication date: 2021-04-01
Also published as: JP2021053552A

Abstract

Provided are a separation membrane module with which it is possible to increase the packing density of tubular separation membranes and to reduce the number of separation membrane units compared to conventional products, and a separation method using this separation membrane module. Separation membrane units 10 are provided in multiple stages in a cylindrical housing 2. In a plan view of the housing 2, separation membrane units 10A in first, fifth, and ninth stages are inserted from a 3 o'clock side, separation membrane units 10B in second, sixth, and tenth stages are inserted from a 12 o'clock side, separation membrane units 10C in third and seventh stages are inserted from a half past 1 o'clock side, and separation membrane units 10D in fourth and eighth stages are inserted from a half past 10 o'clock side.

Description

Separation membrane module and separation method

The present invention relates to a separation membrane module used for separating a part of components from a fluid such as a solution or a mixed gas, and a separation method using this separation membrane module.

A separation membrane module having a tubular separation membrane is known as a device for separating components in a solution or a mixed gas. This tubular separation membrane has a tubular porous ceramic support and a porous separation membrane made of zeolite or the like provided on the outer peripheral surface of the support. In order to separate a specific component from a fluid such as a solution or a mixed gas, the fluid of the solution is brought into contact with one (outer surface) of the tubular separation membrane, and the other (inner surface) is depressurized to release the specific component. A method of vaporizing and separating, a method of vaporizing a solution and bringing it into contact with a separation membrane in a gaseous state, depressurizing the non-contact surface side to separate a specific component, or bringing a pressurized mixed gas into contact with the separation membrane. A method of separating a specific component is known.

As a multi-tube separation membrane module in which a plurality of tubular separation membranes are installed in a housing, Patent Document 1 describes a module in which a separation membrane unit is inserted in the centripetal direction from the side surface of a cylindrical container.

In Patent Document 1, the length of the separation membrane unit in the insertion direction (container centripetal direction) is about the radius of the container or less (FIGS. 4, 5, and 7 of Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-56369

In Patent Document 1, in order to increase the packing density of the tubular separation membrane, it is necessary to install a large number of separation membrane units as shown in FIGS. 4 to 7 of Patent Document 1. For example, in FIGS. 4 to 7 of Patent Document 1, cylindrical containers are arranged so that the direction of the container axis is vertical, and the separation membrane units are arranged in multiple upper and lower stages, and eight separation membranes in one stage. The unit is provided in the centripetal direction. When a large number of separation membrane units are installed in this way, it takes a lot of time and effort to assemble the separation membrane module. In addition, the risk of the fluid to be separated leaking from the sealing portion between each separation membrane unit and the container also increases in proportion to the number of separation membrane units.

The present invention provides a separation membrane module capable of increasing the packing density of a tubular separation membrane and reducing the number of processing units as compared with Patent Document 1, and a separation method using the separation membrane module. The purpose is to do.

The gist of the present invention is as follows.

[1] A separation membrane module having a tubular housing and a processing unit inserted into the housing from an insertion port provided on a side peripheral surface of the housing, and the tip of the processing unit in the insertion direction. A separation membrane module characterized in that the side reaches or near the peripheral surface on the housing side opposite to the insertion port.

[2] The separation membrane module according to [1], wherein the tip side of the processing unit in the insertion direction is located near the inner peripheral surface of the housing on the opposite side of the insertion port.

[3] A support hole is provided on the side peripheral surface of the housing on the side opposite to the insertion port, and the tip end side of the processing unit is inserted into the support hole and held. The separation membrane module of [1].

[4] Any one of [1] to [3], wherein a plurality of the insertion ports are provided at intervals in the axial direction, and the processing unit has at least one of a tubular separation membrane and a heater. Separation membrane module.

[5] The separation membrane module of [4], wherein a plurality of the insertion ports are provided at intervals in the axial direction, and at least a part of the processing unit has the tubular separation membrane.

[6] At least a part of the processing unit is the separation membrane module of [4] or [5] having the heater.

[7] The separation membrane module according to any one of [4] to [6], wherein at least a part of the processing unit has a tubular separation membrane and a heater.

[8] The separation membrane module according to any one of [4] to [6], wherein a part of the processing unit has only a tubular separation membrane.

[9] The separation membrane module according to any one of [4] to [6], wherein a part of the processing unit has only a heater.

[10] The processing unit is any one of [1] to [9] having a support plate perpendicular to the insertion direction and a plurality of tubular separation membranes and / or heaters whose one end side is supported by the support plate. Separation membrane module.

[11] At least a part of the processing unit has a tubular separation membrane, an end tube is connected to one end side of the tubular separation membrane, and the end tube is fixed to one surface side of the support plate. An end cover is attached to the other surface side of the support plate, and an outflow chamber is formed between the support plate and the end cover, and the outflow chamber is formed through the support plate and the communication hole provided in the end pipe. [10] The separation membrane module in which the inside of the tubular separation membrane and the outflow chamber communicate with each other.

[12] The separation membrane module of [11], wherein a pedestal portion surrounding the insertion port is provided on the outer peripheral surface of the housing, and the outer peripheral edge portion of the support plate is fixed to the pedestal portion.

[13] The separation membrane module of [11] or [12] in which the outflow chamber of each processing unit communicates with the collecting pipe via a connecting pipe.

[14] Any of [11] to [13], in which the end covers of all the processing units are located on one half side of the outer peripheral surface of the housing when projected onto a surface perpendicular to the axial direction of the housing. Separation membrane module.

[15] The separation membrane module according to any one of [4] to [14], wherein the tubular separation membrane has a zeolite membrane.

[16] The first to nth (n is 4 or more) processing units are arranged at intervals from one end side to the other end side in the axial direction of the housing, and are 4N + 1th (n + 1) from the one end side. N is an integer of 0 or 1 or more) and the 4 ・ N + 2nd processing units adjacent to it are approximately orthogonal to each other when projected onto a plane perpendicular to the axial direction of the housing, and the 4 ・ N + 3rd and it The adjacent 4 ・ N + 4th processing units are substantially orthogonal to each other when projected onto a plane perpendicular to the axial direction of the housing, and the 4 ・ N + 1st and 4 ・ N + 2nd separation membrane units and 4 The N + 3rd and 4th / N + 4th processing units are any of [1] to [15] separation membrane modules that are oblique when projected onto a plane perpendicular to the axial direction of the housing.

[17] The separation membrane module of [16] having the oblique angle of 45 ° ± 10 °.

[18] The area of the processing unit on the inner circumference of the housing when one processing unit is projected onto a plane perpendicular to the axis of the housing is 10 to 95% of the cross-sectional area of the housing [1] to [17]. ] Any separation membrane module.

[19] A separation method for separating a substance from a mixed fluid by a pervaporation method or a vapor permeation method using the separation membrane module according to any one of [1] to [18].

In the separation membrane module of the present invention, the processing unit inserted into the housing has a length that crosses or is close to the diameter of the housing, and the number of processing units arranged is smaller than that of Patent Document 1. Is enough. Therefore, the separation membrane module can be easily manufactured, and the risk of fluid leakage from the connection portion between the processing unit and the insertion port is reduced.

According to one aspect of the present invention, since the processing unit is provided with a heater, the fluid to be processed can be heated by the heater.

According to one aspect of the present invention, a separation membrane module structure is provided so that the fluid to be separated can contact the tubular separation membrane more uniformly.

According to one aspect of the present invention, by arranging adjacent processing units in the intersecting direction, the contact frequency between the membrane and the fluid can be improved, and the separation efficiency can be improved.

According to one aspect of the present invention, the fluid taken out from each processing unit can be efficiently guided to the collecting pipe, and the configuration of the separation membrane module can be simplified.

The above effect according to the present invention is particularly large when the separation membrane module is enlarged to a commercial scale. The term "larger" as used herein means that the flow rate of the fluid to be treated is, for example, in the case of gas, the lower limit is 3 tons / hour, preferably 7 tons / hour, and the upper limit is 650 tons / hour, preferably 330 tons. / A scale that is like an hour. In the case of a liquid, the scale has a lower limit of 120 tons / hour, preferably 250 tons / hour, and an upper limit of 200,000 tons / hour, preferably 100,000 tons / hour.

It is a perspective side view of the separation membrane module which concerns on embodiment. 2a, 2b, 2c and 2d are cross-sectional views taken along line IIa-IIa, line IIb-IIb, line IIc-IIc and line IId-IId of FIG. It is a top view of the separation membrane module which concerns on embodiment. It is sectional drawing in the longitudinal direction of a separation membrane unit. FIG. 4 is a sectional view taken along line VV of FIG. It is sectional drawing which shows another example of the separation membrane unit. FIG. 6 is a cross-sectional view taken along the line VII-VII of FIG. It is explanatory drawing of the plane view area of a processing unit. It is sectional drawing explaining the fixed structure of a tubular separation membrane.

An example of the separation membrane module according to the embodiment of the present invention will be described with reference to FIGS. 1 to 5.

The separation membrane module 1 of FIGS. 1 to 5 has a substantially cylindrical housing 2 whose vertical direction is the axis direction of the cylinder axis, and a separation membrane unit 10 as a plurality of processing units inserted into the housing 2.

The top and bottom surfaces of the housing 2 are

end plate portions

2a and 2b, respectively. A flat plate may be used instead of the end plate. In the case of a flat plate, it is preferable to use a mirror plate because the cost increases as the plate thickness increases.

The bottom end plate portion 2b is provided with an inflow port 3 for the fluid to be processed, and the top end plate portion is provided with an outflow port 4 for a non-permeable fluid.

When the treatment method of the fluid to be treated is the vapor permeation method (VP) or gas separation, the module may be installed in any of a horizontal direction, a vertical direction, and an oblique direction in the axial direction of the housing 2. However, from the viewpoint of stability of module installation, it is preferable to install the module in the horizontal direction or the vertical direction.

In the case of VP, the fluid to be treated is a steam in which the fluid to be treated is sufficiently dispersed, and in the case of gas separation, the fluid to be treated is sufficiently dispersed. Therefore, the fluid to be processed may flow in parallel or perpendicular to the axial direction of the housing 2. Further, the inflow port 3 of the fluid to be processed may be installed in the direction perpendicular to the axial direction of the housing 2 or in the horizontal direction. It is preferable that the non-permeable fluid outlet 4 is installed on the side opposite to the fluid inlet 3 with the axis of the housing 2 interposed therebetween from the viewpoint of improving the processing efficiency. When the fluid to be processed flows in parallel to the axial direction of the housing 2, even if both the inflow port 3 of the fluid to be processed and the outflow port 4 of the impermeable fluid are installed on the axial center of the housing 2. Good.

When the treatment method of the fluid to be treated is the pervaporation method (PV), the housing 2 may be installed so that the axial direction is horizontal, vertical, or diagonal, but equipment is installed. From the viewpoint of stability, it is preferable to install so that the axial direction is the horizontal direction or the vertical direction.

When the housing 2 is installed in the vertical direction, the inflow port 3 of the fluid to be processed may be installed on either the upper side or the lower side of the module with respect to the vertical direction. It is preferable to install the inflow port 3 under the module in order to prevent air bubbles from accumulating in the shell.

The inflow port 3 of the fluid to be processed may be installed in the horizontal direction with respect to the axial direction of the housing 2 or in the vertical direction. The non-permeable fluid outlet 4 may be installed horizontally or vertically with respect to the axial direction of the housing 2, but is installed in the same direction as the fluid inlet 3 to be processed. It is preferable to do so. It is preferable that the non-permeable fluid outlet 4 is installed on the side opposite to the fluid inlet 3 with the axis of the housing 2 interposed therebetween from the viewpoint of improving the processing efficiency. When the fluid to be processed flows in parallel to the axial direction of the housing 2, even if both the inflow port 3 of the fluid to be processed and the outflow port 4 of the impermeable fluid are installed on the axial center of the housing 2. Good.

When installing the housing 2 in the horizontal direction, it is preferable to install the inflow port 3 on the lower side of the module with respect to the vertical direction in order to prevent air bubbles from accumulating in the shell.

When the axial direction of the housing 2 is installed in the horizontal direction, the installation direction of the inflow port 3 of the fluid to be processed is perpendicular to the axial direction of the housing 2 in order to prevent air bubbles from accumulating in the shell. It is preferable to install it. The non-permeable fluid outlet 4 is preferably installed in the same direction as the fluid inlet 3 to be treated. It is preferable that the non-permeable fluid outlet 4 is installed on the side opposite to the fluid inlet 3 with the axis of the housing 2 interposed therebetween from the viewpoint of improving the processing efficiency.

Further, in any of the above cases, it is preferable that the inflow port 3 and the outflow port 4 are arranged so as to be the farthest positions from each other in the module.

The side peripheral surface of the housing 2 is provided with an insertion port 5 for the separation membrane unit 10 at intervals in the vertical direction. A pedestal portion 6 for mounting the separation membrane unit 10 is provided on the outer peripheral edge portion of the insertion port 5. By providing the pedestal portion 6, the support plate 11 and the insertion port 5 can be easily connected with a simple structure such as a bolt and a nut, and the unit shape can be simplified.
The pedestal portion 6 goes around the insertion port 5. The pedestal portion 6 is slightly raised in the radial direction from the outer peripheral surface of the housing 2. The tip surface of the pedestal portion 6 in the radial direction is flat so that the outer peripheral edge portions of the support plate 11 described later can overlap.

The configuration of the separation membrane unit 10 will be described with reference to FIGS. 4 and 5.

The separation membrane unit 10 includes a support plate 11 on the base end side, a plurality of end tubes 12 standing up from one surface (inward surface) of the support plate 11, and a tubular separation membrane having one end side connected to the end tube 12. 13, an end plug 14 attached to the other end side of each tubular separation membrane 13 and sealing the other end side, an end plate 15 into which each end plug 14 is inserted and held, a support plate 11 and an end. It has a tie rod 16 that connects the plate 15 and an end cover 17 or the like that is covered on the other surface (outward surface) of the support plate 11.

The support plate 11 has a disk shape and has a plurality of permeation fluid passage holes 11a penetrating in the thickness direction.

On the inward facing surface of the support plate 11, the end pipe 12 is erected coaxially with the passage hole 11a. In this embodiment, a counterbore-shaped recess (reference numeral omitted) is provided in the passage hole 11a, the base end side of the end pipe 12 is inserted into the recess, and the end pipe 12 is fixed to the support plate 11 by welding. However, the fixed structure of the end tube 12 is not limited to this. For example, a male screw may be provided on the base end side of the end pipe 12, a through hole having a female screw may be provided in the support plate 11, and the end pipe 12 may be fixed by screwing each other. A female screw may be provided on the end tube 12 side, and a male screw may be provided on the support plate 11. The end tube 12 may be arranged on any side of the support plate 11, but since the end cover 17 can be opened to replace the film, the end tube 12 can be arranged from the space side surrounded by the support plate 11 and the end cover 17. It is preferable to have a structure in which the above is inserted. Further, the end tube 12 may or may not penetrate the support plate 11, but in order to effectively use the entire length of the membrane, the end tube 12 preferably penetrates the support plate 11. ..

As a structure for fixing the tubular separation membrane 13 to the separation membrane unit, through holes are provided in each of the support plate 11 of FIG. 9 and the holding plate 11f provided between the support plate 11 and the end cover 17 to form a tubular shape. Examples thereof include a structure in which the separation membrane 13 is penetrated and the membrane is sealed with an O-ring 11 g. The support plate and the holding plate are fixed by applying pressure by fixing means such as bolts. When an O-ring is used, the peripheral portion of the through hole provided in the support plate 11 is projected so that the O-ring fits in the protruding portion. With such a fixed structure, it is not necessary to machine threads and screw holes, and the cost can be reduced.

As shown in the figure, the end tube 12 is made of a tubular body having a tube hole (reference numeral omitted) penetrating in the direction of the tube axis core line. The tip of the end tube 12 has a small diameter, and the proximal end side of the tubular separation membrane 13 is fitted externally. The connection portion between the base end side of the tubular separation membrane 13 and the tip end side of the end tube 12 is sealed with an O-ring, a gasket, or the like. Tubular separation from the end tube 12 by providing a heat-shrinkable tube that connects and covers from the base end side of the tubular separation membrane 13 to the tip end side of the end tube 12 instead of the O-ring or gasket, or together with the O-ring or gasket. The connection portion with the film 13 may be sealed.

The end plug 14 is connected to the tip of the tubular separation membrane 13. The end plug 14 has a columnar shape or a shape obtained by cutting a part of the columnar shape, and seals the tip of the tubular separation membrane 13. A small diameter portion inserted into the tubular separation membrane 13 is provided at the base end of the end plug 14. The end plug 14 and the tubular separation membrane 13 are sealed in the same manner as the connection portion between the end tube 12 and the tubular separation membrane 13.

In order to reduce the weight of the end plug 14, a recess is provided from the tip surface of the end plug 14. Further, in FIG. 4, another pipe (metal SUS connecting pipe) may be connected to a part of the end pipe 12 connected to the tubular separation membrane 13 on the tubular separation membrane 13 side.

The base end side of the tie rod 16 is fixed to the support plate 11 by screwing or the like. In this embodiment, four tie rods 16 are arranged at equal intervals in the circumferential direction on the outer peripheral edge of the support plate 11, but the number of tie rods 16 is not limited to this. The tip of each tie rod 16 is inserted into a rod insertion hole (reference numeral omitted) provided in the plate 15. The plate 15 is fixedly supported by the tie rod 16 by the stopper 16a provided so as to sandwich the plate 15 and the nut 16b screwed to the tie rod 16.

The plate 15 has a disk shape slightly smaller in diameter than the insertion port 5, and has an opening 15a into which each end plug 14 is inserted. The method of fixing the end plug 14 is not limited to fitting and insertion, and may be fixed to the plate 15 by any other method.

The end cover 17 has a substantially hemispherical shell shape in this embodiment, and its outer peripheral edge portion 17a is airtightly attached to the peripheral edge portion of the outward surface of the support plate 11 via a gasket, an O-ring, or the like. Between the end cover 17 and the support plate 11, there is a permeation fluid outflow chamber 18. The end cover 17 is provided with a permeation fluid outlet 17b. The shape of the end cover 17 is not limited to the above.

The inside of the outflow chamber 18 communicates with each tubular separation membrane 13 via the passage hole 11a and the tube hole of the end pipe 12.

In this embodiment, as shown in FIG. 3, the outlet 17b of each separation membrane unit 10 is connected to the collecting pipe 22 via the connecting pipe 21.

In this embodiment, the arrangement pitch in the axial direction (vertical vertical direction in this embodiment) of the housing 2 of the insertion port 5 provided on the side peripheral surface of the housing 2 is substantially the same.

As shown in FIGS. 2a to 2d, in this embodiment, in the plan view of the housing 2, the arrangement rules of each insertion port 5 and the separation membrane unit 10 inserted from each insertion port 5 are as follows. ..

That is, the separation membrane unit 10 (10A) in the 4th N + 1th stage (N is an integer of 0 or 1 or more) from the top extends from the insertion port 5 on the 3 o'clock side toward 9 o'clock.

The 4 ・ N + 2nd stage separation membrane unit 10 (10B) extends from the insertion port 5 on the 12 o'clock side toward 6 o'clock. The 4 ・ N + 3rd stage separation membrane unit 10 (10C) extends from the insertion port 5 on the 1:30 side toward 7:30. The 4th N + 4th stage separation membrane unit 10 (10D) extends from the insertion port 5 on the 10:30 side toward 4:30.

The separation membrane unit 10 is inserted into each insertion port 5 in the radial direction of the housing 2, that is, in the direction of passing through the center of the housing 2 in the plan view of the housing 2.

As described above, in this embodiment, the separation membrane unit 10 (10A) in the 4th N + 1st stage from the top extends in the 3 o'clock and 9 o'clock directions in a plan view, and the separation membrane unit 10 (10B) immediately below the separation membrane unit 10 (10A) extends in the 3 o'clock and 9 o'clock directions. ) Extend in the 12 o'clock and 6 o'clock directions, and are orthogonal to each other in a plan view.

Further, the separation membrane unit 10 (10C) in the 4th N + 3rd stage from the top extends in the direction of 1:30 and 7:30, and the separation membrane unit 10 (10D) immediately below it extends at 10:30 and 4 It extends in the half-hour direction and is orthogonal in plan view.

Therefore, the separation membrane unit 10 (10A, 10B) of the 4 ・ N + 1st stage and the 4 ・ N + 2nd stage from the top, and the separation membrane unit 10 (10C, 10D) of the 4 ・ N + 3rd stage and the 4 ・ N + 4th stage from the top. Intersect at an angle of 45 ° in plan view.

When the tip of the separation membrane unit 10 is located near the inner peripheral surface of the housing 2 on the opposite side of the insertion port 5, the total of the end tube 12, the tubular separation membrane 13, and the end plug 14 of the separation membrane unit 10. Of the lengths (including the above-mentioned connecting pipes if any), the length L inside the housing (FIG. 8) is smaller than the inner diameter D of the housing 2 and is 1 of the inner diameter D. Greater than / 2 (ie, the radius of the housing 2). The length L is preferably 50 to 97%, more preferably 55 to 93%, and even more preferably 65 to 85% of the inner diameter D. Within the above range, the area of the cross-sectional area of the housing obtained by subtracting the cross-sectional area of the portion existing in the inner diameter D of the unit 10 from the area of the circle that can be calculated by the inner diameter D becomes the smallest, and the inside of the housing. The porosity, which is the portion where the separation membrane does not exist, can be reduced. The total length of the three (the length including the above-mentioned connecting pipe, if any) is preferably 50 to 150%, more preferably 60 to 120%, and 80 to 80% of the inner diameter D of the housing 2. 130% is more preferable, 90 to 125% is particularly preferable, and 105 to 110% is most preferable. Within the above range, it is sufficient to manufacture the minimum necessary length of the separation membrane 13, and the ratio of the length of the fluid to be treated in contact with the separation membrane 13 is maximized, which is preferable.

The total length of the tubular separation membrane 13 may extend within the tubular portion of the housing, or may extend to the pedestal portion 6. From the viewpoint of preventing the fluid to be treated from staying in the pedestal portion 6, the tubular separation membrane 13 preferably has the entire length extending in the tubular portion of the housing.

As described above, in this embodiment, each separation membrane unit 10 has a long length substantially crossing the housing 2 in the radial direction.

In this embodiment, the lower limit of the ratio of the diameter d of the support plate 11 to the inner diameter D of the housing 2 is preferably 10% or more, more preferably 30% or more, further preferably 40% or more, and particularly preferably 65% or more. , 80% or more is most preferable. The upper limit of the ratio of the diameter d of the support plate 11 to the inner diameter D of the housing 2 is preferably 95% or less. By adopting this range, as shown in FIG. 8, the proportion of the cross-sectional area S of the tubular separation membrane relative to the housing cross-sectional area [pi] D ^2/4 is increased, thereby reducing the short path of the fluid to be treated.

As shown in FIG. 8, the housing cross-sectional area (planar viewing area) surrounded by the inner peripheral surface 2C of the housing ² is calculated as πD 2/4. Percentage ratio [S / ( ^{πD 2/4)] · 100} % 10 to 95%, more preferably about 30 to 95%, even 50 to preferably about 95%, preferably in particular about 70 to 95%, and most preferably 85 to 95% .. Within the above range, the porosity inside the housing becomes sufficiently small, so that the fluid efficiently contacts the separation membrane unit 10 and the separation efficiency is improved.

Note that the total length of the three parties of the separation membrane end tube 12 of the unit 10, the tubular separation membrane 13 and end plug 14 and the length L within the ^{housing, [S / (πD 2/} 4)] · 100 It is not necessary to satisfy the preferred conditions of% and% at the same time, and only one of them may be satisfied.

In FIG. 1, the number of installation stages of the separation membrane unit 10 is 10, but the number of stages is not limited to this. Usually, it is about 2 to 28 steps, particularly preferably about 4 to 14 steps, but it is not limited to this.

Two of the separation membrane units 10 (10A, 10B) of the 4 ・ N + 1st stage and the 4 ・ N + 2nd stage from the top are paired, and the separation membrane unit 10 of the 4 ・ N + 3rd stage and the 4 ・ N + 4th stage from the top ( When two of 10C and 10D) are used as another pair and both are used as a set, the symmetry is high when the major axis of the separation membrane module of the present invention is the center of symmetry. It is preferable because the number of separation membrane units 10 can be minimized.

Instead of this, three or more separation membrane units 10 may be arranged as a pair and two or more pairs of separation membrane units may be arranged as a set with the long axis of the separation membrane module of the present invention as the center of symmetry. At this time, it is preferable to arrange the separation membrane unit so as to have high symmetry from the viewpoint of contact efficiency. Further, the number of separation membrane units in each pair may be changed.

When arranging these separation membrane units, the separation membrane units may be arranged in a spiral shape or may be arranged randomly. It is preferable to arrange the space in which the separation membrane unit does not exist so as not to communicate with each other as much as possible from the viewpoint of increasing the contact efficiency of the fluid to be treated and improving the separation efficiency.

Hereinafter, suitable materials and the like of each member constituting the separation membrane module of the present invention will be described.

Examples of the material of the end tube 12 and the end plug 14 include those that do not allow fluid to permeate, such as metal, ceramics, and resin, but are not limited thereto. The material of the support plate 11 and the tie rod 14 is usually a metal material such as stainless steel, but is not particularly limited as long as it has heat resistance and supply under separation conditions and resistance to permeation components, and depending on the application, other materials such as a resin material may be used. The material can be changed.

The tubular separation membrane 13 may be formed only of the separation membrane, but preferably has a tubular porous support and a separation membrane formed on the outer peripheral surface of the porous support. The shape of the separation membrane or the porous support-separation membrane composite having the porous support and the separation membrane is not particularly limited, but may be flat plate, tubular, cylindrical, columnar or prismatic. It may be a honeycomb shape or a monolith shape having a large number of holes extending in the longitudinal direction. In the case of a flat porous support-separation membrane composite, the separation membrane may be formed on either one side or both sides. In the case of a tubular, cylindrical, honeycomb-shaped or monolith-shaped porous support-separation membrane composite, the separation membrane may be formed only on the outer surface or only the inner surface. It may be both an outer surface and an inner surface. It is preferable to form the separation membrane only on the outer surface from the viewpoint that it is easy to grasp the defect at the time of manufacturing and confirm the deterioration state after use.

The type of separation membrane is not particularly limited, but an inorganic separation membrane is preferable from the viewpoint of solvent resistance. Examples of the organic separation membrane include polysulfone, polyimide, and polyamide. Examples of the form of the organic separation membrane include a hollow fiber membrane and an organic membrane formed on a tubular ceramic porous support. Examples of the inorganic separation membrane include a zeolite membrane, a silica membrane, a carbon membrane and the like, and among them, a zeolite membrane is preferably used. As the material of this tubular porous support, silica, α-alumina, γ-alumina, mullite, zirconia, titania, ittoria, silicon nitride, silicon carbide and the like can be used for both the inorganic separation membrane and the organic separation membrane. Examples thereof include ceramic sintered bodies and inorganic porous supports of metal sintered bodies. Among them, an inorganic porous support containing at least one of alumina, silica and mullite is preferable. The average pore diameter of the surface of the porous support is not particularly limited, but the pore diameter is preferably controlled, and is usually 0.02 μm or more, preferably 0.05 μm or more, and more preferably 0.1 μm. As described above, the range is usually 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

Zeolites are crystallized on the surface of the porous support to form a zeolite membrane.
The main zeolite constituting the zeolite membrane usually contains a zeolite having an oxygen 6-10 membered ring structure, and preferably contains a zeolite having an oxygen 6-8 membered ring structure, although it depends on the substance to be separated.

The value of n of the zeolite having an oxygen n-membered ring here indicates that the number of oxygen is the largest among the pores composed of oxygen and T element forming the zeolite skeleton. For example, when pores having a 12-membered oxygen ring and an 8-membered ring are present as in the MOR-type zeolite, it is regarded as a zeolite having a 12-membered oxygen ring.

To give an example of a zeolite having an oxygen 6-10-membered ring structure, AEI, AEL, AFG, ANA, BRE, CAS, CDO, CHA, DAC, DDR, DOH, EAB, EPI, ESV, EUO, FAR, FRA, FER, FAU, GIS, GIU, GOO, HEU, IMF, ITE, ITH, KFI, LEV, LIO, LOS, LTN, MAR, MEP, MER, MEL, MFI, MFS, MON, MSO, MTF, MTN, MTT, MWF, MWW, NAT, NES, NON, PAU, PHI, RHO, RRO, RTE, RTH, RUT, SGT, SOD, STF, STI, STT, TER, TOR, TON, TSC, TUN, UFI, VNI, VSV, There are WEI, YUG, etc.

The zeolite membrane may be a membrane made of zeolite alone or a membrane in which the zeolite powder is dispersed in a binder such as a polymer, or the zeolite is fixed in a film shape on various supports. It may be a zeolite membrane composite. The zeolite membrane may contain a part of amorphous components and the like.

The thickness of the zeolite membrane is not particularly limited, but is usually 0.1 μm or more, preferably 0.6 μm or more, and more preferably 1.0 μm or more. Further, it is usually 100 μm or less, preferably 60 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less.

However, the present invention may use a tubular separation membrane having a separation membrane other than the zeolite membrane.

The outer diameter of the tubular separation membrane 13 is preferably 3 mm or more, more preferably 6 mm or more, further preferably 10 mm or more, preferably 20 mm or less, more preferably 18 mm or less, still more preferably 16 mm or less. If the outer diameter is too small, the strength of the tubular separation membrane may be insufficient and it may be easily broken, and if it is too large, the membrane area per module decreases.

The length of the portion of the tubular separation membrane 13 covered with the zeolite membrane is preferably 20 cm or more, preferably 200 cm or less. A plurality of tubular separation membranes 13 may be arranged in the longitudinal direction to increase the total length. In that case, it is preferable to use a plurality of tubular separation membranes 13 connected to each other by a joint tube. The joint tube may have, for example, a small-diameter portion inserted into the tubular separation membrane 13 on both end sides and a large-diameter portion at the center. When a plurality of tubular separation membranes 13 are connected by a joint pipe, the load may be concentrated on the connecting portion and the membrane may be broken. Therefore, from the viewpoint of increasing the strength of the connecting portion, the length of the small diameter portion of the joint pipe is set to the end. The length in the tubular separation membrane 13 of the tube 12 or the end plug 14 is preferably 2 to 3 times, more preferably 2 to 2.5 times, and further 2 to 2.25 times. preferable. The outer diameter of the small diameter portion of the joint pipe is preferably substantially equal to the inner diameter of the tubular separation membrane 13 from the viewpoint of fitting with the tubular separation membrane 13 with the smallest possible gap. The outer diameter of the large diameter portion of the joint pipe is preferably substantially equal to the outer diameter of the tubular separation membrane 13 from the viewpoint of avoiding concentration of load and from the viewpoint of covering with a heat-shrinkable tube described later with the gap as small as possible. ..

In order to maintain the airtightness of the space inside the tubular separation membrane 13, the tubular separation membrane and the joint tube may be sealed by using a heat-shrinkable tube, and a circumferential groove is formed in the outer peripheral portion of the small diameter portion of the joint tube. May be provided and an O-ring may be attached to seal between the tubular separation membrane 13 and the joint tube. When a heat-shrinkable tube is used, the large diameter portion of the joint tube is preferably about 3 to 5 cm in order to secure an area in contact with the heat-shrinkable tube.

The tubular separation membranes are usually arranged in an amount of 5 to 3000, particularly 50 to 2000, and the shortest distance between the tubular separation membranes is preferably 2 mm to 10 mm. The size of the housing and the number of tubular separation membranes are appropriately changed depending on the amount of fluid to be treated.

In the separation membrane module 1 configured in this way, the fluid to be treated is introduced into the housing 2 from the inflow port 3, and a part of the components of the fluid to be treated permeate through the tubular separation membrane 13 while flowing through the housing 2. It is taken out from the tubular separation membrane 13 to the collecting pipe 22 via the outflow chamber 18, the outlet 17b, and the connecting pipe 21. The fluid that has not permeated flows out of the separation membrane module 1 from the outlet 4.

In the separation membrane module 1, the separation membrane unit 10 extends long in the diameter direction of the housing 2 from each insertion port 5, and is near the inner peripheral surface of the housing 2 on the opposite side of each insertion port 5. Has reached. Therefore, the number of insertion ports 5 provided in the housing 2 is smaller than that in Patent Document 1, and the separation membrane module 1 can be easily manufactured. Further, the risk of fluid leakage from the attachment portion of the separation membrane unit 10 to the insertion port 5 is also reduced.

In this embodiment, the 4 ・ N + 1st stage and the 4 ・ N + 2nd stage

separation membrane units

10A and 10B immediately below the 4 ・ N + 1st stage are orthogonal to each other in a plan view, and the 4 ・ N + 3rd stage and the 4 ・ N + 4 immediately below the

separation membrane unit

10A and 10B are orthogonal to each other. The

separation membrane units

10C and 10D of the stage are orthogonal to each other in a plan view. Further, the

separation membrane units

10A and 10B of the 4 ・ N + 1st stage and the 4 ・ N + 2nd stage, the

separation membrane units

10C and 10D of the 4 ・ N + 3rd stage and the 4 ・ N + 4th stage are approximately 45 ° in plan view. It is diagonally crossed at an angle. Therefore, it is possible to suppress a short path of the fluid to be treated flowing from the inflow port 3 to the outflow port 4, and the flow of the fluid to be treated in an arbitrary horizontal cross section in the housing 2 becomes substantially uniform. Further, the fluid to be treated is dispersed by the separation membrane units 10A to 10D, becomes in a turbulent state, and comes into contact with the tubular separation membrane 13 of each separation membrane unit, so that the membrane separation treatment is efficiently performed.

The permeated fluid taken out from each separation membrane unit 10 joins the collecting pipe 22 and is taken out. In this embodiment, as shown in FIG. 3, the permeated fluid outlet 17a of each separation membrane unit 10 is located only in a range of half a circumference or less (a range of a central angle of 135 ° in FIG. 3) in the plan view of the housing 2. Therefore, the length of the connecting pipe 21 connecting each outlet 17a and the collecting pipe 22 can be shortened, and the pipe layout is simplified. When the number of installation stages of the separation membrane unit 10 is large, instead of collecting the connecting pipes 21 in one collecting pipe 22, two or more collecting pipes 22 are provided and the connecting pipes 21 to be collected are collected in the longitudinal direction of the housing (FIG. 1). Then, it can be divided in any stage (up and down direction). For example, in the case of 8 steps, it is divided into 1st to 4th steps and 5th to 8th steps. When such a structure is adopted, the range of one connecting pipe gathered in one collective pipe 22 is within the above-mentioned "half circumference or less", but it does not have to be within half a circumference as a whole.

In the embodiments of FIGS. 1 to 5 and 8, each separation membrane unit 10 is shorter than the inner diameter of the housing 2, and each separation membrane unit 10 is supported by the housing 2 in a cantilever structure. However, the cantilever structure in this way eliminates the need for a holding structure on the free end side of the separation membrane unit 10, so that the number of parts can be reduced and the cost can be reduced.

However, in the present invention, the separation membrane unit may be supported by the housing 2 in a double-sided structure. That is, a support hole is provided in the housing so as to face each insertion port 5 in the diameter direction of the housing 2, the separation membrane unit is inserted into the housing from the insertion port, and the tip end side of the separation membrane unit is passed through the support hole. In this way, the tip end side of the separation membrane unit may be fixed to form a double-sided structure. By adopting the double-sided structure, it is possible to reduce the load due to the weight of the tubular separation membrane 13 and the load due to the fluid to be treated. Further, since the length of the tubular separation membrane 13 can be increased, the porosity per cross-sectional area of the housing 2 can be reduced, and the separation efficiency of the fluid to be treated can be improved. If a fixing structure for fixing the tubular separation membrane 13 to the support plate 11 by the above-mentioned O-ring is applied to the double-sided structure, the membrane can be replaced from either one end or the other end of the membrane for maintenance. Improves sex.

In the embodiments of FIGS. 1 to 5, the

separation membrane units

10A and 10B and the

separation membrane units

10C and 10D are orthogonal to each other in the plan view of the housing 2, but the angles are not only orthogonal to each other but also close to a right angle (for example, 90). It may intersect at ° ± 10 °, especially 90 ° ± 5 °). Further, the intersecting angle between the

separation membrane units

10A and 10B and the

separation membrane units

10C and 10D is not limited to 45 °, and even if they intersect at 45 ° ± 10 °, particularly 45 ° ± 5 °. Good.

In the present invention, the directivity direction of the separation membrane unit may be other than shown. For example, the directivity direction of the separation membrane unit may gradually change in the clockwise direction or the counterclockwise direction toward the lower stage side. Further, the directivity directions of all the separation membrane units may be the same. For example, the separation membrane unit 10 (10D) from the 4th N + 1st stage (10A) from the top to the 4th N + 4th stage from the top may be arranged in a spiral shape. On the other hand, if the arrangement is not spiral as described above, the separation membrane unit 10 efficiently contacts the fluid to be treated, and the separation efficiency can be improved, which is preferable.

In the present invention, a baffle may be provided in which the plate surface is in the direction intersecting with the longitudinal direction of the tubular separation membrane 13 (for example, in the orthogonal direction). An example thereof is shown in FIGS. 6 and 7. In FIGS. 6 and 7, the baffle 19 has a shape in which a part of a circle is cut out in the chord direction, and has an opening 19a through which the tubular separation membrane 13 is inserted. Four baffles are shown in FIGS. 6 and 7, but are not limited thereto. Other configurations of FIGS. 6 and 7 are the same as those of FIGS. 4 and 5, and the same reference numerals indicate the same parts.

In the above embodiment, the separation membrane unit 10 having only the tubular separation membrane is used as the treatment unit, but a plurality of tubular separation membranes (or tubular separation membrane 13, end) are used as some or all of the treatment units. A rod-shaped connecting body composed of the tube 12 and the end plug 14) may be replaced with a heat exchanger or a heater.

Generally, the temperature of the fluid to be treated drops due to osmotic vaporization by pervaporation. By heating the fluid with a heater, the permeation efficiency can be increased.

In the present invention, as a part of the processing unit, a heat treatment unit dedicated to heat treatment having only a heater may be installed. In this case, the treatment unit other than the heat treatment unit dedicated to heat treatment may have only a tubular separation membrane, or may have both a tubular separation membrane and a heater.

As the heat exchanger, a combination of shell and tube type heat exchangers described in TEMA standard SECTION1 and FIGUREN-1.2 is preferable.
The heater may be an electric heater, a tube heater to which a hot medium such as steam or hot water is supplied, or the like.

When the heat treatment unit is fixed to the module with a cantilever structure, the shape of the tube and heater of the heat exchanger is preferably U-shaped.

When the heat treatment unit is fixed to the module with a double-sided structure, any combination of structures described in TEMA standard 8th Edition SECTION 1 FIGURE N-1.2 may be used, or a spiral shape may be used. ..

When a processing unit having both a tubular separation membrane 13 and a heater is fixed to the module in a cantilever structure, the shape of the tube and heater of the heat exchanger is U from the viewpoint of coexisting the tubular separation membrane 13 and the heater. It is preferably a mold. It is preferable to divide the surface of the processing unit that supports the tubular separation membrane 13 and the heater into two equal parts, install the tubular separation membrane 13 on one side, and install the heater on the other side. Further, from the viewpoint of improving the heating efficiency of the fluid to be treated, it is preferable to install the heat exchanger or the heater so that the area in contact with the fluid to be treated of the module is the largest.

When fixing a processing unit having both a tubular separation membrane 13 and a heater to the module with a double-sided structure, any combination of the structures described in TEMA standard 8th Edition SECTION 1 FIGURE N-1.2 is used. You may. The inlet and outlet of the fluid in the heat exchanger may be provided at one end in the axial direction of the processing unit, and the inlet and outlet may be provided at one end and the other end, respectively. In the latter case, when the processing unit is projected on a plane parallel to the axial direction, it is preferable to design the inlet and the outlet to exist in opposite directions with the axial center of the processing unit in between, from the viewpoint of heating efficiency. ..

In one aspect of the present invention, a heat treatment unit dedicated to heat treatment and a separation treatment unit dedicated to separation treatment provided with only a tubular separation membrane may be installed. In this case, in the membrane separation unit closest to the Nth membrane separation unit, it is preferable to arrange the heat treatment unit so that the temperature difference Δt on the downstream side of the flowing fluid becomes small. Δt is preferably 1 to 60 ° C., more preferably 1 to 30 ° C., and even more preferably 2 to 20 ° C. As an example of arrangement, the heat treatment unit and the separation treatment unit may be alternately arranged in the axial direction of the housing, and one heat treatment unit may be arranged for each of the plurality of separation treatment units. The heat treatment unit and the separation treatment unit can be easily maintained and can be manufactured at a lower cost than the treatment unit provided with both the heater and the tubular separation membrane.

In the separation membrane module of the present invention, the fluid to be treated to be separated or concentrated is not particularly limited as long as it is a mixture of a gas or a liquid composed of a plurality of components that can be separated or concentrated by the separation membrane, and any mixture. However, it is preferably used for a mixture of gases.

For separation or concentration, a separation or concentration method called a pervaporation method (osmotic vaporization method) or a vapor permeation method (steam permeation method) can be used. Since the pervaporation method is a separation or concentration method in which a mixture of liquids is directly introduced into a separation membrane, a process including separation or concentration can be simplified. The separation membrane module of the present invention has a small decrease in separation efficiency due to drift flow, and since the fluid to be treated is in uniform contact with the separation membrane 13, vapor is used from the viewpoint of regardless of the installation direction or the direction of the fluid of the module of the present invention. It is more preferable to use it in the permeation method.

In the present invention, when the mixture to be separated or concentrated is a mixture of gas or liquid composed of a plurality of components, the mixture may be, for example, carbon dioxide, oxygen, nitrogen, hydrogen, methane, ethane, ethylene, propane. , Propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, helium, carbon monoxide, nitrogen monoxide, etc. Mixtures, aromatic compounds such as toluene, lower alcohols such as methanol, ethanol, isopropyl alcohol, butanol, C5 or lower ketones such as acetone, isobutyl ketone and methyl isobutyl ketone, lower glycols such as dimethyl glycol, N Examples include a mixture of liquids in a standard state containing at least one component selected from -methylpyrrolidone, formic acid, acetic acid, butyric acid, propionic acid, sulfuric acid, 3-methyl-1-butanol, DMSO, DMS, water and the like. .. Of the mixture consisting of these gas components or liquid components, the gas component or liquid component having a high permeence is separated by passing through the separation membrane, and the gas component or the liquid component having a low permeence is concentrated on the supply gas side. In addition, as the above-mentioned standard state, it is assumed that SATP is shown.

The above description is an example of the present invention, and the present invention may have aspects other than the above. For example, it is possible to control the flow of fluid by installing a baffle plate or a dispersion plate in the housing 2. Alternatively, a baffle plate facing the inflow port 3 or the outflow port 4 may be installed.

The flow velocity of the fluid to be treated is 0.1 or more and 3.0 m / s or less in the case of the gas phase including the vapor phase, particularly preferably 0.3 or more and 1.5 m / s or less in the case of the liquid phase. It is 005 m / s or more and 1.0 m / s or less, particularly preferably 0.01 or more and 0.5 m / s or less, but is not limited thereto. The flow velocity can be calculated by calculating the cross-sectional area from the inner diameter of the housing 2 and dividing the flow rate of the processing fluid by the value of this cross-sectional area.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.
This application is based on Japanese Patent Application 2019-177339, filed on September 27, 2019, which is incorporated by reference in its entirety.

1 Separation membrane module 2 Housing 5 Outlet 6 Pedestal part 10 Separation membrane unit 11 Support plate 12 End pipe 13 Tubular separation membrane 14 End plug 15 End plate 16 Tie rod 22 Collective piping

Claims

A separation membrane module having a tubular housing and a processing unit inserted into the housing from an insertion port provided on a side peripheral surface of the housing.
The housing is provided with an inflow portion for the fluid to be processed on one end side in the axial direction, and an outflow portion for the fluid that has not penetrated on the other end side.
In the separation membrane module provided with a plurality of outlets at intervals in the axial direction, the insertion port is provided.
A separation membrane module characterized in that the tip end side of the processing unit in the insertion direction reaches the peripheral surface on the housing side opposite to the insertion port or its vicinity.
The separation membrane module according to claim 1, wherein the tip side of the processing unit in the insertion direction is located near the inner peripheral surface of the housing on the side opposite to the insertion port.
A support hole is provided on the side peripheral surface of the housing on the side opposite to the insertion port.
The separation membrane module according to claim 1, wherein the tip end side of the processing unit is inserted into and held in the support hole.
The separation membrane module according to any one of claims 1 to 3, wherein the processing unit has a rod including at least one of a tubular separation membrane and a heater.
The separation membrane module according to claim 4, wherein at least a part of the processing unit has the tubular separation membrane.
At least a part of the processing unit is the separation membrane module according to claim 4 or 5, which has the heater.
The separation membrane module according to any one of claims 4 to 6, wherein at least a part of the processing unit has a tubular separation membrane and a heater as the rod.
The separation membrane module according to any one of claims 4 to 6, wherein a part of the processing unit has only a tubular separation membrane as the rod.
A part of the processing unit is a separation membrane module according to any one of claims 4 to 6, which has only a heater as the rod.
The separation membrane module according to any one of claims 1 to 9, wherein the processing unit has a support plate perpendicular to the insertion direction and a plurality of the rods whose one end side is supported by the support plate.
At least a part of the processing unit has a tubular separation membrane and
An end tube is connected to one end side of the tubular separation membrane, and the end tube is fixed to one side of the support plate.
An end cover is attached to the other surface side of the support plate, and an outflow chamber is formed between the support plate and the end cover.
The separation membrane module according to claim 10, wherein the inside of the tubular separation membrane and the outflow chamber communicate with each other through a communication hole provided in the support plate and the end pipe.
A pedestal portion surrounding the insertion port is provided on the outer peripheral surface of the housing.
The separation membrane module according to claim 11, wherein the outer peripheral edge portion of the support plate is fixed to the pedestal portion.
The separation membrane module according to claim 11 or 12, wherein the outflow chamber of each processing unit communicates with the collective pipe via a connecting pipe.
The separation membrane module according to any one of claims 11 to 13, wherein the end covers of all the processing units are located on a half side of the outer peripheral surface of the housing when projected onto a plane perpendicular to the axial direction of the housing.
The separation membrane module according to any one of claims 4 to 14, wherein the tubular separation membrane has a zeolite membrane.
The first to nth (n is 4 or more) processing units are arranged at intervals from one end side to the other end side in the axial direction of the housing.
The 4th N + 1st (N is an integer of 0 or 1 or more) from one end side and the 4th N + 2nd processing units adjacent to it are substantially orthogonal to each other when projected onto a plane perpendicular to the axial direction of the housing. And
The 4th N + 3rd and the 4th N + 4th processing units adjacent to each other are substantially orthogonal to each other when projected onto a plane perpendicular to the axial direction of the housing.
The 4 ・ N + 1st and 4 ・ N + 2nd separation membrane units and the 4 ・ N + 3rd and 4 ・ N + 4th processing units are oblique when projected onto a plane perpendicular to the axial direction of the housing. The separation membrane module according to any one of claims 1 to 15.
The separation membrane module according to claim 16, wherein the oblique angle is 45 ° ± 10 °.
The separation membrane module according to any one of claims 1 to 17, wherein the area in the inner circumference of the housing when one processing unit is projected onto a plane perpendicular to the axis of the housing is 10 to 95% of the cross-sectional area of the housing.
A separation method for separating a substance from a mixed fluid by a pervaporation method or a vapor permeation method using the separation membrane module according to any one of claims 1 to 18.