JPH11116204A - 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 bodies 5 and the closed vessel 4 having an introducing port 6 of a gas to be treated, recovering port 7 for recovering a separation remaining gas and a discharging port 8 for taking out a separated gaseous hydrogen. One end of the hydrogen separation body is supported in a state of hanging to a diaphragm plate 11 provided so as to separate the closed vessel 4 into upper and lower 2 sections, many through-holes of each hydrogen separation body 5 are devided into 2 through-hole groups of a treating gas introducing passage and a separation remaining gas recovering passage, the non-supporting side end part of each hydrogen separation body 5 is sealed with a fitting member 15 so as to have a space part and then, the gas to be treated introduced from the through-holes of the supporting side end part of the hydrogen separation body 5 is fed and passed to move back and forth in the hydrogen separation body 5, and remaining gas is recoved from the through-holes of the supporting side end part.

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 a conventional tube-type hydrogen separator, a palladium film is formed on the outer surface of a tubular porous substrate, and a gas to be treated is introduced into an airtight container 34 from an inlet 36 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 35, is recovered from the outlet 38 via the upper chamber 42, and the processing residual gas is recovered from the recovery port 37. Is discharged.

On the other hand, in the monolithic hydrogen separator 55, 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 hydrogen separator 55. And as shown in FIG.
When the gas to be treated is introduced into the closed vessel 54 from the inlet 56, it flows into the through-hole from the support-side end of the hydrogen separator 55 via the upper chamber 62, and the hydrogen gas permeates the palladium membrane and passes through the palladium membrane. It is discharged to the outer periphery of the separation body 55.

Therefore, a partition may be further provided at the end on the non-support side of the hydrogen separator 55, or the end on the non-support side of the hydrogen separator 55 may be connected to a pipe communicating with the outside of the vessel 54 by a flange. If the structure is not adopted, the separated hydrogen gas and the residual 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, in the present invention, in a hydrogen separator using a monolith type hydrogen separator,
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.

[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. One end of the body is fixed to a partition plate provided so as to separate the closed container into upper and lower chambers, supported in a suspended manner, and treated through a through hole at a support side end of the hydrogen separator. A hydrogen separation apparatus characterized in that a gas is inserted so as to reciprocate in a hydrogen separator and is recovered from a through hole at the support side end to allow a difference in thermal expansion between the hydrogen separator and a closed vessel. is there.

In the above-mentioned hydrogen separation device, the hydrogen separation membrane is preferably made of palladium or an alloy containing palladium, and a large number of through holes of each hydrogen separator are provided with a gas introduction passage to be treated and a separation residual gas recovery passage. And the non-supporting end of each of the hydrogen separators is sealed with a gap by a capping member to form a through-hole at the supporting-side end of the hydrogen separator. It is preferable that the gas to be treated introduced from above is passed through the hydrogen separator so as to reciprocate and is recovered from the through hole at the end on the support side.

Further, in the hydrogen separation device of the present invention, in the upper chamber of the closed vessel, the introduction port and the gas-to-be-treated channel, and the recovery port and the residual gas recovery path are communicated by a tubular member, and the separated hydrogen gas is separated. Is preferably collected from the outlet provided in the lower chamber.

[0013]

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. 4, for example, the hydrogen separation device is configured by accommodating a plurality of hydrogen separators 75 in a closed container 74 including a container body 72 and a lid 73.

The container body 72 is a bottomed cylindrical body having an outward flange 79 at the outer peripheral edge of the upper end opening, and has an inlet 76 and a recovery port 77 communicating with the outside of the container 74. The lid 73 has an opening. It is a dome type having an outward flange 80 at the outer peripheral edge of the end, and an outlet 78 communicating with the outside of the container 74 is formed at the center of the top of the lid 73. The container main body 72 and the lid 73 constitute an airtight container 74 in which the inside of the container 74 is partitioned into an upper chamber 82 and a lower chamber 83 by airtightly sandwiching a partition plate 81 between outward flanges 79 and 80.

The hydrogen separator 75 is formed by coating a thin film of palladium or palladium alloy on the outer surface of a tubular porous substrate, and hermetically seals the partition plate 81 with an upper opening end opened to the upper chamber 82. And is suspended in the lower chamber 83. Note that the lower opening end is hermetically sealed by a crown member.

In the hydrogen separation device 71 having such a configuration, the gas to be treated is supplied from the inlet 76 to the lower chamber 8 of the closed container 74.
3, only the hydrogen gas in the gas to be treated selectively permeates the separation membrane on the outer surface of the hydrogen separator 75 and flows into the hydrogen separator 75, from the upper opening end via the upper chamber 82. From the outlet 78. On the other hand, gas components other than hydrogen in the gas to be treated do not pass through the separation membrane and are collected at the recovery port 7.
It is discharged from 7.

The hydrogen separator of the present invention uses a monolith type hydrogen separator in the above-described hydrogen separator, and the gas to be treated introduced through a through hole at a support side end of the hydrogen separator. Is collected so as to reciprocate in the hydrogen separator and is recovered from the through hole at the end on the support side. By doing so, even in the case of a monolith-type hydrogen separator, it is not necessary to collect the gas to be processed from the through-hole at the non-support side end, so that the non-support side end is restrained by a tubular member or a partition. Therefore, it is possible to avoid a problem caused by a difference in thermal expansion between the hydrogen separator and the closed vessel.

As an example of a structure in which a gas to be treated can be inserted so as to reciprocate in a hydrogen separator, a large number of through holes of the hydrogen separator are introduced into a gas to be treated (hereinafter, referred to as an introduction passage).
And a separation residual gas recovery path (hereinafter, referred to as a recovery path). The non-support side end of each hydrogen separator is sealed with a gap by a capping member. Can be

Hereinafter, the above structure will be specifically described. First, in a monolith having a large number of through-holes, about half of the through-hole groups are allocated to the introduction path, and the remaining through-hole groups are allocated to the recovery path and divided. Next, when the gas to be treated is introduced from the opening of the support side end face of the hydrogen separator of the group of through holes allocated to the introduction path, the gas to be treated passes through the introduction path to the non-support side end of the hydrogen separator. Reach.

Here, since the non-support side end is sealed with the capping member in a state having a gap, the gas to be processed passes through the gap and flows into the collection passage having a lower pressure. Then, it passes through the hydrogen separator again and is recovered from the opening on the support side end face of the group of through holes allocated to the recovery path.

As described above, the gas to be treated is inserted so as to reciprocate in the hydrogen separator, and in this process, only the hydrogen gas contained in the gas to be treated passes through the hydrogen separation membrane adhered to the inner peripheral surface of the through hole. The light is transmitted and separated outside the monolith. Even when the gas to be treated is inserted as described above, the contact area between the gas to be treated and the hydrogen separation membrane is equal, so that the processing capability of the hydrogen separator is not impaired. Also, since hydrogen separation is performed under high temperature and high pressure conditions,
The pressure of the gas to be treated is always high at the introduction side, and the residual gas does not flow back to the introduction path.

In the above structure, the cap member is a member that hermetically seals the end on the non-support side of the hydrogen separator, and is, for example, a disk-shaped member having a recess that can be fitted into the hydrogen separator. Can be used. The material constituting the capping member is not particularly limited as long as it can withstand high temperature and high pressure during hydrogen separation and can secure airtightness, and an inorganic adhesive or the like can be used. It is preferable to use a material.

The capping member can be joined to the end of the hydrogen separator by a method such as fitting or screwing. In any case, a brazing material or the like is used to secure airtightness. It is necessary to seal. In addition, the end face of the hydrogen separator and the capping member must not be brought into close contact with each other, but must be joined with a gap that allows the gas to be processed to pass through. The extent to which the gap is provided should be appropriately determined depending on the specifications of the hydrogen separator, the conditions for hydrogen separation, and the like.For example, in the case of a monolithic hydrogen separator, the end face of the hydrogen separator is several mm. May be provided.

On the other hand, the support-side end surface of the hydrogen separator needs to reliably divide a large number of through-holes into two groups, that is, an introduction path side and a recovery path side. Is preferred. At this time, as shown in FIGS. 5A and 5B, the sealing member 9 is placed on the upper surface of the opening of one through hole 93a.
When 2 is located, the introduction path side 94 and the recovery path side 95 cannot be isolated, and the gas to be treated and the gas remaining after separation are mixed.
It is necessary to dispose the sealing member 92 so as to avoid the opening of the through hole 93.

As long as the above conditions are satisfied, the shape and arrangement method of the sealing member are not particularly limited.
In addition to the flat plate shown in FIG. 6A and the corrugated plate shown in FIG. 6B, as shown in FIG.
And the outer peripheral side 97. Also, as shown in FIGS. 6A and 6B, the arrangement pattern of the through holes of the monolith 91 is blocked to secure the arrangement space 98 for the sealing member 92, so that the sealing member 92 is arranged. It is also possible to make it easier to set up.

It is preferable that the number of through holes on the introduction path side and the number of through holes on the recovery path side are equal, but it is not always necessary to strictly divide into two. As a material constituting the sealing member, ceramic, metal, heat-resistant resin, or the like can be used, and it is preferable to use metal in that high airtightness can be secured.

[0027]

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. In the present invention, it is assumed that the joining surfaces between the members are air-tightly joined by a brazing material or the like, even if not particularly mentioned.

(Example 1) Hydrogen separation apparatus 1 shown in FIG.
Is placed in a closed container 4 composed of the container body 2 and the lid 3.
The monolith type hydrogen separator 5 is accommodated in the apparatus, and is installed on the floor by three legs 22. Lid 3
The container body 2 is formed with an introduction port 6 and a recovery port 7 communicating with the outside of the container 4, and the container body 2 is formed with an outlet port 8 communicating with the outside of the container 4. The container body 2 and the lid 3 are formed with outward flanges 9 and 10. The inside of the container 4 is closed in the upper chamber 1
2. It is divided into a lower chamber 13.

One end of the hydrogen separator 5 is joined to a socket 14 fixedly fitted to the partition plate 11, and is sealed by a flat plate sealing member 20 inserted vertically into the socket 14. About half of the through holes (introduction channels) are
The remaining through holes (collection paths) are configured to communicate with the collection port 7. In addition, the end on the non-support side of the hydrogen separator 5 is sealed by the capping member 15.

In the present embodiment, the gas to be treated flows from the inlet 6 through the collecting pipe 19 and the tubular member 18 to the sealing member 2.
The hydrogen is supplied into the sockets 14 divided by zero, and flows into about half of the through holes from the upper open end of each hydrogen separator 5. The gas components other than hydrogen in the gas to be processed reach the end on the non-support side of the hydrogen separator 5 without passing through the separation membrane, pass through the gap of the capping member 15, and have a lower pressure. It flows into the recovery path. Then, it passes through the hydrogen separator 5 again and is recovered from the recovery port 7 through the tubular member 16 and the collecting pipe 17 from the through hole on the support end side. On the other hand, the hydrogen gas in the gas to be treated selectively permeates through the separation membrane on the inner surface of the through-hole, flows out of the hydrogen separator 5, and is guided to the outside of the container 4 from the outlet 8 provided in the lower chamber 13. I will

[0031]

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 schematic view showing a tube type hydrogen separator.

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

FIG. 4 is a front sectional view showing an example of a general hydrogen separation device.

FIGS. 5A and 5B are a top view and a schematic perspective view showing one embodiment of a method for disposing a sealing member. FIGS.

FIGS. 6A to 6C are top views (a), (b), and (c) showing another embodiment of a method of disposing a sealing member.

FIGS. 7A and 7B are top views (a) and (b) showing an embodiment in which the arrangement of monolithic through holes is blocked.

[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 ... socket, 15 ... crown member, 16 ... tubular member, 17 ... collecting pipe, 18 ... tubular member,
19 ... collecting pipe, 20 ... sealing member, 22 ... leg, 23 ... drain valve, 34 ... airtight container, 35 ... hydrogen separator, 36 ...
Inlet, 37 ... Recovery port, 38 ... Outlet, 41 ... Partition board,
42 ... upper chamber, 54 ... airtight container, 55 ... hydrogen separator, 56
... Inlet, 61 ... Partition plate, 62 ... Upper chamber, 71 ... Hydrogen separator, 72 ... Container body, 73 ... Cover, 74 ... Sealed container,
75 hydrogen separator, 76 inlet, 77 recovery port, 78
... Outlet, 79,80 ... Outward flange, 81 ... Partition plate,
82: upper chamber, 83: lower chamber, 91: hydrogen separator (monolith), 92: sealing member, 93: through hole, 93a: 1 through hole, 94: introduction path side, 95: recovery path side, 96: center Side, 97: outer peripheral side, 98: space for disposing the sealing member.

Claims (4)

[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 one end of the hydrogen separator is connected to the closed container. Is fixed to a partition plate provided so as to be separated into two upper and lower chambers, supported in a suspended manner, and the gas to be treated introduced from the through hole at the support side end of the hydrogen separator is reciprocated in the hydrogen separator. The hydrogen separation device is characterized in that the thermal separation difference between the hydrogen separator and the closed vessel is allowed by allowing the hydrogen separator and the closed vessel to collect through the through hole at the supporting end. 2. The hydrogen separation apparatus according to claim 1, wherein the hydrogen separation membrane is made of palladium or an alloy containing palladium. 3. A large number of through-holes of each hydrogen separator are divided into two through-hole groups of a gas introduction path to be treated and a residual gas recovery path, and a non-support side end of each hydrogen separator is crowned. By sealing with a gap portion by the attaching member, the gas to be treated introduced from the through hole at the support side end of the hydrogen separator is inserted so as to reciprocate in the hydrogen separator, and the support side end The hydrogen separation device according to claim 1, wherein the hydrogen is recovered from the through hole. 4. In the upper chamber of the closed vessel, the inlet and the gas-to-be-processed, the recovery port and the residual gas recovery path are connected by a tubular member, and the separated hydrogen gas is provided in the lower chamber. The hydrogen separator according to claim 3, wherein the hydrogen is recovered from the outlet.