JPH11116203A - Hydrogen separation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen separation device capable of evading the damage or the like to a hydrogen separation body and the unconformity caused by the difference in the thermal expansion between the hydrogen separation body and a closed vessel even in the case of using a monolith type hydrogen separation body. SOLUTION: The hydrogen separation device is composed of a plural pieces of the monolith type hydrogen separation body 5 and the closed vessel 4 having an introducing port 6 of a gas to be treated, a recovering port 7 for recovering a separation remaining gas and a discharging port 8 for taking out a separated gaseous hydrogen. The difference in the thermal expansion between the hydrogen separation body 5 and the closed vessel 4 is allowed by fixing one end of the hydrogen separation body 5 to a diaphragm plate 11 provided so as to separate the closed vessel 4 into upper and lower 2 sections and supporting in a hanging state, and a flexible part 19 for allowing the difference in the thermal expansion between the hydrogen separation body 5 and the closed vessel 4 is provided in tubular members 16-19 connected to the one end of the non-supported side of the plural pieces of the hydrogen separation bodies and communicating with the recovering port 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a structure of a hydrogen separation device using a hydrogen separation membrane that selectively permeates only hydrogen gas from hydrogen mixed gas.

[0002]

2. Description of the Related Art Hydrogen gas is used in large quantities as a basic material gas for petrochemicals, and is expected to have a great potential as a clean energy source. High-purity hydrogen gas is obtained by converting a natural gas, naphtha or the like as a raw material into a hydrogen-containing gas using a catalyst and further separating the hydrogen gas from the hydrogen-containing gas.

[0003] Specifically, palladium or a palladium alloy can be separated using the property of selectively permeating only hydrogen gas. Usually, a hydrogen separator is used in which a thin film of palladium or a palladium alloy is coated on the surface of a tubular porous substrate such as ceramics (Japanese Patent Application Laid-Open No. Sho 62).
-273030).

Further, in order to improve the processing capacity of such a hydrogen separator, the membrane area of the hydrogen separator per unit volume has been improved, and an integrated structure (a plurality of through holes) has been formed. A monolithic porous substrate was used, and a palladium thin film was applied to the inner surface of the through hole.
A so-called monolith type hydrogen separator has been disclosed (JP-A-8-40703).

[0005] By the way, the hydrogen separation ability of palladium is
Since it is exhibited only at a high temperature and a high pressure of 5 to 10 atm and 300 to 500 ° C., when both ends of a hydrogen separator made of ceramics are fixed to a closed container made of a metal that houses the hydrogen separator, the coefficient of thermal expansion of both is reduced. The difference may damage the hydrogen separator and the like. For this reason, only one end of the hydrogen separator is fixed to the closed vessel and supported in a suspended manner, and the end on the non-support side is unfixed so that the thermal expansion difference between the hydrogen separator and the closed vessel is increased. (JP-A-6-191802).

[0006]

However, when the above-described hanging support is applied to a hydrogen separator using a monolith type hydrogen separator, the following problems occur.

In the conventional tube-type hydrogen separator, a palladium film is formed on the outer surface of the tubular porous substrate, and the gas to be treated is introduced into the closed vessel 64 from the inlet 66 as shown in FIG. Then, the hydrogen gas contained in the gas to be processed permeates to the inner wall side of the tubular hydrogen separator 65 and is recovered from the outlet 68 via the upper chamber 72, and the residual processing gas is recovered from the recovery port 67. Is discharged.

On the other hand, in the monolithic hydrogen separator 85, it is essential to form a palladium film on the inner surface of the through hole of the porous substrate in order to improve the film area per unit volume of the separator 85. As shown in FIG. 4, when the gas to be treated is introduced into the closed vessel 84 from the introduction port 86, the gas flows into the through hole from the support-side end of the separator 85 via the upper chamber 92, and the hydrogen gas is removed. The light is released to the outer periphery of the separator 85 through the palladium membrane.

Therefore, a structure is adopted in which a partition is further provided at the end of the separator 85 on the non-support side, or the end of the separator 85 on the non-support side is connected to a pipe communicating with the outside of the container 84 by a flange. Otherwise, the separated hydrogen gas and the remaining gas to be processed are mixed. However, in such a structure, both ends of the hydrogen separator are fixed to the closed vessel, and it is not possible to avoid a problem caused by a difference in thermal expansion between the hydrogen separator and the closed vessel. That is, an object of the present invention is to avoid problems caused by a difference in thermal expansion between a hydrogen separator and a closed vessel, such as breakage of the hydrogen separator, in a hydrogen separator using a monolith-type hydrogen separator.

[0010]

Means for Solving the Problems According to the present invention, a plurality of through holes are formed in parallel in the longitudinal direction of a porous substrate, and a hydrogen separation membrane is attached to the inner surface of the through holes. A hydrogen separation apparatus comprising: a hydrogen separator; an inlet for the gas to be treated; a recovery port for recovering the residual gas; and a closed vessel having an outlet for extracting the separated hydrogen gas. Body or one end of a bottomed container in which the hydrogen separator is individually housed is fixed to a partition plate provided to separate the closed container into upper and lower chambers, and is supported in a suspended manner to support the hydrogen separator. And a tubular member connected to the non-supporting end of the plurality of hydrogen separators and communicating with the inlet or the recovery port. Flexible part to allow thermal expansion difference with container It is a hydrogen separation device characterized by being provided.

In the above hydrogen separation device, the hydrogen separation membrane is preferably made of palladium or an alloy containing palladium, and a flexible hose is provided on a part of the tubular member so as to be orthogonal to the longitudinal direction of the hydrogen separator. It is preferable to provide a flexible portion by connecting

Further, in the hydrogen separation device of the present invention, only the upper ends of the plurality of hydrogen separators are connected to the upper chamber in an airtight container provided with an inlet in the upper chamber and a recovery port and an outlet in the lower chamber. It is preferable that the lower and upper ends of the plurality of hydrogen separators are connected to the tubular member so as to communicate with the recovery port, while being supported and fixed to the partition plate in a suspended manner so as to communicate with each other.

[0013] Furthermore, in a closed container having an inlet and an outlet in the upper chamber and a recovery port in the lower chamber, each open end of a bottomed container in which a plurality of hydrogen separators are individually incorporated is communicated with the upper chamber. The partition wall plate is supported and fixed in a suspended manner so that only the lower ends of the plurality of hydrogen separators are fixed to the bottom of the bottomed container so as to communicate with the lower chamber; It is also preferable to connect the tubular member so that the upper end of the hydrogen separator communicates with the inlet.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Since the present invention relates to the structure of a hydrogen separation device, first, the configuration of a general hydrogen separation device will be outlined with reference to the illustrated example. As shown in FIG. 5, for example, a hydrogen separator includes a plurality of hydrogen separators 105 in a closed container 104 including a container body 102 and a lid 103.
It is configured to accommodate.

The container main body 102 is a bottomed cylindrical body having an outward flange 109 at the outer peripheral edge of the upper end opening.
An inlet 106 and a recovery port 107 communicating with the outside are formed, and the lid 103 is a dome shape having an outward flange 110 at the outer peripheral edge of the open end, and the center of the top of the lid 103 communicates with the outside of the container 104. Outlet 108 is formed. The container body 102 and the lid 103 are connected to the outward flange 10.
9 and 110, the partition plate 111 is airtightly sandwiched between the container 1
The closed container 104 divides the inside of the chamber 04 into an upper chamber 112 and a lower chamber 113.

The hydrogen separator 105 is formed by depositing a thin film of palladium or palladium alloy on the outer surface of a tubular porous substrate, and is hermetically sealed with the partition plate 111 having an upper opening end opened to the upper chamber 112. Fixed, lower chamber 1
13 in a suspended manner. Note that the lower opening end is hermetically sealed by a crown member.

In the hydrogen separation apparatus 101 having such a configuration, the gas to be treated is supplied from the inlet 106 into the lower chamber 113 of the closed vessel 104, and only the hydrogen gas in the gas to be treated is separated from the separation membrane on the outer surface of the separator 105. Selectively flows into the separator 105 and is recovered from the outlet 108 through the upper chamber 112 from the upper opening end. On the other hand, gas components other than hydrogen in the gas to be treated are discharged from the recovery port 107 without passing through the separation membrane.

The hydrogen separator of the present invention uses a monolith-type hydrogen separator in the hydrogen separator as described above, and the open end of the hydrogen separator on the non-support side is closed by a tubular member outside the sealed container. In addition to the above, the tubular member is provided with a flexible portion that allows thermal expansion of the hydrogen separator. With this structure, even with a monolithic hydrogen separator whose end on the non-support side is restricted by the tubular member, it is possible to avoid a problem due to a difference in thermal expansion between the hydrogen separator and the closed vessel.

The flexible portion is provided in the longitudinal direction of the hydrogen separator in the closed container by giving flexibility to a part of a tubular member communicating the outside of the closed container and the open end on the non-support side of the hydrogen separator. The tubular member may be bent to absorb the difference in thermal expansion between the hydrogen separator and the closed vessel in response to the thermal expansion of. For example, it is preferable to provide a flexible portion by connecting a flexible hose to a portion of the tubular member orthogonal to the longitudinal direction of the hydrogen separator.

As the flexible hose, a commercially available flexible hose in which both ends of a metal bellows have a flange structure can be used, and a flexible hose with a blade is more preferably used. This blade is a tubular body made of a metal net, covers the bellows surface, and has both open ends fixed to a flange or a bellows. Flexible hoses with only bellows have some problem in pressure resistance, and when a high-pressure gas of 5 to 10 atm flows in, they may be damaged by the internal pressure. Although the elongation to a certain extent is suppressed, the pressure resistance can be ensured.

[0021]

Next, the present invention will be described in more detail with reference to the illustrated embodiments, but the present invention is not limited to these embodiments. (Embodiment 1) The hydrogen separator 1 shown in FIG. 1 is configured by housing six monolith-type hydrogen separators 5 in a closed container 4 composed of a container body 2 and a lid 3, Legs 2
2 puts it on the floor. The lid 3 is formed with an inlet 6 communicating with the outside of the container 4, and the container body 2 is formed with a recovery port 7 and an outlet 8 communicating with the outside of the container 4. The inside of the container 4 is partitioned into an upper chamber 12 and a lower chamber 13 by sandwiching a partition plate 11 between 9 and 10 in an airtight manner.

Sockets 14 and 15 are mounted on each of the separators 5 so as to converge through holes at both end surfaces. The socket 14 on the supporting side penetrates the partition plate 11 and is fixedly fitted to the bolt 20. However, the contact surface between the outer peripheral portion of the socket and the partition plate is stopped to provide airtightness between the upper chamber and the lower chamber. To be held. The socket 15 on the non-support side is directly connected to a flexible hose 16 with an 8A blade in the same direction as the separator 5. The flexible hose 16 has a poor effect of buffering the thermal expansion in the longitudinal direction between the closed container 4 and the separator 5, but has an effect of relaxing the stress generated in the lateral direction.

The six flexible hoses 16 are converged by being joined to a ring-shaped metal pipe 17 with a flange, and connected to a 20 A bladed flexible hose 19 via an L-shaped pipe 18. Since the flexible hose 19 is disposed so as to be orthogonal to the longitudinal direction of the separator 5, it can be bent in the up-down direction. That is, it is a flexible portion in this embodiment, and bends at a high temperature to absorb a difference in thermal expansion between the container 4 and the separator 5.

In the present embodiment, the gas to be treated is supplied from the inlet 6 into the upper chamber 12 of the closed vessel 4, and flows into the through-hole of the separator 5 from the upper opening end of each separator 5. The hydrogen gas in the gas to be treated selectively permeates the separation membrane on the inner surface of the through-hole, flows out of the separator 5, and is guided to the outside of the container 4 from the outlet 8 provided in the lower chamber 13. On the other hand, gas components other than hydrogen in the gas to be processed pass through the through-hole without passing through the separation membrane and are connected to the pipe 1 connected to the lower end of the separator 5.
It passes through 6 to 19 and is discharged from the collection port 7 to the outside of the container 4. In addition, as shown in the figure, it is preferable that the separator 5 is accommodated in a metal bottomed container 21 for protection, but in this embodiment, the bottomed container 21 is not essential.

(Embodiment 2) The hydrogen separator 3 shown in FIG.
1 also has a configuration similar to that of the first embodiment, but instead of directly fixing the separator 35 to the partition plate 41, the bottomed container 51 is suspended and fixed to the partition plate 41, and The feature is that the separation body 35 is fixed. That is, in the present embodiment, the lower end of the separator 35 is the supporting side, and the upper end is the non-supporting side.

In this embodiment, the gas to be treated flows into the through-hole of the separator 35 from the upper opening end of each separator 35 through the pipes 49 to 46 from the inlet 36. The hydrogen gas in the gas to be processed selectively permeates through the separation membrane on the inner surface of the through-hole and flows out of the separator 35, and flows from the bottomed vessel 51 to the upper chamber 4
2 and is discharged from the outlet 38 to the outside of the container 34.
On the other hand, gas components other than hydrogen in the gas to be processed pass through the through hole without passing through the separation membrane, pass through the socket 45 connected to the lower end of the separator 5 so as to pass through the bottomed container 51, and pass through the socket 45. It flows into the lower chamber 43 and is discharged from the collection port 37 to the outside of the container 34.

This embodiment is the same as the first embodiment in that the flexible hose 49 becomes a flexible portion. However, the bottomed container 51 protects the separator, supports the separator, and connects the upper chamber and the lower chamber. Since they also serve as partitions for the chamber, they differ in that they are essential components. The socket 44 is supported while being loosely inserted into the support plate 50 so as to secure a degree of freedom in the vertical direction.
A hole is formed to guide the hydrogen gas flowing out of the upper chamber to the upper chamber.

[0028]

As described above, according to the hydrogen separator of the present invention, even when a monolith-type hydrogen separator is used, hydrogen caused by a difference in thermal expansion between the hydrogen separator and the sealed container is obtained. Damage to the separation device can be prevented.

[Brief description of the drawings]

FIG. 1 is a front sectional view showing one embodiment of a hydrogen separation device according to the present invention.

FIG. 2 is a front sectional view showing another embodiment of the hydrogen separation device according to the present invention.

FIG. 3 is a schematic view showing a tube type hydrogen separator.

FIG. 4 is a schematic diagram showing a monolith type hydrogen separator.

FIG. 5 is a front sectional view showing an example of a general hydrogen separation device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Hydrogen separation apparatus, 2 ... Container main body, 3 ... Lid, 4 ... Airtight container, 5 ... Hydrogen separator, 6 ... Inlet, 7 ... Recovery port, 8 ...
Outlet, 9, 10 ... outward flange, 11 ... partition plate, 12
... upper chamber, 13 ... lower chamber, 14, 15 ... socket, 16 ... flexible hose, 17 ... ring-shaped metal pipe, 18 ... L-shaped pipe, 19 ... flexible hose, 20 ... bolt, 21 ...
Bottomed container, 22 legs, 23 drain valve, 31 hydrogen separator, 32 container body, 33 lid, 34 closed container, 35 hydrogen separator, 36 inlet, 37 inlet
38 ... outlet, 39, 40 ... outward flange, 41 ... partition plate, 42 ... upper chamber, 43 ... lower chamber, 44, 45 ... socket,
46: flexible hose, 47: ring-shaped metal tube, 4
8 L-tube, 49 flexible hose, 50 support plate, 51 bottomed container, 52 legs, 53 drain valve,
64: sealed container, 65: hydrogen separator, 66: inlet, 6
7 recovery port, 68 outlet port, 71 partition wall, 72 upper chamber, 84 closed vessel, 85 hydrogen separator, 86 inlet port, 91 partition wall, 92 upper chamber, 101 hydrogen separation Apparatus, 102: container body, 103: lid, 104: sealed container, 1055: hydrogen separator, 106: inlet, 107 ...
Collection port, 108: outlet, 109, 110: outward flange, 111: partition plate, 112: upper chamber, 113: lower chamber.

Claims (5)

[Claims] 1. A plurality of hydrogen separators comprising a plurality of through-holes formed in parallel in the longitudinal direction of a porous substrate, and a hydrogen separation membrane attached to an inner surface of the through-holes; A sealed container having an inlet, a recovery port for recovering the separated residual gas, and an outlet for extracting the separated hydrogen gas, wherein the hydrogen separator or the hydrogen separator is individually separated. The one end of the bottomed container built in is fixed to a partition plate provided so as to separate the closed container into two upper and lower compartments, and is supported in a suspended manner, so that the thermal expansion difference between the hydrogen separator and the closed container is increased. And to the tubular member connected to the end on the non-support side of the plurality of hydrogen separators and communicating with the introduction port or the recovery port,
A hydrogen separation device comprising a flexible portion that allows a difference in thermal expansion between a hydrogen separator and a sealed container. 2. The hydrogen separation apparatus according to claim 1, wherein the hydrogen separation membrane is made of palladium or an alloy containing palladium. 3. The hydrogen separator according to claim 1, wherein a flexible portion is provided by connecting a flexible hose to a part of the tubular member so as to be orthogonal to a longitudinal direction of the hydrogen separator. 4. A sealed container provided with an inlet in the upper chamber and a recovery port and an outlet in the lower chamber, wherein only the upper ends of the plurality of hydrogen separators are connected to the partition plate so as to communicate with the upper chamber. 4. The hydrogen separation device according to claim 3, wherein the hydrogen separation device is supported and fixed in a suspended manner, and each lower end of the plurality of hydrogen separators is connected to a tubular member so as to communicate with a recovery port. 5. Each of the open ends of a bottomed container in which a plurality of hydrogen separators are individually incorporated in an airtight container having an inlet and an outlet in the upper chamber and a recovery port in the lower chamber communicates with the upper chamber. The partition wall plate is supported and fixed in a suspended manner so that only the lower ends of the plurality of hydrogen separators are fixed to the bottom of the bottomed container so as to communicate with the lower chamber; The hydrogen separation device according to claim 3, wherein a tubular member is connected such that an upper end of the hydrogen separator is communicated with the inlet.