JP7765005B2 - Metal foil coated tube, method of manufacturing metal foil coated tube, and hydrogen separation device - Google Patents

Description

This disclosure relates to metal foil-coated tubes, methods for manufacturing metal foil-coated tubes, and hydrogen separation devices.

Problems such as global warming caused by the increase in carbon dioxide emissions resulting from the consumption of fossil fuels are becoming more serious. In recent years, fuel cells, a clean energy source, have been attracting attention as a solution to these problems.

The fuel for fuel cells is hydrogen, and various methods for separating hydrogen have been investigated, including the use of metal foils that selectively allow hydrogen gas to pass through.
For example, Patent Document 1 discloses a cylindrical hydrogen separator comprising a cylindrical hydrogen separation membrane formed by butt-welding the end faces of Nb-Ni-Ti alloy plates to form a cylindrical shape, and a porous body adhered to the inside of the cylindrical hydrogen separation membrane.

The cylindrical hydrogen separator disclosed in Patent Document 1 is manufactured by wrapping a cylindrical hydrogen separation membrane around a porous body and welding the butted or overlapping portions of the cylindrical hydrogen separation membrane. However, this requires advanced technology and poses the risk of reduced airtightness and reduced productivity due to poor welding, etc.

In response to the above problem, Patent Document 2 proposes a hydrogen separation membrane module including a cylindrical support body having a plurality of holes and a hydrogen separation membrane layer disposed on the outer surface of the support body and allowing selective permeation of hydrogen gas from a mixed gas. The hydrogen separation membrane layer is formed into an annular structure from sheet-like hydrogen separation membrane elements having first and second end portions positioned on opposite sides of the support body. The annular structure includes an annular portion surrounding the support body and a joint portion where the first and second end portions are overlapped and fixed to each other, and the joint portion is overlapped on the annular portion so that one of the first and second end portions is folded back onto the annular portion.

JP 2013-208607 A Japanese Patent Application Laid-Open No. 2019-25416

The present inventors have now discovered that there is room for further improvement in the productivity of the hydrogen separation membrane module disclosed in Patent Document 2.

The problem to be solved by this disclosure is to provide a metal foil-coated tube with excellent airtightness and productivity, a method for manufacturing such a metal foil-coated tube, and a hydrogen separation device equipped with such a metal foil-coated tube.

The specific means for achieving the objectives are as follows:
<1> A cylindrical support having a plurality of holes;
a metal foil covering the outer surface of the cylindrical support and having both ends overlapping each other;
a joint formed by sandwiching the overlapping portions of both ends of the metal foil between a first joint member and a second joint member;
an end cap provided at one end in the longitudinal direction of the cylindrical support;
a hollow tube provided at the other end in the longitudinal direction of the cylindrical support;
Equipped with
The joint portion is provided over at least a portion of the cylindrical support body in the longitudinal direction or over the entire longitudinal direction,
the first bonding member is provided in contact with the cylindrical support body, and the second bonding member is provided so as to overlap a part or the whole of the first bonding member via a portion where both end portions of the metal foil overlap.
Metal foil coated tube.
<2> The cylindrical support body has a recessed portion provided in at least a part of the longitudinal direction or the entire longitudinal direction, and the first joining member is provided in the recessed portion.
The metal foil-coated tube according to <1> above.
<3> The metal foil covers 70% or more of the area of the outer surface of the cylindrical support.
The metal foil-coated tube according to <1> or <2> above.
<4> The second bonding member is provided so as to overlap the first bonding member by 1 mm or more in the width direction via a portion where both end portions of the metal foil overlap.
The metal foil-coated tube according to any one of <1> to <3> above.
<5> The metal foil contains at least one of palladium and a palladium alloy,
The metal foil-coated tube according to any one of <1> to <4> above.
<6> A step of preparing a cylindrical support having a plurality of holes, the cylindrical support having an end cap at one end in a longitudinal direction and a hollow tube at the other end;
a step of providing a first joining member in contact with at least a portion of the cylindrical support body in the longitudinal direction or the entirety of the cylindrical support body in the longitudinal direction;
a step of wrapping a metal foil around the outer surface of the cylindrical support body so that both ends of the metal foil overlap each other;
a step of arranging a second bonding member so as to overlap a part or the whole of the first bonding member via a portion where both end portions of the metal foil overlap, and bonding the first bonding member and the second bonding member so as to sandwich the portion where both end portions of the metal foil overlap, thereby forming a bond;
Equipped with
Method for manufacturing metal foil coated tube.
<7> The formation of the joint is performed by irradiating the first joint member and the second joint member with a laser.
The method for producing a metal foil-coated tube according to <6> above.
<8> The metal foil-clad tube according to any one of <1> to <5> above,
a housing vessel that accommodates the metal foil-coated tube and has a gas inlet and a gas outlet;
and an end of the metal foil-covered tube where the hollow tube is provided is connected to or inserted into the hydrogen gas discharge part.
Hydrogen separation device.

The present disclosure provides a metal foil-coated tube with excellent airtightness and productivity, a method for manufacturing the metal foil-coated tube, and a hydrogen separation device equipped with the metal foil-coated tube.

FIG. 1 is a perspective view of one embodiment of a cylindrical support having an end cap on one end and a hollow tube on the other end. FIG. 2 is a cross-sectional view of the cylindrical support member shown in FIG. 1 taken along line AA. FIG. 3 is a perspective view showing one embodiment of a metal foil clad tube. FIG. 4 is a cross-sectional view of the metal foil-covered tube taken along line BB of FIG. FIG. 5 is a perspective view showing one embodiment of a metal foil clad tube. FIG. 6 is a perspective view showing one embodiment of a hydrogen separation device.

The following describes in detail the modes for implementing the present disclosure. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the present disclosure.

In this disclosure, numerical ranges indicated using "~" include the numerical values before and after "~" as the minimum and maximum values, respectively.

In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with the value shown in the synthesis examples.

In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, as long as the purpose of the process is achieved.

In this disclosure, a combination of two or more preferred aspects is a more preferred aspect.

The elements in the drawings shown in this disclosure are not necessarily drawn to scale, with emphasis instead being placed on clearly illustrating the principles of the disclosure.

(Metal foil coated tube)
The metal foil clad tube of the present disclosure comprises:
a cylindrical support having a plurality of holes;
a metal foil covering the outer surface of the cylindrical support and having both ends overlapping each other;
a joint formed by sandwiching the overlapping portions of both ends of the metal foil between a first joint member and a second joint member;
an end cap provided at one end in the longitudinal direction of the cylindrical support;
a hollow tube provided at the other end in the longitudinal direction of the cylindrical support,
The joint portion is provided over at least a portion of the longitudinal direction of the cylindrical support body or over the entire longitudinal direction, the first joint member is provided in contact with the cylindrical support body, and the second joint member is provided so as to overlap a portion or the entirety of the first joint member through the portion where both ends of the metal foil overlap.

As a result of extensive research by the present inventors, it has been found that by adopting the above-mentioned configuration, it is possible to provide a metal foil-covered tube having excellent airtightness and productivity.
The mechanism of action of this excellent effect is not clear, but is presumed as follows.
The metal foil provided in the metal foil covered tube having the above-described configuration has both ends overlapping each other, and the overlapping portions are sandwiched by the joints, so it is presumed that the metal foil has excellent airtightness.
Furthermore, the metal foil-coated tube having the above-described configuration can be manufactured by wrapping the metal foil around the cylindrical support body so that both ends of the metal foil overlap, and then forming a joint that sandwiches the overlapping portion. Therefore, manufacturing the metal foil-coated tube does not require advanced technology, and it is presumed that this method has excellent productivity.

<Cylindrical Support>
The metal foil clad tube of the present disclosure comprises a tubular support having a plurality of holes.

The material constituting the cylindrical support is not particularly limited, and examples thereof include metals, metal oxides, and glass.
Examples of metals include iron, chromium, aluminum, magnesium, copper, nickel, manganese, and alloys thereof.
Examples of the metal oxide include oxides of the metals described above.
Among the above, from the viewpoints of heat resistance, mechanical strength, etc., an alloy of iron and chromium is preferred, and an alloy containing 50 mass% or more of iron and 10.5 mass% or more of chromium (so-called stainless steel) is more preferred.

The cylindrical support can be a sintered body produced by sintering the above-mentioned materials.

From the viewpoint of mechanical strength and hydrogen gas permeability, the porosity of the cylindrical support is preferably 20% to 60%, and more preferably 30% to 50%.
The porosity of the cylindrical support is measured in accordance with JIS R 1634:1998.

There are no particular limitations on the shape of the cylindrical support, as long as it has a cylindrical shape. Examples of cylindrical supports include cylindrical, elliptical, and polygonal shapes. From the perspective of mechanical strength, a cylindrical shape is preferred.

The cylindrical support preferably has a recessed portion provided in at least a part of the longitudinal direction or in the entire longitudinal direction, whereby a first joining member constituting a joining portion, which will be described later, can be provided in the recessed portion.
By providing the first joining member in the recessed portion, the joining portion consisting of the first joining member and the second joining member and the metal foil sandwiched between the joining portions can be prevented from moving on the outer surface of the cylindrical support body, thereby further improving airtightness.
Furthermore, by providing a recessed portion in the first joining member, a planar shape can be formed on the first joining member, thereby improving the weldability between the first joining member and the cylindrical support body using a laser or the like, and further improving airtightness.
1 and 2 show an embodiment of a cylindrical support 1 having a recess 2. In FIG.
Note that Fig. 1 is a perspective view showing one embodiment of the cylindrical support body 1. Fig. 2 is a cross-sectional view of the cylindrical support body 1 taken along line A-A of Fig. 1. Note that although Figs. 1 and 2 show a cylindrical cylindrical support body 1, the present invention is not limited to this.
In FIG. 1, reference numeral 3 denotes an end cap, reference numeral 4 denotes a hollow tube, and reference numeral 5 denotes an opening of the hollow tube.

The thickness of the cylindrical support is not particularly limited as long as it is capable of supporting the metal foil and providing sufficient mechanical strength to the metal foil-coated tube, but may be, for example, 0.1 mm to 10 mm. In Figure 4, the thickness of the cylindrical support 11 is indicated by d1.

The length of the cylindrical support is not particularly limited and can be, for example, 100 mm to 1000 mm.

<Metal foil>
The metal foil-coated tube of the present disclosure includes a metal foil covering the outer surface of a cylindrical support body and overlapping both ends.
The metal foil-coated tube of the present disclosure can be manufactured by wrapping metal foil around a cylindrical support, and it is presumed that this can compensate for the mechanical strength of the metal foil.
The metal foil may cover the entire outer surface of the cylindrical support, or may cover only a part of it. From the viewpoint of airtightness of the metal foil-coated tube, the metal foil preferably covers 70% or more, and more preferably 80% or more of the area of the outer surface of the cylindrical support.

From the viewpoint of selective hydrogen gas permeability, heat resistance, etc., the metal foil preferably contains at least one of palladium and a palladium alloy.
Palladium alloys include alloys of palladium with one or more metals selected from the group consisting of silver, copper, gold, platinum, rhodium, ruthenium, iridium, osmium, indium, gallium, tin, and zinc.
Among the above, an alloy of palladium and silver is preferred from the viewpoint of selective hydrogen permeability.

The sum of the palladium and palladium alloy contents relative to the total mass of the metal foil is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

From the standpoint of selective hydrogen gas permeability, durability, etc., the atomic ratio of palladium in the palladium alloy is preferably 10 at% to 50 at%.

From the standpoint of selective hydrogen gas permeability, heat resistance, durability, etc., the thickness of the metal foil is preferably 0.01 mm to 0.1 mm, and more preferably 0.02 mm to 0.08 mm.

The metal foil has both ends overlapping each other, and the overlapping portions are sandwiched by a joint portion, which will be described later.
From the viewpoint of airtightness of the metal foil coated tube, the width of the overlapping portion is preferably 1 mm to 10 mm, and more preferably 3 mm to 6 mm.

<Joint part>
The metal foil-coated tube of the present disclosure includes a joint portion having a first joint member and a second joint member, where the overlapping portions of the metal foil are sandwiched between the first and second joint members of the joint portion, thereby improving the airtightness of the metal foil-coated tube.

The joint is provided over at least a portion of the cylindrical support body in the longitudinal direction or over the entirety of the cylindrical support body in the longitudinal direction.
The joint is preferably provided over the entire longitudinal length of the cylindrical support, and more preferably extends over part or the entire longitudinal length of the end caps and hollow tube provided at both ends of the cylindrical support.

<First Joining Member>
The first joining member is provided in contact with the cylindrical support body.
When the cylindrical support has a recess, the first joining member is preferably provided in the recess, which may extend partially or entirely along the longitudinal direction of the end cap and the hollow tube.
In addition, when the cylindrical support body does not have a recessed portion, the first joining member may be provided on the outer surface of the cylindrical support body. From the viewpoint of airtightness, it is preferable that the first joining member and the cylindrical support body are joined together.

The material constituting the first joining member is not particularly limited, and the same material as that constituting the cylindrical support body can be used.
From the viewpoint of airtightness and strength of the joint, it is preferable that the material constituting the first joint member is the same as the material constituting the cylindrical support body.
Among the above-mentioned materials, the material constituting the first joining member is preferably a metal such as iron, chromium, aluminum, magnesium, copper, nickel, manganese, or an alloy thereof. By forming the first joining member from the above-mentioned metal, it becomes possible to join the first joining member to the cylindrical support body by laser welding, and the productivity of the metal foil coated tube can be improved.

From the standpoint of airtightness and joint strength, the thickness of the first joining member is preferably 0.1 mm to 1 mm, and more preferably 0.3 mm to 0.7 mm. In Figure 4, the thickness of the first joining member 16 is indicated by d2.

From the standpoint of productivity, the width of the first joining member is preferably 2 mm to 10 mm, and more preferably 3 mm to 8 mm. In Figure 4, the width of the first joining member 16 is indicated by w.

The length of the first joining member is not particularly limited and can be, for example, 100 mm to 1000 mm. In Figure 3, the length of the first joining member 16 is indicated by 1.

<Second Joining Member>
The second bonding member is provided so as to overlap a part or the whole of the first bonding member via the overlapping portion of both ends of the metal foil.
From the viewpoint of airtightness of the metal foil covered tube, the second joint member is preferably provided so as to overlap the entire first joint member via the portion where both ends of the metal foil overlap.

The second joining member is preferably arranged so as to overlap the first joining member by 1 mm or more in the width direction via the overlapping portion of both ends of the metal foil, more preferably so as to overlap by 3 mm or more, and even more preferably so as to overlap by 5 mm or more.
By overlapping the second joining member with the first joining member by 1 mm or more in the width direction, joining of the first joining member and the second joining member using a laser or the like becomes easier, and productivity can be further improved. In addition, by overlapping the second joining member with the first joining member by 1 mm or more in the width direction, the airtightness of the metal foil coated tube and the strength of the joint can be improved.

The material constituting the second joining member, as well as the preferred thickness, width, and length of the second joining member, are the same as those for the first joining member, so further description is omitted here.

<End cap>
The metal foil-coated tube of the present disclosure includes an end cap at one longitudinal end, which allows the one end of the metal foil-coated tube to be sealed, thereby improving airtightness and strength.

The material constituting the end cap is not particularly limited, and the same material as that constituting the cylindrical support body can be used.
From the viewpoint of heat resistance, bonding strength, etc., it is preferable that the material constituting the end caps is the same as the material constituting the cylindrical support body.

<Hollow tube>
The metal foil-clad tube of the present disclosure includes a hollow tube at the other longitudinal end thereof, and hydrogen gas is extracted from an opening in the hollow tube of the metal foil-clad tube.

The material for forming the hollow tube is not particularly limited, and the same material as that for forming the cylindrical support can be used.
From the viewpoint of heat resistance, bonding strength, etc., it is preferable that the material constituting the hollow tube is the same as the material constituting the cylindrical support.

<Sealing part>
The metal foil-coated tube of the present disclosure may be provided with a sealing portion for sealing the boundary between the cylindrical support and the end cap and hollow tube, thereby further improving airtightness and joint strength.

The material constituting the sealing portion is not particularly limited, and the same material as that constituting the cylindrical support can be used.
From the viewpoint of heat resistance, bonding strength, etc., it is preferable that the material constituting the sealing portion is the same as the material constituting the cylindrical support body.

Next, one embodiment of the metal foil coated tube of the present disclosure will be described with reference to Figures 3 to 5. Figures 3 and 5 are perspective views showing one embodiment of the metal foil coated tube of the present disclosure. Figure 4 is a cross-sectional view of the metal foil coated tube shown in Figure 3 taken along line B-B.

As shown in Figures 3 and 4, the metal foil-coated tube 10 comprises a cylindrical support 11, metal foil 12, a joint 13, an end cap 14, and a hollow tube 15.

The metal foil-coated tube 10 shown in Figures 3 and 4 has a cylindrical support 11, end cap 14, and hollow tube 15 with recessed portions.

As shown in Figure 4, the metal foil 12 has overlapping portions at both ends.

As shown in FIGS. 3 and 4, the joint portion 13 includes a first joint member 16 and a second joint member 17 .
The first joint member 16 is provided in the cylindrical support member 11 , the end cap 14 and the recessed portion of the hollow tube 15 so as to be in contact with the cylindrical support member 11 .
The second bonding member 17 is provided so as to overlap the entire first bonding member 16 via the portion where both end portions of the metal foil 12 overlap.

As shown in FIG. 5 , the metal foil clad tube 20 includes a cylindrical support, a metal foil 22 , a joint 23 , an end cap 24 , a hollow tube 25 and a sealing portion 28 .
In FIG. 5, the first and second joining members are designated by the reference numerals 26 and 27, respectively.

(Method for manufacturing metal foil coated tube)
The method for manufacturing a metal foil coated tube of the present disclosure includes the steps of: preparing a cylindrical support body having a plurality of holes, with an end cap at one longitudinal end and a hollow tube at the other longitudinal end; providing a first joining member in contact with at least a portion of the longitudinal direction or the entire longitudinal direction of the cylindrical support body; wrapping metal foil around the outer surface of the cylindrical support body so that both ends overlap; and arranging a second joining member so that it overlaps part or all of the first joining member via the overlapping portion of the metal foil, and joining the first joining member and the second joining member so that they sandwich the overlapping portion of the metal foil to form a joint.

<Step of preparing a cylindrical support>
The method of manufacturing a metal foil-coated tube of the present disclosure includes providing a cylindrical support having a plurality of holes, an end cap at one longitudinal end, and a hollow tube at the other longitudinal end.
The cylindrical support may be a commercially available product or may be manufactured.

The step of preparing the cylindrical support may include the step of providing an end cap at one longitudinal end of the cylindrical support.

In one embodiment, the end cap can be provided by placing and joining an end cap to one end of the cylindrical support.
The joining method is not particularly limited, and can be performed by the same method as that for forming the joining portion described below.

The cylindrical support may be one prepared by sintering the above-mentioned materials using a conventional method, or a commercially available product may be used.

The step of preparing the cylindrical support may include the step of providing a hollow tube at the other longitudinal end of the cylindrical support.

In one embodiment, the hollow tube can be provided by placing and joining a hollow tube to the other end of the cylindrical support.
The joining method is not particularly limited, and can be performed by the same method as that for forming the joining portion described below.

<Step of Providing First Joining Member>
The method for manufacturing a metal foil-coated tube according to the present disclosure includes a step of providing a first joining member in contact with at least a portion of the cylindrical support body in the longitudinal direction or over the entire longitudinal direction.
The cylindrical support body and the first joining member are preferably joined together, and the joining method can be the same as the method for forming the joining portion described below.

A recess may be formed in the cylindrical support body, and the first joining member may be provided in this recess.
The recess may also be formed to extend partially or entirely through the end cap and hollow tube.
The recessed portion can be formed by cutting, or may be formed after the end cap and the hollow tube are provided at the end of the cylindrical support.

<Winding process>
The method for manufacturing a metal foil-coated tube of the present disclosure includes a step of wrapping metal foil around the outer surface of a cylindrical support having a plurality of holes so that both ends of the metal foil overlap.
The metal foil is preferably wrapped around the cylindrical support body so that the overlapping portions of both ends of the metal foil are positioned on the first bonding member.
The metal foil may be prepared by a conventionally known method or may be commercially available.

<Joint Forming Process>
The method for manufacturing a metal foil coated tube of the present disclosure includes a step of positioning a second joining member so that it overlaps part or all of the first joining member through the overlapping portion of the both ends of the metal foil, and joining the first joining member and the second joining member so that they sandwich the overlapping portion of the both ends of the metal foil, thereby forming a joint.

The method for joining the first and second joining members is not particularly limited, and can be performed, for example, by irradiating a laser onto the first and second joining members that are arranged so as to sandwich the overlapping portion of the metal foil. It is preferable that the overlapping portion of the metal foil is also welded by this laser welding.
The method is not limited to the above, and the first and second joining members may be joined using a conventionally known adhesive or the like.

When a laser is used to form a joint, the laser irradiation conditions are not particularly limited. For example, the maximum average power can be 100 W to 500 W, the maximum peak power can be 1 kW to 10 kW, the maximum pulse energy can be 10 J to 100 J, and the pulse width can be 0.2 Hz to 500 Hz.
As the laser irradiation device, for example, JK-702 manufactured by Sumitomo Heavy Industries, Ltd. or a device of the same level can be used.

<Sealing portion forming process>
The method for manufacturing a metal foil-coated tube according to the present disclosure may include a step of forming a tubular sealing portion at the boundary between the cylindrical support and the end cap and hollow tube, and joining the tubular sealing portion to the cylindrical support, the end cap, and the hollow tube. The joining method can be the same as that for forming the joint.

(Hydrogen separation device)
The hydrogen separation device of the present disclosure comprises the metal foil-coated tube and a housing container that houses the metal foil-coated tube and has a gas inlet and a gas outlet, and the end of the metal foil-coated tube that is not provided with an end cap is connected to or inserted into the hydrogen gas outlet.

<Metal foil coated tube>
The metal foil cladding tube has been described above, and therefore will not be described here.

<Housing container>
As shown in FIG. 6 , the hydrogen separation apparatus 100 of the present disclosure includes a housing vessel 103 that includes a gas inlet 101 and a gas outlet 102 .
In addition, Figure 6 shows an embodiment in which the end of the metal foil coated tube 104 where the hollow tube 105 is provided is inserted into the gas exhaust section 102 of the housing container 103, but this is not limited to this, and the above-mentioned end of the metal foil coated tube may be connected to the gas exhaust section.
In FIG. 6, reference numeral 106 denotes a metal foil, and reference numeral 108 denotes an end cap.

A mixed gas containing hydrogen gas, ammonia gas, or the like is introduced into the housing vessel through a gas inlet.
The hydrogen gas contained in the introduced mixed gas permeates the metal foil provided in the metal foil-coated tube and is discharged from the gas discharge portion of the housing vessel to which the end of the metal foil-coated tube where the hollow tube is provided is connected or inserted.
When ammonia gas is introduced into the housing, the ammonia gas is decomposed by the ammonia decomposition catalyst packed in the housing to generate hydrogen gas. The generated hydrogen gas permeates the metal foil of the metal foil-coated tube and is discharged from the gas outlet of the housing to which the end of the metal foil-coated tube, where the hollow tube is provided, is connected or inserted.

Permeation of hydrogen gas through the metal foil can be achieved by carrying out a decompression process so that the pressure inside the cylindrical support provided in the metal foil-coated tube is lower than the pressure inside the housing vessel, or by carrying out a pressurization process so that the pressure inside the housing vessel is higher than the pressure inside the cylindrical support.

Conventional ammonia decomposition catalysts can be used, including catalysts containing iron, cobalt, nickel, molybdenum, lanthanum, cerium, neodymium, ruthenium, rhodium, iridium, palladium, platinum, alloys thereof, nitrides thereof, carbides thereof, oxides thereof, etc.

The material that makes up the housing container is not particularly limited, and the same material as that used to make up the cylindrical support can be used.

As shown in Figure 6, a tube 107 or the like connected to a pump may be connected to the end of the hollow tube 105 of the metal foil-coated tube 104 inserted into the gas exhaust section 102 of the housing container 103. In Figure 6, the pump is indicated by the symbol P.

The above embodiment will be explained in more detail below using examples, but the above embodiment is not limited to these examples.

Example 1
A cylindrical stainless steel cylindrical support was prepared. The cylindrical support had a length of 600 mm, an outer diameter of 30 mm, and an inner diameter of 25 mm. The cylindrical support was a sintered stainless steel body with a porosity of 37% to 38%.

A stainless steel end cap was placed on one end of the cylindrical support, and laser irradiation was performed using JK-702 manufactured by Sumitomo Heavy Industries, Ltd. to weld the cylindrical support and the end cap together.
The end cap had a length of 30 mm and a diameter of 30 mm.

A stainless steel hollow tube was placed at the other end of the cylindrical support, and the cylindrical support and the end cap were welded together by irradiating them with a laser from the device.
The hollow tube had a length of 30 mm, an outer diameter of 30 mm, and an inner diameter of 25 mm.

The cylindrical support, end caps, and hollow tube were machined to form recesses. Specifically, recesses were formed along the entire length of the cylindrical support and extending over a portion of the length of the end caps and hollow tube (9 mm each). A first joining member measuring 618 mm in length, 5 mm in width, and 0.5 mm in thickness was embedded in this recess, and a laser was irradiated onto the first joining member using the above-mentioned device to weld the cylindrical support, end caps, and hollow tube to the first joining member. The first joining member was made of stainless steel, just like the cylindrical support.

A metal foil made of a palladium alloy (silver-palladium alloy) was prepared. The metal foil had a length of 618 mm, a width of 100 mm, and a thickness of 25 μm.
The metal foil was wrapped around the cylindrical support so that both ends of the metal foil overlapped each other and the overlapping portion was positioned on the first joining member.

A second bonding member was placed on the overlapping portion of the metal foil, and a laser was applied using the device to weld the first bonding member and the second bonding member together to form a bonded portion. The overlapping portion of the metal foil was also welded by the laser irradiation.
The second joining member was the same size as the first joining member, was made of stainless steel, and was positioned so as to overlap the entire first joining member via the overlapping portions of both ends of the metal foil.

After forming the joint, a stainless steel sealing portion was placed at the boundary between the cylindrical support and the end cap and hollow tube, and a laser was irradiated using the above-mentioned device to form the sealing portion, resulting in the metal foil-coated tube of the present disclosure.

<Airtightness evaluation>
A helium leak detector was connected to the end of the metal foil-clad tube manufactured in the above example where no end cap was provided, and helium gas was sprayed from the outside of the metal foil-clad tube.
Next, the amount of helium gas leaked into the metal foil-covered tube was measured using a HELIOT 307 manufactured by ULVAC, Inc., and the leakage amount was found to be less than 1×10 ⁻⁸ Pa·m ³ /s.

The metal foil coated tube manufactured in the above examples has excellent productivity because it does not require welding of the metal foil to the cylindrical support body at the butted or overlapping parts of the metal foil, and does not require high technology for its manufacture.
Furthermore, in the evaluation of airtightness, it was found that the amount of leaked helium gas was extremely small, demonstrating excellent airtightness.

1: Cylindrical support, 2: Recessed portion, 3: End cap, 4: Hollow tube, 5: Opening, 10: Metal foil-coated tube, 11: Cylindrical support, 12: Metal foil, 13: Joint portion, 14: End cap, 15: Hollow tube, 16: First joining member, 17: Second joining member, 20: Metal foil-coated tube, 22: Metal foil, 23: Joint portion, 24: End cap, 25: Hollow tube, 26: First joining member, 27: Second joining member, 28: Sealing portion, 100: Hydrogen separation device, 101: Gas inlet, 102: Gas outlet, 103: Housing, 104: Metal foil-coated tube, 105: Hollow tube, 106: Metal foil, 107: Tube, 108: End cap

Claims (8)

A metal foil clad tube used in a hydrogen separation device,
a cylindrical support having a plurality of holes;
a metal foil covering the outer surface of the cylindrical support and having both ends overlapping each other;
a joint formed by sandwiching an overlapping portion of both end portions of the metal foil between a first joint member and a second joint member;
an end cap provided at one end in the longitudinal direction of the cylindrical support;
a hollow tube provided at the other end of the cylindrical support in the longitudinal direction;
Equipped with
The joint portion is provided over at least a portion of the cylindrical support body in the longitudinal direction or over the entire longitudinal direction,
the first bonding member is provided in contact with the cylindrical support body, and the second bonding member is provided so as to overlap a part or the whole of the first bonding member via a portion where both end portions of the metal foil overlap.
Metal foil coated tube. the cylindrical support body has a recessed portion provided in at least a part of the longitudinal direction or the entire longitudinal direction, and the first joining member is provided in the recessed portion.
The metal foil-coated tube according to claim 1 . The metal foil covers 70% or more of the area of the outer surface of the cylindrical support.
The metal foil-coated tube according to claim 1 or 2. The second bonding member is provided so as to overlap the first bonding member by 1 mm or more in the width direction via the overlapping portion of both end portions of the metal foil.
The metal foil-coated tube according to any one of claims 1 to 3. The metal foil contains at least one of palladium and a palladium alloy.
The metal foil-coated tube according to any one of claims 1 to 4. A method for manufacturing a metal foil clad tube used in a hydrogen separation device, comprising:
providing a cylindrical support having a plurality of holes, the cylindrical support having an end cap at one longitudinal end and a hollow tube at the other longitudinal end;
providing a first joining member in contact with at least a portion of the cylindrical support body in the longitudinal direction or the entirety of the cylindrical support body in the longitudinal direction;
a step of wrapping a metal foil around the outer surface of the cylindrical support body so that both ends of the metal foil overlap each other;
a step of placing a second bonding member so as to overlap a part or the whole of the first bonding member via a portion where both end portions of the metal foil overlap, and bonding the first bonding member and the second bonding member so as to sandwich the portion where both end portions of the metal foil overlap, thereby forming a bond;
Equipped with
Method for manufacturing metal foil coated tube. The formation of the joint is performed by irradiating the first joint member and the second joint member with a laser.
The method for producing a metal foil-coated tube according to claim 6. The metal foil-coated tube according to any one of claims 1 to 5,
a housing container that houses the metal foil-coated tube and has a gas inlet and a gas outlet, and an end of the metal foil-coated tube where the hollow tube is provided is connected to or inserted into the gas outlet.
Hydrogen separation device.